WO1996033226A1 - Introduction of long chain branching into linear polyethylenes - Google Patents
Introduction of long chain branching into linear polyethylenes Download PDFInfo
- Publication number
- WO1996033226A1 WO1996033226A1 PCT/US1996/003959 US9603959W WO9633226A1 WO 1996033226 A1 WO1996033226 A1 WO 1996033226A1 US 9603959 W US9603959 W US 9603959W WO 9633226 A1 WO9633226 A1 WO 9633226A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- peroxide
- long chain
- antioxidants
- chain branching
- ethylene
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions 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
- C08L23/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/69—Chromium, molybdenum, tungsten or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
Definitions
- the invention relates to altering linear polyethylenes to provide them with long chain branching.
- the invention relates to a product produced by a process comprising contacting a linear polyethylene with a peroxide and a solid antioxidant in the presence of nitrogen to introduce long chain branching into the linear backbone of linear polyethylenes.
- the process of the invention provides a method of crosslinking resins in the presence of both primary and secondary antioxidants in a single step.
- the use of a nitrogen blanket significantly improves the efficiency of the high temperature peroxide.
- the results include high increase in viscosity, as measured by I 2 , or dynamic viscosity, at significantly low levels of peroxide.
- This process can be implemented over a wide range of compounding equipment with a variety of polyethylene resins produced by Ziegler, chromium or metallocene catalyst.
- the untreated uncrosslinked polyethylene is contacted with a peroxide and an antioxidant under a nitrogen blanket at the feed hopper at a temperature of 180-300°C.
- the amount of the antioxidant will range from 100 to 3000 ppm based on the blend of HOPE, antioxidants and peroxide.
- the LLDPE is compounded with primary and secondary antioxidant.
- the role of antioxidant stabilizers in polyethylene is to protect the polymer from oxidative degradation after compounding and thus preserve its strength properties.
- the mechanism for degradation of polyethylene via oxidation is an autocatalyzed, free radical chain process. During this process hydroperoxides are formed which decompose into radicals and accelerate the degradation. Antioxidants prevent this degradation by (1) scavenging radicals to interrupt the oxidative chain reaction resulting from hydroperoxide decomposition and (2) consuming hydroperoxides.
- the primary antioxidants contain one or more reactive hydrogen atoms which tie up free radicals, particularly peroxy radicals, forming a polymeric hydroperoxide group and relatively stable antioxidant species.
- the phenolic antioxidants are the larges selling primary antioxidant used in plastics today; they include simple phenols, bisphenols, thiobisphenols, and polyphenols. Hindered phenols such as Ciba Geigy's Irganox 1076, 1010, and Ethyl 330 fulfill the first requirement and are considered primary antioxidants. Others include:
- Wingstay L polymeric hindered phenol
- Wingstay S styrenated phenol
- Triisodecyl phosphite [Weston TDP] Triisooctyl phosphite [Weston TIOP]
- Trisnonylphenyl phosphite Didecyl phosphite Di Lauryl phosphite [ (C 12 H 29 ⁇ ) 2 PHO] Trisnonylphenyl phosphite/formaldehyde polymer [Wytox 438] Wytox 320 (alkylaryl phosphite)
- the major group of secondary antioxidants include phosphorus-based antioxidants, generally phosphites.
- the phosphite acts by converting hydroperoxides to non-chain propagating alcohols, while the phosphite itself is oxidized to phosphates. These additives are chosen when processing stability is of concern.
- Trisnonylphenyl phosphite is the most widely used phosphite.
- Typical secondary antioxidants are GE's Weston TNPP, Ciba Geigy's Ultranox 626 and Irgafos 168. An exhaustive list of primary and secondary antioxidants can be found in the reference [Chemical Additives for the Plastics Industry. Radian Corporation, Noyes Data Corporation, NJ, 1987.] Others include:
- Triisodecyl phosphite [Weston TDP] ;
- Triisooctyl phosphite [Weston TIOP] ; TriLauryl phosphite [Weston TLP] ;
- the mixture of primary antioxidant and secondary antioxidant in the LLDPE may comprise up to 3000 pp of the blend.
- the antioxidant is a solid at ambient conditions.
- the amount of peroxide will range from 10 to 1000 ppm based on the blend of HDPE, antioxidant and peroxide. However, preferably, the peroxide amount ranges from 10 to 500 based on the PE weight. Most preferably, the peroxide of the blend is 10-300 ppm.
- the types of peroxides which are used are high temperature peroxides that can undergo almost complete decomposition at normal compounding temperatures (200- 260°C) .
- the half life temperature at 0.1 hours should be greater than 130°C.
- Half life temperature at a given time is the temperature at which one half of the peroxide has decomposed.
- Suitable but non-limiting examples of such peroxide are: dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert butyl peroxy) hexane, tert-butyl cumyl peroxide, di-(2- tert-butylperoxy-isopropyl) benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, cumene hydroperoxide these contain 2 to 20 carbon atoms.
- the peroxide may be pre-blended with the PE or introduced separately as a liquid feed using any of various methods known in the art.
- Nitrogen will be introduced to the zone of polyethylene treatment in accordance with the invention at the feed throat of the compounding extruder so as to minimize exposure to oxygen. Compounding under this condition significantly enhances the crosslinking efficiency of the peroxide.
- the polyethylene employed as the reactant to be treated in accordance with the invention may be either high density polyethylene, sometimes designated by the acronym "HDPE", or linear low density polyethylene sometimes designated by the acronym "LLDPE".
- HDPE will have a specific gravity of 0.94 to 0.97 g/cc
- LLDPE linear low density polyethylene
- polyethylenes which can be used herein will have a density in the range of 0.89 to 0.97 [ASTM D-1505].
- These linear polyethylenes have a substantially linear backbone and contain substantially no long branching.
- the reactant polyethylene may be either a homopolymer of ethylene or a copolymer of ethylene and an alpha olefin of 3 to 10 carbon atoms preferably an alpha olefin of 4 to 10 carbon atoms.
- Preferred monomers include an olefin, preferably a 1-olefin, containing 3 to 10 carbon atoms, e.g., 1-propene, 1-butene, 1-pentene, 1-hexene, 4- methyl-1-pentene, l-heptene, and 1-octene.
- the preferred olefin comonomers are 1-butene, 1-hexene and 1-octene; when the polyethylene resin contains comonomers the resin will contain at least 80 preferably at least 90 mole percent ethylene units.
- the process of the invention can be implemented over a wide range of polyethylene resins produced by Ziegler, chromium or metallocene catalysts, as indicated by the Examples below.
- the polyethylene employed as the reactant to be treated usually has less shear thinning (dependence of viscosity on shear rate) than the peroxide treated product of the invention.
- the MFR which is the ratio I 21 /I 2 measured according to ASTM D-1238 conditions E for I 2 and F for I 21 ] is a reflection of shear thinning; shear thinning appears to increase with increasing numerical value of MFR.
- the polyethylene employed as the reactant to be treated has a lower dynamic viscosity than the product realized by the process of the invention.
- the dynamic viscosity is measured at 190°C using dynamic melt rheometers as outlined in ASTM D4440-84. The increase in viscosity is based on that of the untreated LLDPE.
- the polyethylene employed as the reactant in the process of the invention has a higher I 2 than the product of the process. That is, the effect of the process of the invention is to decrease the I, of polyethylene. Since I 2 is inversely related to the low shear rate viscosity [ASTM D-1238 Condition E] of the resin, the decrease in 12 reflects the increase in viscosity as a result of peroxide use.
- the significantly larger decrease in 12 with the nitrogen blanket illustrates the increased crosslinking efficiency of the peroxide in the presence of a nitrogen blanket.
- the product polyethylenes will contain long chain branching.
- the presence of long chain branching will significantly increase the low shear viscosity of the polyethylene. This increase in viscosity translates into higher melt tension during stretching of the PE melt.
- the increased melt tension allows for the PE to be used in applications which were not readily possible before, such as sheet extrusion, high stalk film blowing, foaming and blow molding.
- long chain branching in the products of the invention, produced by the process of the invention, is indicated by the sharp increase in low shear rate viscosity, decrease in I 2 and increase in MFR when compared to the base resin.
- the amount of long chain branching which can be introduced can be measured in terms of the changes in these properties.
- the process of the invention can be implemented over a wide range of compounding equipment with a variety of polyethylene resins, both homopolymers and copolymers of a density in the range of 0.89 to 0.97, produced by Ziegler, chromium or metallocene catalyst, as indicated by the Examples below. Also, while nitrogen is used to provide an inert atmosphere at the feed throat of the extruder, any other inert (non-oxidizing) gases could also be utilized.
- Example 1 Granular LLDPE (.9 MI, nominal .918 density 1-hexene copolymer) resin produced with a Ziegler catalyst is mixed in with 500 ppm Irganox 1010 and 500 ppm of Irgafos 168.
- Trigonox 101 E5 supplied by Akzo
- the peroxide was added as a 1 percent masterbatch in a granular LLDPE resin.
- the mixtures were compounded on a laboratory 3/4" Brabender twin screw extruder at 220°C and 25 RPM.
- the following table illustrates the influence of peroxide and nitrogen blanket:
- Example B The significantly larger decrease in 12 with the nitrogen blanket (sample B) illustrates the increased crosslinking efficiency of the peroxide in the presence of a nitrogen blanket. Since 12 is inversely related to the low shear rate viscosity of the resin, the decrease in 12 reflects the increase in viscosity as a result of peroxide use.
- Example 2
- Example 2 The compounding conditions were similar to those used in Example 1. The only changes were that a HDPE (.58 MI, nominal .953 density 1-hexene copolymer) polymerized with a chromium oxide catalyst was used as a feedstock instead of the LLDPE and with no secondary antioxidant. Only 500 ppm of Irganox 1010 was used. The results were as follows:
- Example 2 Similar to Example 1, the sample (E) with the nitrogen blanket gave a substantially larger decrease in 12 (or an increase in viscosity) .
- the use of nitrogen blanket increases the crosslinking efficiency of the peroxide.
- This example illustrates the importance of selecting the proper secondary antioxidant to enhance the crosslinking efficiency of the peroxides.
- the compounding conditions were similar to that employed in Example 1, except for a different LLDPE feedstock (.8 MI, .918 density 1-hexene copolymer) and all samples had a nitrogen blanket on the feed throat of the hopper.
- the primary antioxidant Irganox 1010 was present at 500 ppm and the selected secondary antioxidant (phosphite) was also at 500 ppm. % %
- Example J The mixture was compounded on the 2 inch Brampton single screw extruder at 75 lbs/hr at 465°F with a nitrogen blanket at the feed throat.
- Percentage increase in dynamic viscosity at .1 sec-1 @190°C 122.5%. The percentage increase in viscosity was measured relative to the base untreated granular LLDPE resin. Dynamic viscosity is measured by a procedure described in ASTM D4440-84.
- the dynamic viscosity is measured at 190°C using dynamic melt rheometers as outlined in ASTM D4440-84.
- the increase in viscosity is based on that of the untreated LLDPE.
- the invention process provides a highly effective means of modifying the base polyethylene even at the low levels of 100 ppm of the peroxide and in the presence of both the primary and secondary antioxidants.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP53173996A JP2002515077A (en) | 1995-04-19 | 1996-03-25 | Introduction of long-chain branching into linear polyethylene. |
AU53697/96A AU694864B2 (en) | 1995-04-19 | 1996-03-25 | Introduction of long chain branching into linear polyethylenes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US424,484 | 1989-10-20 | ||
US42448495A | 1995-04-19 | 1995-04-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996033226A1 true WO1996033226A1 (en) | 1996-10-24 |
Family
ID=23682786
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/003959 WO1996033226A1 (en) | 1995-04-19 | 1996-03-25 | Introduction of long chain branching into linear polyethylenes |
Country Status (3)
Country | Link |
---|---|
KR (1) | KR19990007827A (en) |
AU (1) | AU694864B2 (en) |
WO (1) | WO1996033226A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1229053A2 (en) * | 2001-01-31 | 2002-08-07 | Fina Technology, Inc. | Method of producing polyethylene resins for use in blow molding |
US7750104B2 (en) | 1998-11-02 | 2010-07-06 | Dow Global Technologie Inc. | Shear thinning ethylene/α-olefin interpolymers and their preparation |
US11098139B2 (en) * | 2018-02-28 | 2021-08-24 | Chevron Phillips Chemical Company Lp | Advanced quality control tools for manufacturing bimodal and multimodal polyethylene resins |
CN114085303A (en) * | 2021-12-21 | 2022-02-25 | 青岛科技大学 | Catalytic system, application thereof and preparation method of syndiotactic 1, 2-polybutadiene |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX2020001927A (en) * | 2017-08-30 | 2020-03-24 | Dow Global Technologies Llc | Peroxide containing polyolefin formulation. |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4006283A (en) * | 1974-12-23 | 1977-02-01 | General Electric Company | Preparation of di-tertiary butyl peroxide crosslink polyolefin materials |
US4015058A (en) * | 1974-11-27 | 1977-03-29 | Union Carbide Corporation | Composition with dicumyl peroxide and process for avoiding scorching of ethylene polymer composition |
US4202790A (en) * | 1978-06-26 | 1980-05-13 | Hercules Incorporated | Peroxide blends |
US4226905A (en) * | 1978-04-18 | 1980-10-07 | Du Pont Canada Inc. | Manufacture of film from partially crosslinked polyethylene |
US4578431A (en) * | 1983-08-31 | 1986-03-25 | Mobil Oil Corporation | Process for improving melt strength of ethylene polymers by treatment with organic peroxide |
US5405917A (en) * | 1992-07-15 | 1995-04-11 | Phillips Petroleum Company | Selective admixture of additives for modifying a polymer |
-
1996
- 1996-03-25 WO PCT/US1996/003959 patent/WO1996033226A1/en not_active Application Discontinuation
- 1996-03-25 AU AU53697/96A patent/AU694864B2/en not_active Ceased
- 1996-03-25 KR KR1019970707350A patent/KR19990007827A/en not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4015058A (en) * | 1974-11-27 | 1977-03-29 | Union Carbide Corporation | Composition with dicumyl peroxide and process for avoiding scorching of ethylene polymer composition |
US4006283A (en) * | 1974-12-23 | 1977-02-01 | General Electric Company | Preparation of di-tertiary butyl peroxide crosslink polyolefin materials |
US4226905A (en) * | 1978-04-18 | 1980-10-07 | Du Pont Canada Inc. | Manufacture of film from partially crosslinked polyethylene |
US4202790A (en) * | 1978-06-26 | 1980-05-13 | Hercules Incorporated | Peroxide blends |
US4578431A (en) * | 1983-08-31 | 1986-03-25 | Mobil Oil Corporation | Process for improving melt strength of ethylene polymers by treatment with organic peroxide |
US5405917A (en) * | 1992-07-15 | 1995-04-11 | Phillips Petroleum Company | Selective admixture of additives for modifying a polymer |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7750104B2 (en) | 1998-11-02 | 2010-07-06 | Dow Global Technologie Inc. | Shear thinning ethylene/α-olefin interpolymers and their preparation |
EP1229053A2 (en) * | 2001-01-31 | 2002-08-07 | Fina Technology, Inc. | Method of producing polyethylene resins for use in blow molding |
EP1229053A3 (en) * | 2001-01-31 | 2004-01-02 | Fina Technology, Inc. | Method of producing polyethylene resins for use in blow molding |
US11098139B2 (en) * | 2018-02-28 | 2021-08-24 | Chevron Phillips Chemical Company Lp | Advanced quality control tools for manufacturing bimodal and multimodal polyethylene resins |
US11708433B2 (en) | 2018-02-28 | 2023-07-25 | Chevron Phillips Chemical Company Lp | Advanced quality control tools for manufacturing bimodal and multimodal polyethylene resins |
CN114085303A (en) * | 2021-12-21 | 2022-02-25 | 青岛科技大学 | Catalytic system, application thereof and preparation method of syndiotactic 1, 2-polybutadiene |
Also Published As
Publication number | Publication date |
---|---|
AU694864B2 (en) | 1998-07-30 |
AU5369796A (en) | 1996-11-07 |
KR19990007827A (en) | 1999-01-25 |
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