WO2009045459A1 - Polyvinylchloride-based polymer alloys - Google Patents

Polyvinylchloride-based polymer alloys Download PDF

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Publication number
WO2009045459A1
WO2009045459A1 PCT/US2008/011397 US2008011397W WO2009045459A1 WO 2009045459 A1 WO2009045459 A1 WO 2009045459A1 US 2008011397 W US2008011397 W US 2008011397W WO 2009045459 A1 WO2009045459 A1 WO 2009045459A1
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WIPO (PCT)
Prior art keywords
polymer composition
blended polymer
polyvinylchloride
weight percent
ethylene
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PCT/US2008/011397
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French (fr)
Inventor
Dennis M. Solar
Steve Fenske
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Seaman Corporation
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Publication of WO2009045459A1 publication Critical patent/WO2009045459A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers

Definitions

  • the present invention generally relates to polyvinylchloride-based (PVC- based) polymer alloys, processes for making same, and products made therefrom.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) a polyvinylchloride; and (ii) an olefinic terpolymer, to methods of making same, and to products formed therefrom.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) a high, or ultra-high, molecular weight polyvinylchloride having a K value of at least about 70; (ii) an ethylene/carbon monoxide/Ci to C 12 alkyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C2 to C- 12 alkenyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C 2 to d 2 alkenyl acetate- modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom.
  • PVC coated fabrics used in inflatable fabric structures exhibit poor abrasion resistance, stiffening upon extended outdoor exposure and/or exposure to hydrocarbon fuels due to plasticizer loss, and exhibit increased air permeability (reduced air retention) compared to vulcanized rubber products historically utilized to produce high end inflatable fabric structures.
  • PVC polyvinylchloride
  • the present invention generally relates to polyvinylchloride-based (PVC- based) polymer alloys, processes for making same, and products made therefrom.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) a polyvinylchloride; and (ii) an olefinic terpolymer, to methods of making same, and to products formed therefrom.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) a high, or ultra-high, molecular weight polyvinylchloride having a K value of at least about 70; (ii) an ethylene/carbon monoxide/Ci to C 12 alkyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C 2 to C 12 alkenyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C 2 to C 12 alkenyl acetate- modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom.
  • the present invention relates to a blended polymer composition
  • a blended polymer composition comprising: (i) at least one high, or ultra-high, molecular weight polyvinylchloride that is highly branched; and (ii) at least one olefinic terpolymer, where the resulting polymer composition has improved air permeability properties when compared to the air permeability properties of the at least one high, or ultrahigh, molecular weight polyvinylchloride that is highly-branched
  • the present invention relates to a blended polymer composition
  • a blended polymer composition comprising: (i) about 17 weight percent to about 93 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 60 weight percent to about 3.5 weight percent of at least one ethylene/carbon monoxide/Ci to C 12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C ⁇ to C 12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C 12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 33 weight percent to about 3.5 weight percent of at least one liquid plasticizer.
  • the present invention relates to a blended polymer composition
  • a blended polymer composition comprising: (i) about 18.5 weight percent to about 89 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 52.5 weight percent to about 5.5 weight percent of at least one ethylene/carbon monoxide/Ci to C 12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 29 weight percent to about 5.5 weight percent of at least one liquid plasticizer.
  • the present invention relates to a blended polymer composition
  • a blended polymer composition comprising: (i) about 22 weight percent to about 87 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 51 weight percent to about 6.5 weight percent of at least one ethylene/carbon monoxide/Ci to C 12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 27 weight percent to about 6.5 weight percent of at least one liquid plasticizer.
  • the present invention relates to a blended polymer composition
  • a blended polymer composition comprising: (i) about 25 weight percent to about 85 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 50 weight percent to about 10 weight percent of at least one ethylene/carbon monoxide/C-i to C 12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 1 2 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C1 2 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 25 weight percent to about 5 weight percent of at least one liquid plasticizer.
  • the present invention relates to a blended polymer composition
  • a blended polymer composition comprising: (i) about 25 weight percent to about 85 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 45 weight percent to about 10 weight percent of at least one ethylene/carbon monoxide/Ci to C 12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; (iii) about 25 weight percent to about 5 weight percent of at least one liquid plasticizer; and (iv) 0 to about 5 weight percent of at least one additive.
  • the present invention generally relates to polyvinylchloride-based (PVC- based) polymer alloys, processes for making same, and products made therefrom.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) a polyvinylchloride; and (ii) an olefinic terpolymer, to methods of making same, and to products formed therefrom.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) a high, or ultra-high, molecular weight polyvinylchloride having a K value of at least about 70; (ii) an ethylene/carbon monoxide/Ci to Ci 2 alkyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C2 to C 12 alkenyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C2 to C12 alkenyl acetate- modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom.
  • the present invention is a blended polymer composition that is formed from a blend of: (i) at least one polyvinylchloride; and (ii) at least one olefinic terpolymer, to methods of making same, and to products formed therefrom.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) one or more high, or ultra-high, molecular weight polyvinylchlorides having K values of at least about 70; (ii) an ethylene/carbon monoxide/Ci to C 12 alkyl acrylate-modified terpolymer, an ethylene/carbon monoxide/C 2 to C 12 alkenyl acrylate-modified terpolymer, an ethylene/carbon monoxide/C 2 to C 12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) one or more high, or ultra-high, molecular weight polyvinylchlorides having K values of at least about 80; (ii) at least one ethylene/carbon monoxide/Ci to Ci 2 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) about 17 weight percent to about 93 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 60 weight percent to about 3.5 weight percent of at least one ethylene/carbon monoxide/Ci to C 12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to Ci 2 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 23 weight percent to about 3.5 weight percent of at least one liquid plasticizer, to methods of making same, and to products formed therefrom.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) about 18.5 weight percent to about 89 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 52.5 weight percent to about 5.5 weight percent of at least one ethylene/carbon monoxide/Ci to Ci 2 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to Ci 2 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to Ci 2 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 29 weight percent to about 5.5 weight percent of at least one liquid plasticizer.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) about 22 weight percent to about 87 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 51 weight percent to about 6.5 weight percent of at least one ethylene/carbon monoxide/Ci to Ci 2 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to Ci 2 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 27 weight percent to about 6.5 weight percent of at least one liquid plasticizer.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) about 25 weight percent to about 85 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 50 weight percent to about 10 weight percent of at least one ethylene/carbon monoxide/Ci to C 12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to Ci 2 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 25 weight percent to about 5 weight percent of at least one liquid plasticizer.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) about 25 weight percent to about 85 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 45 weight percent to about 10 weight percent of at least one ethylene/carbon monoxide/Ci to C 12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C 2 to C 12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; (iii) about 25 weight percent to about 5 weight percent of at least one liquid plasticizer; and (iv) 0 to about 5 weight percent of at least one additive.
  • the present invention relates to polymer alloy compositions comprising a blend of: (i) one or more high, or ultra-high, molecular weight polyvinylchlorides having K values of at least about 70; (ii) an ethylene/carbon monoxide/vinyl acetate-modified terpolymer, an ethylene/carbon monoxide/vinyl acrylate-modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom.
  • any of the embodiments of the present invention can further include various optional components or polymeric additives. Suitable optional components include, but are not limited to, one or more inorganic fillers, thermal and UV stabilizers, fungicides, monomeric plasticizers, processing aids, colorants, dyes, or combinations of two or more thereof.
  • PVCs Polwinylchlorides
  • the polyvinylchloride (PVC) component of the present invention is selected from PVC resins having a molecular weight (M w ) of at least about 120,000, at least about 140,000, at least about 160,000, at least about 180,000, at least about 200,000, at least about 250,000, at least about 300,000, at least about 350,000, at least about 400,000, at least about 450,000, at least about 500,000, or even at least about 600,000.
  • the PVC resin utilized in the polymer alloy compositions of the present invention have a molecular weight (M w ) in the range of about 120,000 to about 600,000, or about 140,000 to about 500,000, or about 180,000 to about 450,000, or even about 200,000 to about 400,000.
  • the polyvinylchloride (PVC) component of the present invention is selected from PVCs having a K value of at least about 70, at least about 75, at least about 77, or even at least about 80. In another embodiment, the polyvinylchloride (PVC) component of the present invention is selected from PVCs having a K value of at least about 82, at least about 88, at least about 92, or even at least about 102.
  • suitable ultra-high molecular weight PVCs are sold by OxyChem (Occidental Petroleum Company). Suitable additional PVCs for use in the present invention are known to those of skill in the art, and as such an exhaustive list thereof is omitted for the sake of brevity.
  • the present invention is not limited to any one type of high, or even ultra-high, molecular weight PVC.
  • the PVC component of the present invention has a polydispersity of less than about 3.0, less than about 2.8, less than about 2.6, less than about 2.5, less than about 2.0, or even less than about 1.8.
  • individual numerical values or range limits can be combined to form non-disclosed ranges.
  • the high, or ultra-high, polyvinylchlorides are highly branched PVCs.
  • the primary method by which to control the molecular weight of a PVC is by temperature control. Under this method, as the temperature at which the polymerization process used to produce the PVC drops the molecular weight of the final polymerization product increases.
  • a higher linearity i.e., less branching
  • a higher degree of crystallinity i.e., due to less branching.
  • the present invention utilizes high, or ultrahigh, molecular weight polyvinylchlorides that are highly branched made via any suitable process.
  • highly branched it is meant that there are at least about 5 or more branches emanating from the polyvinylchloride backbone, at least about 10 or more branches emanating from the polyvinylchloride backbone, at least about 15 or more branches emanating from the polyvinylchloride backbone, or even at least about 25 or more branches emanating from the polyvinylchloride backbone.
  • individual numerical values or range limits can be combined to form non-disclosed ranges.
  • the number of branches formed off of the polyvinylchloride backbone is greater than or equal to at least about 1 percent of the repeating units in the polyvinylchloride backbone, greater than or equal to at least about 5 percent of the repeating units in the polyvinylchloride backbone, greater than or equal to at least about 7.5 percent of the repeating units in the polyvinylchloride backbone, greater than or equal to at least about 10 percent of the repeating units in the polyvinylchloride backbone, greater than or equal to at least about 12.5 percent of the repeating units in the polyvinylchloride backbone, or even greater than or equal to at least about 15 percent of the repeating units in the polyvinylchloride backbone.
  • individual numerical values or range limits can be combined to form non-disclosed ranges.
  • the polyvinylchloride of the present invention has an inherent viscosity of at least about 1 , at least about 1.25, at least about 1.5, at least about 1.75, at least about 2, at least about 2.25, at least about 2.5, at least about 2.75, at least about 3, or even at least about 3.5.
  • individual numerical values or range limits can be combined to form non-disclosed ranges.
  • these terpolymers can be selected from any suitable olefinic terpolymers known to those of skill in the art.
  • suitable olefinic terpolymers include, but are not limited to, ethylene/carbon monoxide/C2 to Ci 2 alkenyl acrylate-modified terpolymers, ethylene/carbon monoxide/C2 to Ci 2 alkenyl acetate-modified terpolymers, or mixtures of two or more thereof.
  • the olefinic terpolymer of the present invention is selected from ethylene/carbon monoxide/vinyl acrylate-modified terpolymers, ethylene/carbon monoxide/vinyl acetate-modified terpolymers, or mixtures of two or more thereof.
  • ethylene/carbon monoxide/C2 to C12 alkenyl acrylate- modified terpolymers examples of suitable ethylene/carbon monoxide/C2 to C12 alkenyl acrylate- modified terpolymers, ethylene/carbon monoxide/C2 to C 12 alkenyl acetate-modified terpolymers are known in the art in, for example, United States Patent No. 3,780,140, the disclosure of which is hereby incorporated by reference.
  • Other suitable olefinic terpolymers are known in the art and are suitable for use in conjunction with the present invention, and are within the scope of the present invention. A detailed discussion of all such suitable olefinic terpolymers herein is omitted for the sake of brevity.
  • any suitable plasticizer can be used herein so long as, in one embodiment, the plasticizer chosen is compatible with the other components of the polymer blend.
  • suitable liquid plasticizers include, but are not limited to, polymeric linear dicarboxylic acid-based (or derived) plasticizers, phthalate plasticizers, and suitable combinations of two or more thereof.
  • Other suitable liquid plasticizers that are compatible with PVC are known to those of skill in the art, and as such an exhaustive list thereof is omitted for the sake of brevity.
  • compositions in accordance with the various embodiments of the present invention are prepared by combining all dry ingredients except the olefinic terpolymers component (e.g., ethylene/carbon monoxide/C 2 to C12 alkenyl acrylate-modified terpolymer) in a high intensity mixer.
  • the liquid components are combined, heated to about 150 0 F and added to the dry ingredients in small increments while mixing, to allow the PVC fraction of the present invention to fully absorb the liquid fraction, resulting in a dry free flowing blend.
  • a final blend temperature of about 240 0 F is required to fully absorb all the liquid components, in particular the liquid polymeric plasticizer.
  • the resulting "dry blend” and olefinic terpolymers component (e.g., ethylene/carbon monoxide/C 2 to C1 2 alkenyl acrylate-modified terpolymers) are then melt blended using a Banbury, single or twin screw extruder with an appropriate screw design, a continuous mixer or Buss Kneader to produce the final blended compound.
  • a Banbury, single or twin screw extruder with an appropriate screw design, a continuous mixer or Buss Kneader
  • the blended melt state compound is applied to, for example, a polyester or nylon base fabric via a calendaring or extrusion coating process to produce the coated fabric product.
  • This product can then be used in various applications including, but not limited to, inflatable fabric applications.
  • a fabric product made in accordance with the present invention can be used as a coating for inflatable fabric structures and geo- membranes.
  • polymer fabric products in accordance with the present invention exhibit improvements in permeability, increased coating tensile strength (e.g., tear resistance), puncture resistance and resistance to stiffening upon intermittent exposure to certain chemicals and hydrocarbon fuels versus standard flexible PVC coated fabrics.
  • an high, or even ultra-high, molecular weight PVC resin (K value greater than about 70, or even about 80), utilized in combination with a liquid polymeric plasticizer and an olefinic terpolymer flexibilizer compound produce an inflatable structure or geo-membrane fabric that provides various improvements.
  • improvements include, but are not limited to, a substantial decrease in air permeability, lower compression set, increased tensile strength, increased puncture resistance, improved abrasion resistance and improved retention of flexibility upon extended exposure to the hostile environments and intermittent exposure to hydrocarbon fuels compared to other PVC-coated fabrics.
  • the resulting fabric also exhibits properties similar to vulcanized rubber coated products used in inflatable boat manufacturing while still being able to be hot air or RF welded to substantially reduce fabrication time, compared to and in conjunction with the use of fabrication adhesives routinely employed for fabrication of vulcanized rubber products, which are more labor intensive and a less efficient process.
  • fabrication adhesives routinely employed for fabrication of vulcanized rubber products, which are more labor intensive and a less efficient process.
  • the above improvements are even realized in connection with those embodiments of the present invention that make use of highly-branched high, or ultra-high, molecular weight PVCs.

Abstract

The present invention generally relates to polyvinylchloride-based (PVC-based) polymer alloys, processes for making same, and products made therefrom. In one embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) a polyvinylchloride; and (ii) an olefinic terpolymer, to methods of making same, and to products formed therefrom. In another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) a high, or ultra-high, molecular weight polyvinylchloride having a K value of at least about 70; (ii) an ethylene/carbon monoxide/C1 to C12 alkyl acrylate-modified terpolymer, an ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, an ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom.

Description

POLYVINYLCHLORIDE-BASED POLYMER ALLOYS
FIELD OF THE INVENTION
The present invention generally relates to polyvinylchloride-based (PVC- based) polymer alloys, processes for making same, and products made therefrom. In one embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) a polyvinylchloride; and (ii) an olefinic terpolymer, to methods of making same, and to products formed therefrom. In another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) a high, or ultra-high, molecular weight polyvinylchloride having a K value of at least about 70; (ii) an ethylene/carbon monoxide/Ci to C12 alkyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C2 to C-12 alkenyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C2 to d2 alkenyl acetate- modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom.
BACKGROUND OF THE INVENTION
Typically, polyvinylchloride (PVC) coated fabrics used in inflatable fabric structures exhibit poor abrasion resistance, stiffening upon extended outdoor exposure and/or exposure to hydrocarbon fuels due to plasticizer loss, and exhibit increased air permeability (reduced air retention) compared to vulcanized rubber products historically utilized to produce high end inflatable fabric structures.
Lower molecular weight (i.e., those having a K value of less than 70) polyvinylchloride (PVC) resin-based alloys or blends exhibit lower abrasion resistance, lower tensile strength, higher air permeability and higher compression set when alloyed with flexible polymeric modifiers. Additionally, PVC-based alloys exhibit less color shift upon extended exposure to UV light compared to other types of polymeric coatings utilized for inflatable boat fabrics. Historically, vulcanized rubber products like HYPALON®, routinely used for inflatable boats, have greater color shift upon extended exposure to UV light and require the use of adhesives for fabrication. Additionally, ultra-high molecular weight polyvinylchlorides (PVCs) have poor air permeability. Thus there is a need in the art for improved PVC-based polymer alloy compositions that exhibit improved chemical and/or physical properties relative to their use for inflatable structures.
SUMMARY OF THE INVENTION
The present invention generally relates to polyvinylchloride-based (PVC- based) polymer alloys, processes for making same, and products made therefrom. In one embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) a polyvinylchloride; and (ii) an olefinic terpolymer, to methods of making same, and to products formed therefrom. In another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) a high, or ultra-high, molecular weight polyvinylchloride having a K value of at least about 70; (ii) an ethylene/carbon monoxide/Ci to C12 alkyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C2 to C12 alkenyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C2 to C12 alkenyl acetate- modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom.
In one embodiment, the present invention relates to a blended polymer composition comprising: (i) at least one high, or ultra-high, molecular weight polyvinylchloride that is highly branched; and (ii) at least one olefinic terpolymer, where the resulting polymer composition has improved air permeability properties when compared to the air permeability properties of the at least one high, or ultrahigh, molecular weight polyvinylchloride that is highly-branched
In another embodiment, the present invention relates to a blended polymer composition comprising: (i) about 17 weight percent to about 93 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 60 weight percent to about 3.5 weight percent of at least one ethylene/carbon monoxide/Ci to C12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C∑ to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 33 weight percent to about 3.5 weight percent of at least one liquid plasticizer. In still another embodiment, the present invention relates to a blended polymer composition comprising: (i) about 18.5 weight percent to about 89 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 52.5 weight percent to about 5.5 weight percent of at least one ethylene/carbon monoxide/Ci to C12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 29 weight percent to about 5.5 weight percent of at least one liquid plasticizer.
In still yet another embodiment, the present invention relates to a blended polymer composition comprising: (i) about 22 weight percent to about 87 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 51 weight percent to about 6.5 weight percent of at least one ethylene/carbon monoxide/Ci to C12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 27 weight percent to about 6.5 weight percent of at least one liquid plasticizer.
In still yet another embodiment, the present invention relates to a blended polymer composition comprising: (i) about 25 weight percent to about 85 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 50 weight percent to about 10 weight percent of at least one ethylene/carbon monoxide/C-i to C12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 25 weight percent to about 5 weight percent of at least one liquid plasticizer.
In still yet another embodiment, the present invention relates to a blended polymer composition comprising: (i) about 25 weight percent to about 85 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 45 weight percent to about 10 weight percent of at least one ethylene/carbon monoxide/Ci to C12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; (iii) about 25 weight percent to about 5 weight percent of at least one liquid plasticizer; and (iv) 0 to about 5 weight percent of at least one additive.
DETAILED DESCRIPTION OF THE INVENTION The present invention generally relates to polyvinylchloride-based (PVC- based) polymer alloys, processes for making same, and products made therefrom. In one embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) a polyvinylchloride; and (ii) an olefinic terpolymer, to methods of making same, and to products formed therefrom. In another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) a high, or ultra-high, molecular weight polyvinylchloride having a K value of at least about 70; (ii) an ethylene/carbon monoxide/Ci to Ci2 alkyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C2 to C12 alkenyl acrylate- modified terpolymer, an ethylene/carbon monoxide/C2 to C12 alkenyl acetate- modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom.
As is noted above, in one embodiment the present invention is a blended polymer composition that is formed from a blend of: (i) at least one polyvinylchloride; and (ii) at least one olefinic terpolymer, to methods of making same, and to products formed therefrom. In another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) one or more high, or ultra-high, molecular weight polyvinylchlorides having K values of at least about 70; (ii) an ethylene/carbon monoxide/Ci to C12 alkyl acrylate-modified terpolymer, an ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, an ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom. In still another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) one or more high, or ultra-high, molecular weight polyvinylchlorides having K values of at least about 80; (ii) at least one ethylene/carbon monoxide/Ci to Ci2 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom.
In still yet another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) about 17 weight percent to about 93 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 60 weight percent to about 3.5 weight percent of at least one ethylene/carbon monoxide/Ci to C12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to Ci2 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 23 weight percent to about 3.5 weight percent of at least one liquid plasticizer, to methods of making same, and to products formed therefrom. In still yet another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) about 18.5 weight percent to about 89 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 52.5 weight percent to about 5.5 weight percent of at least one ethylene/carbon monoxide/Ci to Ci2 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to Ci2 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to Ci2 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 29 weight percent to about 5.5 weight percent of at least one liquid plasticizer. In still yet another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) about 22 weight percent to about 87 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 51 weight percent to about 6.5 weight percent of at least one ethylene/carbon monoxide/Ci to Ci2 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to Ci2 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 27 weight percent to about 6.5 weight percent of at least one liquid plasticizer.
In still yet another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) about 25 weight percent to about 85 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 50 weight percent to about 10 weight percent of at least one ethylene/carbon monoxide/Ci to C12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to Ci2 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and (iii) about 25 weight percent to about 5 weight percent of at least one liquid plasticizer.
In still yet another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) about 25 weight percent to about 85 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80; (ii) about 45 weight percent to about 10 weight percent of at least one ethylene/carbon monoxide/Ci to C12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; (iii) about 25 weight percent to about 5 weight percent of at least one liquid plasticizer; and (iv) 0 to about 5 weight percent of at least one additive. It should be noted that with regard to individual component ranges noted in all of the embodiments above, such individual component ranges from different embodiments can be combined to form alternative non-disclosed embodiments.
In another embodiment, the present invention relates to polymer alloy compositions comprising a blend of: (i) one or more high, or ultra-high, molecular weight polyvinylchlorides having K values of at least about 70; (ii) an ethylene/carbon monoxide/vinyl acetate-modified terpolymer, an ethylene/carbon monoxide/vinyl acrylate-modified terpolymer, or mixtures of two or more thereof; and (iii) at least one liquid plasticizer, to methods of making same, and to products formed therefrom. In addition to the above components disclosed in various embodiments, any of the embodiments of the present invention can further include various optional components or polymeric additives. Suitable optional components include, but are not limited to, one or more inorganic fillers, thermal and UV stabilizers, fungicides, monomeric plasticizers, processing aids, colorants, dyes, or combinations of two or more thereof.
Polwinylchlorides (PVCs):
In one embodiment, the polyvinylchloride (PVC) component of the present invention is selected from PVC resins having a molecular weight (Mw) of at least about 120,000, at least about 140,000, at least about 160,000, at least about 180,000, at least about 200,000, at least about 250,000, at least about 300,000, at least about 350,000, at least about 400,000, at least about 450,000, at least about 500,000, or even at least about 600,000. In another embodiment, the PVC resin utilized in the polymer alloy compositions of the present invention have a molecular weight (Mw) in the range of about 120,000 to about 600,000, or about 140,000 to about 500,000, or about 180,000 to about 450,000, or even about 200,000 to about 400,000. Here, as well as elsewhere in the specification and claims, individual numerical values or range limits can be combined to form non-disclosed ranges. In one embodiment, the above PVC resins are known to those skilled in the art as high, or ultra-high, molecular weight PVCs.
In another embodiment, the polyvinylchloride (PVC) component of the present invention is selected from PVCs having a K value of at least about 70, at least about 75, at least about 77, or even at least about 80. In another embodiment, the polyvinylchloride (PVC) component of the present invention is selected from PVCs having a K value of at least about 82, at least about 88, at least about 92, or even at least about 102. One example of suitable ultra-high molecular weight PVCs are sold by OxyChem (Occidental Petroleum Company). Suitable additional PVCs for use in the present invention are known to those of skill in the art, and as such an exhaustive list thereof is omitted for the sake of brevity. As such, it should be noted that the present invention is not limited to any one type of high, or even ultra-high, molecular weight PVC. In still another embodiment, the PVC component of the present invention has a polydispersity of less than about 3.0, less than about 2.8, less than about 2.6, less than about 2.5, less than about 2.0, or even less than about 1.8. Here, as well as elsewhere in the specification and claims, individual numerical values or range limits can be combined to form non-disclosed ranges.
In still yet another embodiment, the high, or ultra-high, polyvinylchlorides (PVCs) are highly branched PVCs. As is known to those of skill in the art, the primary method by which to control the molecular weight of a PVC is by temperature control. Under this method, as the temperature at which the polymerization process used to produce the PVC drops the molecular weight of the final polymerization product increases. However, there are a number of other consequences from using a low temperature process to produce high, or ultra-high, molecular weight PVCs, they include, among other things, a higher linearity (i.e., less branching), and a higher degree of crystallinity (i.e., due to less branching). In still yet another embodiment, the present invention utilizes high, or ultrahigh, molecular weight polyvinylchlorides that are highly branched made via any suitable process. By highly branched it is meant that there are at least about 5 or more branches emanating from the polyvinylchloride backbone, at least about 10 or more branches emanating from the polyvinylchloride backbone, at least about 15 or more branches emanating from the polyvinylchloride backbone, or even at least about 25 or more branches emanating from the polyvinylchloride backbone. Here, as well as elsewhere in the specification and claims, individual numerical values or range limits can be combined to form non-disclosed ranges.
In still yet another embodiment, by highly branched it is meant that the number of branches formed off of the polyvinylchloride backbone is greater than or equal to at least about 1 percent of the repeating units in the polyvinylchloride backbone, greater than or equal to at least about 5 percent of the repeating units in the polyvinylchloride backbone, greater than or equal to at least about 7.5 percent of the repeating units in the polyvinylchloride backbone, greater than or equal to at least about 10 percent of the repeating units in the polyvinylchloride backbone, greater than or equal to at least about 12.5 percent of the repeating units in the polyvinylchloride backbone, or even greater than or equal to at least about 15 percent of the repeating units in the polyvinylchloride backbone. Here, as well as elsewhere in the specification and claims, individual numerical values or range limits can be combined to form non-disclosed ranges.
In still yet another embodiment, the polyvinylchloride of the present invention has an inherent viscosity of at least about 1 , at least about 1.25, at least about 1.5, at least about 1.75, at least about 2, at least about 2.25, at least about 2.5, at least about 2.75, at least about 3, or even at least about 3.5. Here, as well as elsewhere in the specification and claims, individual numerical values or range limits can be combined to form non-disclosed ranges.
Olefinic Terpolvmer:
Regarding the olefinic terpolymers of the present invention, these terpolymers can be selected from any suitable olefinic terpolymers known to those of skill in the art. Such terpolymers include, but are not limited to, ethylene/carbon monoxide/C2 to Ci2 alkenyl acrylate-modified terpolymers, ethylene/carbon monoxide/C2 to Ci2 alkenyl acetate-modified terpolymers, or mixtures of two or more thereof. In one embodiment, the olefinic terpolymer of the present invention is selected from ethylene/carbon monoxide/vinyl acrylate-modified terpolymers, ethylene/carbon monoxide/vinyl acetate-modified terpolymers, or mixtures of two or more thereof.
Examples of suitable ethylene/carbon monoxide/C2 to C12 alkenyl acrylate- modified terpolymers, ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymers are known in the art in, for example, United States Patent No. 3,780,140, the disclosure of which is hereby incorporated by reference. Other suitable olefinic terpolymers are known in the art and are suitable for use in conjunction with the present invention, and are within the scope of the present invention. A detailed discussion of all such suitable olefinic terpolymers herein is omitted for the sake of brevity.
Liquid Plasticizer:
Regarding the liquid polymeric plasticizer component of any of the above embodiments, any suitable plasticizer can be used herein so long as, in one embodiment, the plasticizer chosen is compatible with the other components of the polymer blend. Suitable liquid plasticizers include, but are not limited to, polymeric linear dicarboxylic acid-based (or derived) plasticizers, phthalate plasticizers, and suitable combinations of two or more thereof. Other suitable liquid plasticizers that are compatible with PVC are known to those of skill in the art, and as such an exhaustive list thereof is omitted for the sake of brevity.
Production Method: In one embodiment, the compositions in accordance with the various embodiments of the present invention are prepared by combining all dry ingredients except the olefinic terpolymers component (e.g., ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer) in a high intensity mixer. The liquid components are combined, heated to about 1500F and added to the dry ingredients in small increments while mixing, to allow the PVC fraction of the present invention to fully absorb the liquid fraction, resulting in a dry free flowing blend. A final blend temperature of about 2400F is required to fully absorb all the liquid components, in particular the liquid polymeric plasticizer.
The resulting "dry blend" and olefinic terpolymers component (e.g., ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymers) are then melt blended using a Banbury, single or twin screw extruder with an appropriate screw design, a continuous mixer or Buss Kneader to produce the final blended compound.
It should be noted that the above production process is exemplary in nature and the present invention is not limited to solely the above production method. Rather, various other production methods could be used to form the blended compositions of the present invention.
In order to produce a fabric product, the blended melt state compound is applied to, for example, a polyester or nylon base fabric via a calendaring or extrusion coating process to produce the coated fabric product. This product can then be used in various applications including, but not limited to, inflatable fabric applications.
In one embodiment, a fabric product made in accordance with the present invention can be used as a coating for inflatable fabric structures and geo- membranes. Among other desirable characteristics, polymer fabric products in accordance with the present invention exhibit improvements in permeability, increased coating tensile strength (e.g., tear resistance), puncture resistance and resistance to stiffening upon intermittent exposure to certain chemicals and hydrocarbon fuels versus standard flexible PVC coated fabrics. While not wishing to be bound to any one or more specific advantages, it is believed that in one embodiment the use of an high, or even ultra-high, molecular weight PVC resin (K value greater than about 70, or even about 80), utilized in combination with a liquid polymeric plasticizer and an olefinic terpolymer flexibilizer compound produce an inflatable structure or geo-membrane fabric that provides various improvements. Such improvements include, but are not limited to, a substantial decrease in air permeability, lower compression set, increased tensile strength, increased puncture resistance, improved abrasion resistance and improved retention of flexibility upon extended exposure to the hostile environments and intermittent exposure to hydrocarbon fuels compared to other PVC-coated fabrics. The resulting fabric also exhibits properties similar to vulcanized rubber coated products used in inflatable boat manufacturing while still being able to be hot air or RF welded to substantially reduce fabrication time, compared to and in conjunction with the use of fabrication adhesives routinely employed for fabrication of vulcanized rubber products, which are more labor intensive and a less efficient process. The above improvements are even realized in connection with those embodiments of the present invention that make use of highly-branched high, or ultra-high, molecular weight PVCs.
Although the invention has been shown and described with respect to certain embodiments, it is obvious that equivalent alterations and modifications will occur to others skilled in the art upon the reading and understanding of this specification. In particular with regard to the various functions performed by the above described components, the terms (including any reference to a "means") used to describe such components are intended to correspond, unless otherwise indicated, to any component which performs the specified function of the described component (e.g., that is functionally equivalent), even though not structurally equivalent to the disclosed structure which performs the function in the herein illustrated exemplary embodiments of the invention. In addition, while a particular feature of the invention may have been disclosed with respect to only one of several embodiments, such feature may be combined with one or more other features of the other embodiments as may be desired and advantageous for any given or particular application.

Claims

CLAIMSWhat is claimed is:
1. A blended polymer composition comprising:
(i) at least one high, or ultra-high, molecular weight polyvinylchloride that is highly branched; and
(ii) at least one olefinic terpolymer, where the resulting polymer composition has improved air permeability properties when compared to the air permeability properties of the at least one high, or ultra-high, molecular weight polyvinylchloride that is highly-branched.
2. The blended polymer composition of claim 1 , wherein the polyvinylchloride portion of the blended polymer composition has a molecular weight of at least 120,000.
3. The blended polymer composition of claim 1 , wherein the polyvinylchloride portion of the blended polymer composition has a molecular weight of at least 200,000.
4. The blended polymer composition of claim 1 , wherein the polyvinylchloride portion of the blended polymer composition has a molecular weight of at least 400,000.
5. The blended polymer composition of claim 1 , wherein the polyvinylchloride portion of the blended polymer composition has a molecular weight of at least 120,000 to about 600,000.
6. The blended polymer composition of claim 1 , wherein the polyvinylchloride portion of the blended polymer composition has a K value of at least about 70.
7. The blended polymer composition of claim 1 , wherein the polyvinylchloride portion of the blended polymer composition has a K value of at least about 75.
8. The blended polymer composition of claim 1 , wherein the polyvinylchloride portion of the blended polymer composition has a K value of at least about 80.
9. The blended polymer composition of claim 1, wherein the polyvinylchloride portion of the blended polymer composition has a K value of at least about 88.
10. The blended polymer composition of claim 1 , wherein the polyvinylchloride portion of the blended polymer composition has a K value of at least about 102.
11. The blended polymer composition of claim 1 , wherein the at least one polyvinylchloride has at least about 5 or more branches emanating from the polyvinylchloride backbone.
12. The blended polymer composition of claim 1 , wherein the at least one polyvinylchloride has at least about 10 or more branches emanating from the polyvinylchloride backbone.
13. The blended polymer composition of claim 1 , wherein the at least one polyvinylchloride has at least about 15 or more branches emanating from the polyvinylchloride backbone.
14. The blended polymer composition of claim 1 , wherein the at least one polyvinylchloride has at least about 25 or more branches emanating from the polyvinylchloride backbone.
15. The blended polymer composition of claim 1 , wherein the at least one olefinic terpolymer is selected from ethylene/carbon monoxide/Ci to C12 alkyl acrylate-modified terpolymers, ethylene/carbon monoxide/C2 to C12 alkenyl acrylate- modified terpolymers, ethylene/carbon monoxide/C2 to Ci2 alkenyl acetate-modified terpolymers, or mixtures of two or more thereof.
16. The blended polymer composition of claim 1 , wherein the at least one olefinic terpolymer is selected from ethylene/carbon monoxide/vinyl acrylate-modified terpolymers, ethylene/carbon monoxide/vinyl acetate-modified terpolymers, or mixtures of two or more thereof.
17. The blended polymer composition of claim 1 , wherein the at least one olefinic terpolymer is selected from ethylene/carbon monoxide/vinyl acetate-modified terpolymers.
18. A blended polymer composition comprising:
(i) about 17 weight percent to about 93 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80;
(ii) about 60 weight percent to about 3.5 weight percent of at least one ethylene/carbon monoxide/Ci to Ci2 alkyl acrylate-modified terpolymer, at least
>, one ethylene/carbon monoxide/C2 to Ci2 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to Ci2 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and
(iii) about 23 weight percent to about 3.5 weight percent of at least one liquid plasticizer.
19. The blended polymer product of claim 18, wherein the one or more polyvinylchlorides are highly-branched polyvinylchlorides.
20. The blended polymer composition of claim 19, wherein the at least one polyvinylchloride has at least about 5 or more branches emanating from the polyvinylchloride backbone.
21. The blended polymer composition of claim 19, wherein the at least one polyvinylchloride has at least about 10 or more branches emanating from the polyvinylchloride backbone.
22. The blended polymer composition of claim 19, wherein the at least one polyvinylchloride has at least about 15 or more branches emanating from the polyvinylchloride backbone.
23. The blended polymer composition of claim 19, wherein the at least one polyvinylchloride has at least about 25 or more branches emanating from the polyvinylchloride backbone.
24. The blended polymer composition of claim 19, wherein the polyvinylchloride portion of the blended polymer composition has a molecular weight of at least 120,000.
25. The blended polymer composition of claim 19, wherein the polyvinylchloride portion of the blended polymer composition has a molecular weight of at least 200,000.
26. The blended polymer composition of claim 19, wherein the polyvinylchloride portion of the blended polymer composition has a molecular weight of at least 400,000.
27. The blended polymer composition of claim 19, wherein the polyvinylchloride portion of the blended polymer composition has a molecular weight of at least 120,000 to about 600,000.
28. The blended polymer composition of claim 18, wherein the polyvinylchloride portion of the blended polymer composition has a K value of at least about 88.
29. The blended polymer composition of claim 18, wherein the polyvinylchloride portion of the blended polymer composition has a K value of at least about 102.
30. The blended polymer composition of claim 18, wherein component (ii) is selected from ethylene/carbon monoxide/vinyl aery late-modified terpolymers, ethylene/carbon monoxide/vinyl acetate-modified terpolymers, or mixtures of two or more thereof.
31. The blended polymer composition of claim 18, wherein component (ii) is selected from ethylene/carbon monoxide/vinyl acetate-modified terpolymers.
32. The blended polymer composition of claim 18, wherein component (iii) is selected from linear dicarboxylic acid-based or derived plasticizers, phthalate plasticizers, or suitable mixtures of two or more thereof.
33. A blended polymer composition comprising:
(i) about 18.5 weight percent to about 89 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80;
(ii) about 52.5 weight percent to about 5.5 weight percent of at least one ethylene/carbon monoxide/C-i to Ci2 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and
(iii) about 29 weight percent to about 5.5 weight percent of at least one liquid plasticizer.
34. A blended polymer composition comprising:
(i) about 22 weight percent to about 87 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80;
(ii) about 51 weight percent to about 6.5 weight percent of at least one ethylene/carbon monoxide/Ci to C12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to Ci2 alkenyl aery late-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and
(iii) about 27 weight percent to about 6.5 weight percent of at least one liquid plastieizer.
35. A blended polymer composition comprising:
(i) about 25 weight percent to about 85 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80;
(ii) about 50 weight percent to about 10 weight percent of at least one ethylene/carbon monoxide/Ci to Ci2 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof; and
(iii) about 25 weight percent to about 5 weight percent of at least one liquid plastieizer.
36. A blended polymer composition comprising:
(i) about 25 weight percent to about 85 weight percent of one or more high, or ultra-high, molecular weight polyvinylchlorides, where the one or more polyvinylchlorides have K values of at least about 80;
(ii) about 45 weight percent to about 10 weight percent of at least one ethylene/carbon monoxide/Ci to C12 alkyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to C12 alkenyl acrylate-modified terpolymer, at least one ethylene/carbon monoxide/C2 to Ci2 alkenyl acetate-modified terpolymer, or mixtures of two or more thereof;
(iii) about 25 weight percent to about 5 weight percent of at least one liquid plastieizer; and
(iv) 0 to about 5 weight percent of at least one additive.
37. The blended polymer composition of claim 36, wherein component (iv) is selected from one or more inorganic fillers, one or more thermal and UV stabilizers, one or more fungicides, one or more monomeric plasticizers, one or more processing aids, one or more colorants, one or more dyes, or combinations of two or more thereof.
PCT/US2008/011397 2007-10-02 2008-10-02 Polyvinylchloride-based polymer alloys WO2009045459A1 (en)

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