WO2004014997A2 - Plasticized polyolefin compositions - Google Patents

Plasticized polyolefin compositions Download PDF

Info

Publication number
WO2004014997A2
WO2004014997A2 PCT/US2003/024667 US0324667W WO2004014997A2 WO 2004014997 A2 WO2004014997 A2 WO 2004014997A2 US 0324667 W US0324667 W US 0324667W WO 2004014997 A2 WO2004014997 A2 WO 2004014997A2
Authority
WO
WIPO (PCT)
Prior art keywords
composition
polyolefin
another embodiment
propylene
copolymer
Prior art date
Application number
PCT/US2003/024667
Other languages
French (fr)
Other versions
WO2004014997A3 (en
Inventor
Chon-Yie Lin
Chia Yung Cheng
Henry Wu-Hsiang Yang
Original Assignee
Exxonmobil Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to AU2003272213A priority Critical patent/AU2003272213A1/en
Priority to BR0313398-2A priority patent/BR0313398A/en
Priority to CA2492839A priority patent/CA2492839C/en
Priority to JP2004527804A priority patent/JP2005535748A/en
Priority to EP03754386.5A priority patent/EP1530611B1/en
Priority to US10/640,435 priority patent/US7619026B2/en
Priority to PCT/US2003/025149 priority patent/WO2004014998A2/en
Priority to BR0313549-7A priority patent/BR0313549A/en
Priority to EP03785201.9A priority patent/EP1539870B1/en
Priority to CA2495019A priority patent/CA2495019C/en
Priority to SG200701530-8A priority patent/SG145599A1/en
Priority to AU2003258173A priority patent/AU2003258173C1/en
Priority to CA 2675730 priority patent/CA2675730C/en
Priority to JP2005506610A priority patent/JP4874648B2/en
Priority to US10/782,228 priority patent/US7531594B2/en
Publication of WO2004014997A2 publication Critical patent/WO2004014997A2/en
Publication of WO2004014997A3 publication Critical patent/WO2004014997A3/en
Priority to US11/118,925 priority patent/US7662885B2/en
Priority to US11/406,926 priority patent/US7652093B2/en
Priority to US11/854,943 priority patent/US7985801B2/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/01Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016Plasticisers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00Polymer mixtures characterised by way of preparation
    • C08L2314/06Metallocene or single site catalysts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]

Definitions

  • the present invention relates to plasticized polyolefins comprising a polyolefin and non-functionalized plasticizer such as C 6 to C 0 o paraffins. More particularly, the present invention relates to plasticized polyolefins such as propylene polymers having improved processability and properties such as flexibility and impact resistance.
  • Polyolefins are useful in any number of everyday articles.
  • plasticized polyolefin with improved softness, better flexibility (lower flexural modulus), a depressed glass transition temperature, and improved impact strength (improved Gardner impact) at low temperatures (below 0°C), while not influencing the melting temperature of the polyolefin, the polyolefin crystallization rate, its clarity, and with minimal migration of the plasticizer to the surface of articles made therefrom. Further, there is a need for a plasticized polypropylene that can be used in such applications as food containers and toys.
  • the present invention relates to plasticized polyolefin compositions comprising a polyolefin and a non-functionalized plasticizer; wherein the non- functionalized plasticizer may comprise C 6 to C 20 o paraffins (including branched and normal paraffins) having a pour point of less than -5°C.
  • the non-functionalized plasticizer is an isoparaffin comprising C 6 to C 25 isoparaffins.
  • the non-functionalized plasticizer is a polyalphaolefin comprising C 10 to oo n-paraffins.
  • the polyolefin may be a polypropylene homopolymer, copolymer, impact copolymer, or blends thereof, and may include a plastomer.
  • desirable articles of manufacture made from compositions of the invention include films, sheets, fibers, woven and nonwoven fabrics, tubes, pipes, automotive components, fiirniture, sporting equipment, food storage containers, transparent and semi- transparent articles, toys, tubing and pipes, and medical devices.
  • the compositions of the invention may be characterized by having an improved (decreased) T g relative to the starting polyolefin, while maintaining other desirable properties.
  • Figure 1 is a graphical representation of the Storage Modulus (F) as a function of temperature for various plasticized propylene homopolymer examples cited herein;
  • FIG. 2 is a graphical representation of the Tan ⁇ as a function of temperature for various plasticized propylene homopolymer examples cited herein;
  • FIG. 3 is a graphical representation of the Tan ⁇ as a function of temperature for various plasticized propylene copolymer examples cited herein;
  • FIG. 4 is a graphical representation of the Tan ⁇ as a function of temperature for various plasticized propylene impact copolymer examples cited herein;
  • Figure 5 is a graphical representation of the melting heat flow from
  • Figure 6 is a graphical representation of the crystallization heat flow from DSC as a function of temperature for various samples plasticized propylene homopolymer samples illustrative of the invention;
  • Figure 7 is a graphical representation of the melting heat flow from
  • Figure 8 is a graphical representation of the crystallization heat flow from DSC as a function of temperature for various plasticized propylene copolymer samples illustrative of the invention.
  • Figure 9 is a graphical representation of the melting heat flow from
  • Figure 10 is a graphical representation of the crystallization heat flow from DSC as a function of temperature for various plasticized propylene impact copolymer samples illustrative of the invention
  • Figure 11 is a graphical representation of the shear viscosity as a function of shear rate for various plasticized propylene homopolymer samples illustrative of the invention.
  • Figure 12 is a graphical representation of the shear viscosity as a function of shear rate for various plasticized propylene copolymer samples illustrative of the invention.
  • Figure 13 is a graphical representation of the shear viscosity as a function of shear rate for various plasticized propylene impact copolymer samples illustrative of the invention.
  • Figure 14 is a graphical representation of the molecular weight distribution for various plasticized propylene homopolymer samples illustrative of the invention. DETAILED DESCRIPTION OF THE INVENTION
  • the present invention is a plasticized polyolefin composition
  • a polyolefin and a non-functionalized plasticizer (NFP).
  • the NFP may be an aliphatic hydrocarbon, or paraffin, typically comprising C 6 to C 2 oo paraffins.
  • paraffins includes all isomers of C 6 to C 200 paraffins including branched and linear structures, and blends thereof.
  • the individual paraffins may include saturated cyclic hydrocarbons.
  • the NFP has a pour point of less than 0°C, and a viscosity (ASTM D445-97) of from 0.1 to 3000 cSt at 100°C.
  • Useful NFPs may include so called polyalphaolefms (PAOs) and isoparaffins.
  • compositions of the present invention can be characterized in that the glass transition temperature (T g ) of the composition decreases by at least 2°C for every 4 wt% of NFP present in the composition in one embodiment; and decreases by at least 3°C for every 4 wt% of NFP present in the composition in another embodiment; and decreases from at least 4 to 10°C for every 4 wt% of NFP present in the composition in yet another embodiment, while the melting and crystallization temperatures of the polyolefin remain constant (within 1 to 2°C).
  • the compositions of the invention are characterized in that the NFP is compatible and miscible with propylene polymers and does not form a separate phase. This is evidenced by, for example, the T g profile observed for the compositions by DMTA (Dynamic Mechanical Thermal Analysis).
  • polyolefin and NFP can be blended by any suitable means.
  • plasticized polyolefin compositions described herein are useful in any number of applications, including transparent components such as in cook and storage ware, and in other articles such as furniture, automotive components, toys, sportswear, medical devices, sterilizable medical devices and sterilization containers, nonwoven fibers and fabrics and articles therefrom such as drapes, gowns, filters, hygiene products, diapers, and films, oriented films, sheets, tubes, pipes and other items where softness, high impact strength, and impact strength below freezing is important.
  • plasticized polyolefins of the invention Any number of techniques can be used to process the plasticized polyolefins of the invention to form these articles including injection molding, extrusion, thermoforming, blow molding, rotomolding, spunbonding, meltblowing, fiber spinning, blown film, stretching for oriented films, and other common processing methods.
  • Polyolefins may be plasticized, or blended with, the NFP of the present invention to form more flexible, yet impact resistant, compositions.
  • the polyolefin is selected from polypropylene homopolymer, polypropylene copolymers, and blends thereof.
  • the homopolymer may be atactic polypropylene, isotactic polypropylene, syndiotactic polypropylene and blends thereof.
  • the copolymer can be a random copolymer, a block copolymer, and blends thereof.
  • polymer blends include so called impact copolymers, elastomers and plastomers, any of which may be physical blends or in situ blends of polypropylene and polypropylene copolymer.
  • the method of making the polypropylene is not critical, as it can be made by slurry, solution, or gas phase processes, and by using either Ziegler-Natta-type catalysts, metallocene-type catalysts, or a combination thereof.
  • Such catalysts are well known in the art, and are described in, for example, ZIEGLER CATALYSTS (Gerhard Fink, Rolf Mulhaupt and Hans H.
  • the polyolefin may be a propylene homopolymer.
  • a desirable propylene homopolymer has a molecular weight distribution (Mw/Mn) ranging from 1.5 to 10, and from 2.0 to 7 in another embodiment, and from 2.0 to 5 in yet another embodiment, and from 2.0 to 4 in yet another embodiment.
  • the Gardner impact strength, tested on 0.125 inch disk at 23°C, of the propylene homopolymer may range from 20 in-lb to 1000 in-lb in one embodiment, and from 30 in-lb to 500 in-lb in another embodiment, and from 40 in-lb to 400 in-lb in yet another embodiment.
  • the 1% secant flexural modulus of the propylene homopolymer ranges from 100 MPa to 2300 MPa, and from 200 MPa to 2100 MPa in another embodiment, and from 300 MPa to 2000 MPa in yet another embodiment, wherein a desirable polyolefin may exhibit any combination of any upper flexural modulus limit with any lower flexural modulus limit.
  • the melt flow rate (MFR) (ASTM D 1238, 230°C, 2.16 kg) of propylene homopolymer ranges from 0.1 dg/min to 2500 dg/min in one embodiment, and from 0.3 to 500 dg/min in another embodiment.
  • the polypropylene homopolymer or copolymer useful in the present invention may have some level of isotacticity.
  • isotactic polypropylene is a useful polyolefin, and highly isotactic polypropylene in another embodiment.
  • isotactic is defined as having at least
  • isotactic pentads according to analysis by 13c-NMR_
  • “highly isotactic” is defined as having at least 60% isotactic pentads according to analysis by I ⁇ C.NMR n a desirable embodiment, a polypropylene homopolymer having at least 85% isotacticity is the polyolefin, and at least 90% isotacticity in yet another embodiment.
  • the polyolefin is a propylene copolymer, either random, or block, of propylene derived units and units selected from ethylene and C 4 to C 20 ⁇ -olefin derived units, and from ethylene and C 4 to C 10 ⁇ -olefin derived units in another embodiment.
  • the ethylene or C 4 to C 20 ⁇ -olefin derived units are present from 0.1 wt% to 50 wt% of the copolymer in one embodiment, and from 0.5 to 30 wt% in another embodiment, and from 1 to 15 wt% in yet another embodiment, and from 0.1 to 5 wt% in yet another embodiment, wherein a desirable copolymer comprises ethylene and C 4 to C 20 ⁇ -olefin derived units in any combination of any upper wt% limit with any lower wt% limit described herein.
  • the propylene copolymer will have a weight average molecular weight of from greater than 8,000 g/mol in one embodiment, and greater than 10,000 g/mol in another embodiment, and greater than 12,000 g/mol in yet another embodiment, and greater than 20,000 g/mol in yet another embodiment, and less than 1,000,000 g/mol in yet another embodiment, and less than 800,000 in yet another embodiment, wherein a desirable copolymer may comprise any upper molecular weight limit with any lower molecular weight limit described herein.
  • 0.125 inch disk at 23°C, of the propylene copolymer ranges from 20 in-lb to 1000 in-lb, and from 30 in-lb to 500 in-lb in another embodiment, and from 40 in-lb to 400 in-lb in yet another embodiment.
  • the propylene copolymer may possess a 1% secant flexural modulus ranging from 100 MPa to 2300 MPa, and from 200 MPa to 2100 MPa in another embodiment, and from 300 MPa to 2000 MPa in yet another embodiment, wherein a desirable polyolefin may exhibit any combination of any upper flexural modulus limit with any lower flexural modulus limit.
  • the melt flow rate (MFR) (ASTM D 1238, 230°C) of desirable copolymers ranges from 0.1 dg/min to 2500 dg/min in one embodiment, and from 0.1 to 500 dg/min in another embodiment.
  • the polyolefin may be a so called "impact copolymer” or block copolymer.
  • This impact copolymer may be a reactor blend (in situ blend) or a physical blend.
  • a suitable impact copolymer comprises from 40% to 95% by weight Component A and from 5% to 60% by weight Component B based on the total weight of the impact copolymer; wherein Component A comprises propylene homopolymer or copolymer, the copolymer comprising 10% or less by weight ethylene, butene, hexene or octene comonomer; and wherein Component B comprises propylene copolymer, wherein the copolymer comprises from 5% to 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 95% to about 30% by weight propylene.
  • Component B consists essentially of propylene and from about 30% to about 65% by weight ethylene.
  • Component B comprises ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, ethylene-acrylate copolymers, ethylene- vinyl acetate, styrene-butadiene copolymers, ethylene-acrylic ester copolymers, polybutadiene, polyisoprene, natural rubber, isobutylene, hydrocarbon resin (being characterized by a molecular weight less than 5000, a T g of about 50 to 100°C and a softening point less than about 140°C), rosin, and mixtures thereof.
  • Component B has a molecular weight distribution of less than 3.5. In yet another embodiment, Component B has a weight average molecular weight of at least 20,000.
  • a useful impact copolymer is disclosed in, for example, US 6,342,566 and US 6,384,142.
  • 0.125 inch disk at -29°C, of the propylene impact copolymer ranges from 20 in-lb to 1000 in-lb, and from 30 in-lb to 500 in-lb in another embodiment, and from 40 in-lb to 400 in-lb in yet another embodiment.
  • the 1% secant flexural modulus of the propylene impact copolymer may range from 100 MPa to 2300 MPa in one embodiment, and from 200 MPa to 2100 MPa in another embodiment, and from 300 MPa to 2000 MPa in yet another embodiment, wherein a desirable polyolefin may exhibit any combination of any upper flexural modulus limit with any lower flexural modulus limit.
  • melt flow rate (MFR) (ASTM D 1238, 230°C, 2.16 kg) of desirable homopolymers ranges from 0.1 dg/min to 2500 dg/min in one embodiment, and from 0.3 to 500 dg/min in another embodiment.
  • Another suitable polyolefin comprises a blend of a polypropylene homopolymer or copolymer with a so called "plastomer".
  • the plastomers that are useful in the present invention may be described as polyolefin copolymers having a density of from 0.85 to 0.915 g/cm 3 and a melt index (MI) between 0.10 and 30 dg/min (ASTM D 1238; 190°C, 2.1 kg).
  • the useful plastomer is a copolymer of ethylene derived units and at least one of C 3 to C 10 ⁇ -olefin derived units, the copolymer having a density in the range of less than 0.915 g/cm 3 .
  • the amount of comonomer (C 3 to C ⁇ 0 ⁇ -olefin derived units) present in the plastomer ranges from 2 wt% to 35 wt% in one embodiment, and from 5 wt% to 30 wt% in another embodiment, and from 15 wt% to 25 wt% in yet another embodiment, and from 20 wt% to 30 wt% in yet another embodiment.
  • the plastomer useful in the invention has a melt index (MI) of between 0.10 and 20 dg/min in one embodiment, and from 0.2 to 10 dg/min in another embodiment, and from 0.3 to 8 dg/min in yet another embodiment.
  • MI melt index
  • the average molecular weight of useful plastomers ranges from 10,000 to 800,000 in one embodiment, and from 20,000 to 700,000 in another embodiment.
  • the 1% secant flexural modulus (ASTM D 790) of useful plastomers ranges from 10 MPa to 150 MPa in one embodiment, and from 20 MPa to 100 MPa in another embodiment.
  • the plastomer that is useful in compositions of the present invention has a melting temperature (T m ) of from 30 to 80°C (first melt peak) and from 50 to 125°C (second melt peak) in one embodiment, and from 40 to 70°C (first melt peak) and from 50 to 100°C (second melt peak) in another embodiment.
  • T m melting temperature
  • Plastomers useful in the present invention are metallocene catalyzed copolymers of ethylene derived units and higher ⁇ -olefin derived units such as propylene, 1 -butene, 1 -hexene and 1 -octene, and which contain enough of one or more of these comonomer units to yield a density between 0.860 and 0.900 g/cm 3 in one embodiment.
  • the molecular weight distribution (Mw/Mn) of desirable plastomers ranges from 1.5 to 5 in one embodiment, and from 2.0 to 4 in another embodiment.
  • Examples of a commercially available plastomers are EXACT 4150, a copolymer of ethylene and 1 -hexene, the 1 -hexene derived units making up from 18 to 22 wt% of the plastomer and having a density of 0.895 g/cm 3 and MI of 3.5 dg/min (ExxonMobil Chemical Company, Houston, TX); and EXACT 8201, a copolymer of ethylene and 1 -octene, the 1 -octene derived units making up from 26 to 30 wt% of the plastomer, and having a density of 0.882 g/cm 3 and MI of 1.0 dg/min (ExxonMobil Chemical Company, Houston, TX).
  • the polyolefin suitable for use in the present invention can be in any physical form when used to blend with the NFP of the invention.
  • reactor granules defined as the granules of polymer that are isolated from the polymerization reactor prior to any processing procedures, are used to blend with the NFP of the invention.
  • the reactor granules have an average diameter of from 50 ⁇ m to 10 mm in one embodiment, and from 10 ⁇ m to 5 mm in another embodiment.
  • the polyolefin is in the form of pellets, such as, for example, having an average diameter of from 1 mm to 10 mm that are formed from melt extrusion of the reactor granules.
  • the polyolefin suitable for the composition excludes physical blends of polypropylene with other polyolefins, and in particular, excludes physical blends of polypropylene with low molecular weight (500 to 10,000 g/mol) polyethylene or polyethylene copolymers, meaning that, low molecular weight polyethylene or polyethylene copolymers are not purposefully added in any amount to the polyolefin (e.g., polypropylene homopolymer or copolymer) compositions of the invention, such as is the case in, for example, WO 01/18109 Al.
  • polyolefin e.g., polypropylene homopolymer or copolymer
  • the polyolefin is present in the compositions of the present invention from 40 wt% to 99.9 wt% in one embodiment, and from 50 wt% to 99 wt% in another embodiment, and from 60 wt% to 98 wt% in yet another embodiment, and from 70 wt% to 97 wt% in yet another embodiment, and from 80 wt% to 97 wt% in yet another embodiment, and from 90 wt% to 98 wt% in yet another embodiment, wherein a desirable range may be any combination of any upper wt% limit with any lower wt% limit described herein.
  • Desirable polyolefins for use in the present invention may thus be described by any embodiment herein, or any combination of the embodiments described herein.
  • the polyolefin compositions of the present invention include a non-functionalized plastizer ("NFP").
  • NFP non-functionalized plastizer
  • the NFP of the present invention is a compound comprising carbon and hydrogen, and does not include to an appreciable extent functional groups selected from hydroxide, aryls and substituted aryls, halogens, alkoxys, carboxylates, esters, carbon unsaturation, acrylates, oxygen, nitrogen, and carboxyl.
  • the NFP consists of C 6 to C 0 o paraffins
  • the NFP consists essentially of C 6 to C 0 o paraffins, and consists essentially of C 8 to C 10 o paraffins in another embodiment.
  • the term "paraffin” includes all isomers such as n-paraffins, branched paraffins, isoparaffins, and may include cyclic aliphatic species, and blends thereof, and may be derived synthetically by means known in the art, or from refined crude oil in such a way as to meet the requirements described for desirable NFPs described herein. It will be realized that the classes of materials described herein that are useful as an NFPs can be utilized alone or admixed with other NFPs described herein in order to obtain the desired properties.
  • the NFP may be present in the polyolefin compositions of the invention from 0.1 wt% to 60 wt% in one embodiment, and from 0.5 wt% to 40 wt% in another embodiment, and from 1 wt% to 20 wt% in yet another embodiment, and from 2 wt% to 10 wt% in yet another embodiment, wherein a desirable range may comprise any upper wt% limit with any lower wt% limit described herein.
  • the NFP may also be described by any number of, or any combination of, parameters described herein.
  • the NFP of the present invention has a pour point (ASTM D97) of from less than 0°C in one embodiment, and less than -5°C in another embodiment, and less than -10°C in another embodiment, less than -20°C in yet another embodiment, less than -40°C in yet another embodiment, less than -50°C in yet another embodiment, and less than -60°C in yet another embodiment, and greater than -120°C in yet another embodiment, and greater than -200°C in yet another embodiment, wherein a desirable range may include any upper pour point limit with any lower pour point limit described herein.
  • the NFP is a paraffin or other compound having a pour point of less than -30°C, and between -30°C and -90°C in another embodiment, in the viscosity range of from 0.5 to 200 cSt at 40°C (ASTM D445-97).
  • the NFP may have a dielectric constant at 20°C of less than 3.0 in one embodiment, and less than 2.8 in another embodiment, less than 2.5 in another embodiment, and less than 2.3 in yet another embodiment, and less than 2.1 in yet another embodiment.
  • Polyethylene and polypropylene each have a dielectric constant (1 kHz, 23°C) of at least 2.3 (CRC HANDBOOK OF CHEMISTRY AND PHYSICS (David R. Lide, ed. 82 d ed. CRC Press 2001).
  • the NFP has a viscosity (ASTM D445-97) of from 0.1 to 3000 cSt at 100°C, and from 0.5 to 1000 cSt at 100°C in another embodiment, and from 1 to 250 cSt at 100°C in another embodiment, and from 1 to 200 cSt at 100°C in yet another embodiment, and from 10 to 500 cSt at 100°C in yet another embodiment, wherein a desirable range may comprise any upper viscosity limit with any lower viscosity limit described herein.
  • the NFP has a specific gravity (ASTM D 4052, 15.6/15.6°C) of less than 0.920 g/cm 3 in one embodiment, and less than 0.910 g/cm 3 in another embodiment, and from 0.650 to 0.900 g/cm 3 in another embodiment, and from 0.700 to 0.860 g/cm 3 , and from 0.750 to 0.855 g/cm 3 in another embodiment, and from 0.790 to 0.850 g/cm 3 in another embodiment, and from 0.800 to 0.840 g/cm 3 in yet another embodiment, wherein a desirable range may comprise any upper specific gravity limit with any lower specific gravity limit described herein.
  • the NFP has a boiling point of from 100°C to 800°C in one embodiment, and from 200°C to 600°C in another embodiment, and from 250 °C to 500°C in yet another embodiment. Further, the NFP has a weight average molecular weight (GPC or GC) of less than 20,000 g/mol in one embodiment, and less than 10,000 g/mol in yet another embodiment, and less than 5,000 g/mol in yet another embodiment, and less than 4,000 g/mol in yet another embodiment, and less than 2,000 g/mol in yet another embodiment, and less than 500 g/mol in yet another embodiment, and greater than 100 g/mol in yet another embodiment, wherein a desirable molecular weight range can be any combination of any upper molecular weight limit with any lower molecular weight limit described herein.
  • a compound suitable as an NFP for polyolefins of the present invention may be selected from commercially available compounds such as so called “isoparaffins", “polyalphaolefins” (PAOs) and “polybutenes” (a subgroup of PAOs). These three classes of compounds can be described as paraffins which can include branched, cyclic, and normal structures, and blends thereof. These NFPs can be described as comprising C 6 to C 200 paraffins in one embodiment, and C 8 to Cioo paraffins in another embodiment.
  • isoparaffins are described as follows. These paraffins are desirably isoparaffins, meaning that the paraffin chains possess C ⁇ to C 10 alkyl branching along at least a portion of each paraffin chain.
  • the C 6 to C 20 o paraffins may comprise C 6 to C 25 isoparaffins in one embodiment, and C 8 to C 20 isoparaffins in another embodiment.
  • the isoparaffins are saturated aliphatic hydrocarbons whose molecules have at least one carbon atom bonded to at least three other carbon atoms or at least one side chain (i.e., a molecule having one or more tertiary or quaternary carbon atoms), and preferably wherein the total number of carbon atoms per molecule is in the range between 6 to 50, and between 10 and 24 in another embodiment, and from 10 to 15 in yet another embodiment. Narious isomers of each carbon number will typically be present.
  • the isoparaffins may also include cycloparaffins with branched side chains, generally as a minor component of the isoparaffin.
  • the density (ASTM 4052, 15.6/15.6°C) of these isoparaffins ranges from 0.70 to 0.83 g/cm 3 ; a pour point of below -40°C in one embodiment, and below -50°C in another embodiment; a viscosity (ASTM 445, 25°C) of from 0.5 to 20 cSt at 25°C; and average molecular weights in the range of 100 to 300 g/mol.
  • the isoparaffins are commercially available under the tradename ISOPAR (ExxonMobil Chemical Company, Houston TX), and are described in, for example, US 6,197,285, 3,818,105 and 3,439,088, and sold commercially as ISOPAR series of isoparaffins, some of which are summarized in Table 1 below.
  • ISOPAR ExxonMobil Chemical Company, Houston TX
  • the isoparaffins are a mixture of branched and normal paraffins having from 6 to 50 carbon atoms, and from 10 to 24 carbon atoms in another embodiment, in the molecule.
  • the isoparaffin composition has an a branch paraffim.n-paraffin ratio ranging from 0.5:1 to 9:1 in one embodiment, and from 1:1 to 4:1 in another embodiment.
  • the isoparaffins of the mixture in this embodiment contain greater than 50 wt% (by total weight of the isoparaffin composition) mono-methyl species, for example, 2-methyl, 3 -methyl, 4-methyl, 5- methyl or the like, with minimum formation of branches with substituent groups of carbon number greater than 1, such as, for example, ethyl, propyl, butyl or the like, based on the total weight of isoparaffins in the mixture.
  • the isoparaffins of the mixture contain greater than 70 wt% of the mono-methyl species, based on the total weight of the isoparaffins in the mixture.
  • the isoparaffinic mixture boils within a range of from 100°C to 350°C in one embodiment, and within a range of from 110°C to 320°C in another embodiment.
  • the paraffinic mixture is generally fractionated into cuts having narrow boiling ranges, for example, 35°C boiling ranges.
  • These branch paraffin/n-paraffin blends are described in, for example, US 5,906,727.
  • the paraffins suitable as the NFP of the invention also include so called PAOs, which are described as follows.
  • the PAOs useful in the present invention comprise C 6 to C 0 o paraffins, and C 10 to C 10 o n-paraffins in another embodiment.
  • the PAOs are dimers, trimers, tetramers, pentamers, etc. of C 4 to C 12 ⁇ -olefins in one embodiment, and C 5 to C 12 ⁇ -olefins in another embodiment.
  • Suitable olefms include 1 -butene, 1-pentene, 1 -hexene, 1-heptene, 1 -octene, 1- nonene, 1-decene, 1-undodecene and 1-dodecene.
  • the olefin is 1-decene
  • the NFP is a mixture of dimers, trimers, tetramers and pentamers (and higher) of 1-decene.
  • the PAOs are described more particularly in, for example, US 5,171,908, and US 5,783,531 and in SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS 1-52 (Leslie R. Rudnick & Ronald L. Shubkin, ed. Marcel Dekker, Inc. 1999).
  • the PAOs of the present invention possess a weight average molecular weight of from 100 to 20,000 in one embodiment, and from 200 to 10,000 in another embodiment, and from 200 to 7,000 in yet another embodiment, and from 200 to 2,000 in yet another embodiment, and from 200 to 500 in yet another embodiment.
  • PAOs have viscosities in the range of 0.1 to 150 cSt at 100°C, and from 0.1 to 3000 cSt at 100°C in another embodiment (ASTM 445).
  • the PAOs useful in the present invention have pour points of less than 0°C in one embodiment, less than -10°C in another embodiment, and less than -20°C in yet another embodiment, and less than -40°C in yet another embodiment. Desirable PAOs are commercially available as SHF and SuperSyn PAOs (ExxonMobil Chemical Company, Houston TX), some of which are summarized in the Table 2 below.
  • polybutenes are another useful NFP of the present invention and are described as follows.
  • the polybutene processing oil is a low molecular weight (less than 15,000 number average molecular weight; less than 60,000 weight average molecular weight) homopolymer or copolymer of olefin derived units having from 3 to 8 carbon atoms in one embodiment, preferably from 4 to 6 carbon atoms in another embodiment.
  • the polybutene is a homopolymer or copolymer of a C 4 raffmate.
  • polybutene polymers An embodiment of such low molecular weight polymers termed “polybutene” polymers is described in, for example, SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS 357-392 (Leslie R. Rudnick & Ronald L. Shubkin, ed., Marcel Dekker 1999) (hereinafter "polybutene processing oil” or “polybutene”).
  • the polybutene is a copolymer of at least isobutylene derived units, 1 -butene derived units, and 2-butene derived units.
  • the polybutene is a homopolymer, copolymer, or terpolymer of the three units, wherein the isobutylene derived units are from 40 to 100 wt% of the copolymer, the 1 -butene derived units are from 0 to 40 wt% of the copolymer, and the 2-butene derived units are from 0 to 40 wt% of the copolymer.
  • the polybutene is a copolymer or terpolymer of the three units, wherein the isobutylene derived units are from 40 to 99 wt% of the copolymer, the 1 -butene derived units are from 2 to 40 wt% of the copolymer, and the 2-butene derived units are from 0 to 30 wt% of the copolymer.
  • the polybutene is a terpolymer of the three units, wherein the isobutylene derived units are from 40 to 96 wt% of the copolymer, the 1 -butene derived units are from 2 to 40 wt% of the copolymer, and the 2-butene derived units are from 2 to 20 wt% of the copolymer.
  • the polybutene is a homopolymer or copolymer of isobutylene and 1 -butene, wherein the isobutylene derived units are from 65 to 100 wt% of the homopolymer or copolymer, and the 1 -butene derived units are from 0 to 35 wt% of the copolymer.
  • Polybutene processing oils useful in the invention typically have a number average molecular weight (Mn) of less than 10,000 g/mol in one embodiment, less than 8000 g/mol in another embodiment, and less than 6000 g/mol in yet another embodiment.
  • Mn number average molecular weight
  • the polybutene oil has a number average molecular weight of greater than 400 g/mol, and greater than 700 g/mol in another embodiment, and greater than 900 g/mol in yet another embodiment.
  • a preferred embodiment can be a combination of any lower molecular weight limit with any upper molecular weight limit described herein.
  • the polybutene has a number average molecular weight of from 400 g/mol to 10,000 g/mol, and from 700 g/mol to 8000 g/mol in another embodiment, and from 900 g/mol to 3000 g/mol in yet another embodiment.
  • Useful viscosities of the polybutene processing oil ranges from 10 to 6000 cSt (centiStokes) at 100°C in one embodiment, and from 35 to 5000 cSt at 100°C in another embodiment, and is greater than 35 cSt at 100°C in yet another embodiment, and greater than 100 cSt at 100°C in yet another embodiment.
  • polybutenes are the PARAPOLTM Series of processing oils (Infmeum, Linden, NJ), such as PARAPOLTM 450, 700, 950, 1300, 2400 and 2500.
  • the commercially available PARAPOLTM Series of polybutene processing oils are synthetic liquid polybutenes, each individual formulation having a certain molecular weight, all formulations of which can be used in the composition of the invention.
  • the molecular weights of the PARAPOLTM oils are from 420 Mn (PARAPOLTM 450) to 2700 Mn (PARAPOLTM 2500) as determined by gel permeation chromatography.
  • the MWD of the PARAPOLTM oils range from 1.8 to 3 in one embodiment, and from 2 to 2.8 in another embodiment; the pour points of these polybutenes are less than 25°C in one embodiment, less than 0°C in another embodiment, and less than - 10°C in yet another embodiment, and between -80°C and 25°C in yet another embodiment; and densities (IP 190/86 at 20°C) range from 0.79 to 0.92 g/cm 3 , and from 0.81 to 0.90 g/cm 3 in another embodiment.
  • Table 3 shows some of the properties of the PARAPOLTM oils useful in embodiments of the present invention, wherein the viscosity was determined as per ASTM D445-97, and the number average molecular weight (M ⁇ ) by gel permeation chromatography.
  • M ⁇ number average molecular weight
  • Desirable NFPs for use in the present invention may thus be described by any embodiment described herein, or any combination of the embodiments described herein.
  • the NFP is a C 6 to C 200 paraffin having a pour point of less than 25°C.
  • the NFP comprises an aliphatic hydrocarbon having a viscosity of from 0.1 to 1000 cSt at 100°C.
  • the NFP is selected from n-paraffins, branched isoparaffins, and blends thereof having from 8 to 25 carbon atoms.
  • the NFP is characterized in one embodiment in that, when blended with the polyolefin to form a plasticized composition, the NFP is compatible and miscible with the propylene polymer and does not form a separate phase.
  • plasticizers such as is commonly used for poly(vinyl chloride) are substantially absent.
  • plasticizers such as phthalates, adipates, trimellitate esters, polyesters, and other functionalized plasticizers as disclosed in, for example, US 3,318,835; US 4,409,345; WO 02/31044 Al; and PLASTICS ADDITIVES 499-504 (Geoffrey Pritchard, ed., Chapman & Hall 1998) are substantially absent.
  • substantially absent it is meant that these compounds are not added deliberately to the compositions.
  • Oils such as naphthenic and other aromatic containing oils are present to less than 0.5 wt% of the compositions of the invention in a further embodiment.
  • aromatic moieties and carbon-carbon unsaturation are substantially absent from the non-functionalized plasticizers used in the present invention in yet another embodiment.
  • Aromatic moieties include a compound whose molecules have the ring structure characteristic of benzene, naphthalene, phenanthrene, anthracene, etc.
  • substantially absent it is meant that these aromatic compounds or moieties are not added deliberately to the compositions, and if present, are present to less than 0.5 wt% of the composition of the NFP.
  • most “mineral oils” are substantially absent from the compositions of the present invention.
  • compositions of the present invention are substantially absent.
  • polyethylene homopolymer and copolymer having a weight average molecular weight of from 500 to 10,000 is substantially absent.
  • polyethylene compatibilizers are disclosed in, for example, WO 01/18109 Al. By “substantially absent”, it is meant that these compounds are not added deliberately to the compositions.
  • the polyolefin compositions of the present invention may also contain other additives.
  • additives include antioxidants, nucleating agents, acid scavengers, stabilizers, anticorrosion agents, blowing agents, other UN absorbers such as chain-breaking antioxidants, etc., quenchers, antistatic agents, slip agents, pigments, dyes and fillers and cure agents such as peroxide.
  • Dyes and other colorants common in the industry may be present from 0.01 to 10 wt% in one embodiment, and from 0.1 to 6 wt% in another embodiment.
  • Suitable nucleating agents are disclosed by, for example, H. ⁇ . Beck in Heterogeneous Nucleating Agents for Polypropylene Crystallization, 11 J. APPLIED POLY. SCI.
  • nucleating agents examples include sodium benzoate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, aluminum 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, dibenzylidene sorbitol, di(p-tolylidene) sorbitol, di(p-ethylbenzylidene) sorbitol, bis(3,4-dimethylbenzylidene) sorbitol, and N',N'-dicyclohexyl-2,6- naphthalenedicarboxamide, and salts of disproportionated rosin esters.
  • the foregoing list is intended to be illustrative of suitable choices of nucleating agents for inclusion in the subject
  • antioxidants and stabilizers such as organic phosphites, hindered amines, and phenolic antioxidants may be present in the polyolefin compositions of the invention from 0.001 to 2 wt% in one embodiment, and from 0.01 to 0.8 wt% in another embodiment, and from 0.02 to 0.5 wt% in yet another embodiment.
  • organic phosphites that are suitable are tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168) and di(2,4-di- tert-butylphenyl)pentaerithritol diphosphite (ULTRANOX 626).
  • Non-limiting examples of hindered amines include poly[2-N,N'-di(2,2,6,6-tetramethyl-4- piperidinyl)-hexanediamine-4-( 1 -amino- 1 , 1 ,3 ,3-tetramethylbutane)sym-triazine] (CHIMASORB 944); bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate (TINUVIN 770).
  • Non-limiting examples of phenolic antioxidants include pentaerythrityl tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1010); and l,3,5-Tri(3,5-di-tert-butyl-4-hydroxybenzyl-isocyanurate (IRGANOX 3114).
  • Fillers may be present from 0.1 to 50 wt% in one embodiment, and from 0.1 to 25 wt% of the composition in another embodiment, and from 0.2 to 10 wt% in yet another embodiment.
  • Desirable fillers include but not limited to titanium dioxide, silicon carbide, silica (and other oxides of silica, precipitated or not), antimony oxide, lead carbonate, zinc white, lithopone, zircon, corundum, spinel, apatite, Barytes powder, barium sulfate, magnesiter, carbon black, dolomite, calcium carbonate, talc and hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr or Fe and CO 3 and/or HPO 4 , hydrated or not; quartz powder, hydrochloric magnesium carbonate, glass fibers, clays, alumina, and other metal oxides and carbonates, metal hydroxides, chrome, phosphorous and brominated flame retardants, antimony trioxide, silica, silicone, and
  • NFP may be blended with a filler, desirably a porous filler.
  • the NFP and filler may be blended by, for example, a tumbler or other wet blending apparatus.
  • the NFP and filler in this embodiment are blended for a time suitable to form a homogenous composition of NFP and filler, desirably from 1 minute to 5 hours in one embodiment.
  • This NFP/fiUer blend may then be blended with the polyolefin useful in the invention in order to effectuate plastication of the polyolefin.
  • a porous filler may be contacted with the NFP, or some portion thereof, prior to contacting the filler with the polyolefin.
  • the porous filler, polyolefin and NFP are contacted simultaneously (or in the same blending apparatus).
  • the NFP may be present from 0.1 to 60 wt% of the composition, and from 0.2 to 40 wt% in another embodiment, and from 0.3 to 20 wt% in yet another embodiment.
  • Fatty acid salts may also be present in the polyolefin compositions of the present invention. Such salts may be present from 0.001 to 1 wt% of the composition in one embodiment, and from 0.01 to 0.8 wt% in another embodiment.
  • fatty acid metal salts include lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, and erucic acid, suitable metals including Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb and so forth.
  • Preferable fatty acid salts are selected from magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, and magnesium oleate.
  • the resultant plasticized polyolefin of the present invention may be processed by any suitable means such as by calendering, casting, coating, compounding, extrusion, foamed, laminated, blow molding, compression molding, injection molding, thermoforming, transfer molding, cast molding, rotational molding, casting such as for films, spun or melt bonded such as for fibers, or other forms of processing such as described in, for example, PLASTICS PROCESSING (Radian Corporation, Noyes Data Corp. 1986). More particularly, with respect to the physical process of producing the blend, sufficient mixing should take place to assure that a uniform blend will be produced prior to conversion into a finished product.
  • the components of the polyolefmic composition of the present invention may be blended by any suitable means to form the plasticized polyolefin, which is then suitable for further processing into useful articles.
  • the polyolefin and NFP are blended, or melt blended, in an apparatus such as an extruder or Brabender mixer.
  • the polyolefin may also be blended with the NFP using a tumbler, double-cone blender, ribbon blender, or other suitable blender.
  • the polyolefin and NFP are blended by a combination of, for example, a tumbler, followed by melt blending in an extruder.
  • the polyolefin suitable for use in the present invention can be in any physical form when used to blend with the NFP of the invention.
  • reactor granules defined as the granules of polymer that are isolated from the polymerization reactor, are used to blend with the NFP of the invention.
  • the reactor granules have an average diameter of from 10 ⁇ m to 5 mm, and from 50 ⁇ m to 10 mm in another embodiment.
  • the polyolefin is in the form of pellets, such as, for example, having an average diameter of from 1 mm to 6 mm that are formed from melt extrusion of the reactor granules.
  • One method of blending the NFP with the polyolefin is to contact the components in a tumbler, the polyolefin being in the form of reactor granules. This works particularly well with polypropylene homopolymer. This can then be followed, if desired, by melt blending in an extruder.
  • Another method of blending the components is to melt blend the polyolefin pellets with the NFP directly in an extruder or Brabender.
  • simple solid state blends of the pellets serve equally as well as pelletized melt state blends of raw polymer granules, of granules with pellets, or of pellets of the two components since the forming process includes a remelting and mixing of the raw material.
  • a pelletized melt blend would be preferred over simple solid state blends of the constituent pellets and/or granules.
  • the polyolefinic compositions of the present invention are suitable for such articles as automotive components, wire and cable jacketing, pipes, agricultural films, geomembranes, toys, sporting equipment, medical devices, casting and blowing of packaging films, extrusion of tubing, pipes and profiles, sporting equipment, outdoor furniture (e.g., garden furniture) and playground equipment, boat and water craft components, and other such articles.
  • the compositions are suitable for automotive components such as bumpers, grills, trim parts, dashboards and instrument panels, exterior door and hood components, spoiler, wind screen, hub caps, mirror housing, body panel, protective side molding, and other interior and external components associated with automobiles, trucks, boats, and other vehicles.
  • Other useful articles and goods may be formed economically by the practice of our invention including: crates, containers, packaging, labware, such as roller bottles for culture growth and media bottles, office floor mats, instrumentation sample holders and sample windows; liquid storage containers such as bags, pouches, and bottles for storage and IN infusion of blood or solutions; packaging material including those for any medical device or drugs including unit-dose or other blister or bubble pack as well as for wrapping or containing food preserved by irradiation.
  • Other useful items include medical tubing and valves for any medical device including infusion kits, catheters, and respiratory therapy, as well as packaging materials for medical devices or food which is irradiated including trays, as well as stored liquid, particularly water, milk, or juice, containers including unit servings and bulk storage containers as well as transfer means such as tubing, pipes, and such.
  • These devices may be made or formed by any useful forming means for forming polyolefins.
  • This will include, at least, molding including compression molding, injection molding, blow molding, and transfer molding; film blowing or casting; extrusion, and thermoforming; as well as by lamination, pultrusion, protrusion, draw reduction, rotational molding, spinbonding, melt spinning, melt blowing; or combinations thereof.
  • Use of at least thermoforming or film applications allows for the possibility of and derivation of benefits from uniaxial or biaxial orientation of the radiation tolerant material.
  • the present invention is a plasticized polyolefin composition
  • a plasticized polyolefin composition comprising from 99.9 wt% to 60 wt% polyolefin; and from 0.1 wt% to 40 wt% of a ⁇ FP; wherein the ⁇ FP comprises C 6 to C 200 paraffins having a pour point of less than -5°C.
  • the non- functionalized plasticizer comprises C 8 to C 100 paraffins.
  • the ⁇ FP comprises C 6 to C50 isoparaffins, and C ⁇ 0 to C 10 o n-paraffins in yet another embodiment.
  • the plasticized polyolefin of the present invention is a blend of a polyolefin and a non-functionalized plasticizer, wherein the non-functionalized plasticizer is a compound having a pour point of less than - 30°C in the viscosity range of from 0.5 to 200 cSt at 40°C (ASTM D445-97) in one embodiment, and between -30°C and -90°C in the viscosity range of from 0.5 to 200 cSt at 40°C (ASTM D445-97) in another embodiment.
  • compositions of the invention are characterized in that the T g of the polyolefin decreases from 4 to 10°C for every 4 wt% of NFP added to the composition, while the T m remains within 1 to 2 °C.
  • the NFP of the present invention can be described by any number of physical and chemical properties described herein.
  • the non-functionalized plasticizer has a pour point of less than -30°C; and a viscosity of from 0.1 to 3000 cSt at 100°C in another embodiment; and a dielectric constant at 20°C of less than 2.1 in yet another embodiment; and a specific gravity of less than 0.91 g/cm in yet another embodiment.
  • aromatic moieties are substantially absent.
  • the NFP possesses a weight average molecular weight of from 100 to 25,000 g/mol; and from 200 to 10,000 g/mol in another embodiment.
  • the polyolefin suitable for compositions of the invention can be described by any number of embodiments.
  • the polyolefin comprises isotactic segments.
  • the polyolefin is selected from propylene homopolymers, propylene copolymers, and propylene impact copolymers, and mixtures thereof.
  • the polyolefin is isotactic polypropylene.
  • the polyolefin is a copolymer comprises propylene derived units and units selected from ethylene derived units and C to C 20 ⁇ -olefin derived units.
  • the polyolefin is a propylene impact copolymer comprising from 40% to 95% by weight of a Component A and from 5% to 60% by weight of a Component B based on the total weight of copolymer; wherein Component A comprises propylene homopolymer or copolymer, the copolymer comprising 10% or less by weight ethylene, butene, hexene or octene comonomer; and wherein Component B comprises propylene copolymer, wherein the copolymer comprises from 5% to 70% by weight ethylene, butene, hexene and/or octene comonomer, and from 95% to 30% by weight propylene.
  • Component A comprises propylene homopolymer or copolymer, the copolymer comprising 10% or less by weight ethylene, butene, hexene or octene comonomer
  • Component B comprises propylene copolymer, wherein the copo
  • the polyolefin may further comprise a plastomer.
  • compositions of the present invention may be described in a further embodiment wherein polyethylene having a weight average molecular weight of from 500 to 10,000 is substantially absent.
  • the present invention also includes a method of plasticizing a polyolefin comprising blending a polyolefin with a non-functionalized plasticizer; wherein the non-functionalized plasticizer comprises C 6 to C 20 o paraffins having a pour point of less than -5°C.
  • the blending comprises melt blending. The melt blending is performed in an extruder in one embodiment.
  • the blending comprises wet blending of solid polyolefin.
  • the polyolefin is in the form of reactor granules in one embodiment, and extruded pellets in another embodiment, or a blend thereof. If reactor granules are used, the reactor granules have an average diameter of from 10 ⁇ m to 5 mm in one embodiment.
  • An article of manufacture can be formed from compositions of the invention, non-limiting examples of such articles include films, sheets, fibers, woven and nonwoven fabrics, tubes, pipes, automotive components, fu ⁇ uture, sporting equipment, food storage containers, transparent and semi-transparent articles, toys, tubing and pipes, and medical devices.
  • the glass transition temperature (T g ) and storage modulus (E') were determined as follows by dynamic mechanical thermal analysis ("DMT A"). Dynamic mechanical testing was conducted by oscillating a solid rectangular beam, fixed at one end, trough an arbitrary angle of deflection. The force and angle of deflection are used to calculate stress and strain respectively. The ratio of the stress to strain yields a modulus. Varying the temperature during the test yields information about the behavior of the material as a function of temperature.
  • the test parameters include a single cantilever; frequency of 1 Hz, start temperature of -130°C, max temperature of 60°C. Temperature is increased at a rate of 2°C/min. Tan ⁇ is the ratio of E"/E' where E" is the loss modulus and E' is the storage modulus or elastic modulus.
  • the glass transition temperature is determined by the temperature when of Tan ⁇ reaches its maximal value.
  • Crystallization temperature (T c ) and melting temperature (T m ) was measured as follows: Differential Scanning Calorimetry (DSC, at a heating rate of 10° C/minute). As an example, about 6 to 10 mg of a sheet of the polymer or plasticized polymer was pressed at approximately 150° C to 200° C is removed with a punch die. The sample is placed in a Differential Scarming Calorimeter (Perkin Elmer 7 Series Thermal Analysis System) and heated to 200°C and held for 10 minutes. The sample is cooled at 10°C/min. to attain a final temperature of 25°C.
  • DSC Differential Scanning Calorimetry
  • the thermal output is recorded and the inflection point in the thermal output data, indicating a change in the heat capacity is determined by electronically differentiating the thermal output data.
  • the maximum in the differential thermal output data corresponds to the crystallization temperature of the sample.
  • the sample is held at 25°C for 10 minutes and heated at 10°C/min to 200°C.
  • the thermal input is recorded and the inflection point in the thermal input data, indicating a change in the heat capacity is determined by electronically differentiating the thermal input data.
  • the maximum in the differential thermal input data corresponds to the melting temperature of the sample.
  • the shear viscosity as a function of shear rate was determined by a dual-barrel capillary rheometer.
  • the capillary rheometer (Rosand Model RAH7/2 by Bohun Instruments) is equipped with a 30:1 length to diameter ratio capillary. A total mass of 25-30g of pellets were packed into the capillary barrels and preheated at 230°C for 10 minutes to remove any entrained air before the test. Each test was performed at 230°C over the shear rate range of from 30 to 3000 s '1 . Corrections to the data for entrance pressure losses (i.e., the Bagley correction) were performed online via simultaneous pressure loss measurements for the flow of the material through an orifice that was installed into the second barrel of the rheometer.
  • the components of the present invention can be blended by any suitable means.
  • the examples below demonstrate one method of blending the components.
  • reactor granules of metallocene produced propylene homopolymers were first blended in a tumble blender with the addition of antioxidants, i.e., 600 ppm of Irganox 1076, and 260 ppm of calcium stearate, and 4 wt% of NFP for plasticized samples to achieve a homogeneous mixing of blend components.
  • the blended polymers were compounded and pelletized using a 57 mm twin screw extruder at extrusion temperature of 230°C.
  • reactor granules of propylene random copolymer were first blended in a tumble blender with reactor granules and the addition of antioxidants, i.e., 825 ppm of calcium stearate, 800 ppm of Ultranox 626, 500 ppm of TLNUViN 622 and 2500 ppm of Millad 3940, and 5 wt% of NFP for plasticized samples to achieve a homogeneous mixing of blend components.
  • the blended polymers were compounded and pelletized using a 30 mm twin screw extruder at extrusion temperature of 216°C.
  • the reactor granules of propylene impact copolymers were first blended in a tumble blender with reactor granules and the addition of antioxidants, i.e., 800 ppm of calcium stearate, 1500 ppm of IRGANOX 1010, 500 ppm of ULTRANOX 626 and 675 ppm of sodium benzoate, and 5 wt% of NFP for plasticized samples to achieve a homogeneous mixing of blend components.
  • the blended polymers were compounded and pelletized using a 30 mm single screw extruder at extrusion temperature of 205°C.
  • samples 6-9 a 10 wt% plasticized metallocene propylene homopolymers were prepared in the same manner as described above for samples 1-5.
  • samples 21- 24 the 10 wt% plasticized metallocene produced propylene homopolymers, prepared in the same manner as described above for samples 6-9, were dry blend with neat propylene polymers (AchieveTM 3854), in pellet form, to attain the 4 wt% active plasticized samples in the blends.
  • Standard ASTM tensile and HDT bars and Gardner impact discs were prepared using 120 ton injection molding equipment. Physical properties of the samples prepared are in the Tables below. Molded parts from the invention plasticized polypropylene homopolymers show a significant decrease in flexural and tensile modulus at a loading of 4 wt% PAO or isoparaffin, while maintaining their tensile strength, room temperature Izod Impact resistance and heat deflection temperature. For comparison, molded samples were also prepared with erucamide (Table 11), a common lubricant designed to reduce molded part surface friction of 4 wt% concentration. The effect of the erucamide on the flexural modulus is insignificant.
  • a typical spunbond process consists of a continuous filament extrusion, followed by drawing, web formation by the use of some type of ejector, and bonding the web.
  • the polymer pellets are first fed into an extruder.
  • the pellets simultaneously are melted and forced through the system by a heating melting screw.
  • a spinning pump meters the molten polymer through a filter to a spinneret where the molten polymer is extruded under pressure through capillaries, at a rate of 0.4 grams per hole per minute.
  • the spinneret contains a few hundred capillaries, measuring 0.4 mm in diameter.
  • the polymer is melted at about 30-50°C above its melting point to achieve sufficiently low melt viscosity for extrusion.
  • the fibers exiting the spinneret are quenched and drawn into fine fibers measuring about 16 microns in diameter.
  • the solidified fiber is laid randomly on a moving belt to form a random netlike structure known in the art as web.
  • the 25 basis weight (grams per square meter) of web is obtained by controlling the belt moving speed.
  • the web is bonded to achieve its final strength using a heated textile calender known in the art as thermobond calender.
  • the calender consists of two heated steel rolls; one roll is plain and the other bears a pattern of raised points.
  • the web is conveyed to the calender wherein a fabric is formed by pressing the web between the rolls at a bonding temperature of about 138°C.
  • Cast films were prepared using the following operations. Cast monolayer films were fabricated on a Killion cast film line. This line has three 24:1 L/D 2.54 cm diameter extruder, which feed polymer into a feedblock. The feedblock diverts molten polymer from the extruder to a 20.32 cm wide Cloeren die. Molten polymer exits the die at a temperature of 230°C and is cast on a chill roll (20.3 cm diameter, 25.4 cm roll face) at 21°C. The casting unit is equipped with adjustable winding speeds to obtain film of the targeted thickness.
  • the resin properties of plasticized propylene homopolymers, propylene copolymers and propylene impact copolymers are listed, respectively, in Tables 5-7.
  • the addition of NFP in the propylene polymers improve the melt flowability, as indicated by the significant increase of melt flow rate.
  • the improvement of melt flowability can be characterized by the decrease of shear viscosity as a function of shear rate range, as illustrated in Figures 11-13.
  • the increase of melt flowability in the current invention is mainly due to the plasticizing effect of NFP, and the polymer molecular weight is unchanged. This is evident in the comparison of molecular weight distribution, as shown in Figure 14.
  • the improvement of melt flowability usually benefit the fabrication processes, i.e., fiber spinning, film casting, extrusion, injection molding, in terms of better draw-down, lower extruder torque, thin wall injection and faster cycle time.
  • the NFP in the current invention provides a significant depression in the storage modulus of propylene polymers.
  • the storage modulus of plasticized propylene polymers are drastically reduced as a function of temperature relative to the unplasticized polyolefins.
  • a propylene polymer having lower a storage modulus (or "elastic modulus) at any particular range of temperature indicates the ability to provide better flexibility for the end- use at that particular temperature conditions.
  • the NFP in the current invention demonstrates the ability to depress T g without altering the melting temperature and crystallization temperature of propylene polymers, as illustrated in Figures 5-10.
  • Traditional methods to depress T g include the incorporation of comonomers as in the case for the propylene copolymers, which also depresses the melting temperature and crystallization temperature of polymer.
  • Polymers having lower T g without compromising the melting characteristics are very desirable and can provide better impact resistance, particularly for below freezing temperature impact resistance while maintaining the ability for high temperature usage.
  • the plasticized polyolefins of the present invention provide this.
  • the NFP in the current invention is compatible and miscible with the propylene polymer, as determined by, for example, the single T g profile of the plasticized propylene homopolymer and propylene copolymer. This is shown graphically in Figures 2-3.
  • the NFP in the current invention is also compatible and miscible with the propylene impact copolymer, as determined by, for example, the two T g profile of the plasticized propylene impact copolymer, being the lower T g profile for the ethylene-propylene rubber phase and the higher T g profile for the propylene polymer phase. This is shown graphically in Figure 4.
  • NFP substantially improves the impact resistance of molded parts without the significant decrease of heat deflection temperature.
  • Gardner impact strength at both room and freezing temperatures, has improved from 350% to 400% for propylene homopolymers, from 140 to 165% for propylene copolymers, and from 20 to 40% for propylene impact copolymers due to the addition of 4-5 wt% of NFP. It is anticipated that further increase of impact resistance is attainable by the increase of NFP concentration in the propylene polymers. Other measures of impact resistance, including Izod impact at room and freezing temperatures, are also significantly improved.
  • Another advantage of the current invention is that the heat deflection temperature of plasticized polyolefins is not compromised (either maintained or only slightly reduced) which is crucial for applications requiring maintenance of molded article dimensions at high temperature. Further indication of toughness improvement is shown by the significant increase of elongation at yield and break. Many applications require good conformability during the end- use. A higher elongation facilitates the compliance of molded articles to the deformation during either the conversion process or at the end-use.
  • the NFP also demonstrate the ability to provide substantial softness improvement in spunbond nonwoven fabrics, as provided by the lower "total hand" in Table 12. In many applications, particularly in personal hygiene and health care, a soft nonwoven is very desirable for skin contact comfort.
  • the current invention not only provides the improvement in softness but also maintains the necessary tensile strength, tear resistance and fabric uniformity.
  • the NFP particularly the Isopar-V plasticized propylene homopolymer (Sample 2) provides improvement in the tear and impact resistance, as indicated by the relatively high (relative to the unplasticized polyolefin) Elmendorf tear in both machine direction (MD) and transverse direction (TD) and dart impact at both room and freezing temperatures.
  • the optical properties i.e., haze and gloss, are also improved.
  • the improvement offers advantages in many film applications, for examples, food packaging, stationery cover, tape, medical and electronic packaging.
  • Total hand is based on measurements on fabrics at 25 gsm (grams per square meter).
  • Films properties are based on 2 mil thickness.

Abstract

The present invention relates to plasticized polyolefin compositions comprising a polyolefin and a non-functionalized plasticizer; wherein the non-functionalized plasticizer may comprise C6 to C200 paraffins (including branched and normal paraffins) having a pour point of less than -5 °C. In one embodiment, the non-functionalized plasticizer is an isoparaffin comprising C6 to C25 isoparaffins. In another embodiment the non-functionalized plasticizer is a polyalphaolefin compising C10 to C100 n-paraffins. The polyolefin may be a polypropylene homopolymer, copolymer, impact copolymer, or blends thereof, and may include a plastomer. Non-limiting examples of desirable article of manufacture made from compositions of the invention includes films, tubes, pipes, sheets, fibers, woven and nonwoven fabrics, automotive components, furniture, sporting equipment, food storage containers, transparent and semi-transparent articles, toys, tubing and pipes, and medical devices.

Description

PLASTICIZED POLYOLEFIN COMPOSITIONS
FIELD OF THE INVENTION
[0001] The present invention relates to plasticized polyolefins comprising a polyolefin and non-functionalized plasticizer such as C6 to C 0o paraffins. More particularly, the present invention relates to plasticized polyolefins such as propylene polymers having improved processability and properties such as flexibility and impact resistance.
BACKGROUND OF THE INVENTION
[0002] Polyolefins are useful in any number of everyday articles.
However, one drawback to many polyolefins, especially polypropylene homopolymers and copolymers, is the relatively high glass transition temperature. This characteristic makes these polyolefins brittle, especially at low temperatures. Given that there is a desire to make articles that can withstand a broad range of temperatures, there is a need to provide a polyolefin that can maintain its desirable characteristics such as high temperature performance, etc., while improving upon the impact strength and toughness. In particular, it would be advantageous to provide a propylene polymer possessing improved toughness without sacrificing its toughness and other desirable properties.
[0003] Addition of a plasticizer or other substance to a polyolefin is one option to improve such properties as impact strength and toughness. There are some disclosures towards such an end, such as US 4,960,820; US 4,132,698; US 3,201,364; WO 02/31044; WO 01/18109 Al; and EP 0 300 689 A2. These disclosures are directed towards polyolefins and elastomers blended with functionalized plasticizers. The functionalized plasticizers are materials such as mineral oils which contain aromatic groups, and high (greater than -20°C) pour point compounds. Use of these compounds typically does not preserve the transparency of the polyolefin, and impact strength is often not improved. [0004] Other background references include EP 0 448 259 A, EP 1 028
145 A, US Patent Nos. 4,073,782, and 3,415,925.
[0005] What is needed is a plasticized polyolefin with improved softness, better flexibility (lower flexural modulus), a depressed glass transition temperature, and improved impact strength (improved Gardner impact) at low temperatures (below 0°C), while not influencing the melting temperature of the polyolefin, the polyolefin crystallization rate, its clarity, and with minimal migration of the plasticizer to the surface of articles made therefrom. Further, there is a need for a plasticized polypropylene that can be used in such applications as food containers and toys.
[0006] It would be particularly desirable to plasticize polyolefins by using a simple, non-reactive compound such as a paraffin. However, it has been taught that aliphatic or paraffinic compounds would impair the properties of polyolefins, and was thus not recommended. (See, e.g., CHEMICAL ADDITIVES FOR PLASTICS INDUSTRY 107-116 (Radian Corp., Noyes Data Corporation, NJ 1987); WO 01/18109 Al). The inventors of the present invention have found, surprisingly, that paraffinic compounds are useful plasticizers for polyolefins. The present invention is directed towards such a plasticized polyolefin.
SUMMARY OF THE INVENTION
[0007] The present invention relates to plasticized polyolefin compositions comprising a polyolefin and a non-functionalized plasticizer; wherein the non- functionalized plasticizer may comprise C6 to C20o paraffins (including branched and normal paraffins) having a pour point of less than -5°C. In one embodiment, the non-functionalized plasticizer is an isoparaffin comprising C6 to C25 isoparaffins. In another embodiment the non-functionalized plasticizer is a polyalphaolefin comprising C10 to oo n-paraffins. The polyolefin may be a polypropylene homopolymer, copolymer, impact copolymer, or blends thereof, and may include a plastomer. Non-limiting examples of desirable articles of manufacture made from compositions of the invention include films, sheets, fibers, woven and nonwoven fabrics, tubes, pipes, automotive components, fiirniture, sporting equipment, food storage containers, transparent and semi- transparent articles, toys, tubing and pipes, and medical devices. The compositions of the invention may be characterized by having an improved (decreased) Tg relative to the starting polyolefin, while maintaining other desirable properties.
BRIEF DESCRIPTION OF DRAWINGS
[0008] Figure 1 is a graphical representation of the Storage Modulus (F) as a function of temperature for various plasticized propylene homopolymer examples cited herein;
[0009] Figure 2 is a graphical representation of the Tan δ as a function of temperature for various plasticized propylene homopolymer examples cited herein;
[0010] Figure 3 is a graphical representation of the Tan δ as a function of temperature for various plasticized propylene copolymer examples cited herein;
[0011] Figure 4 is a graphical representation of the Tan δ as a function of temperature for various plasticized propylene impact copolymer examples cited herein;
[0012] Figure 5 is a graphical representation of the melting heat flow from
DSC as a function of temperature for various plasticized propylene homopolymer samples illustrative of the invention;
[0013] Figure 6 is a graphical representation of the crystallization heat flow from DSC as a function of temperature for various samples plasticized propylene homopolymer samples illustrative of the invention; [0014] Figure 7 is a graphical representation of the melting heat flow from
DSC as a function of temperature for various plasticized propylene copolymer samples illustrative of the invention;
[0015] Figure 8 is a graphical representation of the crystallization heat flow from DSC as a function of temperature for various plasticized propylene copolymer samples illustrative of the invention;
[0016] Figure 9 is a graphical representation of the melting heat flow from
DSC as a function of temperature for various plasticized propylene impact copolymer samples illustrative of the invention;
[0017] Figure 10 is a graphical representation of the crystallization heat flow from DSC as a function of temperature for various plasticized propylene impact copolymer samples illustrative of the invention;
[0018] Figure 11 is a graphical representation of the shear viscosity as a function of shear rate for various plasticized propylene homopolymer samples illustrative of the invention;
[0019] Figure 12 is a graphical representation of the shear viscosity as a function of shear rate for various plasticized propylene copolymer samples illustrative of the invention;
[0020] Figure 13 is a graphical representation of the shear viscosity as a function of shear rate for various plasticized propylene impact copolymer samples illustrative of the invention; and
[0021] Figure 14 is a graphical representation of the molecular weight distribution for various plasticized propylene homopolymer samples illustrative of the invention. DETAILED DESCRIPTION OF THE INVENTION
[0022] The present invention is a plasticized polyolefin composition comprising a polyolefin and a non-functionalized plasticizer (NFP). The NFP may be an aliphatic hydrocarbon, or paraffin, typically comprising C6 to C2oo paraffins. The term "paraffins", as used herein, includes all isomers of C6 to C200 paraffins including branched and linear structures, and blends thereof. The individual paraffins may include saturated cyclic hydrocarbons. Desirably, the NFP has a pour point of less than 0°C, and a viscosity (ASTM D445-97) of from 0.1 to 3000 cSt at 100°C. Useful NFPs may include so called polyalphaolefms (PAOs) and isoparaffins.
[0023] Certain compositions of the present invention can be characterized in that the glass transition temperature (Tg) of the composition decreases by at least 2°C for every 4 wt% of NFP present in the composition in one embodiment; and decreases by at least 3°C for every 4 wt% of NFP present in the composition in another embodiment; and decreases from at least 4 to 10°C for every 4 wt% of NFP present in the composition in yet another embodiment, while the melting and crystallization temperatures of the polyolefin remain constant (within 1 to 2°C). Further, the compositions of the invention are characterized in that the NFP is compatible and miscible with propylene polymers and does not form a separate phase. This is evidenced by, for example, the Tg profile observed for the compositions by DMTA (Dynamic Mechanical Thermal Analysis).
[0024] The polyolefin and NFP can be blended by any suitable means.
For example, they may be blended in a tumbler, an extruder, or a combination thereof. The enhanced properties of the plasticized polyolefin compositions described herein are useful in any number of applications, including transparent components such as in cook and storage ware, and in other articles such as furniture, automotive components, toys, sportswear, medical devices, sterilizable medical devices and sterilization containers, nonwoven fibers and fabrics and articles therefrom such as drapes, gowns, filters, hygiene products, diapers, and films, oriented films, sheets, tubes, pipes and other items where softness, high impact strength, and impact strength below freezing is important. Any number of techniques can be used to process the plasticized polyolefins of the invention to form these articles including injection molding, extrusion, thermoforming, blow molding, rotomolding, spunbonding, meltblowing, fiber spinning, blown film, stretching for oriented films, and other common processing methods.
[0025] The invention is described further below with respect to the polyolefin, the NFP, and embodiments therein.
Polyolefin
[0026] Polyolefins may be plasticized, or blended with, the NFP of the present invention to form more flexible, yet impact resistant, compositions. In one aspect of the invention, the polyolefin is selected from polypropylene homopolymer, polypropylene copolymers, and blends thereof. The homopolymer may be atactic polypropylene, isotactic polypropylene, syndiotactic polypropylene and blends thereof. The copolymer can be a random copolymer, a block copolymer, and blends thereof. In particular, polymer blends include so called impact copolymers, elastomers and plastomers, any of which may be physical blends or in situ blends of polypropylene and polypropylene copolymer. The method of making the polypropylene is not critical, as it can be made by slurry, solution, or gas phase processes, and by using either Ziegler-Natta-type catalysts, metallocene-type catalysts, or a combination thereof. Such catalysts are well known in the art, and are described in, for example, ZIEGLER CATALYSTS (Gerhard Fink, Rolf Mulhaupt and Hans H. Brintzinger, eds., Springer-Nerlag 1995); Resconi et al., Selectivity in Propene Polymerization with Metallocene Catalysts, 100 CHEM. REV. 1253-1345 (2000); and I, II METALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000).
[0027] The polyolefin may be a propylene homopolymer. A desirable propylene homopolymer has a molecular weight distribution (Mw/Mn) ranging from 1.5 to 10, and from 2.0 to 7 in another embodiment, and from 2.0 to 5 in yet another embodiment, and from 2.0 to 4 in yet another embodiment. The Gardner impact strength, tested on 0.125 inch disk at 23°C, of the propylene homopolymer may range from 20 in-lb to 1000 in-lb in one embodiment, and from 30 in-lb to 500 in-lb in another embodiment, and from 40 in-lb to 400 in-lb in yet another embodiment. In yet another embodiment, the 1% secant flexural modulus of the propylene homopolymer ranges from 100 MPa to 2300 MPa, and from 200 MPa to 2100 MPa in another embodiment, and from 300 MPa to 2000 MPa in yet another embodiment, wherein a desirable polyolefin may exhibit any combination of any upper flexural modulus limit with any lower flexural modulus limit. The melt flow rate (MFR) (ASTM D 1238, 230°C, 2.16 kg) of propylene homopolymer ranges from 0.1 dg/min to 2500 dg/min in one embodiment, and from 0.3 to 500 dg/min in another embodiment.
[0028] The polypropylene homopolymer or copolymer useful in the present invention may have some level of isotacticity. Thus, in one embodiment, isotactic polypropylene is a useful polyolefin, and highly isotactic polypropylene in another embodiment. As used herein, "isotactic" is defined as having at least
10% isotactic pentads according to analysis by 13c-NMR_ As used herein, "highly isotactic" is defined as having at least 60% isotactic pentads according to analysis by I^C.NMR n a desirable embodiment, a polypropylene homopolymer having at least 85% isotacticity is the polyolefin, and at least 90% isotacticity in yet another embodiment.
[0029] In another embodiment of the invention, the polyolefin is a propylene copolymer, either random, or block, of propylene derived units and units selected from ethylene and C4 to C20 α-olefin derived units, and from ethylene and C4 to C10 α-olefin derived units in another embodiment. The ethylene or C4 to C20 α-olefin derived units are present from 0.1 wt% to 50 wt% of the copolymer in one embodiment, and from 0.5 to 30 wt% in another embodiment, and from 1 to 15 wt% in yet another embodiment, and from 0.1 to 5 wt% in yet another embodiment, wherein a desirable copolymer comprises ethylene and C4 to C20 α-olefin derived units in any combination of any upper wt% limit with any lower wt% limit described herein. The propylene copolymer will have a weight average molecular weight of from greater than 8,000 g/mol in one embodiment, and greater than 10,000 g/mol in another embodiment, and greater than 12,000 g/mol in yet another embodiment, and greater than 20,000 g/mol in yet another embodiment, and less than 1,000,000 g/mol in yet another embodiment, and less than 800,000 in yet another embodiment, wherein a desirable copolymer may comprise any upper molecular weight limit with any lower molecular weight limit described herein.
[0030] In yet another embodiment, the Gardner impact strength, tested on
0.125 inch disk at 23°C, of the propylene copolymer ranges from 20 in-lb to 1000 in-lb, and from 30 in-lb to 500 in-lb in another embodiment, and from 40 in-lb to 400 in-lb in yet another embodiment. Further, the propylene copolymer may possess a 1% secant flexural modulus ranging from 100 MPa to 2300 MPa, and from 200 MPa to 2100 MPa in another embodiment, and from 300 MPa to 2000 MPa in yet another embodiment, wherein a desirable polyolefin may exhibit any combination of any upper flexural modulus limit with any lower flexural modulus limit. The melt flow rate (MFR) (ASTM D 1238, 230°C) of desirable copolymers ranges from 0.1 dg/min to 2500 dg/min in one embodiment, and from 0.1 to 500 dg/min in another embodiment.
[0031] In another embodiment, the polyolefin may be a so called "impact copolymer" or block copolymer. This impact copolymer may be a reactor blend (in situ blend) or a physical blend. In one embodiment, a suitable impact copolymer comprises from 40% to 95% by weight Component A and from 5% to 60% by weight Component B based on the total weight of the impact copolymer; wherein Component A comprises propylene homopolymer or copolymer, the copolymer comprising 10% or less by weight ethylene, butene, hexene or octene comonomer; and wherein Component B comprises propylene copolymer, wherein the copolymer comprises from 5% to 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 95% to about 30% by weight propylene. In one embodiment of the impact copolymer, Component B consists essentially of propylene and from about 30% to about 65% by weight ethylene. In another embodiment, Component B comprises ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, ethylene-acrylate copolymers, ethylene- vinyl acetate, styrene-butadiene copolymers, ethylene-acrylic ester copolymers, polybutadiene, polyisoprene, natural rubber, isobutylene, hydrocarbon resin (being characterized by a molecular weight less than 5000, a Tg of about 50 to 100°C and a softening point less than about 140°C), rosin, and mixtures thereof. In another embodiment, Component B has a molecular weight distribution of less than 3.5. In yet another embodiment, Component B has a weight average molecular weight of at least 20,000. A useful impact copolymer is disclosed in, for example, US 6,342,566 and US 6,384,142.
[0032] In yet another embodiment, the Gardner impact strength, tested on
0.125 inch disk at -29°C, of the propylene impact copolymer ranges from 20 in-lb to 1000 in-lb, and from 30 in-lb to 500 in-lb in another embodiment, and from 40 in-lb to 400 in-lb in yet another embodiment. Further, the 1% secant flexural modulus of the propylene impact copolymer may range from 100 MPa to 2300 MPa in one embodiment, and from 200 MPa to 2100 MPa in another embodiment, and from 300 MPa to 2000 MPa in yet another embodiment, wherein a desirable polyolefin may exhibit any combination of any upper flexural modulus limit with any lower flexural modulus limit. The melt flow rate (MFR) (ASTM D 1238, 230°C, 2.16 kg) of desirable homopolymers ranges from 0.1 dg/min to 2500 dg/min in one embodiment, and from 0.3 to 500 dg/min in another embodiment.
[0033] Another suitable polyolefin comprises a blend of a polypropylene homopolymer or copolymer with a so called "plastomer". The plastomers that are useful in the present invention may be described as polyolefin copolymers having a density of from 0.85 to 0.915 g/cm3 and a melt index (MI) between 0.10 and 30 dg/min (ASTM D 1238; 190°C, 2.1 kg). In one embodiment, the useful plastomer is a copolymer of ethylene derived units and at least one of C3 to C10 α-olefin derived units, the copolymer having a density in the range of less than 0.915 g/cm3. The amount of comonomer (C3 to Cι0 α-olefin derived units) present in the plastomer ranges from 2 wt% to 35 wt% in one embodiment, and from 5 wt% to 30 wt% in another embodiment, and from 15 wt% to 25 wt% in yet another embodiment, and from 20 wt% to 30 wt% in yet another embodiment.
[0034] The plastomer useful in the invention has a melt index (MI) of between 0.10 and 20 dg/min in one embodiment, and from 0.2 to 10 dg/min in another embodiment, and from 0.3 to 8 dg/min in yet another embodiment. The average molecular weight of useful plastomers ranges from 10,000 to 800,000 in one embodiment, and from 20,000 to 700,000 in another embodiment. The 1% secant flexural modulus (ASTM D 790) of useful plastomers ranges from 10 MPa to 150 MPa in one embodiment, and from 20 MPa to 100 MPa in another embodiment. Further, the plastomer that is useful in compositions of the present invention has a melting temperature (Tm) of from 30 to 80°C (first melt peak) and from 50 to 125°C (second melt peak) in one embodiment, and from 40 to 70°C (first melt peak) and from 50 to 100°C (second melt peak) in another embodiment.
[0035] Plastomers useful in the present invention are metallocene catalyzed copolymers of ethylene derived units and higher α-olefin derived units such as propylene, 1 -butene, 1 -hexene and 1 -octene, and which contain enough of one or more of these comonomer units to yield a density between 0.860 and 0.900 g/cm3 in one embodiment. The molecular weight distribution (Mw/Mn) of desirable plastomers ranges from 1.5 to 5 in one embodiment, and from 2.0 to 4 in another embodiment. Examples of a commercially available plastomers are EXACT 4150, a copolymer of ethylene and 1 -hexene, the 1 -hexene derived units making up from 18 to 22 wt% of the plastomer and having a density of 0.895 g/cm3 and MI of 3.5 dg/min (ExxonMobil Chemical Company, Houston, TX); and EXACT 8201, a copolymer of ethylene and 1 -octene, the 1 -octene derived units making up from 26 to 30 wt% of the plastomer, and having a density of 0.882 g/cm3 and MI of 1.0 dg/min (ExxonMobil Chemical Company, Houston, TX).
[0036] The polyolefin suitable for use in the present invention can be in any physical form when used to blend with the NFP of the invention. In one embodiment, reactor granules, defined as the granules of polymer that are isolated from the polymerization reactor prior to any processing procedures, are used to blend with the NFP of the invention. The reactor granules have an average diameter of from 50 μm to 10 mm in one embodiment, and from 10 μm to 5 mm in another embodiment. In another embodiment, the polyolefin is in the form of pellets, such as, for example, having an average diameter of from 1 mm to 10 mm that are formed from melt extrusion of the reactor granules.
[0037] In one embodiment of the invention, the polyolefin suitable for the composition excludes physical blends of polypropylene with other polyolefins, and in particular, excludes physical blends of polypropylene with low molecular weight (500 to 10,000 g/mol) polyethylene or polyethylene copolymers, meaning that, low molecular weight polyethylene or polyethylene copolymers are not purposefully added in any amount to the polyolefin (e.g., polypropylene homopolymer or copolymer) compositions of the invention, such as is the case in, for example, WO 01/18109 Al.
[0038] The polyolefin is present in the compositions of the present invention from 40 wt% to 99.9 wt% in one embodiment, and from 50 wt% to 99 wt% in another embodiment, and from 60 wt% to 98 wt% in yet another embodiment, and from 70 wt% to 97 wt% in yet another embodiment, and from 80 wt% to 97 wt% in yet another embodiment, and from 90 wt% to 98 wt% in yet another embodiment, wherein a desirable range may be any combination of any upper wt% limit with any lower wt% limit described herein.
[0039] Desirable polyolefins for use in the present invention may thus be described by any embodiment herein, or any combination of the embodiments described herein.
Non-functionalized Plasticizer
[0040] The polyolefin compositions of the present invention include a non-functionalized plastizer ("NFP"). The NFP of the present invention is a compound comprising carbon and hydrogen, and does not include to an appreciable extent functional groups selected from hydroxide, aryls and substituted aryls, halogens, alkoxys, carboxylates, esters, carbon unsaturation, acrylates, oxygen, nitrogen, and carboxyl. By "appreciable extent", it is meant that these groups and compounds comprising these groups are not deliberately added to the NFP, and if present at all, are present to less than 5 wt% by weight of the NFP in one embodiment, and less than 1 wt% in another embodiment, and less than 0.5 wt% in yet another embodiment.
[0041] In one embodiment, the NFP consists of C6 to C 0o paraffins, and
C8 to oo paraffins in another embodiment. In another embodiment, the NFP consists essentially of C6 to C 0o paraffins, and consists essentially of C8 to C10o paraffins in another embodiment. For purposes of the present invention and description herein, the term "paraffin" includes all isomers such as n-paraffins, branched paraffins, isoparaffins, and may include cyclic aliphatic species, and blends thereof, and may be derived synthetically by means known in the art, or from refined crude oil in such a way as to meet the requirements described for desirable NFPs described herein. It will be realized that the classes of materials described herein that are useful as an NFPs can be utilized alone or admixed with other NFPs described herein in order to obtain the desired properties.
[0042] The NFP may be present in the polyolefin compositions of the invention from 0.1 wt% to 60 wt% in one embodiment, and from 0.5 wt% to 40 wt% in another embodiment, and from 1 wt% to 20 wt% in yet another embodiment, and from 2 wt% to 10 wt% in yet another embodiment, wherein a desirable range may comprise any upper wt% limit with any lower wt% limit described herein.
[0043] The NFP may also be described by any number of, or any combination of, parameters described herein. In one embodiment, the NFP of the present invention has a pour point (ASTM D97) of from less than 0°C in one embodiment, and less than -5°C in another embodiment, and less than -10°C in another embodiment, less than -20°C in yet another embodiment, less than -40°C in yet another embodiment, less than -50°C in yet another embodiment, and less than -60°C in yet another embodiment, and greater than -120°C in yet another embodiment, and greater than -200°C in yet another embodiment, wherein a desirable range may include any upper pour point limit with any lower pour point limit described herein. In one embodiment, the NFP is a paraffin or other compound having a pour point of less than -30°C, and between -30°C and -90°C in another embodiment, in the viscosity range of from 0.5 to 200 cSt at 40°C (ASTM D445-97). Most mineral oils, which typically include aromatic moieties and other functional groups, have a pour point of from 10°C to -20°C at the same viscosity range.
[0044] The NFP may have a dielectric constant at 20°C of less than 3.0 in one embodiment, and less than 2.8 in another embodiment, less than 2.5 in another embodiment, and less than 2.3 in yet another embodiment, and less than 2.1 in yet another embodiment. Polyethylene and polypropylene each have a dielectric constant (1 kHz, 23°C) of at least 2.3 (CRC HANDBOOK OF CHEMISTRY AND PHYSICS (David R. Lide, ed. 82d ed. CRC Press 2001).
[0045] The NFP has a viscosity (ASTM D445-97) of from 0.1 to 3000 cSt at 100°C, and from 0.5 to 1000 cSt at 100°C in another embodiment, and from 1 to 250 cSt at 100°C in another embodiment, and from 1 to 200 cSt at 100°C in yet another embodiment, and from 10 to 500 cSt at 100°C in yet another embodiment, wherein a desirable range may comprise any upper viscosity limit with any lower viscosity limit described herein.
[0046] The NFP has a specific gravity (ASTM D 4052, 15.6/15.6°C) of less than 0.920 g/cm3 in one embodiment, and less than 0.910 g/cm3 in another embodiment, and from 0.650 to 0.900 g/cm3 in another embodiment, and from 0.700 to 0.860 g/cm3, and from 0.750 to 0.855 g/cm3 in another embodiment, and from 0.790 to 0.850 g/cm3 in another embodiment, and from 0.800 to 0.840 g/cm3 in yet another embodiment, wherein a desirable range may comprise any upper specific gravity limit with any lower specific gravity limit described herein. The NFP has a boiling point of from 100°C to 800°C in one embodiment, and from 200°C to 600°C in another embodiment, and from 250 °C to 500°C in yet another embodiment. Further, the NFP has a weight average molecular weight (GPC or GC) of less than 20,000 g/mol in one embodiment, and less than 10,000 g/mol in yet another embodiment, and less than 5,000 g/mol in yet another embodiment, and less than 4,000 g/mol in yet another embodiment, and less than 2,000 g/mol in yet another embodiment, and less than 500 g/mol in yet another embodiment, and greater than 100 g/mol in yet another embodiment, wherein a desirable molecular weight range can be any combination of any upper molecular weight limit with any lower molecular weight limit described herein.
[0047] A compound suitable as an NFP for polyolefins of the present invention may be selected from commercially available compounds such as so called "isoparaffins", "polyalphaolefins" (PAOs) and "polybutenes" (a subgroup of PAOs). These three classes of compounds can be described as paraffins which can include branched, cyclic, and normal structures, and blends thereof. These NFPs can be described as comprising C6 to C200 paraffins in one embodiment, and C8 to Cioo paraffins in another embodiment.
[0048] The so called "isoparaffins" are described as follows. These paraffins are desirably isoparaffins, meaning that the paraffin chains possess C\ to C10 alkyl branching along at least a portion of each paraffin chain. The C6 to C20o paraffins may comprise C6 to C25 isoparaffins in one embodiment, and C8 to C20 isoparaffins in another embodiment.
[0049] More particularly, the isoparaffins are saturated aliphatic hydrocarbons whose molecules have at least one carbon atom bonded to at least three other carbon atoms or at least one side chain (i.e., a molecule having one or more tertiary or quaternary carbon atoms), and preferably wherein the total number of carbon atoms per molecule is in the range between 6 to 50, and between 10 and 24 in another embodiment, and from 10 to 15 in yet another embodiment. Narious isomers of each carbon number will typically be present. The isoparaffins may also include cycloparaffins with branched side chains, generally as a minor component of the isoparaffin. The density (ASTM 4052, 15.6/15.6°C) of these isoparaffins ranges from 0.70 to 0.83 g/cm3; a pour point of below -40°C in one embodiment, and below -50°C in another embodiment; a viscosity (ASTM 445, 25°C) of from 0.5 to 20 cSt at 25°C; and average molecular weights in the range of 100 to 300 g/mol. The isoparaffins are commercially available under the tradename ISOPAR (ExxonMobil Chemical Company, Houston TX), and are described in, for example, US 6,197,285, 3,818,105 and 3,439,088, and sold commercially as ISOPAR series of isoparaffins, some of which are summarized in Table 1 below.
Table 1. ISOPAR Series Isoparaffins
Figure imgf000016_0001
ISOPAR G 161-176 -57 0.75 1.46 <0.01
ISOPAR H 178-188 -63 0.76 1.8 <0.01
ISOPAR K 179-196 -60 0.76 1.85 <0.01
ISOPAR L 188-207 -57 0.77 1.99 <0.01
ISOPAR M 223-254 -57 0.79 3.8 <0.01
ISOPAR V 272-311 -63 0.82 14.8 O.01
[0050] In another embodiment, the isoparaffins are a mixture of branched and normal paraffins having from 6 to 50 carbon atoms, and from 10 to 24 carbon atoms in another embodiment, in the molecule. The isoparaffin composition has an a branch paraffim.n-paraffin ratio ranging from 0.5:1 to 9:1 in one embodiment, and from 1:1 to 4:1 in another embodiment. The isoparaffins of the mixture in this embodiment contain greater than 50 wt% (by total weight of the isoparaffin composition) mono-methyl species, for example, 2-methyl, 3 -methyl, 4-methyl, 5- methyl or the like, with minimum formation of branches with substituent groups of carbon number greater than 1, such as, for example, ethyl, propyl, butyl or the like, based on the total weight of isoparaffins in the mixture. In one embodiment, the isoparaffins of the mixture contain greater than 70 wt% of the mono-methyl species, based on the total weight of the isoparaffins in the mixture. The isoparaffinic mixture boils within a range of from 100°C to 350°C in one embodiment, and within a range of from 110°C to 320°C in another embodiment. In preparing the different grades, the paraffinic mixture is generally fractionated into cuts having narrow boiling ranges, for example, 35°C boiling ranges. These branch paraffin/n-paraffin blends are described in, for example, US 5,906,727.
[0051] Other suitable isoparaffins are also commercial available under the trade names SHELLSOL (by Shell), SOLTROL (by Chevron Phillips) and SASOL (by Sasol Limited). SHELLSOL is a product of the Royal Dutch/Shell Group of Companies, for example Shellsol TM (boiling point = 215-260°C). SOLTROL is a product of Chevron Phillips Chemical Co. LP, for example SOLTROL 220 (boiling point = 233-280°C). SASOL is a product of Sasol Limited (Johannesburg, South Africa), for example SASOL LPA-210, SASOL-47 (boiling point = 238-274°C).
[0052] The paraffins suitable as the NFP of the invention also include so called PAOs, which are described as follows. The PAOs useful in the present invention comprise C6 to C 0o paraffins, and C10 to C10o n-paraffins in another embodiment. The PAOs are dimers, trimers, tetramers, pentamers, etc. of C4 to C12 α-olefins in one embodiment, and C5 to C12 α-olefins in another embodiment. Suitable olefms include 1 -butene, 1-pentene, 1 -hexene, 1-heptene, 1 -octene, 1- nonene, 1-decene, 1-undodecene and 1-dodecene. In one embodiment, the olefin is 1-decene, and the NFP is a mixture of dimers, trimers, tetramers and pentamers (and higher) of 1-decene. The PAOs are described more particularly in, for example, US 5,171,908, and US 5,783,531 and in SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS 1-52 (Leslie R. Rudnick & Ronald L. Shubkin, ed. Marcel Dekker, Inc. 1999).
[0053] The PAOs of the present invention possess a weight average molecular weight of from 100 to 20,000 in one embodiment, and from 200 to 10,000 in another embodiment, and from 200 to 7,000 in yet another embodiment, and from 200 to 2,000 in yet another embodiment, and from 200 to 500 in yet another embodiment. Generally, PAOs have viscosities in the range of 0.1 to 150 cSt at 100°C, and from 0.1 to 3000 cSt at 100°C in another embodiment (ASTM 445). The PAOs useful in the present invention have pour points of less than 0°C in one embodiment, less than -10°C in another embodiment, and less than -20°C in yet another embodiment, and less than -40°C in yet another embodiment. Desirable PAOs are commercially available as SHF and SuperSyn PAOs (ExxonMobil Chemical Company, Houston TX), some of which are summarized in the Table 2 below.
Table 2. SHF and SuperSyn Series Polyalphaolefins
PAO specific gravity Viscosity @ 100°C, VI Pour Point, °C (g/cm3; 15.6/15.6°C) cSt
SHF-20 0.798 1.68 - -63
SHF-21 0.800 1.70 - -57
SHF-23 0.802 1.80 - -54
SHF-41 0.818 4.00 123 -57
SHF-61/63 0.826 5.80 133 -57
SHF-82/83 0.833 7.90 135 -54
SHF-101 0.835 10.0 136 -54
SHF-403 0.850 40.0 152 -39
SHF-1003 0.855 107 179 -33
SuperSyn 2150 0.850 150 214 -42
SuperSyn 2300 0.852 300 235 -30
SuperSyn 21000 0.856 1,000 305 -18
SuperSyn 23000 0.857 3,000 388 -9
[0054] Polybutenes, a subset of PAOs, are another useful NFP of the present invention and are described as follows. In one embodiment of the invention, the polybutene processing oil is a low molecular weight (less than 15,000 number average molecular weight; less than 60,000 weight average molecular weight) homopolymer or copolymer of olefin derived units having from 3 to 8 carbon atoms in one embodiment, preferably from 4 to 6 carbon atoms in another embodiment. In yet another embodiment, the polybutene is a homopolymer or copolymer of a C4 raffmate. An embodiment of such low molecular weight polymers termed "polybutene" polymers is described in, for example, SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS 357-392 (Leslie R. Rudnick & Ronald L. Shubkin, ed., Marcel Dekker 1999) (hereinafter "polybutene processing oil" or "polybutene").
[0055] Described yet another way, the polybutene is a copolymer of at least isobutylene derived units, 1 -butene derived units, and 2-butene derived units. In one embodiment, the polybutene is a homopolymer, copolymer, or terpolymer of the three units, wherein the isobutylene derived units are from 40 to 100 wt% of the copolymer, the 1 -butene derived units are from 0 to 40 wt% of the copolymer, and the 2-butene derived units are from 0 to 40 wt% of the copolymer. In another embodiment, the polybutene is a copolymer or terpolymer of the three units, wherein the isobutylene derived units are from 40 to 99 wt% of the copolymer, the 1 -butene derived units are from 2 to 40 wt% of the copolymer, and the 2-butene derived units are from 0 to 30 wt% of the copolymer. In yet another embodiment, the polybutene is a terpolymer of the three units, wherein the isobutylene derived units are from 40 to 96 wt% of the copolymer, the 1 -butene derived units are from 2 to 40 wt% of the copolymer, and the 2-butene derived units are from 2 to 20 wt% of the copolymer. In yet another embodiment, the polybutene is a homopolymer or copolymer of isobutylene and 1 -butene, wherein the isobutylene derived units are from 65 to 100 wt% of the homopolymer or copolymer, and the 1 -butene derived units are from 0 to 35 wt% of the copolymer.
[0056] Polybutene processing oils useful in the invention typically have a number average molecular weight (Mn) of less than 10,000 g/mol in one embodiment, less than 8000 g/mol in another embodiment, and less than 6000 g/mol in yet another embodiment. In one embodiment, the polybutene oil has a number average molecular weight of greater than 400 g/mol, and greater than 700 g/mol in another embodiment, and greater than 900 g/mol in yet another embodiment. A preferred embodiment can be a combination of any lower molecular weight limit with any upper molecular weight limit described herein. For example, in one embodiment of the polybutene of the invention, the polybutene has a number average molecular weight of from 400 g/mol to 10,000 g/mol, and from 700 g/mol to 8000 g/mol in another embodiment, and from 900 g/mol to 3000 g/mol in yet another embodiment. Useful viscosities of the polybutene processing oil ranges from 10 to 6000 cSt (centiStokes) at 100°C in one embodiment, and from 35 to 5000 cSt at 100°C in another embodiment, and is greater than 35 cSt at 100°C in yet another embodiment, and greater than 100 cSt at 100°C in yet another embodiment.
[0057] Commercial examples of polybutenes are the PARAPOL™ Series of processing oils (Infmeum, Linden, NJ), such as PARAPOL™ 450, 700, 950, 1300, 2400 and 2500. The commercially available PARAPOL™ Series of polybutene processing oils are synthetic liquid polybutenes, each individual formulation having a certain molecular weight, all formulations of which can be used in the composition of the invention. The molecular weights of the PARAPOL™ oils are from 420 Mn (PARAPOL™ 450) to 2700 Mn (PARAPOL™ 2500) as determined by gel permeation chromatography. The MWD of the PARAPOL™ oils range from 1.8 to 3 in one embodiment, and from 2 to 2.8 in another embodiment; the pour points of these polybutenes are less than 25°C in one embodiment, less than 0°C in another embodiment, and less than - 10°C in yet another embodiment, and between -80°C and 25°C in yet another embodiment; and densities (IP 190/86 at 20°C) range from 0.79 to 0.92 g/cm3, and from 0.81 to 0.90 g/cm3 in another embodiment.
[0058] Below, Table 3 shows some of the properties of the PARAPOL™ oils useful in embodiments of the present invention, wherein the viscosity was determined as per ASTM D445-97, and the number average molecular weight (Mπ) by gel permeation chromatography. Table 3. PARAPOL™ Grades of polybutenes
Grade M„ Viscosity @ 100°C, cSt
450 420 10.6
700 700 78
950 950 230
1300 1300 630
2400 2350 3200
2500 2700 4400
[0059] Desirable NFPs for use in the present invention may thus be described by any embodiment described herein, or any combination of the embodiments described herein. For example, in one embodiment, the NFP is a C6 to C200 paraffin having a pour point of less than 25°C. Described another way, the NFP comprises an aliphatic hydrocarbon having a viscosity of from 0.1 to 1000 cSt at 100°C. Described yet another way, the NFP is selected from n-paraffins, branched isoparaffins, and blends thereof having from 8 to 25 carbon atoms. The NFP is characterized in one embodiment in that, when blended with the polyolefin to form a plasticized composition, the NFP is compatible and miscible with the propylene polymer and does not form a separate phase.
[0060] In one embodiment of compositions of the present invention, conventional plasticizers such as is commonly used for poly(vinyl chloride) are substantially absent. In particular, plasticizers such as phthalates, adipates, trimellitate esters, polyesters, and other functionalized plasticizers as disclosed in, for example, US 3,318,835; US 4,409,345; WO 02/31044 Al; and PLASTICS ADDITIVES 499-504 (Geoffrey Pritchard, ed., Chapman & Hall 1998) are substantially absent. By "substantially absent", it is meant that these compounds are not added deliberately to the compositions. [0061] Oils such as naphthenic and other aromatic containing oils are present to less than 0.5 wt% of the compositions of the invention in a further embodiment. Also, aromatic moieties and carbon-carbon unsaturation are substantially absent from the non-functionalized plasticizers used in the present invention in yet another embodiment. Aromatic moieties include a compound whose molecules have the ring structure characteristic of benzene, naphthalene, phenanthrene, anthracene, etc. By "substantially absent", it is meant that these aromatic compounds or moieties are not added deliberately to the compositions, and if present, are present to less than 0.5 wt% of the composition of the NFP. Thus, most "mineral oils" are substantially absent from the compositions of the present invention.
[0062] In another embodiment of compositions of the present invention, conventional plasticizers, elastomers, or "compatibilizers" such as low molecular weight polyethylene are substantially absent. In particular, polyethylene homopolymer and copolymer having a weight average molecular weight of from 500 to 10,000 is substantially absent. Such polyethylene compatibilizers are disclosed in, for example, WO 01/18109 Al. By "substantially absent", it is meant that these compounds are not added deliberately to the compositions.
Blending and Articles of Manufacture
[0063] The polyolefin compositions of the present invention may also contain other additives. Those additives include antioxidants, nucleating agents, acid scavengers, stabilizers, anticorrosion agents, blowing agents, other UN absorbers such as chain-breaking antioxidants, etc., quenchers, antistatic agents, slip agents, pigments, dyes and fillers and cure agents such as peroxide. Dyes and other colorants common in the industry may be present from 0.01 to 10 wt% in one embodiment, and from 0.1 to 6 wt% in another embodiment. Suitable nucleating agents are disclosed by, for example, H.Ν. Beck in Heterogeneous Nucleating Agents for Polypropylene Crystallization, 11 J. APPLIED POLY. SCI. 673-685 (1967) and in Heterogeneous Nucleation Studies on Polypropylene, 21 J. POLY. SCI.: POLY. LETTERS 347-351 (1983). Examples of suitable nucleating agents are sodium benzoate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, aluminum 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, dibenzylidene sorbitol, di(p-tolylidene) sorbitol, di(p-ethylbenzylidene) sorbitol, bis(3,4-dimethylbenzylidene) sorbitol, and N',N'-dicyclohexyl-2,6- naphthalenedicarboxamide, and salts of disproportionated rosin esters. The foregoing list is intended to be illustrative of suitable choices of nucleating agents for inclusion in the subject polypropylene formulations.
[0064] In particular, antioxidants and stabilizers such as organic phosphites, hindered amines, and phenolic antioxidants may be present in the polyolefin compositions of the invention from 0.001 to 2 wt% in one embodiment, and from 0.01 to 0.8 wt% in another embodiment, and from 0.02 to 0.5 wt% in yet another embodiment. Non-limiting examples of organic phosphites that are suitable are tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168) and di(2,4-di- tert-butylphenyl)pentaerithritol diphosphite (ULTRANOX 626). Non-limiting examples of hindered amines include poly[2-N,N'-di(2,2,6,6-tetramethyl-4- piperidinyl)-hexanediamine-4-( 1 -amino- 1 , 1 ,3 ,3-tetramethylbutane)sym-triazine] (CHIMASORB 944); bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate (TINUVIN 770). Non-limiting examples of phenolic antioxidants include pentaerythrityl tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1010); and l,3,5-Tri(3,5-di-tert-butyl-4-hydroxybenzyl-isocyanurate (IRGANOX 3114).
[0065] Fillers may be present from 0.1 to 50 wt% in one embodiment, and from 0.1 to 25 wt% of the composition in another embodiment, and from 0.2 to 10 wt% in yet another embodiment. Desirable fillers include but not limited to titanium dioxide, silicon carbide, silica (and other oxides of silica, precipitated or not), antimony oxide, lead carbonate, zinc white, lithopone, zircon, corundum, spinel, apatite, Barytes powder, barium sulfate, magnesiter, carbon black, dolomite, calcium carbonate, talc and hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr or Fe and CO3 and/or HPO4, hydrated or not; quartz powder, hydrochloric magnesium carbonate, glass fibers, clays, alumina, and other metal oxides and carbonates, metal hydroxides, chrome, phosphorous and brominated flame retardants, antimony trioxide, silica, silicone, and blends thereof. These fillers may particularly include any other fillers and porous fillers and supports known in the art, and may have the NFP of the invention pre-contacted, or pre- absorbed into the filler prior to addition to the polyolefin in one embodiment.
[0066] More particularly, in one embodiment of the present invention, the
NFP, or some portion of the NFP, may be blended with a filler, desirably a porous filler. The NFP and filler may be blended by, for example, a tumbler or other wet blending apparatus. The NFP and filler in this embodiment are blended for a time suitable to form a homogenous composition of NFP and filler, desirably from 1 minute to 5 hours in one embodiment. This NFP/fiUer blend may then be blended with the polyolefin useful in the invention in order to effectuate plastication of the polyolefin. In another embodiment, a porous filler may be contacted with the NFP, or some portion thereof, prior to contacting the filler with the polyolefin. In another embodiment, the porous filler, polyolefin and NFP are contacted simultaneously (or in the same blending apparatus). In any case, the NFP may be present from 0.1 to 60 wt% of the composition, and from 0.2 to 40 wt% in another embodiment, and from 0.3 to 20 wt% in yet another embodiment.
[0067] Fatty acid salts may also be present in the polyolefin compositions of the present invention. Such salts may be present from 0.001 to 1 wt% of the composition in one embodiment, and from 0.01 to 0.8 wt% in another embodiment. Examples of fatty acid metal salts include lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, and erucic acid, suitable metals including Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb and so forth. Preferable fatty acid salts are selected from magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, and magnesium oleate.
[0068] The resultant plasticized polyolefin of the present invention may be processed by any suitable means such as by calendering, casting, coating, compounding, extrusion, foamed, laminated, blow molding, compression molding, injection molding, thermoforming, transfer molding, cast molding, rotational molding, casting such as for films, spun or melt bonded such as for fibers, or other forms of processing such as described in, for example, PLASTICS PROCESSING (Radian Corporation, Noyes Data Corp. 1986). More particularly, with respect to the physical process of producing the blend, sufficient mixing should take place to assure that a uniform blend will be produced prior to conversion into a finished product.
[0069] More particularly, the components of the polyolefmic composition of the present invention may be blended by any suitable means to form the plasticized polyolefin, which is then suitable for further processing into useful articles. In one aspect of the invention, the polyolefin and NFP are blended, or melt blended, in an apparatus such as an extruder or Brabender mixer. The polyolefin may also be blended with the NFP using a tumbler, double-cone blender, ribbon blender, or other suitable blender. In yet another embodiment, the polyolefin and NFP are blended by a combination of, for example, a tumbler, followed by melt blending in an extruder. Extrusion technology for polypropylene is described in more detail in, for example, PLASTICS EXTRUSION TECHNOLOGY 26-37 (Friedhelm Hensen, ed. Hanser Publishers 1988) and in POLYPROPYLENE HANDBOOK 304-348 (Edward P. Moore, Jr. ed., Hanser Publishers 1996).
[0070] The polyolefin suitable for use in the present invention can be in any physical form when used to blend with the NFP of the invention. In one embodiment, reactor granules, defined as the granules of polymer that are isolated from the polymerization reactor, are used to blend with the NFP of the invention. The reactor granules have an average diameter of from 10 μm to 5 mm, and from 50 μm to 10 mm in another embodiment. Alternately, the polyolefin is in the form of pellets, such as, for example, having an average diameter of from 1 mm to 6 mm that are formed from melt extrusion of the reactor granules. [0071] One method of blending the NFP with the polyolefin is to contact the components in a tumbler, the polyolefin being in the form of reactor granules. This works particularly well with polypropylene homopolymer. This can then be followed, if desired, by melt blending in an extruder. Another method of blending the components is to melt blend the polyolefin pellets with the NFP directly in an extruder or Brabender.
[0072] Thus, in the cases of injection molding of various articles, simple solid state blends of the pellets serve equally as well as pelletized melt state blends of raw polymer granules, of granules with pellets, or of pellets of the two components since the forming process includes a remelting and mixing of the raw material. In the process of compression molding of medical devices, however, little mixing of the melt components occurs, and a pelletized melt blend would be preferred over simple solid state blends of the constituent pellets and/or granules. Those skilled in the art will be able to determine the appropriate procedure for blending of the polymers to balance the need for intimate mixing of the component ingredients with the desire for process economy.
[0073] The polyolefinic compositions of the present invention are suitable for such articles as automotive components, wire and cable jacketing, pipes, agricultural films, geomembranes, toys, sporting equipment, medical devices, casting and blowing of packaging films, extrusion of tubing, pipes and profiles, sporting equipment, outdoor furniture (e.g., garden furniture) and playground equipment, boat and water craft components, and other such articles. In particular, the compositions are suitable for automotive components such as bumpers, grills, trim parts, dashboards and instrument panels, exterior door and hood components, spoiler, wind screen, hub caps, mirror housing, body panel, protective side molding, and other interior and external components associated with automobiles, trucks, boats, and other vehicles.
[0074] Other useful articles and goods may be formed economically by the practice of our invention including: crates, containers, packaging, labware, such as roller bottles for culture growth and media bottles, office floor mats, instrumentation sample holders and sample windows; liquid storage containers such as bags, pouches, and bottles for storage and IN infusion of blood or solutions; packaging material including those for any medical device or drugs including unit-dose or other blister or bubble pack as well as for wrapping or containing food preserved by irradiation. Other useful items include medical tubing and valves for any medical device including infusion kits, catheters, and respiratory therapy, as well as packaging materials for medical devices or food which is irradiated including trays, as well as stored liquid, particularly water, milk, or juice, containers including unit servings and bulk storage containers as well as transfer means such as tubing, pipes, and such.
[0075] These devices may be made or formed by any useful forming means for forming polyolefins. This will include, at least, molding including compression molding, injection molding, blow molding, and transfer molding; film blowing or casting; extrusion, and thermoforming; as well as by lamination, pultrusion, protrusion, draw reduction, rotational molding, spinbonding, melt spinning, melt blowing; or combinations thereof. Use of at least thermoforming or film applications allows for the possibility of and derivation of benefits from uniaxial or biaxial orientation of the radiation tolerant material.
[0076] In one embodiment, the present invention is a plasticized polyolefin composition comprising from 99.9 wt% to 60 wt% polyolefin; and from 0.1 wt% to 40 wt% of a ΝFP; wherein the ΝFP comprises C6 to C200 paraffins having a pour point of less than -5°C. In another embodiment, the non- functionalized plasticizer comprises C8 to C100 paraffins. In yet another embodiment, the ΝFP comprises C6 to C50 isoparaffins, and Cι0 to C10o n-paraffins in yet another embodiment.
[0077] Described another way, the plasticized polyolefin of the present invention is a blend of a polyolefin and a non-functionalized plasticizer, wherein the non-functionalized plasticizer is a compound having a pour point of less than - 30°C in the viscosity range of from 0.5 to 200 cSt at 40°C (ASTM D445-97) in one embodiment, and between -30°C and -90°C in the viscosity range of from 0.5 to 200 cSt at 40°C (ASTM D445-97) in another embodiment.
[0078] The composition can also be described by any number of physical and chemical properties. For example, in one embodiment, the compositions of the invention are characterized in that the Tg of the polyolefin decreases from 4 to 10°C for every 4 wt% of NFP added to the composition, while the Tm remains within 1 to 2 °C.
[0079] The NFP of the present invention can be described by any number of physical and chemical properties described herein. For example, in one embodiment the non-functionalized plasticizer has a pour point of less than -30°C; and a viscosity of from 0.1 to 3000 cSt at 100°C in another embodiment; and a dielectric constant at 20°C of less than 2.1 in yet another embodiment; and a specific gravity of less than 0.91 g/cm in yet another embodiment. In a further embodiment of the NFP, aromatic moieties are substantially absent.
[0080] Further, the NFP possesses a weight average molecular weight of from 100 to 25,000 g/mol; and from 200 to 10,000 g/mol in another embodiment.
[0081] The polyolefin suitable for compositions of the invention can be described by any number of embodiments. In one embodiment, the polyolefin comprises isotactic segments. In another embodiment, the polyolefin is selected from propylene homopolymers, propylene copolymers, and propylene impact copolymers, and mixtures thereof. In yet another embodiment, the polyolefin is isotactic polypropylene. And in yet another embodiment, the polyolefin is a copolymer comprises propylene derived units and units selected from ethylene derived units and C to C20 α-olefin derived units.
[0082] In yet another embodiment, the polyolefin is a propylene impact copolymer comprising from 40% to 95% by weight of a Component A and from 5% to 60% by weight of a Component B based on the total weight of copolymer; wherein Component A comprises propylene homopolymer or copolymer, the copolymer comprising 10% or less by weight ethylene, butene, hexene or octene comonomer; and wherein Component B comprises propylene copolymer, wherein the copolymer comprises from 5% to 70% by weight ethylene, butene, hexene and/or octene comonomer, and from 95% to 30% by weight propylene.
[0083] The polyolefin may further comprise a plastomer.
[0084] The compositions of the present invention may be described in a further embodiment wherein polyethylene having a weight average molecular weight of from 500 to 10,000 is substantially absent.
[0085] The present invention also includes a method of plasticizing a polyolefin comprising blending a polyolefin with a non-functionalized plasticizer; wherein the non-functionalized plasticizer comprises C6 to C20o paraffins having a pour point of less than -5°C. In one embodiment, the blending comprises melt blending. The melt blending is performed in an extruder in one embodiment.
[0086] In one embodiment, the blending comprises wet blending of solid polyolefin. The polyolefin is in the form of reactor granules in one embodiment, and extruded pellets in another embodiment, or a blend thereof. If reactor granules are used, the reactor granules have an average diameter of from 10 μm to 5 mm in one embodiment.
[0087] An article of manufacture can be formed from compositions of the invention, non-limiting examples of such articles include films, sheets, fibers, woven and nonwoven fabrics, tubes, pipes, automotive components, fuπuture, sporting equipment, food storage containers, transparent and semi-transparent articles, toys, tubing and pipes, and medical devices. EXAMPLES
[0088] The present invention, while not meant to be limiting by, may be better understood by reference to the following examples and Tables.
[0089] The glass transition temperature (Tg) and storage modulus (E') were determined as follows by dynamic mechanical thermal analysis ("DMT A"). Dynamic mechanical testing was conducted by oscillating a solid rectangular beam, fixed at one end, trough an arbitrary angle of deflection. The force and angle of deflection are used to calculate stress and strain respectively. The ratio of the stress to strain yields a modulus. Varying the temperature during the test yields information about the behavior of the material as a function of temperature. The test parameters include a single cantilever; frequency of 1 Hz, start temperature of -130°C, max temperature of 60°C. Temperature is increased at a rate of 2°C/min. Tan δ is the ratio of E"/E' where E" is the loss modulus and E' is the storage modulus or elastic modulus. The glass transition temperature is determined by the temperature when of Tan δ reaches its maximal value.
[0090] Crystallization temperature (Tc) and melting temperature (Tm) was measured as follows: Differential Scanning Calorimetry (DSC, at a heating rate of 10° C/minute). As an example, about 6 to 10 mg of a sheet of the polymer or plasticized polymer was pressed at approximately 150° C to 200° C is removed with a punch die. The sample is placed in a Differential Scarming Calorimeter (Perkin Elmer 7 Series Thermal Analysis System) and heated to 200°C and held for 10 minutes. The sample is cooled at 10°C/min. to attain a final temperature of 25°C. The thermal output is recorded and the inflection point in the thermal output data, indicating a change in the heat capacity is determined by electronically differentiating the thermal output data. The maximum in the differential thermal output data corresponds to the crystallization temperature of the sample. The sample is held at 25°C for 10 minutes and heated at 10°C/min to 200°C. The thermal input is recorded and the inflection point in the thermal input data, indicating a change in the heat capacity is determined by electronically differentiating the thermal input data. The maximum in the differential thermal input data corresponds to the melting temperature of the sample.
[0091] Molecular weight distribution was determined using Gel Permeation
Chromatography.
[0092] The shear viscosity as a function of shear rate was determined by a dual-barrel capillary rheometer. The capillary rheometer (Rosand Model RAH7/2 by Bohun Instruments) is equipped with a 30:1 length to diameter ratio capillary. A total mass of 25-30g of pellets were packed into the capillary barrels and preheated at 230°C for 10 minutes to remove any entrained air before the test. Each test was performed at 230°C over the shear rate range of from 30 to 3000 s'1. Corrections to the data for entrance pressure losses (i.e., the Bagley correction) were performed online via simultaneous pressure loss measurements for the flow of the material through an orifice that was installed into the second barrel of the rheometer.
[0093] Softness or "hand" of spunbond nonwoven fabric as it is known in the art was measured using the Thwing- Albert Handle-O-Meter (Model 211-10- B/America.) The quality of "hand" is considered to be the combination of resistance due to the surface friction and flexibility of a fabric material. The Hand-O-Meter measures the above two factors using and LNDT (Linear Variable Differential Transformer) to detect the resistance that a blade encounters when forcing a specimen of material into a slot of parallel edges. A 3 Vi digit digital voltmeter (DVM) indicates the resistance directly in grams. The "total hand" of any given sheet of material is the average of four readings taken on both sides and both directions of a test sample and is recorded in grams per standard width of sample material. A decrease in "total hand" indicates the improvement of fabric softness.
[0094] Other test methods are as described in the text of the Tables that follow. [0095] The components of the present invention can be blended by any suitable means. The examples below demonstrate one method of blending the components. For samples 1-5, reactor granules of metallocene produced propylene homopolymers were first blended in a tumble blender with the addition of antioxidants, i.e., 600 ppm of Irganox 1076, and 260 ppm of calcium stearate, and 4 wt% of NFP for plasticized samples to achieve a homogeneous mixing of blend components. The blended polymers were compounded and pelletized using a 57 mm twin screw extruder at extrusion temperature of 230°C. For samples 10- 14, reactor granules of propylene random copolymer were first blended in a tumble blender with reactor granules and the addition of antioxidants, i.e., 825 ppm of calcium stearate, 800 ppm of Ultranox 626, 500 ppm of TLNUViN 622 and 2500 ppm of Millad 3940, and 5 wt% of NFP for plasticized samples to achieve a homogeneous mixing of blend components. The blended polymers were compounded and pelletized using a 30 mm twin screw extruder at extrusion temperature of 216°C. For samples 15-19, the reactor granules of propylene impact copolymers were first blended in a tumble blender with reactor granules and the addition of antioxidants, i.e., 800 ppm of calcium stearate, 1500 ppm of IRGANOX 1010, 500 ppm of ULTRANOX 626 and 675 ppm of sodium benzoate, and 5 wt% of NFP for plasticized samples to achieve a homogeneous mixing of blend components. The blended polymers were compounded and pelletized using a 30 mm single screw extruder at extrusion temperature of 205°C. For samples 6-9, a 10 wt% plasticized metallocene propylene homopolymers were prepared in the same manner as described above for samples 1-5. For samples 21- 24, the 10 wt% plasticized metallocene produced propylene homopolymers, prepared in the same manner as described above for samples 6-9, were dry blend with neat propylene polymers (Achieve™ 3854), in pellet form, to attain the 4 wt% active plasticized samples in the blends.
[0096] Standard ASTM tensile and HDT bars and Gardner impact discs were prepared using 120 ton injection molding equipment. Physical properties of the samples prepared are in the Tables below. Molded parts from the invention plasticized polypropylene homopolymers show a significant decrease in flexural and tensile modulus at a loading of 4 wt% PAO or isoparaffin, while maintaining their tensile strength, room temperature Izod Impact resistance and heat deflection temperature. For comparison, molded samples were also prepared with erucamide (Table 11), a common lubricant designed to reduce molded part surface friction of 4 wt% concentration. The effect of the erucamide on the flexural modulus is insignificant.
[0097] A typical spunbond process consists of a continuous filament extrusion, followed by drawing, web formation by the use of some type of ejector, and bonding the web. The polymer pellets are first fed into an extruder. In the extruder, the pellets simultaneously are melted and forced through the system by a heating melting screw. At the end of the screw, a spinning pump meters the molten polymer through a filter to a spinneret where the molten polymer is extruded under pressure through capillaries, at a rate of 0.4 grams per hole per minute. The spinneret contains a few hundred capillaries, measuring 0.4 mm in diameter. The polymer is melted at about 30-50°C above its melting point to achieve sufficiently low melt viscosity for extrusion. The fibers exiting the spinneret are quenched and drawn into fine fibers measuring about 16 microns in diameter. The solidified fiber is laid randomly on a moving belt to form a random netlike structure known in the art as web. The 25 basis weight (grams per square meter) of web is obtained by controlling the belt moving speed. After web formation, the web is bonded to achieve its final strength using a heated textile calender known in the art as thermobond calender. The calender consists of two heated steel rolls; one roll is plain and the other bears a pattern of raised points. The web is conveyed to the calender wherein a fabric is formed by pressing the web between the rolls at a bonding temperature of about 138°C.
[0098] Cast films were prepared using the following operations. Cast monolayer films were fabricated on a Killion cast film line. This line has three 24:1 L/D 2.54 cm diameter extruder, which feed polymer into a feedblock. The feedblock diverts molten polymer from the extruder to a 20.32 cm wide Cloeren die. Molten polymer exits the die at a temperature of 230°C and is cast on a chill roll (20.3 cm diameter, 25.4 cm roll face) at 21°C. The casting unit is equipped with adjustable winding speeds to obtain film of the targeted thickness.
[0099] The resin properties of plasticized propylene homopolymers, propylene copolymers and propylene impact copolymers are listed, respectively, in Tables 5-7. The addition of NFP in the propylene polymers improve the melt flowability, as indicated by the significant increase of melt flow rate. The improvement of melt flowability can be characterized by the decrease of shear viscosity as a function of shear rate range, as illustrated in Figures 11-13. In contrast to the peroxide degrading, or so called "vis-breaking", process, the increase of melt flowability in the current invention is mainly due to the plasticizing effect of NFP, and the polymer molecular weight is unchanged. This is evident in the comparison of molecular weight distribution, as shown in Figure 14. The improvement of melt flowability usually benefit the fabrication processes, i.e., fiber spinning, film casting, extrusion, injection molding, in terms of better draw-down, lower extruder torque, thin wall injection and faster cycle time.
[00100] The NFP in the current invention provides a significant depression in the storage modulus of propylene polymers. As illustrated in Figure 1, the storage modulus of plasticized propylene polymers are drastically reduced as a function of temperature relative to the unplasticized polyolefins. A propylene polymer having lower a storage modulus (or "elastic modulus) at any particular range of temperature indicates the ability to provide better flexibility for the end- use at that particular temperature conditions.
[00101] The NFP in the current invention demonstrates the ability to depress Tg without altering the melting temperature and crystallization temperature of propylene polymers, as illustrated in Figures 5-10. Traditional methods to depress Tg include the incorporation of comonomers as in the case for the propylene copolymers, which also depresses the melting temperature and crystallization temperature of polymer. Polymers having lower Tg without compromising the melting characteristics are very desirable and can provide better impact resistance, particularly for below freezing temperature impact resistance while maintaining the ability for high temperature usage. The plasticized polyolefins of the present invention provide this.
[00102] The NFP in the current invention is compatible and miscible with the propylene polymer, as determined by, for example, the single Tg profile of the plasticized propylene homopolymer and propylene copolymer. This is shown graphically in Figures 2-3. The NFP in the current invention is also compatible and miscible with the propylene impact copolymer, as determined by, for example, the two Tg profile of the plasticized propylene impact copolymer, being the lower Tg profile for the ethylene-propylene rubber phase and the higher Tg profile for the propylene polymer phase. This is shown graphically in Figure 4.
[00103] The summary of injection molded properties are provided in Tables
8-10, respectively, for propylene homopolymers, propylene copolymers and propylene impact copolymers. The addition of NFP substantially improves the impact resistance of molded parts without the significant decrease of heat deflection temperature. For example, Gardner impact strength, at both room and freezing temperatures, has improved from 350% to 400% for propylene homopolymers, from 140 to 165% for propylene copolymers, and from 20 to 40% for propylene impact copolymers due to the addition of 4-5 wt% of NFP. It is anticipated that further increase of impact resistance is attainable by the increase of NFP concentration in the propylene polymers. Other measures of impact resistance, including Izod impact at room and freezing temperatures, are also significantly improved.
[00104] Another advantage of the current invention is that the heat deflection temperature of plasticized polyolefins is not compromised (either maintained or only slightly reduced) which is crucial for applications requiring maintenance of molded article dimensions at high temperature. Further indication of toughness improvement is shown by the significant increase of elongation at yield and break. Many applications require good conformability during the end- use. A higher elongation facilitates the compliance of molded articles to the deformation during either the conversion process or at the end-use.
[00105] The NFP also demonstrate the ability to provide substantial softness improvement in spunbond nonwoven fabrics, as provided by the lower "total hand" in Table 12. In many applications, particularly in personal hygiene and health care, a soft nonwoven is very desirable for skin contact comfort. The current invention not only provides the improvement in softness but also maintains the necessary tensile strength, tear resistance and fabric uniformity.
[00106] Comparison of film properties are listed in Table 13. The NFP, particularly the Isopar-V plasticized propylene homopolymer (Sample 2) provides improvement in the tear and impact resistance, as indicated by the relatively high (relative to the unplasticized polyolefin) Elmendorf tear in both machine direction (MD) and transverse direction (TD) and dart impact at both room and freezing temperatures. In addition, the optical properties, i.e., haze and gloss, are also improved. The improvement offers advantages in many film applications, for examples, food packaging, stationery cover, tape, medical and electronic packaging.
[00107] While the present invention has been described and illustrated by reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to many different variations not illustrated herein. For these reasons, then, reference should be made solely to the appended claims for purposes of determining the scope of the present invention. Further, certain features of the present invention are described in terms of a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges formed by any combination of these limits are within the scope of the invention unless otherwise indicated.
[00108] All priority documents are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted. Further, all documents cited herein, including testing procedures, are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted.
Table 4. List of Components in Examples
Figure imgf000037_0001
TABLE 5 Resin properties of plasticized metallocene propylene homopolymer
Figure imgf000038_0002
Figure imgf000038_0001
TABLE 6 Resin properties of plasticized propylene random copolymer
Figure imgf000039_0002
TABLE 7 Resin properties of plasticized propylene impact copolymer
Figure imgf000039_0003
Figure imgf000039_0001
TABLE 8. Molded part properties of metallocene propylene homopolymers
Figure imgf000040_0001
a. Samples too brittle to perform this test. b. Samples failed at the lowest hammer weight.
TABLE 9 Molded part properties of propylene random copolymers
Figure imgf000041_0002
Figure imgf000041_0001
TABLE 10 Molded part properties of propylene impact copolymers
Figure imgf000042_0002
Figure imgf000042_0001
TABLE 11 Molded part properties of metallocene propylene homopolymers
Figure imgf000043_0002
Figure imgf000043_0001
TABLE 12
Softness properties per total hand of spunbond nonwoven fabrics made of metallocene propylene homopolymers
Figure imgf000044_0001
Total hand is based on measurements on fabrics at 25 gsm (grams per square meter).
TABLE 13 Cast film properties of metallocene propylene homopolymers
Figure imgf000045_0001
Films properties are based on 2 mil thickness.

Claims

1. A plasticized polyolefin composition comprising from 99.9 wt% to 60 wt% polyolefin; and from 0.1 wt% to 40 wt% of a non-functionalized plasticizer; wherein the non-functionalized plasticizer comprises C6 to C 0o paraffins having a pour point of less than -5°C.
2. The composition of Claim 1, wherein the non-functionalized plasticizers comprises C8 to Cioo paraffins.
3. The composition of Claim 1, wherein the non-functionalized plasticizers comprises C6 to C50 isoparaffins.
4. The composition of Claim 1, wherein the non-functionalized plasticizers comprises C10 to C10o n-paraffins.
5. The composition of any of the preceding Claims, wherein the Tg of the polyolefin decreases by at least 2°C for every 4 wt% of non-functionalized plasticizer added to the composition, while the Tm remains constant.
6. The composition of Claim 5, wherein the Tg of the polyolefin decreases from 4 to 10°C for every 4 wt% of non-functionalized plasticizer added to the composition, while the Tm remains constant.
7. The composition of any of the preceding Claims, wherein the non- functionalized plasticizer has a pour point of less than -30°C.
8. The composition of any of the preceding Claims, wherein the non- functionalized plasticizer has a viscosity of from 0.1 to 3000 cSt at 100°C.
9. The composition of any of the preceding Claims, wherein the non- functionalized plasticizer has a viscosity of from 1 to 3000 cSt at 100°C.
10. The composition of any of the preceding Claims, wherein the non- functionalized plasticizer has a viscosity of from 2 to 300 cSt at 100°C.
11. The composition of any of the preceding Claims, wherein the non- functionalized plasticizer has a dielectric constant at 20°C of less than 2.1.
12. The composition of any of the preceding Claims, wherein the non- functionalized plasticizer has a specific gravity of less than 0.91 g/cm3.
13. The composition of any of the preceding Claims, wherein aromatic moieties are substantially absent from the non-functionalized plasticizer.
14. The composition of any of the preceding Claims, wherein plasticizers such as phthalates, adipates, trimellitate esters, and polyesters are substantially absent.
15. The composition of any of the preceding Claims, wherein the weight average molecular weight of the non-functionalized plasticizer is from 100 to 25,000 g/mol.
16. The composition of Claim 15, wherein the weight average molecular weight of the non-functionalized plasticizer is from 200 to 25,000 g/mol.
17. The composition of Claim 16, wherein the weight average molecular weight of the non-functionalized plasticizer is from 200 to 10,000 g/mol.
18. The composition of any of the preceding Claims, wherein the polyolefin comprises segments that are isotactic.
19. The composition of any of the preceding Claims, wherein the polyolefin is selected from propylene homopolymers, propylene copolymers, propylene random copolymers, propylene block copolymers, propylene impact copolymers, and mixtures thereof.
20. The composition of Claim 19, wherein the propylene homopolymer is isotactic polypropylene.
21. The composition of any of Claims 1 to 17, wherein the polyolefin is a copolymer comprising propylene derived units and units selected from ethylene derived units and C4 to C 0 α-olefin derived units.
22. The composition of any of Claims 1 to 17, wherein the polyolefin is a propylene impact copolymer comprising from 40% to 95% by weight of a Component A and from 5% to 60% by weight of a Component B based on the total weight of copolymer; wherein Component A comprises propylene homopolymer or copolymer, the copolymer comprising 10% or less by weight ethylene, butene, hexene or octene comonomer; and wherein Component B comprises propylene copolymer, wherein the copolymer comprises from 5% to 70% by weight ethylene, butene, hexene and/or octene comonomer, and from 95% to 30% by weight propylene.
23. The composition of any of the preceding Claims, further comprising a plastomer.
24. The composition of any of the preceding Claims, wherein polyethylene having a weight average molecular weight of from 500 to 10,000 is substantially absent.
25. A method of plasticizing a polyolefin comprising blending a polyolefin with a non-functionalized plasticizer; wherein the polyolefin and the non- functionalized plasticizer are as defined in any of claims 1 to 24.
26. The method of Claim 25, wherein the blending comprises melt blending.
27. The method of Claim 26, wherein the melt blending is performed in an extruder.
28. The method of Claim 25, wherein the blending comprises wet blending of solid polyolefin.
29. The method of any of Claims 25 to 28, wherein the polyolefin is in the form of reactor granules or extruded pellets.
30. The method of any of Claim 29, wherein the reactor granules have an average diameter of from 10 μm to 5 mm.
31. An article of manufacture selected from films, sheets, fibers, woven and nonwoven fabrics, tubes, pipes, automotive components, furniture, sporting equipment, food storage containers, transparent and semi- transparent articles, toys, tubing and pipes, and medical devices comprising the composition of any of Claims 1 to 24, or made by the method of any of Claims 25 to 30.
PCT/US2003/024667 2002-08-12 2003-08-04 Plasticized polyolefin compositions WO2004014997A2 (en)

Priority Applications (18)

Application Number Priority Date Filing Date Title
AU2003272213A AU2003272213A1 (en) 2002-08-12 2003-08-04 Plasticized polyolefin compositions
BR0313398-2A BR0313398A (en) 2002-08-12 2003-08-04 Plasticized Polyolefin Compositions
CA2492839A CA2492839C (en) 2002-08-12 2003-08-04 Plasticized polyolefin compositions
JP2004527804A JP2005535748A (en) 2002-08-12 2003-08-04 Plastic polyolefin composition
EP03754386.5A EP1530611B1 (en) 2002-08-12 2003-08-04 Plasticized polyolefin compositions
CA2495019A CA2495019C (en) 2002-08-12 2003-08-12 Plasticized polyolefin compositions
CA 2675730 CA2675730C (en) 2002-08-12 2003-08-12 Plasticized polyolefin compositions
BR0313549-7A BR0313549A (en) 2002-08-12 2003-08-12 Plasticized Polyolefin Compositions
EP03785201.9A EP1539870B1 (en) 2002-08-12 2003-08-12 Plasticized polyolefin compositions
US10/640,435 US7619026B2 (en) 2002-08-12 2003-08-12 Plasticized polyolefin compositions
SG200701530-8A SG145599A1 (en) 2002-08-12 2003-08-12 Plasticized polypropylene impact copolymers
AU2003258173A AU2003258173C1 (en) 2002-08-12 2003-08-12 Plasticized polyolefin compositions
PCT/US2003/025149 WO2004014998A2 (en) 2002-08-12 2003-08-12 Plasticized polyolefin compositions
JP2005506610A JP4874648B2 (en) 2002-08-12 2003-08-12 Plasticized polyolefin composition
US10/782,228 US7531594B2 (en) 2002-08-12 2004-02-19 Articles from plasticized polyolefin compositions
US11/118,925 US7662885B2 (en) 2002-08-12 2005-04-29 Method to make an article comprising polymer concentrate
US11/406,926 US7652093B2 (en) 2002-08-12 2006-04-19 Plasticized polyolefin compositions
US11/854,943 US7985801B2 (en) 2002-08-12 2007-09-13 Fibers and nonwovens from plasticized polyolefin compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US40266502P 2002-08-12 2002-08-12
US60/402,665 2002-08-12

Publications (2)

Publication Number Publication Date
WO2004014997A2 true WO2004014997A2 (en) 2004-02-19
WO2004014997A3 WO2004014997A3 (en) 2004-08-12

Family

ID=31715879

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/US2003/024667 WO2004014997A2 (en) 2002-08-12 2003-08-04 Plasticized polyolefin compositions
PCT/US2003/025149 WO2004014998A2 (en) 2002-08-12 2003-08-12 Plasticized polyolefin compositions

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/US2003/025149 WO2004014998A2 (en) 2002-08-12 2003-08-12 Plasticized polyolefin compositions

Country Status (10)

Country Link
US (6) US7632887B2 (en)
EP (3) EP1530611B1 (en)
JP (2) JP2005535748A (en)
KR (1) KR101008786B1 (en)
CN (1) CN100345896C (en)
AU (3) AU2003272213A1 (en)
BR (2) BR0313398A (en)
CA (3) CA2492839C (en)
SG (1) SG145599A1 (en)
WO (2) WO2004014997A2 (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007011541A1 (en) 2005-07-15 2007-01-25 Exxonmobil Chemical Patents Inc. Elastomeric compositions
WO2007120147A1 (en) * 2006-04-19 2007-10-25 Exxonmobil Chemical Patents Inc. Articles from plasticized thermoplastic polylefin compositions
US7413784B2 (en) 2006-06-19 2008-08-19 Advanced Elastomer Systems, L.P. Thermoplastic vulcanizates for potable water applications
JP2008539340A (en) * 2005-04-29 2008-11-13 エクソンモービル・ケミカル・パテンツ・インク Polypropylene fibers and nonwovens
US7662885B2 (en) 2002-08-12 2010-02-16 Exxonmobil Chemical Patents Inc. Method to make an article comprising polymer concentrate
US7795366B2 (en) 2002-08-12 2010-09-14 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions
US8476360B2 (en) 2002-08-12 2013-07-02 Exxonmobil Chemical Patents Inc. Calendered films of plasticized blends of plastomer and impact copolymer
CN104098844A (en) * 2014-08-04 2014-10-15 山东瀚氏汽车零部件有限公司 Yellowing-resistant PP (Polypropylene)/HDPE (High Density Polyethylene) plastic for automotive interior part and preparation method
US9328440B2 (en) 2011-05-20 2016-05-03 The Procter & Gamble Company Fibers of polymer-wax compositions
EP3087139A4 (en) * 2013-12-23 2017-12-06 Arlanxeo Singapore Pte. Ltd. Ultra pure rubber
US9972416B2 (en) 2012-09-25 2018-05-15 Dow Global Technologies Llc Modified ethylene-based polymer compositions and methods of their production
EP3336113A1 (en) 2016-12-13 2018-06-20 Afton Chemical Corporation Microstructure-controlled copolymers of ethylene and c3-c10 alpha-olefins
US10385200B2 (en) 2014-06-30 2019-08-20 Arlanxeo Singapore Pte. Ltd. Anti-agglomerants for the rubber industry
US10584297B2 (en) 2016-12-13 2020-03-10 Afton Chemical Corporation Polyolefin-derived dispersants
US10611886B2 (en) 2013-12-23 2020-04-07 Arlanxeo Singapore Pte. Ltd. Anti-agglomerants for the rubber industry
US10647842B2 (en) 2013-12-23 2020-05-12 Arlanxeo Singapore Pte. Ltd. Anti-agglomerants for elastomeric ethylene/A-olefin copolymers
US10703865B2 (en) 2013-12-23 2020-07-07 Arlanxeo Singapore Pte. Ltd. Highly pure halogenated rubbers
US11090407B2 (en) 2017-03-09 2021-08-17 The Procter & Gamble Company Thermoplastic polymeric materials with heat activatable compositions
US11110013B2 (en) 2014-09-10 2021-09-07 The Procter & Gamble Company Nonwoven webs with hydrophobic and hydrophilic layers
US11129919B2 (en) 2016-03-09 2021-09-28 The Procter & Gamble Company Absorbent article with activatable material
WO2022084081A1 (en) * 2020-10-22 2022-04-28 Basell Poliolefine Italia S.R.L. Polymer composition for injection molding

Families Citing this family (150)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7271209B2 (en) 2002-08-12 2007-09-18 Exxonmobil Chemical Patents Inc. Fibers and nonwovens from plasticized polyolefin compositions
US7629416B2 (en) * 2002-08-12 2009-12-08 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US7652092B2 (en) * 2002-08-12 2010-01-26 Exxonmobil Chemical Patents Inc. Articles from plasticized thermoplastic polyolefin compositions
US7531594B2 (en) * 2002-08-12 2009-05-12 Exxonmobil Chemical Patents Inc. Articles from plasticized polyolefin compositions
CA2492839C (en) 2002-08-12 2011-02-01 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US8663799B2 (en) * 2002-08-12 2014-03-04 Exxonmobil Chemical Patents Inc. Polypropylene based fibers and nonwovens
US8003725B2 (en) * 2002-08-12 2011-08-23 Exxonmobil Chemical Patents Inc. Plasticized hetero-phase polyolefin blends
US7622523B2 (en) * 2002-08-12 2009-11-24 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US7652094B2 (en) * 2002-08-12 2010-01-26 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US20050155271A1 (en) * 2002-09-09 2005-07-21 Holy Norman L. Whale-safe rope
US8192813B2 (en) * 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
US7442739B1 (en) 2003-11-12 2008-10-28 Henkel Corporation Hot melt pressure sensitive adhesives
JP4364198B2 (en) * 2003-12-12 2009-11-11 Nok株式会社 Damper
EP1718700B8 (en) * 2004-02-12 2012-10-03 ExxonMobil Chemical Patents Inc. Plasticized polyolefin compositions
US20050215972A1 (en) * 2004-03-29 2005-09-29 Roe Donald C Disposable absorbent articles with zones comprising elastomeric components
US7820875B2 (en) 2004-03-29 2010-10-26 The Procter & Gamble Company Disposable absorbent articles being adaptable to wearer's anatomy
US8198200B2 (en) * 2004-03-29 2012-06-12 The Procter & Gamble Company Web materials having both plastic and elastic properties
NL1025884C2 (en) * 2004-04-05 2005-10-07 Iku Holding Montfoort Bv Use of a metal salt of a fatty acid for damping vibrations, method for assembling a mirror adjustment mechanism, mirror adjustment mechanism.
US7645829B2 (en) 2004-04-15 2010-01-12 Exxonmobil Chemical Patents Inc. Plasticized functionalized propylene copolymer adhesive composition
CN101432356B (en) 2004-08-13 2011-09-28 埃克森美孚化学专利公司 Polymeric compositions, uses and methods of production
JP2006069181A (en) * 2004-09-06 2006-03-16 Brother Ind Ltd Ink cartridge for inkjet recorder ink cartridge and inkjet recorder
CN101044203B (en) * 2004-10-08 2011-03-23 埃克森美孚化学专利公司 Combinations of tackifier and polyalphaolefin oil
WO2006065649A1 (en) 2004-12-17 2006-06-22 Exxonmobil Chemical Patents Inc. Heterogeneous polymer blends and molded articles therefrom
US8389615B2 (en) 2004-12-17 2013-03-05 Exxonmobil Chemical Patents Inc. Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin
GB0501102D0 (en) * 2005-01-19 2005-02-23 Bp Chem Int Ltd Process
US8013069B2 (en) 2005-01-31 2011-09-06 Exxonmobil Chemical Patents Inc. Polymer blends and pellets and methods of producing same
US7803876B2 (en) 2005-01-31 2010-09-28 Exxonmobil Chemical Patent Inc. Processes for producing polymer blends and polymer blend pellets
WO2006083505A1 (en) * 2005-01-31 2006-08-10 Exxonmobil Chemical Patents Inc. Polymeric compositions including their uses and methods of production
ATE453683T1 (en) * 2005-02-02 2010-01-15 Exxonmobil Chem Patents Inc MODIFIED POLYETHYLENE COMPOSITIONS
EP1688234A3 (en) * 2005-02-04 2006-10-11 The Procter & Gamble Company A process for forming a container by stretch blow molding and container formed thereby
JP2006248159A (en) * 2005-03-14 2006-09-21 Seiko Epson Corp Ink cartridge and method of producing the same
US8071667B2 (en) * 2005-06-02 2011-12-06 Nalco Company Compositions comprising (poly) alpha olefins
GB0511319D0 (en) * 2005-06-03 2005-07-13 Exxonmobil Chem Patents Inc Polymeric compositions
GB0511320D0 (en) * 2005-06-03 2005-07-13 Exxonmobil Chem Patents Inc Elastomeric structures
KR20080031734A (en) 2005-06-24 2008-04-10 엑손모빌 케미칼 패턴츠 인코포레이티드 Functionalized propylene copolymer adhesive composition
JP2007002120A (en) * 2005-06-24 2007-01-11 Fuji Xerox Co Ltd Flame-retardant resin composition and flame-retardant resin molded article
US8921244B2 (en) * 2005-08-22 2014-12-30 The Procter & Gamble Company Hydroxyl polymer fiber fibrous structures and processes for making same
JP5007105B2 (en) * 2005-11-22 2012-08-22 三菱鉛筆株式会社 Resin composition for liquid container and liquid container comprising the same
JP5007104B2 (en) * 2005-11-22 2012-08-22 三菱鉛筆株式会社 Resin composition for liquid container and liquid container comprising the same
US20070142242A1 (en) * 2005-12-15 2007-06-21 Gleeson James W Lubricant oil compositions containing GTL base stock(s) and/or base oil(s) and having improved resistance to the loss of viscosity and weight and a method for improving the resistance to loss of viscosity and weight of GTL base stock(s) and/or base oil(s) lubricant oil formulations
WO2007081491A1 (en) * 2006-01-10 2007-07-19 Exxonmobil Chemical Patents Inc. Films incorporating polymeric material combinations, articles made therefrom, and methods of making such films and articles
US20090035546A1 (en) * 2007-07-30 2009-02-05 Fina Technology, Inc. Polyethylene films
US20080045102A1 (en) * 2006-08-15 2008-02-21 Gerald Timothy Keep Controlled flow polymer blends and products including the same
US7615589B2 (en) * 2007-02-02 2009-11-10 Exxonmobil Chemical Patents Inc. Properties of peroxide-cured elastomer compositions
JP5309129B2 (en) * 2007-04-09 2013-10-09 エクソンモービル・ケミカル・パテンツ・インク Flexible heterogeneous isotactic polypropylene composition
GB2449418B (en) * 2007-05-11 2010-11-03 Amcor Flexibles Winterbourne Ltd Porous films
EP2158263B1 (en) * 2007-06-21 2015-03-04 ExxonMobil Chemical Patents Inc. Crosslinked polyethylene articles and processes to produce same
US8852474B2 (en) 2007-07-17 2014-10-07 The Procter & Gamble Company Process for making fibrous structures
US7972986B2 (en) 2007-07-17 2011-07-05 The Procter & Gamble Company Fibrous structures and methods for making same
US20090022983A1 (en) * 2007-07-17 2009-01-22 David William Cabell Fibrous structures
US10024000B2 (en) * 2007-07-17 2018-07-17 The Procter & Gamble Company Fibrous structures and methods for making same
US20090043049A1 (en) * 2007-08-07 2009-02-12 Chapman Bryan R Plasticized Polyolefin Compositions
WO2009035580A1 (en) * 2007-09-13 2009-03-19 Exxonmobil Research And Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
WO2009035579A1 (en) * 2007-09-13 2009-03-19 Exxonmobil Research And Engineering Company In-line blending of plasticizers with a base polymer
CN101945940B (en) 2007-12-20 2014-04-09 埃克森美孚研究工程公司 Polypropylene ethylene-propylene copolymer blends and in-line process to produce them
EP2083046A1 (en) * 2008-01-25 2009-07-29 ExxonMobil Chemical Patents Inc. Thermoplastic elastomer compositions
EP2103634A1 (en) 2008-03-20 2009-09-23 ExxonMobil Chemical Patents Inc. Production of propylene-based polymers
EP2460640B1 (en) * 2008-05-05 2014-08-27 A. Schulman, Inc. Multilayer clear over color polyolefin sheets and layered backing structure
US7867433B2 (en) * 2008-05-30 2011-01-11 Exxonmobil Chemical Patents Inc. Polyolefin-based crosslinked articles
US8765832B2 (en) 2011-10-14 2014-07-01 Exxonmobil Chemical Patents Inc. Polyolefin-based crosslinked compositions and methods of making them
US7988903B2 (en) * 2008-07-02 2011-08-02 Zeon Chemicals L.P. Fast curing vulcanizable multi-part elastomer composition, and process for blending, injection molding and curing of elastomer composition
CN101376440B (en) * 2008-09-26 2011-12-28 深圳市通产丽星股份有限公司 packing soft tube
CN101721277A (en) * 2008-10-22 2010-06-09 3M创新有限公司 Medical tape and medical product prepared by same
US9925694B2 (en) 2009-02-24 2018-03-27 Gala Industries, Inc. Continuous bagging processes and systems
US8955294B2 (en) * 2009-02-24 2015-02-17 Gala Industries, Inc. Continuous bagging processes and systems
FR2943064B1 (en) * 2009-03-12 2013-12-06 Total Raffinage Marketing HYDROCARBON DILUENT WITH LOW VOC RATES FOR CONSTRUCTION MATERIALS
US20100247887A1 (en) * 2009-03-26 2010-09-30 Fina Technology, Inc. Polyolefin films for in-mold labels
US20110059277A1 (en) * 2009-09-04 2011-03-10 Rainer Kolb Elastomeric Surface Coatings for Plastic Articles
WO2010147706A2 (en) * 2009-06-16 2010-12-23 Exxonmobil Chemical Patents Inc. Polyolefin compositions for coating applications
US20100316820A1 (en) * 2009-06-16 2010-12-16 Rainer Kolb Composite Materials Comprising Propylene-Based Polymer Blend Coatings
US8217116B2 (en) * 2009-07-15 2012-07-10 Braskem America, Inc. Polypropylene composition for buried structures
US20110052930A1 (en) * 2009-08-28 2011-03-03 Jinder Jow High Gloss Thermoformed Article and Process for Producing Same
WO2011030893A1 (en) * 2009-09-14 2011-03-17 出光興産株式会社 Spun-bonded nonwoven fabric and fiber product
WO2011053406A1 (en) 2009-10-29 2011-05-05 Exxonmobil Chemical Patents Inc. Pressure-sensitive hot melt adhesive compositions
WO2011053956A1 (en) * 2009-11-02 2011-05-05 The Procter & Gamble Company Fibrous elements and fibrous structures employing same
ES2464128T3 (en) * 2009-11-02 2014-05-30 The Procter & Gamble Company Fibrous polypropylene elements and manufacturing processes
ES2588209T3 (en) 2009-11-02 2016-10-31 The Procter & Gamble Company Fibrous structures and methods to manufacture them
TW201116569A (en) * 2009-11-13 2011-05-16 Richell Corp Resin composition and resin forming article for medical and biochemical use
US8609760B2 (en) 2009-11-18 2013-12-17 Exxonmobil Chemical Patents Inc. Blend partner with natural rubber for elastomeric compounds
WO2011123584A1 (en) 2010-03-31 2011-10-06 The Procter & Gamble Company Fibrous structures and methods for making same
KR101846362B1 (en) 2010-06-22 2018-04-09 다우 글로벌 테크놀로지스 엘엘씨 Crosslinked compositions and articles prepared therefrom
JP5685317B2 (en) 2010-10-15 2015-03-18 エクソンモービル ケミカル パテンツ インコーポレイテッド Polypropylene-based adhesive composition
BR112013010313A2 (en) * 2010-10-28 2016-09-20 Lummus Novolen Technology Gmbh non woven and polypropylene yarn with additive
US20120123374A1 (en) * 2010-11-09 2012-05-17 Richeson Galen C Meltblown Nonwoven Compositions and Methods for Making Them
WO2012129489A2 (en) * 2011-03-24 2012-09-27 Henkel Corporation Stretch film lamination adhesive
WO2012174204A2 (en) 2011-06-17 2012-12-20 Fiberweb, Inc. Vapor permeable, substantially water impermeable multilayer article
US9827755B2 (en) 2011-06-23 2017-11-28 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
WO2012178027A2 (en) 2011-06-23 2012-12-27 Fiberweb, Inc. Vapor-permeable, substantially water-impermeable multilayer article
US9765459B2 (en) 2011-06-24 2017-09-19 Fiberweb, Llc Vapor-permeable, substantially water-impermeable multilayer article
SG11201400246SA (en) * 2011-08-30 2014-03-28 Chevron Phillips Chemical Co Hyperbranched polymers and methods of making and using same
US10059081B2 (en) 2011-12-22 2018-08-28 Exxonmobil Chemical Patents Inc. Fibers and nonwoven materials prepared therefrom
US8829094B2 (en) * 2011-12-22 2014-09-09 Fina Technology, Inc. Use of nucleation in ICP resins
BR112014025301B1 (en) 2012-04-12 2020-12-15 Dow Global Technologies Llc POLYOLEFINE MIXTURE COMPOSITION, ARTICLE AND PROCESS TO PRODUCE A COMPOSITION
US20130281596A1 (en) * 2012-04-18 2013-10-24 Rachna Mohan Compositions Comprising a Propylene-Based Elastomer and a Polyalphaolefin, Methods of Making the Same, and Articles Made Therefrom
WO2014020007A1 (en) * 2012-08-01 2014-02-06 Shell Internationale Research Maatschappij B.V. Cable fill composition
KR102173723B1 (en) * 2012-08-31 2020-11-03 다우 글로벌 테크놀로지스 엘엘씨 Heat-resistant polyolefin compositions suitable for films
US9605186B2 (en) 2012-09-19 2017-03-28 Exxonmobil Chemical Patents Inc. Adhesive compositions of ethylene-based and propylene-based polymers
WO2014046834A1 (en) 2012-09-19 2014-03-27 Exxonmobil Chemical Patents Inc. Adhesive compositions of propylene-based and ethylene-based polymers
EP2945978B1 (en) * 2013-01-18 2017-07-05 Sartorius Stedim Fmt Sas Film comprising a contact layer for the wall of a single-use pouch
BR112015019579B1 (en) * 2013-02-28 2020-10-13 Dow Global Technologies Llc mixing composition, process for making an injection molded article, molded article and article
WO2014159724A1 (en) 2013-03-12 2014-10-02 Fitesa Nonwoven, Inc. Extensible nonwoven fabric
US9226480B2 (en) * 2013-05-23 2016-01-05 T.F.H. Publications, Inc. Pet chew toys of rubber and polyamide, and methods of manufacture thereof
EP3011089B1 (en) * 2013-06-18 2020-12-02 ExxonMobil Chemical Patents Inc. Fibers and nonwoven materials prepared therefrom
JP6142085B2 (en) * 2013-06-18 2017-06-07 エクソンモービル ケミカル パテンツ インコーポレイテッド Fibers and nonwoven materials prepared therefrom
US9315657B2 (en) * 2013-07-12 2016-04-19 Sumitomo Chemical Company, Limited Propylene resin composition
DE102013014918A1 (en) 2013-07-15 2015-01-15 Ewald Dörken Ag Bicomponent fiber for the production of spunbonded nonwovens
EP3094681B1 (en) 2014-01-15 2021-01-20 ExxonMobil Chemical Patents Inc. Propylene-based impact copolymers
US11267916B2 (en) 2014-02-07 2022-03-08 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins
US10308740B2 (en) 2014-02-07 2019-06-04 Eastman Chemical Company Amorphous propylene-ethylene copolymers
US10696765B2 (en) 2014-02-07 2020-06-30 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and propylene polymer
US10647795B2 (en) 2014-02-07 2020-05-12 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins
US10723824B2 (en) 2014-02-07 2020-07-28 Eastman Chemical Company Adhesives comprising amorphous propylene-ethylene copolymers
US9399686B2 (en) 2014-02-07 2016-07-26 Eastman Chemical Company Amorphous propylene-ethylene copolymers
AU2015283172B2 (en) * 2014-06-30 2019-11-07 Tarkett Gdl Polyvinyl chloride-free decorative surface coverings
CN104086889A (en) * 2014-07-09 2014-10-08 安徽宁国市高新管业有限公司 Anti-aging MPP (modified polypropylene) electric tube
CN104448550A (en) * 2014-11-12 2015-03-25 合肥市瑞宏重型机械有限公司 Plastic composite sheet
ES2772677T3 (en) * 2015-02-25 2020-07-08 Borealis Ag Propylene copolymer composition with improved long-term mechanical properties
US10011709B2 (en) * 2015-02-26 2018-07-03 Exxonmobil Chemical Patents Inc. Compositions comprising propylene-based elastomers and polyalphaolefins
EP3303675A4 (en) 2015-06-05 2019-01-09 ExxonMobil Chemical Patents Inc. Spunbond fabrics comprising propylene-based elastomer compositions and methods thereof
CN105254814B (en) * 2015-11-02 2017-12-01 四川省金核辐照技术有限公司 A kind of PP composite material of resistance to radiated by gamma-ray and preparation method thereof
US9701801B2 (en) * 2015-11-05 2017-07-11 Fina Technology, Inc. Use of nucleation to improve slip bloom in metallocene polypropylene resins
US10844529B2 (en) 2016-05-02 2020-11-24 Exxonmobil Chemicals Patents Inc. Spunbond fabrics comprising propylene-based elastomer compositions and methods for making the same
CN109661554B (en) 2016-08-08 2021-05-11 提克纳有限责任公司 Thermally conductive polymer composition for heat sink
KR102086055B1 (en) 2016-09-23 2020-03-06 주식회사 엘지화학 Polypropylene-based resin composition
KR102083001B1 (en) 2016-09-23 2020-02-28 주식회사 엘지화학 Olefin based copolymer and preparation method thereof
CN106847393A (en) * 2017-02-27 2017-06-13 合肥中科富华新材料有限公司 A kind of high fire-retardance water-proof wire and preparation method
EP3626690A4 (en) 2017-05-19 2021-03-10 Sekisui Chemical Co., Ltd. Intermediate film for laminated glass, and laminated glass
WO2018212332A1 (en) * 2017-05-19 2018-11-22 積水化学工業株式会社 Intermediate film for laminated glass, and laminated glass
EP3635048A4 (en) * 2017-06-09 2020-12-16 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and propylene polymer
PT3635047T (en) * 2017-06-09 2023-06-29 Synthomer Adhesive Tech Llc Amorphous propylene-ethylene copolymers
WO2018227040A1 (en) * 2017-06-09 2018-12-13 Eastman Chemical Company Amorphous propylene-ethylene copolymers
WO2018227038A1 (en) * 2017-06-09 2018-12-13 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and propylene polymer
PT3635049T (en) * 2017-06-09 2023-09-20 Synthomer Adhesive Tech Llc Adhesive composition comprising amorphous propylene/ethylene copolymers and polyolefins
KR102317015B1 (en) * 2017-11-08 2021-10-26 주식회사 엘지화학 Homo polypropylene resin for non-woven fabric and preparation method thereof
DE112019008021B4 (en) * 2018-01-24 2024-03-14 Nike Innovate C.V. RESIN COMPOSITION AND SOLE STRUCTURE FOR AN ARTICLE OF FOOTWEAR
CN111836856B (en) 2018-01-29 2023-05-26 埃克森美孚化学专利公司 Rubber blend, article thereof and method of making the same
CN108417303A (en) * 2018-03-20 2018-08-17 安徽凌宇电缆科技有限公司 A kind of flexible fire-proof cable oxygen barrier layer fire clay material and preparation method thereof
KR102335355B1 (en) * 2018-03-30 2021-12-06 현대자동차 주식회사 Bumper beam for car vehicle
EP3814390A2 (en) * 2018-06-28 2021-05-05 ExxonMobil Chemical Patents Inc. Polyethylene compositions, wires and cables, and methods for making the same
US10941295B2 (en) 2018-10-13 2021-03-09 International Business Machines Corporation Molecular glasses as rheological modifiers in high-performance polymers
CN112930370A (en) * 2018-10-26 2021-06-08 格雷斯公司 Polypropylene random copolymer composition for cold and hot water pipe applications
JP7305346B2 (en) * 2018-12-25 2023-07-10 矢崎エナジーシステム株式会社 Crosslinking agent masterbatch
IT201900002609A1 (en) * 2019-02-22 2020-08-22 Prysmian Spa METHOD FOR EXTRACTING CROSS-LINKING BYPRODUCTS FROM A CROSS-LINKED ELECTRICAL INSULATION SYSTEM OF A POWER CABLE AND ITS POWER CABLE.
KR20200142635A (en) * 2019-06-12 2020-12-23 현대자동차주식회사 Composition of thermoplastic elastomer
WO2021108160A1 (en) 2019-11-25 2021-06-03 Exxonmobil Chemical Patents Inc. Hot melt pressure-sensitive adhesives and processes for making same
WO2021195070A1 (en) 2020-03-26 2021-09-30 Exxonmobil Chemical Patents Inc. Processes for making 3-d objects from blends of polypropylene and semi-amorphous polymers
KR20230125191A (en) 2020-11-10 2023-08-29 네나 게쓰너 게엠바하 Filter media comprising non-woven electrets
EP4263684A1 (en) * 2020-12-18 2023-10-25 Synthomer Adhesive Technologies LLC Recycled polyolefin compositions comprising random alpha-olefinic copolymers and additional polymers
CN113912941B (en) * 2021-10-26 2023-07-18 金发科技股份有限公司 Polypropylene composite material and preparation method and application thereof
US20230303811A1 (en) * 2022-03-22 2023-09-28 Celanese International Corporation Polymer Composition Blend and Membranes Made Therefrom

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3318835A (en) 1961-11-15 1967-05-09 Eastman Kodak Co Compositions containing polypropylene and an ester plasticizer
US3415925A (en) 1967-08-01 1968-12-10 Grace W R & Co Process for preparing permeable polyethylene film
US4073782A (en) 1975-01-31 1978-02-14 Ube Industries, Ltd. Wrapping film
US4409345A (en) 1981-01-06 1983-10-11 Chisso Corporation Polyolefin resin composition
EP0448259A2 (en) 1990-03-09 1991-09-25 Union Carbide Chemicals And Plastics Company, Inc. Process for the extrusion of low density polyethylene
EP1028145A1 (en) 1999-02-10 2000-08-16 Sumitomo Rubber Industries, Ltd. Low modulus of elasticity-rubber composition
WO2001018109A1 (en) 1999-09-03 2001-03-15 Exxon Chemical Patents Inc. Plasticized polypropylene thermoplastics
WO2002031044A1 (en) 2000-10-12 2002-04-18 Duraban Oy Polyalphaolefin plastisizers for elastomers

Family Cites Families (706)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2567016A (en) 1947-10-21 1951-09-04 Standard Oil Dev Co Hydrocarbon rubber plasticized with a polyvinyl compound
US2817693A (en) 1954-03-29 1957-12-24 Shell Dev Production of oils from waxes
DE1769723U (en) 1956-05-26 1958-07-03 Walter Wischnewsky PIVOT BEARINGS, IN PARTICULAR FOR METALLIC REVERSIBLE AND PIVOTING PANEL WINDOWS.
FR1167244A (en) 1957-02-26 1958-11-21 Pechiney Plasticizer for polymers
DE2756458A1 (en) 1976-12-21 1978-06-22 Gen Electric DRIP-RETARDED, PLASTICIZED THERMOPLASTIC COMPOSITION
NL260367A (en) 1960-01-23
US3201364A (en) 1960-08-26 1965-08-17 Monsanto Co Polypropylene plasticized with mineral oil
US3235529A (en) * 1960-09-06 1966-02-15 Dow Chemical Co Free flowing polystyrene powders containing 10-40% plasticizer
NL122826C (en) 1960-10-17
US3228896A (en) * 1961-05-16 1966-01-11 Phillips Petroleum Co Method of making microporous polyolefin articles and product therefrom
BE620076A (en) 1961-07-11
NL283031A (en) * 1961-09-11
GB1044028A (en) 1962-07-24 1966-09-28 Grace W R & Co Improvements relating to filled polyolefine
US3541039A (en) 1962-08-27 1970-11-17 Pennwalt Corp Flexible polymeric vinylidene fluoride compositions
BE637093A (en) 1962-09-10
US3239478A (en) * 1963-06-26 1966-03-08 Shell Oil Co Block copolymer adhesive compositions and articles prepared therefrom
US3281390A (en) 1963-08-06 1966-10-25 Container Corp Polypropylene plasticized with petrolatum
US3308086A (en) * 1963-08-30 1967-03-07 Union Carbide Corp Ethylene copolymers with vinyl esters plasticized with phosphate and carboxylic esters
GB1089906A (en) * 1963-09-27 1967-11-08 Union Carbide Corp Plasticized ethylene-acrylic acid copolymers
FR86048E (en) 1964-03-06 1965-11-26 Ethylene Plastique Sa Plasticized polyolefin compositions
GB1044503A (en) 1964-03-23 1966-10-05 Grace W R & Co Cold-worked polyolefin compositions
US3439088A (en) * 1964-06-16 1969-04-15 Exxon Research Engineering Co Cosmetic preparations-wax rouge and foundation make-up
DE1264054B (en) 1964-09-14 1968-03-21 Rexall Drug Chemical Process for mixing lubricants and anti-stick agents into polyolefins
NL130672C (en) 1965-04-09
DE1921649U (en) 1965-04-26 1965-08-19 Wilhelm Kirschner FALL PROTECTION NET.
DE1961981U (en) 1965-08-02 1967-06-08 Henkel & Cie Gmbh DEVICE FOR HANGING FILTER HOSES IN FILTER SYSTEMS OF ATOMIZING DRYERS.
DE1248927B (en) * 1965-08-19 1967-08-31 Chemische Werke Hüls Aktiengesellschaft, Mari Use of dibenzylbenzenes as plasticizers for polyamides
NL6614153A (en) 1965-10-07 1967-04-10
DE1669020B2 (en) 1966-02-03 1973-10-18 Politechnika Warszawska, Warschau Process for the production of a tear-off corrosion protection coating material
US3299568A (en) * 1966-03-01 1967-01-24 Research Corp Compositions plasticized with sulphur
US3475368A (en) 1966-03-09 1969-10-28 Nypel Of Delaware Inc Plasticized nylon composition and process for making the same
US3945975A (en) * 1966-05-23 1976-03-23 Protective Treatments, Inc. Sealing adhesive strands and compositions therefor
US3338778A (en) 1966-09-28 1967-08-29 Eastman Kodak Co Thermoplastic adhesive of polypropylene, cellulose ester, polyvinyl acetate, sucrose acetate isobutyrate, and polyalkylene glycol
US3551943A (en) 1966-12-19 1971-01-05 Exxon Research Engineering Co Controlled degradation
FR1536425A (en) 1967-07-06 1968-08-16 Rhone Poulenc Sa 6-oxo-phthalate heptyl
AT309789B (en) * 1967-11-20 1973-09-10 Buss Ag Mixing and kneading device for plastic masses
US3536796A (en) 1967-11-29 1970-10-27 Grace W R & Co Process for reducing shrinkage in preparing porous plastic sheet
FR1566388A (en) 1968-02-20 1969-05-09
DE1769062A1 (en) 1968-03-28 1971-08-12 Huels Chemische Werke Ag Plasticized polyamides
FR1580539A (en) 1968-07-25 1969-09-05
US3563934A (en) * 1969-04-22 1971-02-16 Gen Electric Stabilized,plasticized polyphenylene oxide compositions
DE1921649A1 (en) 1969-04-28 1970-11-19 Arbrisseau Sa Adhesives and similar compositions
US3590528A (en) 1969-09-25 1971-07-06 Princeton Chemical Res Inc Decomposable polybutene-1 agricultural mulch film
BE756871A (en) 1969-11-14 1971-03-01 Ibm TRANSMISSION OF COORDINATES FOR CHARACTER RECOGNITION DEVICES
GB1352311A (en) 1970-01-20 1974-05-08 Du Pont Coated yarns
DE2013826A1 (en) 1970-03-23 1971-10-07 Exxon Chemie Gmbh Back coating compounds for carpet tiles
DE2019945A1 (en) 1970-04-24 1971-11-04 Basf Ag Polystyrene moulding materials for prepnof foam bodies
FR2194767B1 (en) 1972-08-04 1975-03-07 Shell France
FR2133524B2 (en) 1970-06-05 1975-10-10 Shell Berre Raffinage
US3935344A (en) * 1970-10-15 1976-01-27 Owens-Corning Fiberglas Corporation Sizing composition and glass fibers treated therewith
FR2094870A5 (en) 1970-12-28 1972-02-04 Ouest Indle Comprimes
US3686385A (en) 1971-02-05 1972-08-22 Mobil Oil Corp Formation of elastic and high-tenacity fibers from butene-1 homopolymers and copolymers
DE2108293A1 (en) 1971-02-20 1972-08-31 Metallgesellschaft Ag Polyolefine - base articles - plasticised in presence of pvc
US3925504A (en) 1971-05-06 1975-12-09 Union Carbide Corp Poly(hydroxy ether) polymers blended with cyclic ester polymers
GB1390359A (en) 1971-05-13 1975-04-09 Shell Int Research Process for the preparation of lubricating oil with high viscosity index
US3818105A (en) 1971-08-23 1974-06-18 Exxon Research Engineering Co Composition and process for lubricating the skin
US3828105A (en) 1971-11-04 1974-08-06 Alexandre Soc Hairdressing composition and process for preparation thereof
CA1003778A (en) 1972-04-06 1977-01-18 Peter Ladeur Hydrocarbon conversion process
US4169822A (en) 1972-05-25 1979-10-02 The Norton Company Hot melt sealants
US3925947A (en) 1972-06-26 1975-12-16 Novagard Corp Automobile window sealing
DE2254128C3 (en) 1972-11-04 1975-08-14 Chemische Werke Huels Ag, 4370 Marl Thermoplastic molding compound made from polybutene-I
BE805417A (en) 1972-12-29 1974-01-16 Hardwicke Chemical Co LIQUID MIXTURE OF N-BUTYL-SULFONAMIDES AND THEIR USE FOR THE PLASTIFICATION OF A SYNTHETIC RESIN
IT981300B (en) 1973-03-12 1974-10-10 Snam Progetti SYNTHETIC LUBRICANT OILS FROM THERMAL CRACKING OF VERY HIGH VISCOSITY POLYMERS
GB1452911A (en) 1973-03-17 1976-10-20 Dunlop Ltd Adhesives
SU455976A1 (en) 1973-03-30 1975-01-05 Всесоюзный Научно-Исследовательский Институт Медицинского Приборостроения Polymer composition
US3896245A (en) 1973-04-04 1975-07-22 Protective Treatments Pressure sensitive adhesive strips and sheets
US4207373A (en) 1973-04-25 1980-06-10 Allied Chemical Corporation Highly filled polyolefin compositions
FR2233339B1 (en) * 1973-06-12 1976-07-23 Mitsui Petrochemical Indus
US3882197A (en) 1973-06-21 1975-05-06 Du Pont Alpha-olefin copolymer blends
US3888949A (en) 1973-06-21 1975-06-10 Du Pont Blends of propylene-alpha-olefin copolymers and polypropylene
US3839261A (en) 1973-06-22 1974-10-01 Itt Esters of phenylindan used as plasticizers and crosslinking agents
US4038238A (en) * 1973-08-29 1977-07-26 The Dow Chemical Company Low density rapid-setting polyurethanes
JPS5634017B2 (en) 1973-09-13 1981-08-07
US3821148A (en) 1973-09-28 1974-06-28 Exxon Research Engineering Co Plasticized thermoplastic block copolymers
ZA747886B (en) 1973-12-29 1975-12-31 British Industrial Plastics Improvements in or relating to plasticized aminoplast resin compositions
US4206101A (en) * 1974-01-03 1980-06-03 E. I. Du Pont De Nemours And Company Melt extrudable cold water-soluble films
US4041002A (en) 1974-03-19 1977-08-09 Asahi Kasei Kogyo Kabushiki Kaisha Thermoplastic resin composition
US4132698A (en) * 1974-03-20 1979-01-02 Exxon Research & Engineering Co. Elastomeric thermoplastics
JPS50128300A (en) * 1974-03-28 1975-10-09
US3988276A (en) 1974-04-12 1976-10-26 Novagard Corporation Solid polysulfide containing hot melt sealants, adhesives and the like
DE2424681C3 (en) 1974-05-21 1980-10-23 Basf Ag, 6700 Ludwigshafen Thermoplastic polyamide or copolyamide compositions containing plasticizers
JPS5122740A (en) 1974-08-16 1976-02-23 Kenzo Hamada
US4010127A (en) * 1974-10-15 1977-03-01 Showa Yuka Kk Polyethylene composition
US4113802A (en) * 1974-11-14 1978-09-12 Montedison S.P.A. Process for preparing polypropylene compositions having high impact strength at low temperatures
US4006115A (en) * 1974-12-26 1977-02-01 Monsanto Company Phthalate ester containing nylon composition
US4063002A (en) 1975-04-14 1977-12-13 Wilson Jr Floyd Insulated glass and sealant therefor
JPS51144998A (en) * 1975-06-07 1976-12-13 Furukawa Electric Co Ltd:The Semiconductive adhesive composition
GB1516420A (en) 1975-08-28 1978-07-05 Mitsubishi Chem Ind Tacky polyolefin films
US4094850A (en) 1975-10-06 1978-06-13 Monsanto Company Flame retardant composition
US4153594A (en) 1976-04-08 1979-05-08 Wilson Jr Floyd Insulated glass and sealant therefore
CS187003B1 (en) 1976-04-30 1979-01-31 Rudolf Puffr Process for preparing polyamides
US4097543A (en) 1976-05-12 1978-06-27 Mobil Oil Corporation Selective disproportionation of toluene
US4092282A (en) 1976-05-24 1978-05-30 Cities Service Company Hot melt sealant composition
US4041103A (en) 1976-06-07 1977-08-09 Shell Oil Company Blends of certain hydrogenated block copolymers
DE2632957A1 (en) 1976-07-22 1978-01-26 Bayer Ag Polyamide moulding compsn. contg. nitrile rubber - which acts as plasticiser, giving flexible high impact strength body
US4110185A (en) 1976-11-10 1978-08-29 Becton, Dickinson And Company Irradiation sterilization of semi-crystalline polymers
US5206276A (en) 1976-12-21 1993-04-27 Lee Jr Gim F Flame retardant flexibilized polyphenylene ether compositions
US4684682A (en) 1980-10-17 1987-08-04 General Electric Company Flame retardant flexibilized polyphenylene ether compositions
US4104216A (en) 1977-03-07 1978-08-01 Gulf Oil Corporation Copolymers containing an alpha-olefin and an alpha, beta-ethylenically unsaturated carboxylic acid plasticized with long-chain fatty acid
US4369284A (en) * 1977-03-17 1983-01-18 Applied Elastomerics, Incorporated Thermoplastic elastomer gelatinous compositions
US4399248A (en) 1977-05-04 1983-08-16 Rohm And Haas Company Plasticizer, plasticized resin composition and process for preparation thereof
US4136072A (en) * 1977-05-24 1979-01-23 Arco Polymers, Inc. Thermoplastic polyolefin film compositions
JPS5846142B2 (en) 1977-07-05 1983-10-14 三菱電線工業株式会社 Poly 4-methylpentene-1 composition
US4147831A (en) * 1977-08-31 1979-04-03 Johnson & Johnson Pressure-sensitive adhesive compositions
US4154712A (en) 1977-09-30 1979-05-15 General Electric Company Low molecular weight polyphenylene ether compositions
US4311628A (en) * 1977-11-09 1982-01-19 Monsanto Company Thermoplastic elastomeric blends of olefin rubber and polyolefin resin
US4154244A (en) 1977-11-21 1979-05-15 Baxter Travenol Laboratories, Inc. Balloon-type catheter
US4131587A (en) 1977-11-29 1978-12-26 Exxon Research & Engineering Co. Plasticization of neutralized sulfonated elastomeric polymer
US4118362A (en) 1977-11-29 1978-10-03 Exxon Research & Engineering Co. Plasticization of neutralized sulfonated elastomeric polymer
US4118359A (en) 1977-11-29 1978-10-03 Exxon Research & Engineering Co. Plasticization of neutralized sulfonated elastomeric polymer
US4153588A (en) 1977-11-29 1979-05-08 Exxon Research & Engineering Co. Metal neutralized sulfonated EPDM terpolymers and compositions thereof
US4157992A (en) 1977-11-29 1979-06-12 Exxon Research & Engineering Co. Elastomeric blend compositions having improved weathering stability
US4175069A (en) 1977-11-29 1979-11-20 Exxon Research & Engineering Co. Plasticization of neutralized sulfonated elastomeric polymer
US4138378A (en) * 1977-12-23 1979-02-06 Phillips Petroleum Company Liquid polyalkene in thermoplastic elastomer sealant formulation
US4210570A (en) 1978-01-06 1980-07-01 Eastman Kodak Company Blends of substantially amorphous olefin copolymers, compatible tackifying resins and plasticizing oils useful as hot melt, pressure-sensitive adhesives
US4189411A (en) * 1978-01-19 1980-02-19 General Electric Company Modified polyphenylene ether compositions having lower melt viscosities
US4288480A (en) 1978-06-12 1981-09-08 Scott Paper Company Pressure sensitive adhesive composition and coated product
US4221887A (en) 1978-07-17 1980-09-09 Exxon Research & Engineering Co. Plasticization of quaternary phosphonium ion containing polymers
US4170586A (en) 1978-09-11 1979-10-09 Gulf Oil Corporation Plasticized butene-1 polymer compositions
US4229337A (en) 1978-10-02 1980-10-21 Exxon Research & Engineering Co. Aromatic amide plasticizer for ionic polymers
US4335034A (en) 1978-12-18 1982-06-15 J. P. Stevens & Co., Inc. Thermoplastic compositions and automotive carpeting backed therewith
SU812800A1 (en) 1978-12-26 1981-03-15 Кировский Политехнический Институт Rubber mixture based on low unsaturated rubber
US4237083A (en) 1979-02-13 1980-12-02 Evans Products Company Process of manufacturing a microporous sheet material
SU857179A1 (en) 1979-03-01 1981-08-23 Кировский Политехнический Институт Rubber mixture
US4325850A (en) * 1979-05-21 1982-04-20 W. R. Grace & Co. Processing and product enhancement additives for polyolefin film
JPS5856534B2 (en) 1979-08-28 1983-12-15 チッソ株式会社 Polyolefin resin composition
US4288358A (en) 1979-08-30 1981-09-08 Eastman Kodak Company Blends of propylene/1-butene or 1-pentene/higher α-olefin copolymers, compatible tackifying resins and plasticizing oils useful as hot-melt, pressure-sensitive adhesives
US4467065A (en) * 1979-09-10 1984-08-21 Becton Dickinson And Company Semi-crystalline polymers stabilized for irradiation sterilization
US4274932A (en) 1979-09-10 1981-06-23 Becton Dickinson And Company Semi-crystalline polymers stabilized for irradiation sterilization
MX151778A (en) 1979-10-22 1985-03-08 Kimberly Clark Co IMPROVEMENTS TO SANITARY TOWEL
FR2472000A1 (en) * 1979-12-20 1981-06-26 Rhone Poulenc Ind PROCESS FOR IMPROVING COMPATIBILITY OF PLASTIFIERS AND LOADS IN POLYMERS
US4304713A (en) 1980-02-29 1981-12-08 Andrew Corporation Process for preparing a foamed perfluorocarbon dielectric coaxial cable
AU6831481A (en) 1980-03-28 1981-10-01 Imperial Chemical Industries Ltd. Plasticised chlorinated rubber composition
US4347332A (en) 1980-06-19 1982-08-31 American Can Company Polyamide/polyethylene copolymer film and method for producing
US4403007A (en) 1980-08-11 1983-09-06 E. I. Du Pont De Nemours & Co. Filled thermoplastic compositions based on ethylene interpolymers and polyester, polyether and polyether ester plasticizers
US4438228A (en) 1980-08-11 1984-03-20 E. I. Du Pont De Nemours And Company Filled and plasticized blends of linear low density polyethylene
US4592851A (en) * 1980-09-02 1986-06-03 Exxon Research And Engineering Co. Lubricating oil composition and method for providing improved thermal stability
US4321334A (en) * 1980-09-04 1982-03-23 Shell Oil Company Melt crystallization of butene-1 polymers
CS215313B1 (en) 1980-09-23 1982-08-27 Bohumil Kloboucek Hydroisolation thermoplastic material
US4358384A (en) 1980-10-06 1982-11-09 Smith International Inc. Composite grease for rock bit bearings
US4289668A (en) 1980-10-14 1981-09-15 The Standard Oil Company Polymer systems plasticized with hydroxy fatty acids
EP0050548B1 (en) 1980-10-16 1985-01-16 Rhone-Poulenc Specialites Chimiques Quick setting adhesives comprising an aqueous latex of plasticized polyvinyl acetate
US4327007A (en) * 1980-12-22 1982-04-27 Allied Chemical Corporation Polyethylene terephthalate composition containing aliphatic plasticizer and nucleating agent
JPS57151642A (en) 1981-02-12 1982-09-18 Union Carbide Corp Plasticized polyarylate composition
DE3105364A1 (en) 1981-02-13 1982-09-02 Bayer Ag, 5090 Leverkusen POLYAMIDE MOLDS
US4542053A (en) 1981-02-17 1985-09-17 Protective Treatments, Inc. Bonding system for wear surfaces
US4403005A (en) 1981-02-17 1983-09-06 Protective Treatments, Inc. Systems for protecting steel
JPS57141811A (en) * 1981-02-25 1982-09-02 Furukawa Electric Co Ltd Polyolefin series electrically insulating film and method of producing same
US4335026A (en) 1981-03-27 1982-06-15 Johnson & Johnson Products Inc. Pressure-sensitive adhesive compositions having high shear and low peel resistance
US4552801A (en) 1981-04-01 1985-11-12 American Can Company Plasticized EVOH and process and products utilizing same
US4352823A (en) 1981-04-13 1982-10-05 Nabisco Brands, Inc. Coextruded chewing gum containing a soft non-SBR gum core portion
US4430289A (en) * 1981-04-21 1984-02-07 The Dow Chemical Company Process for reducing block and increasing slip of linear low density polyethylene copolymer extrusion-blown films
US4452820A (en) 1981-06-05 1984-06-05 Nabisco Brands, Inc. Gum base and chewing gum containing same
US4387108A (en) 1981-06-12 1983-06-07 Warner-Lambert Company Non-stick chewing gum composition and method of preparation
US4451589A (en) 1981-06-15 1984-05-29 Kimberly-Clark Corporation Method of improving processability of polymers and resulting polymer compositions
DE3125062C2 (en) 1981-06-26 1984-11-22 Degussa Ag, 6000 Frankfurt Process for the production of abrasion-resistant coated catalysts and the use of a catalyst obtained in this way
WO1983000697A1 (en) 1981-08-21 1983-03-03 Ethyl Corp Polyester composition
DE3277772D1 (en) * 1981-09-09 1988-01-14 Sumitomo Naugatuck Thermoplastic composition
US4379169A (en) * 1981-11-09 1983-04-05 Nabisco Brands, Inc. New gum base and chewing gum containing same
US4399251A (en) 1981-12-07 1983-08-16 General Electric Company Compositions comprising a thermoplastic resin and an olefin mold release agent
EP0083049A3 (en) 1981-12-28 1984-02-22 General Electric Company Composition of ppe and ps-grafted epdm and plasticizer
US4497926A (en) * 1981-12-28 1985-02-05 Raychem Corporation Elastomer based adhesive compositions
US4434258A (en) * 1982-01-15 1984-02-28 E. I. Du Pont De Nemours And Company Organic acid containing filled and plasticized thermoplastic compositions based on ethylene interpolymers
US4749734A (en) * 1982-02-23 1988-06-07 Becton, Dickinson And Company Radiation stabilization of polymeric material
CA1207481A (en) 1982-02-23 1986-07-08 Joel L. Williams Radiation stabilization of polymeric material
US4774277A (en) 1982-03-26 1988-09-27 Exxon Research & Engineering Co. Blends of polyolefin plastics with elastomeric plasticizers
JPS58185632A (en) 1982-04-23 1983-10-29 Iic Kagaku Kogyo Kk Polyolefin resin composition
US4460729A (en) * 1982-05-13 1984-07-17 Ethyl Corporation Polyester composition
US4483886A (en) 1982-05-27 1984-11-20 Exxon Research & Engineering Co. Method for making free-flowing, melt-coated rubber pellets
US4440829A (en) * 1982-06-29 1984-04-03 Protective Treatments, Inc. Coated bonding tapes having improved peel strength combined with low temperature flexibility
CA1205236A (en) 1982-06-30 1986-05-27 Bp Corporation North America Inc. Plasticized thermoplastic polymer
US4532305A (en) 1982-06-30 1985-07-30 Union Carbide Corporation Thermoplastic polymer plasticized with a poly(aryl ether)
US4469770A (en) 1982-12-27 1984-09-04 Xerox Corporation Styrene butadiene plasticizer toner composition blends
US4459311A (en) 1983-01-03 1984-07-10 Nabisco Brands, Inc. Process for preparing gum base
US4461872A (en) 1983-02-22 1984-07-24 E. I. Du Pont De Nemours And Company Blends of a propylene/α-olefin copolymer with isotactic prolypropylene
US4450250A (en) 1983-03-28 1984-05-22 Eastman Kodak Company Polyester adhesives
US4897178A (en) 1983-05-02 1990-01-30 Uop Hydrocracking catalyst and hydrocracking process
US4518615A (en) 1983-08-23 1985-05-21 Warner-Lambert Company Non-adhesive chewing gum base composition
US4504604A (en) * 1983-11-25 1985-03-12 The Goodyear Tire & Rubber Company Energy absorbing rubber composition
DE3347075A1 (en) 1983-12-24 1985-07-04 Bayer Ag, 5090 Leverkusen SOFTENED POLYVINYL ALCOHOL
FR2560884B1 (en) * 1984-03-06 1986-10-03 Inst Francais Du Petrole VINYLIDENE POLYFLUORIDE COMPOSITIONS WITH IMPROVED FLEXIBILITY AND THEIR USE, IN PARTICULAR IN THE MANUFACTURE OF FLEXIBLE TUBES
DK165628C (en) 1984-03-09 1993-05-24 Fuji Kagaku Shikogyo RURAL TAPE FOR MULTIPLE USE
NL8401253A (en) 1984-04-18 1985-11-18 Shell Int Research PROCESS FOR PREPARING HYDROCARBONS.
CA1216119A (en) 1984-05-16 1987-01-06 Mitsui Chemicals, Incorporated Process for producing stretched article of ultrahigh- molecular weight polyethylene
US4536537A (en) * 1984-06-21 1985-08-20 Shell Oil Company Rubberless high impact polypropylene
US4542122A (en) 1984-06-29 1985-09-17 Exxon Research And Engineering Co. Cobalt catalysts for the preparation of hydrocarbons from synthesis gas and from methanol
US4568663A (en) 1984-06-29 1986-02-04 Exxon Research And Engineering Co. Cobalt catalysts for the conversion of methanol to hydrocarbons and for Fischer-Tropsch synthesis
CA1268875A (en) 1984-07-09 1990-05-08 Takashi Nagai Polyester composition
US4764535A (en) 1984-08-06 1988-08-16 Q'so, Inc. Thermally applied sealants and process
US4665130A (en) 1984-08-31 1987-05-12 Shell Oil Company Packaging film and sheet capable of forming peelable seals with good optics
WO1986001744A1 (en) * 1984-09-10 1986-03-27 Toray Industries, Inc. Method for ion-exchange or adsorption
FR2572417B1 (en) 1984-10-30 1987-05-29 Atochem ADHESIVE COMPOSITIONS BASED ON POLYPROPYLENE MODIFIED BY Grafting of an Unsaturated Monomer
US4551507A (en) 1984-12-17 1985-11-05 Allied Corporation Polyester composition containing tertiary and quaternary amine carboxylate salts
US4579901A (en) * 1984-12-21 1986-04-01 General Electric Company Modified polyphenylene ether compositions having improved flow
EP0194808B1 (en) * 1985-03-08 1989-05-17 Unitika Ltd. Polyester resin composition for forming an impact resistant article
US4666968A (en) 1985-03-19 1987-05-19 Caschem, Inc. Ester plasticizers for polyarethane compositions
JPS61252254A (en) * 1985-04-30 1986-11-10 Idemitsu Kosan Co Ltd Polyolefin resin composition
US4670341A (en) 1985-05-17 1987-06-02 W. R. Grace & Co. Hollow fiber
US4645791A (en) * 1985-06-24 1987-02-24 Ford Motor Company Environmentally durable elastomer composition with excellent low temperature dynamic properties
US4921594A (en) 1985-06-28 1990-05-01 Chevron Research Company Production of low pour point lubricating oils
US4616052A (en) 1985-07-05 1986-10-07 Becton, Dickinson And Company High temperature creep resistant thermoplastic elastomer compositions
US4745143A (en) 1985-07-12 1988-05-17 Allied-Signal Inc. Salt resistant polyamide composition
ES2001020A6 (en) 1985-07-19 1988-04-16 Asahi Chemical Ind Hydrogenated block copolymer compositions.
US4663220A (en) * 1985-07-30 1987-05-05 Kimberly-Clark Corporation Polyolefin-containing extrudable compositions and methods for their formation into elastomeric products including microfibers
JPH072900B2 (en) 1985-08-01 1995-01-18 モンサント カンパニ− Polyester composition containing phthalimide ester
US4604322A (en) 1985-08-06 1986-08-05 Hercules Incorporated Metallizable polypropylene film
DE3681241D1 (en) 1985-08-16 1991-10-10 Dow Chemical Co EXPANDABLE POLYVINYL (IDEN) AROMATIC PARTICLES, METHOD FOR THEIR PRODUCTION AND MOLDED OBJECTS.
GB8523460D0 (en) 1985-09-23 1985-10-30 Ici Plc Filamentary yarn & film
JPS6280289A (en) 1985-10-03 1987-04-13 Yamasa Shoyu Co Ltd Method for deoxidizing alcohol
EP0240563B1 (en) 1985-10-07 1990-05-09 BAXTER INTERNATIONAL INC. (a Delaware corporation) High temperature slip agent for polyolefin film
DE3536957A1 (en) 1985-10-17 1987-04-23 Basf Ag MIXTURES CROSS-LINKABLE BY PHOTOPOLYMERISATION
US4693838A (en) * 1985-10-29 1987-09-15 Exxon Chemical Patents Inc. Multifunctional viscosity index improver
US4975177A (en) 1985-11-01 1990-12-04 Mobil Oil Corporation High viscosity index lubricants
US4908166A (en) 1985-11-22 1990-03-13 University Of Dayton Method for preparing polyolefin composites containing a phase change material
US4666959A (en) 1985-12-10 1987-05-19 El Paso Products Company Radiation sterilizable propylene polymer compositions and articles manufactured therefrom
FR2594126B1 (en) * 1986-02-11 1988-08-05 Rhone Poulenc Chimie LOW HARDNESS SILICONE ELASTOMERIC SUPPORT FOR ELASTOFORMING STAMPING
US5254378A (en) * 1986-05-08 1993-10-19 Minnesota Mining And Manufacturing Company Radiation resistant polypropylene articles and method for preparing same
DE3617318A1 (en) 1986-05-23 1987-11-26 Centralen Inst Khim Promisleno MASS FOR THE PRODUCTION OF MICROPOROUS SEPARATORS AND METHOD FOR THE PRODUCTION THEREOF
GB8613161D0 (en) 1986-05-30 1986-07-02 Exxon Chemical Patents Inc Sealable films
FR2602515B1 (en) 1986-08-08 1988-12-02 Atochem VINYLIDENE POLYFLUORIDE SHEATH POLYAMIDE
CA1273415A (en) * 1986-09-12 1990-08-28 Alvin Charles Levy Filled cables
US4870117A (en) * 1986-09-12 1989-09-26 American Telephone And Telegraph Company, At&T Bell Laboratories Filled cables
US5028647A (en) 1986-10-24 1991-07-02 Allied-Signal Inc. Polyester composition containing an ester of an ethoxylated aromatic alcohol
US4726989A (en) * 1986-12-11 1988-02-23 Minnesota Mining And Manufacturing Microporous materials incorporating a nucleating agent and methods for making same
US4827064A (en) 1986-12-24 1989-05-02 Mobil Oil Corporation High viscosity index synthetic lubricant compositions
JPS63202636A (en) 1987-02-17 1988-08-22 Toyo Tire & Rubber Co Ltd Rubber composition for tire tread
FR2613722B1 (en) 1987-04-07 1990-11-23 Bp Chimie Sa PROCESS FOR THE MANUFACTURE OF PROPYLENE HOMOPOLYMER OR COPOLYMER GRANULES
US5213744A (en) 1987-04-21 1993-05-25 Exxon Chemical Patents Inc. Process for making polyolefin films
IT1204529B (en) 1987-04-24 1989-03-03 Grace W R & Co MULTI-LAYER FILM FOR THE PACKAGING OF ITEMS IN CONTROLLED ATMOSPHERE
US4833172A (en) 1987-04-24 1989-05-23 Ppg Industries, Inc. Stretched microporous material
GB8715530D0 (en) * 1987-07-02 1987-08-12 Ici Plc Microporous products
EP0300682A1 (en) 1987-07-13 1989-01-25 The University Of Tennessee Research Corporation A homogeneous, lipsome-based signal amplification method for assays involving enzymes
US5149736A (en) 1987-07-13 1992-09-22 Raychem Corporation Heat resistant gel compositions
CA1332772C (en) 1987-07-13 1994-10-25 Jose Pereyra Gamarra Heat resistant gel compositions
US4833195A (en) 1987-07-20 1989-05-23 Bp Performance Polymers, Inc. High flow drapable polymer compositions
US4857646A (en) * 1987-08-24 1989-08-15 Ciba-Geigy Corporation Modified beta-quinacridone pigment
US4904731A (en) 1987-09-04 1990-02-27 Shell Oil Company Polymeric composition
FR2620079B1 (en) 1987-09-04 1990-01-19 Arjomari Prioux HIGH-MOULDABILITY REINFORCED THERMOPLASTIC SHEET
US4814375A (en) * 1987-09-24 1989-03-21 The West Company High strength elastomers for pharmaceutical products
DE3735502A1 (en) 1987-10-20 1989-05-03 Rxs Schrumpftech Garnituren Crosslinkable plastic compound, in particular for use in scan regions of electron irradiation units
US4853428A (en) 1987-11-02 1989-08-01 Ford Motor Company Elastomer compositions with superior low temperature flexibility
US4845137A (en) * 1987-11-05 1989-07-04 Becton, Dickinson And Company Polyolefin compositions of high clarity and resistance to oxidation
MY103793A (en) * 1987-11-05 1993-09-30 Mitsui Petrochemical Ind Olefin resin composition for injection molding
US4824718A (en) * 1987-12-04 1989-04-25 Minnesota Mining And Manufacturing Company Porous film
JPH072939B2 (en) * 1987-12-07 1995-01-18 不易糊工業株式会社 Removable solid adhesive
US4937399A (en) 1987-12-18 1990-06-26 Exxon Research And Engineering Company Method for isomerizing wax to lube base oils using a sized isomerization catalyst
US4943672A (en) 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
US5093197A (en) * 1987-12-21 1992-03-03 Entek Manufacturing Inc. Microporous filaments and fibers
US5230843A (en) * 1987-12-21 1993-07-27 Entek Manufacturing Inc. Process of forming microporous fibers and filaments
ATE141343T1 (en) 1987-12-21 1996-08-15 Entek Mfg MICROPOROUS FILAMENTS OR FIBERS, METHOD FOR PRODUCING THE SAME AND ARTICLES MADE THEREFROM
EP0321868A2 (en) 1987-12-22 1989-06-28 Air Products And Chemicals, Inc. Water-based vinyl acetate-ethylene emulsion copolymer contact adhesive
FR2626005A1 (en) 1988-01-14 1989-07-21 Shell Int Research PROCESS FOR PREPARING A BASIC LUBRICATING OIL
US4827073A (en) 1988-01-22 1989-05-02 Mobil Oil Corporation Process for manufacturing olefinic oligomers having lubricating properties
US5008204A (en) 1988-02-02 1991-04-16 Exxon Chemical Patents Inc. Method for determining the compositional distribution of a crystalline copolymer
US5264493A (en) 1988-02-19 1993-11-23 Fina Research, S.A. Process for the treatment of polypropylene
DE3809236A1 (en) 1988-03-18 1989-09-28 Lohmann Therapie Syst Lts USE OF KETOGROUPLED CYCLIC COMPOUNDS
JPH01282280A (en) 1988-05-09 1989-11-14 Mitsui Toatsu Chem Inc Hot-melt adhesive composition
US4833192A (en) * 1988-05-12 1989-05-23 Baychem International, Inc. Compatible polymer blends useful as melt adhesives (II)
JPH01293102A (en) 1988-05-23 1989-11-27 Tokuyama Soda Co Ltd Microporous hollow yarn membrane and its production
US4960820A (en) 1988-05-24 1990-10-02 Shell Oil Company Compositions and articles using high melt flow poly-1-butene and polypropylene blends
BR8902321A (en) 1988-05-24 1990-01-09 Shell Oil Co PROCESS FOR THE PRODUCTION OF A COMPOSITION UNDERSTANDING A POLYMER OF BUT-1-ENO AND A POLYMER OF PROPYLENE AND ARTICLE
US6013727A (en) 1988-05-27 2000-01-11 Exxon Chemical Patents, Inc. Thermoplastic blend containing engineering resin
KR920003034B1 (en) * 1988-06-21 1992-04-13 동양나이론 주식회사 Resin making material
US5105038A (en) * 1988-06-23 1992-04-14 Mobil Oil Corporation Synthetic polyolefin lubricant blends
US5624986A (en) 1988-06-30 1997-04-29 H. B. Fuller Licensing & Financing Inc. Hot melt adhesive having controlled property change
KR100197327B1 (en) 1988-07-15 1999-06-15 치어즈 엠. 노우드 Syndiotactic polypropylene
US5091454A (en) * 1988-08-03 1992-02-25 Velsicol Chemical Corporation Hot melt adhesive composition
US5026756A (en) 1988-08-03 1991-06-25 Velsicol Chemical Corporation Hot melt adhesive composition
US4996094A (en) * 1988-09-26 1991-02-26 Mobil Oil Corporation One-sided cling/one-sided slip stretch wrap films
US5382630A (en) 1988-09-30 1995-01-17 Exxon Chemical Patents Inc. Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distribution
JPH02107270A (en) 1988-10-18 1990-04-19 Terumo Corp Gasket and medical instrument using the same
US4863785A (en) * 1988-11-18 1989-09-05 The James River Corporation Nonwoven continuously-bonded trilaminate
US4952457A (en) 1988-12-05 1990-08-28 Monsanto Company Laminated safety glass and polymeric laminate for use therein
IT1227893B (en) 1988-12-14 1991-05-14 Himont Inc Centerville Road Ne POLYPROPYLENE COMPOSITIONS WITH GOOD TRANSPARENCY AND IMPROVED IMPACT RESISTANCE
US5075269A (en) 1988-12-15 1991-12-24 Mobil Oil Corp. Production of high viscosity index lubricating oil stock
KR900009719A (en) 1988-12-16 1990-07-05 엠. 데이비드 레오나이드 New Ethylene-Propylene Copolymer
US4923588A (en) 1988-12-16 1990-05-08 Exxon Research And Engineering Company Wax isomerization using small particle low fluoride content catalysts
EP0389695A1 (en) 1989-03-28 1990-10-03 Neste Oy Gastight material
CA2012729C (en) 1989-04-07 1997-05-20 Takashi Kuroda Dulled stretched molding and process for producing the same
DE3911725C2 (en) 1989-04-11 1997-09-25 Basf Ag Process for the production of tack-free, highly elastic, multifilament polyurethane elastomer threads, elastomer threads produced by this process and their use
DE3912949A1 (en) 1989-04-20 1990-10-25 Huels Chemische Werke Ag MELT ADHESIVE AND COATING
IT1230133B (en) 1989-04-28 1991-10-14 Himont Inc PLASTIC-ELASTIC POLYPROPYLENE COMPOSITIONS
US4957958A (en) 1989-05-23 1990-09-18 Ethyl Corporation Aromatic bis sulfonamide-containing nylon or polyester
US5264474A (en) 1989-05-23 1993-11-23 Mtm Americas Inc. Polymer compositions
US5171628A (en) 1989-05-25 1992-12-15 Exxon Chemical Patents Inc. Low creep polypropylene textiles
US4959402A (en) 1989-06-08 1990-09-25 Becton, Dickinson And Company High clarity radiation stable polymeric compostion and articles therefrom
US4994552A (en) * 1989-06-08 1991-02-19 Becton, Dickinson And Company High clarity radiation stable polymeric composition and articles therefrom
JPH0321611A (en) 1989-06-19 1991-01-30 Nippon Unicar Co Ltd Formable kneaded resin mixture
US5258419A (en) 1989-06-26 1993-11-02 Minnesota Mining And Manufacturing Company Methods of preparing radiation resistant heat sealable polymer blends
JP2544994B2 (en) 1989-06-28 1996-10-16 日本石油化学株式会社 Injection molding materials and vehicle exterior materials
JPH0783758B2 (en) 1989-07-20 1995-09-13 株式会社ニッショー Platelet storage bag and composite bag using the same
US6025448A (en) * 1989-08-31 2000-02-15 The Dow Chemical Company Gas phase polymerization of olefins
US5049605A (en) * 1989-09-20 1991-09-17 Milliken Research Corporation Bis(3,4-dialkylbenzylidene) sorbitol acetals and compositions containing same
JP3015967B2 (en) 1989-10-02 2000-03-06 旭化成工業株式会社 Multilayer packaging film and method for producing the same
US5442004A (en) 1989-10-05 1995-08-15 Raychem Limited Gels
US5036034A (en) 1989-10-10 1991-07-30 Fina Technology, Inc. Catalyst for producing hemiisotactic polypropylene
FR2654109B1 (en) 1989-11-08 1992-12-31 Norsolor Sa THERMOPLASTIC ELASTOMER BASED ON POLYNORBORNENE AND VINYL POLYCHLORIDE.
US4948840A (en) * 1989-11-14 1990-08-14 Himont Incorporated Thermoplastic elastomer of propylene polymer material and crosslinked ethylene-propylene rubber
FR2654433B1 (en) 1989-11-16 1992-01-17 Norsolor Sa THERMOPLASTIC COMPOSITIONS WITH ELASTIC MEMORY AND PREPARATION METHOD THEREOF.
JP2977595B2 (en) * 1989-11-20 1999-11-15 三井化学株式会社 Syndiotactic polypropylene molded article and method for producing the same
JP2894823B2 (en) * 1989-12-06 1999-05-24 三井化学株式会社 Method for producing radiation-resistant polypropylene resin composition and radiation-resistant molded article
US4995884A (en) * 1989-12-08 1991-02-26 Henkel Corporation Polyalphaolefin emulsions for fiber and textile applications
US5389711A (en) * 1990-02-14 1995-02-14 Shell Oil Company Plasticisers for salt functionalized polyvinyl aromatics
JP2537690B2 (en) 1990-03-16 1996-09-25 豊田合成株式会社 Ethylene propylene rubber compound
US5080942A (en) * 1990-05-23 1992-01-14 Minnesota Mining And Manufacturing Company High stretch elastomeric pre-stretched tubes
DE4117411C2 (en) 1990-05-31 1998-08-06 Nok Corp Membrane element and storage element with such a membrane element
AU636487B2 (en) 1990-06-18 1993-04-29 Kimberly-Clark Worldwide, Inc. A nonwoven web with improved barrier properties
US5157067A (en) 1990-06-27 1992-10-20 Ferro Corporation Liquid colorant/additive concentrate for incorporation into plastics
AU638336B2 (en) 1990-07-05 1993-06-24 Mobil Oil Corporation Production of high viscosity index lubricants
AU640490B2 (en) 1990-07-05 1993-08-26 Mobil Oil Corporation Production of high viscosity index lubricants
US5106447A (en) * 1990-07-17 1992-04-21 National Starch And Chemical Investment Holding Corporation Bonding method employing hot melt adhesives for insulation assembly
US5415791A (en) * 1990-08-02 1995-05-16 Oiles Corporation Lubricating composition and a sliding member comprising the composition
US5143978A (en) * 1990-08-28 1992-09-01 Himont Incorporated Dynamically partially crosslinked thermoplastic elastomer containing polybutene-1
US5331019A (en) 1990-09-04 1994-07-19 Becton, Dickinson And Company Lubricious radiation stable polymeric composition and articles therefrom
JP3169376B2 (en) 1990-09-20 2001-05-21 大日本インキ化学工業株式会社 Granular colorant and method for producing the same
DE4030563A1 (en) 1990-09-27 1992-04-02 Hoechst Ag MOLDS BASED ON POLYETHYLENE WITH A MEDIUM MOLE WEIGHT OF AT LEAST 500,000 G / MOL
US5162436A (en) 1990-10-04 1992-11-10 Bridgestone/Firestone, Inc. Heat weldable roof sheeting and method for coating roofs
US5124384A (en) 1990-11-16 1992-06-23 Air Products And Chemicals, Inc. Transparent caulks containing fumed silica
US5256717A (en) 1990-12-19 1993-10-26 National Starch And Chemical Investment Holding Corporation Hot melt adhesives useful in temporary bonding operations
US5106899A (en) 1990-12-19 1992-04-21 General Electric Company Plasticized polyphenylene ether compositions
JP2905603B2 (en) * 1990-12-21 1999-06-14 株式会社トクヤマ Polypropylene resin composition
US5114763A (en) * 1990-12-28 1992-05-19 Exxon Chemical Patents Inc. Tackified polyethylene layers in stretch/cling films
EP0513470A3 (en) 1991-05-13 1993-03-17 Monsanto Company Adipate compositions
ES2155492T3 (en) 1991-05-27 2001-05-16 Basell Polyolefine Gmbh PROCEDURE FOR OBTAINING POLYOLEFINS WITH A LARGE DISTRIBUTION OF MOLECULAR WEIGHTS.
JP3135288B2 (en) * 1991-07-19 2001-02-13 三井化学株式会社 Polypropylene film with high rigidity and excellent impact resistance
US5308904A (en) 1991-07-23 1994-05-03 Mitsubishi Kasei Corporation Resin composition, porous film or sheet
US5116626A (en) 1991-07-25 1992-05-26 Wm. Wrigley Jr. Company Transparent base and gum composition
US5264277A (en) * 1991-09-09 1993-11-23 Mobil Oil Corp. Multi-layer opaque film structures of reduced surface friction and process for producing same
KR930006226A (en) 1991-09-30 1993-04-21 원본미기재 Elastic composite nonwoven fabrics and methods of making the same
US5173317A (en) 1991-10-29 1992-12-22 Wm. Wrigley Jr. Company Gum compositions containing vinyl laurate/vinyl acetate copolymer
TW209877B (en) * 1991-11-04 1993-07-21 Shell Internat Res Schappej B V
IT1250045B (en) 1991-11-07 1995-03-30 Butterfly Srl PROCEDURE FOR THE PRODUCTION OF PLASTICIZED POLYVINYL ALCOHOL AND ITS USE FOR THE PREPARATION OF BIODEGRADABLE STARCH-BASED THERMOPLASTIC COMPOSITIONS.
US5171908A (en) 1991-11-18 1992-12-15 Mobil Oil Corporation Synthetic polyolefin lubricant oil
US5180865A (en) * 1991-12-06 1993-01-19 Pennzoil Products Company Base oil for shear stable multi-viscosity lubricants and lubricants therefrom
AT401775B (en) * 1991-12-18 1996-11-25 Semperit Ag VEHICLE TIRES
US6153703A (en) 1991-12-20 2000-11-28 Exxon Research And Engineering Company Semicrystalline polymer blend compositions with enhanced interspherulitic and interlamellar strength
US5674919A (en) * 1991-12-27 1997-10-07 Mitsui Petrochemical Industries, Ltd. Biaxially oriented film of high molecular weight polyethylene, process for preparing the same, surface-modified biaxially oriented film of high molecular weight polyethylene and process for preparing the same
JPH05202249A (en) * 1992-01-27 1993-08-10 Mitsui Toatsu Chem Inc Polypropylene film having high rigidity and excelent impact resistance
JPH05202339A (en) * 1992-01-27 1993-08-10 Sekisui Chem Co Ltd Production of hot-melt adhesive and hot-melt adhesive
US5437877A (en) 1992-03-03 1995-08-01 Wm. Wrigley Jr. Company Wax-free chewing gum with initial soft bite
US5286500A (en) * 1992-03-03 1994-02-15 Wm. Wrigley Jr. Company Wax-free chewing gum base
US5462754A (en) 1992-03-03 1995-10-31 Wm. Wrigley Jr. Company Abhesive chewing gum with improved sweetness profile
US6245870B1 (en) 1992-03-20 2001-06-12 Fina Technology, Inc. Process for producing syndiotactic/isotactic block polyolefins
US6184326B1 (en) 1992-03-20 2001-02-06 Fina Technology, Inc. Syndiotactic polypropylene
JP3193446B2 (en) 1992-04-07 2001-07-30 大日精化工業株式会社 Olefin-based thermoplastic elastomer composition
JPH05287132A (en) * 1992-04-09 1993-11-02 Mitsui Petrochem Ind Ltd Olefin-based thermoplastic elastomer composition
DE69327192T2 (en) 1992-05-11 2000-04-27 Fuji Photo Film Co Ltd Shaped articles for light-sensitive photographic materials
US5356709A (en) 1992-05-14 1994-10-18 Baxter International, Inc. Non-PVC coextruded medical grade port tubing
US5424080A (en) 1992-06-30 1995-06-13 Wm. Wrigley Jr. Company Wax-free chewing gum base
DE4226081A1 (en) * 1992-08-06 1994-02-10 Henkel Kgaa Thermoplastic hot melt adhesive
ZA935964B (en) 1992-08-18 1994-03-15 Shell Res Ltd Process for the preparation of hydrocarbon fuels
US7134236B2 (en) 1994-04-19 2006-11-14 Applied Elastomerics, Inc. Gelatinous elastomer compositions and articles for use as fishing bait
US6867253B1 (en) * 1994-04-19 2005-03-15 Applied Elastomerics, Inc. Tear resistant, crystalline midblock copolymer gels and articles
US5356986A (en) 1992-08-28 1994-10-18 E. I. Du Pont De Nemours And Company Plasticized fluoropolymers
US5376716A (en) 1992-08-31 1994-12-27 Rexene Products Company Radiation resistant polypropylene resins
JP3373516B2 (en) 1992-09-15 2003-02-04 ザ・ダウ・ケミカル・カンパニー Impact modification of thermoplastics
US5736197A (en) 1992-11-30 1998-04-07 Poly-Wall International, Inc. Method of waterproofing rigid structural materials
BE1006477A3 (en) 1992-12-07 1994-09-06 Solvay Thermoplastic composition, method of preparation and use.
EP0603500B1 (en) 1992-12-21 1998-09-09 Mitsubishi Chemical Corporation Porous film or sheet, battery separator and lithium battery
IT1256260B (en) 1992-12-30 1995-11-29 Montecatini Tecnologie Srl ATACTIC POLYPROPYLENE
BE1006614A3 (en) 1993-01-25 1994-11-03 Solvay Polymer compositions intended for the manufacture of pipes for the transportation of hydrocarbons and products containing same.
US5331047A (en) 1993-02-17 1994-07-19 Himont Incorporated Olefin polymer films
KR970011464B1 (en) 1993-03-12 1997-07-11 주식회사 유공 Polypropylene resin component
DE69400411D1 (en) 1993-03-23 1996-10-02 Atochem Elf Sa Composition consisting of an unsaturated elastomer and a plasticizer from the family of polyphenylmethanes
EP0618261B1 (en) 1993-04-02 1998-06-03 Shell Internationale Researchmaatschappij B.V. Conveyor belts derived from hot melt compositions, based on hydrogenated block copolymers derived from a vinyl aromatic and a conjugated diene
US5290886A (en) * 1993-04-20 1994-03-01 Advanced Elastomer Systems, L.P. Thermoplastic elastomers having improved low temperature properties
CA2119600A1 (en) 1993-04-22 1994-10-23 Francis A. Schurb Compounded latex saturants for porous backings
AU680263B2 (en) 1993-05-25 1997-07-24 Exxon Chemical Patents Inc. Novel polyolefin fibers and their fabrics
DE4317655A1 (en) 1993-05-27 1994-12-01 Basf Ag Multi-phase block copolymers of propylene
GB2278363B (en) 1993-05-28 1996-10-30 Chaloke Pungtrakul A method for the prevention of blocking in linear low density polyethylene films
EP0812854B2 (en) 1993-06-07 2011-04-20 Mitsui Chemicals, Inc. Novel transition metal compound, olefin polymerization catalyst comprising said compound, process for olefin polymerization using said catalyst and propylene homo- and copolymer
CA2125246C (en) 1993-06-07 2001-07-03 Junichi Imuta Transition metal compound and olefin polymerization catalyst using the same
DE4322145C2 (en) 1993-07-02 2002-07-18 Benecke Ag J H Film or molded body made of a multi-phase plastic and its use for the production of composite films
TW272986B (en) * 1993-07-28 1996-03-21 Mitsui Petroleum Chemicals Ind
US5360868A (en) * 1993-08-30 1994-11-01 Himont Incorporated Polyolefin compositions having a high balance of stiffness and impact strength
DE4333128A1 (en) 1993-09-29 1995-03-30 Hoechst Ag Process for the preparation of polyolefins
DE69415040T2 (en) 1993-10-12 1999-07-15 Fuller H B Licensing Financ POLYSTYRENE ETHYLENE / BUTHYLENE POLYSTYRENE MELT GLUE
JP3523922B2 (en) 1993-12-22 2004-04-26 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー Free flowing powder composition, process for its preparation and uniform layer derived therefrom
US5489646A (en) * 1994-01-10 1996-02-06 Koch Industries, Inc. Lower alkyl biphenyls as plasticizers
CA2140096C (en) 1994-01-24 2001-07-24 Joel L. Williams Polyolefin composition of improved ductility and article therefrom
JP3325377B2 (en) 1994-02-01 2002-09-17 三菱樹脂株式会社 Porous film or sheet and method for producing the same
JP3325376B2 (en) 1994-02-01 2002-09-17 三菱樹脂株式会社 Porous film or sheet and method for producing the same
CN1085219C (en) * 1994-02-04 2002-05-22 埃克森美孚化学专利公司 Dual donor catalyst system for polymerization of olefins
US5747573A (en) 1994-02-07 1998-05-05 H. B. Fuller Licensing & Financing, Inc. High heat resistant hot melt adhesive
US5489473A (en) 1994-04-07 1996-02-06 Borden, Inc. Biaxially and monoaxially oriented polypropylene cold seal release film
AT406683B (en) 1994-04-14 2000-07-25 Semperit Ag RUBBER BLEND
JP2886107B2 (en) * 1994-04-19 1999-04-26 三菱化学株式会社 Thermoplastic elastomer sheet molding
DE4417191C1 (en) 1994-05-17 1995-08-31 Frisetta Gmbh Kunststoffwerke Plasticiser system free from highly volatile cpds., useful in plastics, esp. polyamide
US5614297A (en) * 1994-05-19 1997-03-25 Viskase Corporation Polyolefin stretch film
WO1995032091A1 (en) 1994-05-24 1995-11-30 Exxon Chemical Patents Inc. Fibers and fabrics incorporating lower melting propylene polymers
DE4420991A1 (en) * 1994-06-16 1995-12-21 Danubia Petrochem Deutschland Polypropylene for thermo-forming
US5492943A (en) * 1994-06-20 1996-02-20 Hollister Incorporated Adhesive skin barrier composition for ostomy appliance
JP3380043B2 (en) 1994-06-30 2003-02-24 三菱樹脂株式会社 Stretch film for food packaging
US5552489A (en) 1994-07-22 1996-09-03 Exxon Chemical Patents Inc. Tackifiers and a process to obtain tackifiers
IT1274606B (en) 1994-08-09 1997-07-18 Spherilene Srl MIXTURES OF ATACTIC POLYPROPYLENE AND SYNDIOTACTIC POLYPROPYLENE
EP0699519A3 (en) 1994-08-30 1998-04-22 Shell Internationale Researchmaatschappij B.V. Co moulded multi-layer polymer blend system, and shaped articles derived therefrom
TW383277B (en) * 1994-08-30 2000-03-01 Shell Int Research Comoulded multi-layer polymer blend system, and air bag covers derived therefrom
GB9418352D0 (en) 1994-09-12 1994-11-02 Bp Chem Int Ltd Plasticizer composition
CA2160618A1 (en) * 1994-10-19 1996-04-20 Yasuhiro Nohara Propylene resin composition, molded articles thereof and propylene resin laminate
US5610217A (en) 1994-10-31 1997-03-11 The Gates Corporation Ethylene-alpha-olefin belting
TW337532B (en) 1994-11-16 1998-08-01 Shell Int Research A chemical resistant composition and its use
US5601858A (en) * 1994-12-29 1997-02-11 Warner-Lambert Company Non-stick chewing gum
EP0805842B1 (en) 1995-01-25 2007-08-15 Findley Adhesives Inc. Hot melt adhesive having improved wet strength properties
JPH08208963A (en) 1995-02-02 1996-08-13 New Japan Chem Co Ltd Polyester resin composition
DE19504425A1 (en) 1995-02-10 1996-08-14 Hella Kg Hueck & Co Hot melt adhesives for vehicle lights and vehicle headlights
US5663230A (en) 1995-02-15 1997-09-02 Concrete Sealants, Inc. Water stop composition and methods of preparing same
US5594074A (en) 1995-02-21 1997-01-14 Shell Oil Company Process for improving processability of ultra low melt viscosity polymer
TR199600222A2 (en) * 1995-03-24 1996-10-21 Shell Int Research Compositions containing monovinyl aromatic block copolymer and microgranules and powders derived therefrom, suitable for use in rotary molding and similar processes.
JPH08269417A (en) * 1995-03-29 1996-10-15 Sekisui Chem Co Ltd Hot melt adhesive composition
DE69633420T2 (en) * 1995-03-31 2005-09-29 Basell North America Inc. High energy radiation resistant polyolefin compositions and articles made therefrom
US5728760A (en) * 1995-04-11 1998-03-17 Great Lakes Chemical Corporation Use of ring-brominated benzoate compounds as flame retardants and/or plasticizers
CA2219402A1 (en) * 1995-05-22 1996-11-28 Louis E. Winslow Protective adhesive article
US5728754A (en) 1995-06-05 1998-03-17 The International Group, Inc. Cable filling and flooding compounds
US5569693A (en) 1995-06-05 1996-10-29 Borden Inc. High stretch film for pallet wrapping
US5789529A (en) 1995-06-13 1998-08-04 Ube Industries, Ltd. Polyamide resin composition and tubular molding comprising the same
US5698650A (en) 1995-06-14 1997-12-16 Exxon Chemical Patents Inc. Elastomeric vehicle brake parts and power transmission belts
JP3474677B2 (en) 1995-06-19 2003-12-08 花王株式会社 Porous sheet and absorbent article using the same
JPH09104053A (en) 1995-07-21 1997-04-22 Union Carbide Chem & Plast Technol Corp Method for extrusion of polyethylene
AU6058196A (en) 1995-07-21 1997-01-30 Union Carbide Chemicals & Plastics Technology Corporation Process for the extrusion of polyethylene
US5869560A (en) * 1995-07-27 1999-02-09 Taisei Corporation Sealing materials and building components useful for clean rooms
AU6954196A (en) * 1995-08-22 1997-03-19 Blue Coral, Inc. Universal auto lotion
CN1091453C (en) 1995-08-29 2002-09-25 埃克森美孚化学专利公司 Radiation tolerant polypropylene and its useful articles
CA2228475C (en) 1995-09-06 2008-10-14 Minnesota Mining And Manufacturing Company Epihalohydrin electrical stress controlling material
US5552482A (en) * 1995-09-08 1996-09-03 Montell North America Inc. Thermoplastic elastomers with improved extrusion performance
JP3042976B2 (en) * 1995-09-11 2000-05-22 河西工業株式会社 Manufacturing method for automotive interior parts
US5741563A (en) 1995-09-18 1998-04-21 Exxon Chemical Patents Inc. Shrink films from propylene polymers
JPH09111061A (en) * 1995-10-13 1997-04-28 Tokuyama Corp Thermoplastic resin composition
GB2307206B (en) 1995-11-15 1999-06-09 Courtaulds Films Polymeric films
US5869555A (en) * 1995-11-16 1999-02-09 H. B. Fuller Licensing & Financing Inc. Polymeric composition in pellet form
US6037384A (en) 1995-11-28 2000-03-14 Dainippon Ink And Chemicals, Inc. Expanded material and laminate
KR19990071757A (en) 1995-11-30 1999-09-27 만셀 케이쓰 로드니 Products made of polypropylene, higher alpha-olefin copolymers
US5833839A (en) * 1995-12-08 1998-11-10 Exxon Research And Engineering Company High purity paraffinic solvent compositions, and process for their manufacture
FR2742444B1 (en) * 1995-12-13 1998-01-16 Atochem Elf Sa POLYOL-BASED PLASTIC COMPOSITION HAVING CONTROLLED VISCOSITY
JPH09176359A (en) * 1995-12-27 1997-07-08 Hitachi Chem Co Ltd Production of polyolefin resin foamed material
US6902786B2 (en) * 1996-01-04 2005-06-07 Nichiban Company, Limited Pressure-sensitive adhesive compositions for surface-protecting films
JP3612374B2 (en) * 1996-02-02 2005-01-19 出光興産株式会社 Polyolefin resin composition
US6797765B2 (en) 1996-02-14 2004-09-28 Edizone, Lc Gelatinous elastomer
US5749111A (en) 1996-02-14 1998-05-12 Teksource, Lc Gelatinous cushions with buckling columns
ID17196A (en) 1996-03-14 1997-12-11 Dow Chemical Co ADHESIVE INGREDIENTS THAT CONTAIN OLEFIN POLYMER
US5916953A (en) * 1996-03-15 1999-06-29 Bp Amoco Corporation Stiff, strong, tough glass-filled olefin polymer
JPH09255827A (en) * 1996-03-22 1997-09-30 Toyo Ink Mfg Co Ltd Polypropylene resin composition
US5916959A (en) 1996-03-29 1999-06-29 H.B. Fuller Licensing & Financing, Inc. Radial styrene-isoprene-styrene based hot melt pressure sensitive adhesive
AT406684B (en) 1996-04-09 2000-07-25 Danubia Petrochem Polymere USE OF POLYPROPYLENE TO IMPROVE STABILITY TO IONIZING RADIATION
US5866748A (en) * 1996-04-23 1999-02-02 Exxon Research And Engineering Company Hydroisomerization of a predominantly N-paraffin feed to produce high purity solvent compositions
US5910362A (en) 1996-04-25 1999-06-08 Chisso Corporation Polyolefin fiber and non-woven fabric produced by using the same
US5929147A (en) 1996-06-18 1999-07-27 Montell North America Inc. Embrittlement-resistant polyolefin composition and flexible articles therefrom
WO1997048766A1 (en) 1996-06-20 1997-12-24 The Yokohama Rubber Co., Ltd. Processes for producing rubber composition
US6380292B1 (en) 1996-06-21 2002-04-30 Bostik Findley, Inc. Hydrophilic hot melt adhesive
ATE195745T1 (en) 1996-06-26 2000-09-15 Ciba Sc Holding Ag DEGRADATION OF POLYMERS THROUGH NOR-NECK CONNECTIONS
US5741840A (en) 1996-07-03 1998-04-21 H.B. Fuller Licensing & Financing, Inc. Cohesively failing hot melt pressure sensitive adhesive
EP0818475A1 (en) 1996-07-11 1998-01-14 Fina Research S.A. Syndiotactic/atactic block polyolefins, catalysts and processes for producing the same
DE19628147C2 (en) 1996-07-12 2003-02-20 Aesculap Ag & Co Kg Surgical device for fixing bone elements
CA2255793A1 (en) 1996-07-12 1998-01-22 H.B. Fuller Licensing & Financing, Inc. Low application temperature hot melt with excellent heat and cold resistance
JP2001522379A (en) 1996-08-06 2001-11-13 エクソンモービル・ケミカル・パテンツ・インク Method for processing polyethylene and polyethylene / elastomer blends
US6297301B1 (en) 1996-08-06 2001-10-02 Exxonmobil Chemical Patents Inc. Thermoplastic elastomer compositions having improved processing properties
BE1010655A3 (en) 1996-09-30 1998-11-03 Ucb Sa Compositions polyamides plasticized.
US6086996A (en) * 1996-10-11 2000-07-11 Illinois Tool Works Inc. Ethylene-propylene copolymer low noise film additive
US5948557A (en) 1996-10-18 1999-09-07 Ppg Industries, Inc. Very thin microporous material
US6786994B2 (en) 1996-11-04 2004-09-07 Foto-Wear, Inc. Heat-setting label sheet
DE19648895A1 (en) 1996-11-26 1998-05-28 Clariant Gmbh Polar modified polypropylene waxes
EP0994153B1 (en) 1996-11-29 2003-10-15 Riken Technos Corporation Thermoplastic elastomeric resin composition
US6245856B1 (en) 1996-12-17 2001-06-12 Exxon Chemical Patents, Inc. Thermoplastic olefin compositions
US5739200A (en) 1996-12-17 1998-04-14 The Dow Chemical Company Plasticizied α-olefin/vinylidene aromatic monomer of hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers
US6362252B1 (en) * 1996-12-23 2002-03-26 Vladimir Prutkin Highly filled polymer composition with improved properties
US6114457A (en) 1997-02-07 2000-09-05 Exxon Chemical Patents Inc. High melt strength polyethylene compositions
CN1113915C (en) 1997-02-07 2003-07-09 埃克森美孚化学专利公司 Thermoplastic elastomer compositions from branched olefin copolymers
AT408229B (en) 1997-02-11 2001-09-25 Borealis Ag USE OF THERMOPLASTIC ELASTOMERS TO IMPROVE THE STABILITY OF POLYOLEFINS TO IONIZING RADIATION
CN1249740A (en) * 1997-02-28 2000-04-05 新日本理化株式会社 p-hydroxybenzoic esters, plasticizer contg. same, polyamide resin composition, and molded objects
US5994482A (en) 1997-03-04 1999-11-30 Exxon Chemical Patents, Inc. Polypropylene copolymer alloys and process for making
US6080818A (en) 1997-03-24 2000-06-27 Huntsman Polymers Corporation Polyolefin blends used for non-woven applications
US6107240A (en) 1997-03-26 2000-08-22 Engelhard Corporation Catalyst composition containing an intimately mixed oxide of cerium and praseodymium
US5783531A (en) 1997-03-28 1998-07-21 Exxon Research And Engineering Company Manufacturing method for the production of polyalphaolefin based synthetic greases (LAW500)
US5869562A (en) * 1997-03-28 1999-02-09 H. B. Fuller Licensing & Financing, Inc. Hot melt pressure sensitive adhesive designed for use on high density spun polyolefin film
FI971338A (en) * 1997-04-02 1998-10-03 Upofloor Oy Plastic based material
US6342320B2 (en) * 1997-04-23 2002-01-29 Valence Technology, Inc. Electrochemically stable plasticizer
EP0979074A4 (en) * 1997-05-01 2003-07-09 Novogen Inc Treatment or prevention of menopausal symptoms and osteoporosis
JP3387775B2 (en) * 1997-05-22 2003-03-17 株式会社大協精工 Sealing stopper for syringe and prefilled syringe
US5849806A (en) 1997-05-23 1998-12-15 Shell Oil Company Resilient polyurethane foams of polydiene diols and tackifying resin
KR100591817B1 (en) 1997-05-27 2006-06-20 아크조 노벨 엔.브이. Cross-linking compositions
US6207754B1 (en) * 1997-05-29 2001-03-27 Exxon Chemical Patents, Inc. Low modulus thermoplastic olefin compositions
JPH1112402A (en) * 1997-06-24 1999-01-19 Mitsui Chem Inc Propylene resin composition for extruded film and extruded film
DE19729833A1 (en) 1997-07-11 1999-01-14 Clariant Gmbh Polypropylene wax
DE19730425A1 (en) 1997-07-16 1999-01-21 Henkel Teroson Gmbh Heat-curing laundry-resistant shell sealant
US6027557A (en) 1997-07-17 2000-02-22 Marathon Ashland Petroleum Llc Oxidized blends of asphalt and paraffinic base stock fluxing component having improved low temperature properties
US5925707A (en) 1997-07-30 1999-07-20 Shell Oil Company Oil gel formulations containing high vinyl content hydrogenated styrene-butadiene-styrene block copolymers
JPH1149903A (en) * 1997-08-01 1999-02-23 Nippon Porikemu Kk Polyethylene resin composition and film made therefrom
US5969021A (en) * 1997-08-07 1999-10-19 Fina Technology, Inc. Method of improving crystallization rate and temperature of syndiotactic polypropylene and compositions and products made therefrom
US6635715B1 (en) 1997-08-12 2003-10-21 Sudhin Datta Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers
US6525157B2 (en) 1997-08-12 2003-02-25 Exxonmobile Chemical Patents Inc. Propylene ethylene polymers
US6921794B2 (en) 1997-08-12 2005-07-26 Exxonmobil Chemical Patents Inc. Blends made from propylene ethylene polymers
US6017615A (en) 1997-08-25 2000-01-25 Huntsman Polymers Corporation Film product comprising novel polyolefins
WO1999013477A1 (en) * 1997-09-09 1999-03-18 Nkt Research Center A/S An electrically insulating material, method for the preparation thereof, and insulated objects comprising said material
US6316068B1 (en) 1997-09-10 2001-11-13 Asahi Kasei Kabushiki Kaisha Elastomer composition
US6165599A (en) 1997-09-15 2000-12-26 Applied Extrusion Technologies, Inc. Biaxially oriented film prepared from metallocene catalyzed polypropylene
US6497965B1 (en) 1997-10-09 2002-12-24 Applied Extrusion Technologies, Inc. Slip agents and polypropylene films prepared therefrom
US6042902A (en) * 1997-10-20 2000-03-28 Hoechst Celanese Corporation Adhesives for making multilayer films comprising liquid crystalline polymers and poly(ethylene terephthalate) or polycarbonate
US6090989A (en) 1997-10-20 2000-07-18 Mobil Oil Corporation Isoparaffinic lube basestock compositions
FI974178A0 (en) * 1997-11-07 1997-11-07 Borealis As Polypropensammansaettningar
US6197910B1 (en) 1997-12-10 2001-03-06 Exxon Chemical Patents, Inc. Propylene polymers incorporating macromers
US6184327B1 (en) 1997-12-10 2001-02-06 Exxon Chemical Patents, Inc. Elastomeric propylene polymers
WO1999029775A1 (en) * 1997-12-11 1999-06-17 Sumitomo Chemical Company, Limited Thermoplastic elastomer composition, powder, pellets, and moldings
SE511215C2 (en) 1997-12-22 1999-08-23 Asea Brown Boveri Dielectric gelling composition, use thereof, insulated electric DC cable comprising such composition and process for making it
US6359071B1 (en) * 1998-01-13 2002-03-19 The Yokohama Rubber Co., Ltd. Thermoplastic elastomer composition, process for producing the same, and pneumatic tire and hose made with the same
US6096420A (en) 1998-01-30 2000-08-01 Tredegar Corporation Thin plastic film
ATE266054T1 (en) * 1998-02-12 2004-05-15 Trespaphan Gmbh SEALABLE BIAXIAL ORIENTED POLYPROPYLENE FILM WITH IMPROVED BARRIER PROPERTIES
US5968455A (en) 1998-02-17 1999-10-19 Brickley; James Lawrence Ultraviolet air sterilization device and mobile unit incorporating sterilization device
US6300407B1 (en) 1998-03-06 2001-10-09 Rohm And Haas Company Polymeric (meth)acrylate plasticizers and processing aids for elastomers
TW524779B (en) 1998-05-01 2003-03-21 Ind Tech Res Inst Process for chemically oxidizing wastewater with reduced sludge production
US6207606B1 (en) 1998-05-15 2001-03-27 Univation Technologies, Llc Mixed catalysts and their use in a polymerization process
US6177190B1 (en) 1998-05-29 2001-01-23 3M Innovative Properties Company Radiation curable poly(1-alkene) based pressure-sensitive adhesives
US6027674A (en) 1998-06-03 2000-02-22 Yates; Paul M. Resilient cushion method of manufacture
KR100598192B1 (en) 1998-06-05 2006-07-07 닛폰 포리프로 가부시키가이샤 Propylene block copolymer and propylene resin composition
US6310134B1 (en) 1998-06-30 2001-10-30 Eastman Chemical Company Adhesion-promoting primer compositions for polyolefin substrates
EP1098934A1 (en) 1998-07-01 2001-05-16 Exxon Chemical Patents Inc. Elastic blends comprising crystalline polymer and crystallizable polymers of propylene
US6288171B2 (en) 1998-07-01 2001-09-11 Advanced Elastomer Systems, L.P. Modification of thermoplastic vulcanizates using random propylene copolymers
WO2000001745A1 (en) 1998-07-02 2000-01-13 Exxon Chemical Patents Inc. Propylene olefin copolymers
JP2000038484A (en) * 1998-07-22 2000-02-08 Tokuyama Corp Polypropylene composition
CA2341167A1 (en) 1998-08-26 2000-03-09 Exxon Chemical Patents Inc. Branched polypropylene compositions
JP2002523585A (en) 1998-09-01 2002-07-30 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー Polymer molding materials, use of the molding materials in the foam generation process, foaming methods, foamed molding materials and products containing foamed molding materials
US6165949A (en) 1998-09-04 2000-12-26 Exxon Research And Engineering Company Premium wear resistant lubricant
US6080301A (en) 1998-09-04 2000-06-27 Exxonmobil Research And Engineering Company Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins
DE19841303A1 (en) 1998-09-10 2000-03-23 Hauke Malz Leak sealant for tanks and other vessels for hazardous substances comprises optionally plasticised thermoplastic or reactive plastic material which is molded to fit leak and sets after reasonable working time
US6197285B1 (en) 1998-09-16 2001-03-06 Exxon Chemical Patents Inc. Use of isoparaffin extenders for clear gel cosmetic compounds
EP0990675A1 (en) 1998-10-02 2000-04-05 Bridgestone/Firestone, Inc. Non-black, mineral-filled roof accessories
JP4023927B2 (en) * 1998-10-09 2007-12-19 三菱化学株式会社 Thermoplastic elastomer composition
US6303067B1 (en) 1998-11-13 2001-10-16 3M Innovative Properties Company Method of stretching films according to an overbias or overstretch stretch profile
JP2000154281A (en) 1998-11-18 2000-06-06 Tokyo Printing Ink Mfg Co Ltd Polyolefin resin composition
US6084031A (en) * 1998-11-30 2000-07-04 Advanced Elastomer Systems, L.P. TPV from hydrosilylation crosslinking of acrylic modified bromo XP-50 butyl rubber
US6294631B1 (en) 1998-12-15 2001-09-25 Exxonmobil Chemical Patents Inc. Hyperbranched polymers by coordination polymerization
US6258903B1 (en) 1998-12-18 2001-07-10 Univation Technologies Mixed catalyst system
US6503984B2 (en) 1998-12-22 2003-01-07 Advanced Elastomer Systems, L.P. TPE composition that exhibits excellent adhesion to textile fibers
US6583076B1 (en) 1999-01-08 2003-06-24 Kimberly-Clark Worldwide, Inc. Nonwoven fabrics prepared using visbroken single-site catalyzed polypropylene
US6190769B1 (en) * 1999-02-19 2001-02-20 E. I. Du Pont De Nemours And Company Abrasive filaments of plasticized polyamides
DE60020688D1 (en) 1999-04-01 2005-07-14 Foto Wear Inc POLYMERIC COMPOSITION AND PRINT OR COPIER UNITS TRANSFER SHEET THAT CONTAINS THIS COMPOSITION
FR2792321B1 (en) 1999-04-19 2003-12-12 Atochem Elf Sa PROCESS FOR PRODUCING POLYPROPYLENE RESIN WITH CONTROLLED RHEOLOGY
ES2316912T3 (en) 1999-05-13 2009-04-16 Exxonmobil Chemical Patents Inc. ELASTIC FIBERS AND ARTICLES PRODUCED WITH THE SAME, INCLUDING CRYSTALLINE AND CRYSTALLIZABLE PROPYLENE POLYMERS.
US6750284B1 (en) 1999-05-13 2004-06-15 Exxonmobil Chemical Patents Inc. Thermoplastic filled membranes of propylene copolymers
US6500563B1 (en) 1999-05-13 2002-12-31 Exxonmobil Chemical Patents Inc. Elastic films including crystalline polymer and crystallizable polymers of propylene
JP3821605B2 (en) * 1999-05-21 2006-09-13 化薬アクゾ株式会社 Organic peroxide composition
US6423800B1 (en) 1999-05-26 2002-07-23 Fina Technology, Inc. Pelletized polyolefin having ultra-high melt flow and its articles of manufacture
CA2310925C (en) 1999-06-11 2005-10-11 Kuraray Co., Ltd. Multilayered structure
TW462886B (en) 1999-06-21 2001-11-11 Kao Corp Absorbent article
BE1012775A3 (en) * 1999-07-06 2001-03-06 Solvay Flexible polymer compositions propylene.
US6143818A (en) 1999-08-04 2000-11-07 Ato Findley, Inc. Hot melt adhesive based on ethylene-propylene rubber (EPR) and semicrystalline olefinic polymers
US6194498B1 (en) * 1999-08-10 2001-02-27 Ppg Industries Ohio, Inc. Non-fogging plasticizer and its use in resinous compositions
JP2001049056A (en) 1999-08-12 2001-02-20 Mitsui Chemicals Inc Olefinic thermoplastic rubber composition
JP2001064523A (en) 1999-08-27 2001-03-13 Sumitomo Chem Co Ltd Plasticizer for theroplastic resin, theroplastic resin composition containing it and method for plasticizing thermoplastic resin using it
EP1234003B2 (en) * 1999-09-21 2011-08-10 Teknor Apex Company A thermoplastic vulcanisate, the thermoplastic vulcanisate containing a foaming agent and foam of the thermoplastic vulcanisate
US6191078B1 (en) * 1999-09-21 2001-02-20 Exxonmobil Research And Engineering Company Part-synthetic, aviation piston engine lubricant
JP2001106628A (en) 1999-10-06 2001-04-17 Kuraray Plast Co Ltd Substrate film for pasting and pasting material
US6271323B1 (en) 1999-10-28 2001-08-07 Univation Technologies, Llc Mixed catalyst compounds, catalyst systems and their use in a polymerization process
JP2001131509A (en) 1999-11-09 2001-05-15 Yazaki Corp Non-halogenated resin composition for adhesive tape, film which is formed from the same and is used for adhesive tape, and adhesive tape
US6861143B2 (en) 1999-11-17 2005-03-01 Pirelli Cavi E Sistemi S.P.A. Cable with recyclable covering
EP1104783A1 (en) 1999-11-29 2001-06-06 Dunlop Tech GmbH Floor- and wall covering
US20010007896A1 (en) 1999-12-10 2001-07-12 Agarwal Pawan Kumar Propylene diene copolymers
EP2045304B1 (en) 1999-12-22 2017-10-11 ExxonMobil Chemical Patents Inc. Polypropylene-based adhesive compositions
US6231970B1 (en) 2000-01-11 2001-05-15 E. Khashoggi Industries, Llc Thermoplastic starch compositions incorporating a particulate filler component
EP1116747A1 (en) 2000-01-14 2001-07-18 Sumitomo Rubber Industries, Ltd. Low-modulus polymer composition and sealant using the same
BR0105177A (en) 2000-01-18 2002-01-15 Basell Technology Co Bv Process for producing substantially amorphous propylene homopolymers or copolymers
US6329468B1 (en) 2000-01-21 2001-12-11 Bostik Findley, Inc. Hot melt adhesive based on semicrystalline flexible polyolefins
US6492465B1 (en) 2000-02-08 2002-12-10 Exxonmobil Chemical Patents, Inc. Propylene impact copolymers
KR100695546B1 (en) * 2000-02-09 2007-03-15 미쓰이 가가쿠 가부시키가이샤 Lower foggy thermoplastic elastomer composition, and process for producing the composition and its use
JP2001226865A (en) 2000-02-10 2001-08-21 Idemitsu Unitech Co Ltd Nonwoven fabric, method for producing the same and sanitary material
JP2001233992A (en) 2000-02-21 2001-08-28 Ishizuka Glass Co Ltd Molding auxiliary, its manufcturing method, and polymeric composite compounded with holding auxiliary
US6372379B1 (en) 2000-02-25 2002-04-16 Abbas M. Samii Microporous membrane battery separator for silver zinc batteries
JP3515469B2 (en) * 2000-02-29 2004-04-05 リケンテクノス株式会社 Flame-retardant resin composition and molded part using the same
DE10010001A1 (en) 2000-03-02 2001-09-06 Celanese Ventures Gmbh Membranes useful in fuel cells comprise a blend of sulfonated aryl polymer, aminated or nitrated polyether(ether)sulfone and plasticizer
JP3394740B2 (en) 2000-03-16 2003-04-07 アイセロ化学株式会社 Packaging film
JP2001279031A (en) 2000-03-30 2001-10-10 Taiko Kk Polyolefin resin composition
US20020049276A1 (en) 2000-04-05 2002-04-25 Zwick Paul D. Thermoplastic elastomer gel compositions and method of making same
FR2807384B1 (en) * 2000-04-07 2002-06-21 Look Cycle Int AUTOMATIC FIXING DEVICE AND CYCLIST PEDAL PROVIDED WITH SUCH A DEVICE
US6720376B2 (en) * 2000-04-07 2004-04-13 Mitsui Chemicals, Inc. Thermoplastic elastomer composition with high resistance to thermal deterioration
US6342209B1 (en) * 2000-05-04 2002-01-29 Revlon Consumer Products Corporation Cosmetic compositions containing film forming polymers plasticized with esters and malic acid
US6372847B1 (en) 2000-05-10 2002-04-16 Exxon Mobil Chemical Patents, Inc. Polyolefin compositions having improved low temperature toughness
KR100366569B1 (en) 2000-05-26 2003-01-09 주식회사 엘지씨아이 A composition of thermoplastic resin
JP3710993B2 (en) 2000-05-31 2005-10-26 株式会社大林組 Foam-type fireproof composition having water resistance
US6476135B1 (en) 2000-06-07 2002-11-05 Basell Poliolefine Italia S.P.A. Polyolefin composition containing low viscosity propylene homopolymer, fiber and extensible non-woven fabric prepared therefrom
US6932592B2 (en) 2000-06-22 2005-08-23 Exxonmobil Chemical Patents Inc. Metallocene-produced very low density polyethylenes
JP2002038114A (en) 2000-07-26 2002-02-06 Aicello Chemical Co Ltd Tackifying master batch and adhesive film using the same
EP1179563B1 (en) 2000-08-11 2004-05-19 Japan Polychem Corporation Resin composition for heat-shrinkable polypropylene shrink label and film comprising same
US6858767B1 (en) 2000-08-11 2005-02-22 Uniroyal Chemical Company, Inc. Process for producing liquid polyalphaolefin polymer, metallocene catalyst therefor, the resulting polymer and lubricant containing same
GB0020080D0 (en) 2000-08-15 2000-10-04 Borealis Tech Oy Injection moulding
EP1180534B1 (en) 2000-08-18 2006-01-11 Riken Technos Corporation Thermoplastic resin composition and laminates thereof
NL1016055C2 (en) 2000-08-30 2002-03-01 Dsm Nv Thermoplastic elastomer with improved properties.
CN1255410C (en) * 2000-09-01 2006-05-10 美利肯公司 Fluorinated and alkylated alditol derivatives and polyolefin articles containing same
US6855422B2 (en) * 2000-09-21 2005-02-15 Monte C. Magill Multi-component fibers having enhanced reversible thermal properties and methods of manufacturing thereof
EP1201406B1 (en) 2000-09-29 2002-10-30 Duo-Plast AG A multilayer strech film having cling properties, a method of preparation thereof and its use for strech wrapping operations
US6399707B1 (en) * 2000-09-29 2002-06-04 Exxonmobil Chemical Patents Inc. Impact copolymer and plastomer blend
FI110157B (en) * 2000-10-12 2002-12-13 Duraban Oy Antimicrobial polyalphaolefin composition and its use, process for the preparation of styrene-butadiene block copolymers containing thermoplastic elastomers and their use
US20060167184A1 (en) * 2000-10-18 2006-07-27 Waddell Walter H Innerliners for use in tires
US7714043B2 (en) 2000-10-18 2010-05-11 Exxonmobil Chemical Patents Inc. Tire innerliners having improved cold temperature properties
FR2815561A1 (en) 2000-10-25 2002-04-26 Yves Adelhanoff Recovery of polyolefin wastes, especially polyethylene and polypropylene for recycling, involves preparing waste for agglomeration and the addition of plasticizer or elastomer
US6509128B1 (en) * 2000-10-25 2003-01-21 3M Innovative Properties Company Imagewise printing of adhesives and limited coalescence polymerization method
WO2002036651A1 (en) 2000-10-30 2002-05-10 Exxonmobil Chemical Patents Inc. Graft-modified polymers based on novel propylene ethylene copolymers
KR100387649B1 (en) 2000-11-01 2003-06-27 현대자동차주식회사 Composition of polypropylene resin
US7744950B2 (en) * 2000-12-06 2010-06-29 Prysmian Cavi E Sistemi Energia S.R.L. Process for producing a cable with a recyclable coating comprising a thermoplastic polymer and a dielectric liquid
JP2002283877A (en) * 2001-03-28 2002-10-03 Mitsubishi Chemicals Corp Air bag storing cover
US6657009B2 (en) 2000-12-29 2003-12-02 Kimberly-Clark Worldwide, Inc. Hot-melt adhesive having improved bonding strength
US6451915B1 (en) * 2000-12-29 2002-09-17 Advanced Elastomer Systems, L.P. Thermoplastic elastomers having improved processing and physical property balance
US6388013B1 (en) 2001-01-04 2002-05-14 Equistar Chemicals, Lp Polyolefin fiber compositions
DE10104236A1 (en) 2001-01-31 2002-08-01 Bayer Ag Rubber compounds containing terpolymers
CN1257802C (en) 2001-01-31 2006-05-31 株式会社普利司通 Elastic members for ink jet rocording apparatus, ink tank and ink-jet recording apparatus
US20020156144A1 (en) 2001-02-09 2002-10-24 Williams Kevin Alan UV-curable, non-chlorinated adhesion promoters
EP1409584B1 (en) 2001-02-13 2010-01-20 GLS Corporation Removable seal of essentially gas-impermeable thermoplastic elastomer
US6531214B2 (en) * 2001-02-14 2003-03-11 3M Innovative Properties Company Replacement for plasticized polyvinyl chloride
US6656385B2 (en) 2001-02-21 2003-12-02 The Procter & Gamble Company Functionalized cubic liquid crystalline phase materials and methods for their preparation and use
US20020155267A1 (en) 2001-02-22 2002-10-24 Bader Michael John Multi-layer hermetically sealable film
CA2338900A1 (en) 2001-02-28 2002-08-28 Bayer Inc. Articles for dynamic load applications
US6632385B2 (en) 2001-03-23 2003-10-14 First Quality Nonwovens, Inc. Condrapable hydrophobic nonwoven web and method of making same
JP3881271B2 (en) * 2001-03-29 2007-02-14 三井化学株式会社 Thermoplastic elastomer composition and use thereof
US6632850B2 (en) * 2001-04-04 2003-10-14 3M Innovative Properties Company Microporous materials and methods of making the same
US20030022977A1 (en) * 2001-04-06 2003-01-30 Hall James E. Soft gel compatibilized polymer compound having low hysteresis
EP1377616A1 (en) 2001-04-12 2004-01-07 ExxonMobil Chemical Patents Inc. Propylene ethylene copolymers
US6403692B1 (en) * 2001-04-19 2002-06-11 Dow Global Technologies Inc. Filled thermoplastic composition
US20020168518A1 (en) 2001-05-10 2002-11-14 The Procter & Gamble Company Fibers comprising starch and polymers
US6653360B2 (en) 2001-05-23 2003-11-25 Chakra V. Gupta Flexible foamed polyethylene
AU2002257288A1 (en) * 2001-06-08 2002-12-23 Texas Petrochemicals Lp Improved cling film with enhanced polyisobutylene tackifier
WO2003008496A1 (en) 2001-07-17 2003-01-30 Basell Polyolefine Gmbh Multistep process for the (co)polymerization of olefins
US6713529B2 (en) * 2001-08-10 2004-03-30 Illinois Tool Works, Inc. Phase-change ink composition
US6583207B2 (en) 2001-08-30 2003-06-24 Velsicol Chemical Corporation Liquid benzoate ester compositions and aqueous polymer compositions containing same as plasticizers
US6906160B2 (en) 2001-11-06 2005-06-14 Dow Global Technologies Inc. Isotactic propylene copolymer fibers, their preparation and use
US6960635B2 (en) 2001-11-06 2005-11-01 Dow Global Technologies Inc. Isotactic propylene copolymers, their preparation and use
WO2003040201A1 (en) 2001-11-06 2003-05-15 Dow Global Technologies Inc. Isotactic propylene copolymers, their preparation and use
WO2003040204A1 (en) 2001-11-09 2003-05-15 Japan Polypropylene Corporation Propylene block copolymer
JP3827561B2 (en) * 2001-11-22 2006-09-27 三井化学株式会社 Olefinic thermoplastic elastomer and molded article thereof
US6900147B2 (en) 2001-11-28 2005-05-31 Kimberly-Clark Worldwide, Inc. Nonwoven webs having improved necking uniformity
WO2003048252A1 (en) * 2001-12-05 2003-06-12 Dsm Ip Assets B.V. Thermoplastic elastomer with improved properties
US6849672B2 (en) 2002-01-15 2005-02-01 H.B. Fuller Licensing & Financing Inc. Superabsorbent thermoplastic composition and article including same
EP1331258A1 (en) 2002-01-23 2003-07-30 KRATON Polymers Research B.V. Pressure sensitive adhesive compositions
US20030144415A1 (en) 2002-01-29 2003-07-31 Dsm N.V. Process for the preparation of a thermoplastic elastomer comprising a partially vulcanized rubber concentrate
US20030181584A1 (en) 2002-02-07 2003-09-25 Kraton Polymers U.S. Llc Elastomeric articles prepared from controlled distribution block copolymers
ATE315612T1 (en) 2002-02-11 2006-02-15 Dsm Ip Assets Bv THERMOPLASTIC POLYMER COMPOSITION
AU2003223188A1 (en) 2002-03-22 2003-10-13 Exxonmobil Chemical Patents Inc. Adhesives
US6787593B2 (en) * 2002-03-27 2004-09-07 Lear Corporation Sound-deadening composites of metallocene copolymers for use in vehicle applications
EP1357150A1 (en) 2002-04-24 2003-10-29 Materials Engineering Research Laboratory Limited Rubber compounds cured at low temperatures
US6706828B2 (en) * 2002-06-04 2004-03-16 Crompton Corporation Process for the oligomerization of α-olefins having low unsaturation
US6753373B2 (en) * 2002-06-20 2004-06-22 Kris W. Winowiecki Polyolefin compositions and method of use thereof in molded products
JP2004035623A (en) 2002-06-28 2004-02-05 Tonen Chem Corp Modified polypropylene and method for producing the same
WO2004009699A1 (en) 2002-07-19 2004-01-29 Shell Internationale Research Maatschappij B.V. Composition comprising epdm and a paraffinic oil
JP2005534802A (en) 2002-07-31 2005-11-17 エクソンモービル・ケミカル・パテンツ・インク Silane crosslinkable polyethylene
GB0313018D0 (en) * 2002-08-10 2003-07-09 Emtelle Uk Ltd Signal transmitting cable
US7531594B2 (en) 2002-08-12 2009-05-12 Exxonmobil Chemical Patents Inc. Articles from plasticized polyolefin compositions
CA2492839C (en) * 2002-08-12 2011-02-01 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US7271209B2 (en) 2002-08-12 2007-09-18 Exxonmobil Chemical Patents Inc. Fibers and nonwovens from plasticized polyolefin compositions
US7998579B2 (en) * 2002-08-12 2011-08-16 Exxonmobil Chemical Patents Inc. Polypropylene based fibers and nonwovens
US7652092B2 (en) 2002-08-12 2010-01-26 Exxonmobil Chemical Patents Inc. Articles from plasticized thermoplastic polyolefin compositions
US7622523B2 (en) * 2002-08-12 2009-11-24 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US7629416B2 (en) * 2002-08-12 2009-12-08 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US7795366B2 (en) * 2002-08-12 2010-09-14 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions
US7652094B2 (en) * 2002-08-12 2010-01-26 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US7662885B2 (en) 2002-08-12 2010-02-16 Exxonmobil Chemical Patents Inc. Method to make an article comprising polymer concentrate
US8003725B2 (en) 2002-08-12 2011-08-23 Exxonmobil Chemical Patents Inc. Plasticized hetero-phase polyolefin blends
US6844381B2 (en) * 2002-08-15 2005-01-18 Fina Technology, Inc. Modification of syndiotactic polypropylene with mineral oil
US6855777B2 (en) 2002-08-22 2005-02-15 Sunoco, Inc. (R&M) Very low melt viscosity resin
US6992146B2 (en) 2002-08-22 2006-01-31 Sunoco Inc. (R&M) Very low melt viscosity resin
US6905760B1 (en) * 2002-08-29 2005-06-14 Asahi Kasei Life And Living Corporation Polypropylene-based wrap film
FR2844283B1 (en) 2002-09-11 2006-10-27 Soprema POLYRETHANE MODIFIED BITUMIN BINDER MIXTURE MEMBRANE AND PROCESS FOR PRODUCING THE SAME
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
EP1558655B1 (en) 2002-10-15 2012-08-29 ExxonMobil Chemical Patents Inc. Multiple catalyst system for olefin polymerization and polymers produced therefrom
US7700707B2 (en) 2002-10-15 2010-04-20 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
US7541402B2 (en) 2002-10-15 2009-06-02 Exxonmobil Chemical Patents Inc. Blend functionalized polyolefin adhesive
MXPA05004374A (en) 2002-10-24 2005-10-18 Advanced Design Concept Gmbh Elastomeric multicomponent fibers, nonwoven webs and nonwoven fabrics.
WO2004048464A1 (en) 2002-11-27 2004-06-10 Mitsubishi Chemical Corporation Release agent, layered pressure-sensitive adhesive product, and layered pressure-sensitive adhesive tape
US7312167B2 (en) 2002-12-23 2007-12-25 Kimberly-Clark Worldwide, Inc. Breathable multilayer films for use in absorbent articles
US7010641B2 (en) 2003-01-31 2006-03-07 Agilent Technologies, Inc. Integrated circuit routing resource optimization algorithm for random port ordering
JP4345327B2 (en) 2003-03-12 2009-10-14 富士ゼロックス株式会社 Biodegradable polymer, method for producing the same, and molded article
US6984696B2 (en) 2003-03-28 2006-01-10 Exxonmobil Chemical Patents Inc. Elastic blends of semicrystalline propylene polymers and high glass transition temperature materials
US7037989B2 (en) 2003-05-27 2006-05-02 Exxonmobil Chemical Patents Inc. Copolymers of ethylene and/or α-olefins and vicinally disubstituted olefins
US20040241309A1 (en) * 2003-05-30 2004-12-02 Renewable Lubricants. Food-grade-lubricant
US6946522B2 (en) 2003-06-30 2005-09-20 Advanced Elastomer Systems L.P. Thermoplastic elastomers with improved coring properties
US7459635B2 (en) 2003-07-25 2008-12-02 Prysmian Cavi E Sistemi Energia S.R.L. Continuous process for manufacturing electrical cables
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
JP2007508426A (en) 2003-10-10 2007-04-05 エクソンモービル・ケミカル・パテンツ・インク Compositions of polypropylene and polyamide
EP1687346B1 (en) 2003-11-14 2012-06-06 ExxonMobil Chemical Patents Inc. Propylene-based elastomers and uses thereof
US20050106978A1 (en) * 2003-11-18 2005-05-19 Cheng Chia Y. Elastic nonwoven fabrics made from blends of polyolefins and processes for making the same
US20050130544A1 (en) 2003-11-18 2005-06-16 Cheng Chia Y. Elastic nonwoven fabrics made from blends of polyolefins and processes for making the same
US20050170117A1 (en) * 2004-01-31 2005-08-04 Cleveland Rafael L. Multi-layered hose
US7645829B2 (en) 2004-04-15 2010-01-12 Exxonmobil Chemical Patents Inc. Plasticized functionalized propylene copolymer adhesive composition
US7589145B2 (en) 2004-04-15 2009-09-15 Exxonmobil Chemical Patents Inc. Syndiotactic rich polyolefins
US7226977B2 (en) 2004-04-19 2007-06-05 Sunoco, Inc. ( R&M) High melt flow rate thermoplastic polyolefins produced in-reactor
EP1745100B1 (en) 2004-05-05 2009-12-02 Dow Global Technologies Inc. Scratch resistant propylene polymer composition
US7294675B2 (en) 2004-06-09 2007-11-13 Advanced Elastomer Systems, L.P. Soft thermoplastic vulcanizate compositions
EP1607440A1 (en) 2004-06-18 2005-12-21 Borealis Technology OY Modified polypropylene composition
CN101432356B (en) 2004-08-13 2011-09-28 埃克森美孚化学专利公司 Polymeric compositions, uses and methods of production
CN101044203B (en) * 2004-10-08 2011-03-23 埃克森美孚化学专利公司 Combinations of tackifier and polyalphaolefin oil
US7745526B2 (en) 2004-11-05 2010-06-29 Exxonmobil Chemical Patents Inc. Transparent polyolefin compositions
US7829623B2 (en) * 2004-11-05 2010-11-09 Exxonmobil Chemical Patents Inc. Thermoplastic vulcanizates having improved fabricability
ATE467658T1 (en) 2004-12-17 2010-05-15 Exxonmobil Chem Patents Inc HOMOGENEOUS POLYMER BLEND AND ARTICLES THEREOF
WO2006065649A1 (en) 2004-12-17 2006-06-22 Exxonmobil Chemical Patents Inc. Heterogeneous polymer blends and molded articles therefrom
WO2006065663A1 (en) 2004-12-17 2006-06-22 Exxonmobil Chemical Patents Inc. Polymer blends and nonwoven articles therefrom
US8389615B2 (en) * 2004-12-17 2013-03-05 Exxonmobil Chemical Patents Inc. Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin
DE602005015359D1 (en) 2004-12-17 2009-08-20 Exxonmobil Chem Patents Inc FOILS OF POLYMER BLENDS
EP1700895A1 (en) 2005-03-11 2006-09-13 National Starch and Chemical Investment Holding Corporation Peelable hot melt adhesive
GB0511320D0 (en) 2005-06-03 2005-07-13 Exxonmobil Chem Patents Inc Elastomeric structures
GB0511319D0 (en) 2005-06-03 2005-07-13 Exxonmobil Chem Patents Inc Polymeric compositions
US7951872B2 (en) 2005-06-22 2011-05-31 Exxonmobil Chemical Patents Inc. Heterogeneous polymer blend with continuous elastomeric phase and process of making the same
DE102005032547B4 (en) 2005-07-12 2010-01-07 Texas Instruments Deutschland Gmbh Wafer clamp assembly for receiving a wafer during a deposition process
US8513347B2 (en) * 2005-07-15 2013-08-20 Exxonmobil Chemical Patents Inc. Elastomeric compositions
WO2007084219A1 (en) 2006-01-17 2007-07-26 Exxonmobil Chemical Patents Inc. Process for making dynamically-loaded articles comprising propylene-based elastomers, composition for use in such processes, and article made using such processes
US7413784B2 (en) 2006-06-19 2008-08-19 Advanced Elastomer Systems, L.P. Thermoplastic vulcanizates for potable water applications
US8212098B2 (en) 2007-01-18 2012-07-03 Exxonmobil Research & Engineering Company HF alkylation process with internal acid regeneration
US7615589B2 (en) 2007-02-02 2009-11-10 Exxonmobil Chemical Patents Inc. Properties of peroxide-cured elastomer compositions
US20080234157A1 (en) 2007-03-20 2008-09-25 Yoon Beth A Alkylaromatic lubricant fluids
US7639915B2 (en) 2007-06-28 2009-12-29 Draka Comteq B.V. Optical fiber cable having a deformable coupling element
US20090043049A1 (en) 2007-08-07 2009-02-12 Chapman Bryan R Plasticized Polyolefin Compositions
US8013054B2 (en) 2008-08-08 2011-09-06 Exxonmobil Chemical Patents Inc. Elastomeric compositions having improved properties

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3318835A (en) 1961-11-15 1967-05-09 Eastman Kodak Co Compositions containing polypropylene and an ester plasticizer
US3415925A (en) 1967-08-01 1968-12-10 Grace W R & Co Process for preparing permeable polyethylene film
US4073782A (en) 1975-01-31 1978-02-14 Ube Industries, Ltd. Wrapping film
US4409345A (en) 1981-01-06 1983-10-11 Chisso Corporation Polyolefin resin composition
EP0448259A2 (en) 1990-03-09 1991-09-25 Union Carbide Chemicals And Plastics Company, Inc. Process for the extrusion of low density polyethylene
EP1028145A1 (en) 1999-02-10 2000-08-16 Sumitomo Rubber Industries, Ltd. Low modulus of elasticity-rubber composition
WO2001018109A1 (en) 1999-09-03 2001-03-15 Exxon Chemical Patents Inc. Plasticized polypropylene thermoplastics
WO2002031044A1 (en) 2000-10-12 2002-04-18 Duraban Oy Polyalphaolefin plastisizers for elastomers

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"CRC HANDBOOK OF CHEMISTRY AND PHYSICS", 2001, CRC PRESS
"Heterogeneous Nucleation Studies on Polypropylene", J. POLY. SCI.: POLY. LETTERS, vol. 21, 1983, pages 347 - 351
"PLASTICS ADDITIVES", 1998, CHAPMAN & HALL, pages: 499 - 504
CHEMICAL ADDITIVES FOR PLASTICS INDUSTRY, pages 107 - 116
H.N. BECK: "Heterogeneous Nucleating Agents for Polypropylene Crystallization", J. APPLIED POLY. SCI., vol. 11, no. 1, 1967, pages 673 - 685, XP002321230, DOI: doi:10.1002/app.1967.070110505
RADIAN CORP., NOYES DATA CORPORATION, 1987

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7662885B2 (en) 2002-08-12 2010-02-16 Exxonmobil Chemical Patents Inc. Method to make an article comprising polymer concentrate
US8476360B2 (en) 2002-08-12 2013-07-02 Exxonmobil Chemical Patents Inc. Calendered films of plasticized blends of plastomer and impact copolymer
US7795366B2 (en) 2002-08-12 2010-09-14 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions
US7759415B2 (en) 2002-08-12 2010-07-20 Exxonmobil Chemical Patents Inc. Method to make an article comprising polymer concentrate
JP2008539340A (en) * 2005-04-29 2008-11-13 エクソンモービル・ケミカル・パテンツ・インク Polypropylene fibers and nonwovens
WO2007011541A1 (en) 2005-07-15 2007-01-25 Exxonmobil Chemical Patents Inc. Elastomeric compositions
WO2007120147A1 (en) * 2006-04-19 2007-10-25 Exxonmobil Chemical Patents Inc. Articles from plasticized thermoplastic polylefin compositions
US7413784B2 (en) 2006-06-19 2008-08-19 Advanced Elastomer Systems, L.P. Thermoplastic vulcanizates for potable water applications
US10151055B2 (en) 2011-05-20 2018-12-11 The Procter & Gamble Company Fibers of polymer-wax compositions
US11339514B2 (en) 2011-05-20 2022-05-24 The Procter & Gamble Company Fibers of polymer-wax compositions
US9328440B2 (en) 2011-05-20 2016-05-03 The Procter & Gamble Company Fibers of polymer-wax compositions
US9926653B2 (en) 2011-05-20 2018-03-27 The Procter & Gamble Company Fibers of polymer-wax compositions
US9972416B2 (en) 2012-09-25 2018-05-15 Dow Global Technologies Llc Modified ethylene-based polymer compositions and methods of their production
US10611886B2 (en) 2013-12-23 2020-04-07 Arlanxeo Singapore Pte. Ltd. Anti-agglomerants for the rubber industry
US10584195B2 (en) 2013-12-23 2020-03-10 Arlanxeo Singapore Pte. Ltd. Ultra pure rubber
US10703865B2 (en) 2013-12-23 2020-07-07 Arlanxeo Singapore Pte. Ltd. Highly pure halogenated rubbers
US10647842B2 (en) 2013-12-23 2020-05-12 Arlanxeo Singapore Pte. Ltd. Anti-agglomerants for elastomeric ethylene/A-olefin copolymers
EP3087139A4 (en) * 2013-12-23 2017-12-06 Arlanxeo Singapore Pte. Ltd. Ultra pure rubber
US10385200B2 (en) 2014-06-30 2019-08-20 Arlanxeo Singapore Pte. Ltd. Anti-agglomerants for the rubber industry
CN104098844A (en) * 2014-08-04 2014-10-15 山东瀚氏汽车零部件有限公司 Yellowing-resistant PP (Polypropylene)/HDPE (High Density Polyethylene) plastic for automotive interior part and preparation method
US11110013B2 (en) 2014-09-10 2021-09-07 The Procter & Gamble Company Nonwoven webs with hydrophobic and hydrophilic layers
US11839531B2 (en) 2014-09-10 2023-12-12 The Procter And Gamble Company Nonwoven webs with hydrophobic and hydrophilic layers
US11129919B2 (en) 2016-03-09 2021-09-28 The Procter & Gamble Company Absorbent article with activatable material
WO2018111849A1 (en) 2016-12-13 2018-06-21 Afton Chemical Corporation Microstructure-controlled copolymers of ethylene and c3-c10 alpha-olefins
US10584297B2 (en) 2016-12-13 2020-03-10 Afton Chemical Corporation Polyolefin-derived dispersants
WO2019117993A1 (en) 2016-12-13 2019-06-20 Afton Chemical Corporation Microstructure-controlled copolymers of ethylene and c3-c10 alpha-olefins
US10221267B2 (en) 2016-12-13 2019-03-05 Afton Chemical Corporation Microstructure-controlled copolymers of ethylene and C3-C10 alpha-olefins
EP3336113A1 (en) 2016-12-13 2018-06-20 Afton Chemical Corporation Microstructure-controlled copolymers of ethylene and c3-c10 alpha-olefins
US11091613B2 (en) 2016-12-13 2021-08-17 Afton Chemical Corporation Microstructure-controlled copolymers of ethylene and C3-C10 alpha-olefins
US11090407B2 (en) 2017-03-09 2021-08-17 The Procter & Gamble Company Thermoplastic polymeric materials with heat activatable compositions
WO2022084081A1 (en) * 2020-10-22 2022-04-28 Basell Poliolefine Italia S.R.L. Polymer composition for injection molding

Also Published As

Publication number Publication date
JP2005535748A (en) 2005-11-24
AU2009202306B2 (en) 2011-10-13
US20040106723A1 (en) 2004-06-03
EP1530611A2 (en) 2005-05-18
WO2004014997A3 (en) 2004-08-12
US20040054040A1 (en) 2004-03-18
CA2675730A1 (en) 2004-02-19
AU2009202306A1 (en) 2009-07-02
US20070100053A1 (en) 2007-05-03
AU2003258173C1 (en) 2009-11-26
JP2006508236A (en) 2006-03-09
AU2003258173A1 (en) 2004-02-25
SG145599A1 (en) 2008-09-29
BR0313398A (en) 2005-06-28
CA2675730C (en) 2012-04-10
EP1539870B1 (en) 2016-06-22
US20100035498A1 (en) 2010-02-11
WO2004014998A3 (en) 2004-09-16
CA2492839A1 (en) 2004-02-19
US7619027B2 (en) 2009-11-17
CA2495019A1 (en) 2004-02-19
CN100345896C (en) 2007-10-31
US7619026B2 (en) 2009-11-17
WO2004014998A9 (en) 2004-12-02
EP2083043B1 (en) 2017-01-18
BR0313549A (en) 2005-06-21
AU2003272213A1 (en) 2004-02-25
EP1539870A2 (en) 2005-06-15
CN1675298A (en) 2005-09-28
WO2004014998A8 (en) 2005-05-19
US8211968B2 (en) 2012-07-03
US8217112B2 (en) 2012-07-10
US7632887B2 (en) 2009-12-15
WO2004014998A2 (en) 2004-02-19
CA2495019C (en) 2011-10-04
JP4874648B2 (en) 2012-02-15
CA2492839C (en) 2011-02-01
KR20050075747A (en) 2005-07-21
US20100152346A1 (en) 2010-06-17
AU2003258173B2 (en) 2009-07-09
EP1530611B1 (en) 2013-12-04
KR101008786B1 (en) 2011-01-14
US20060189763A1 (en) 2006-08-24
EP2083043A1 (en) 2009-07-29
US7652093B2 (en) 2010-01-26

Similar Documents

Publication Publication Date Title
EP1530611B1 (en) Plasticized polyolefin compositions
US7652094B2 (en) Plasticized polyolefin compositions
US7875670B2 (en) Articles from plasticized polyolefin compositions
KR101161887B1 (en) Thermoplastic olefinic compositions
US7795366B2 (en) Modified polyethylene compositions
CA2595946C (en) Modified polyethylene compositions
KR101008821B1 (en) Plasticized polyolefin compositions

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2492839

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 193/DELNP/2005

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 1020057002168

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 20038190834

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2004527804

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2003754386

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2003754386

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020057002168

Country of ref document: KR