CA2347501A1 - Shear thinning ethylene/.alpha.-olefin interpolymers and their preparation - Google Patents

Shear thinning ethylene/.alpha.-olefin interpolymers and their preparation Download PDF

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Publication number
CA2347501A1
CA2347501A1 CA002347501A CA2347501A CA2347501A1 CA 2347501 A1 CA2347501 A1 CA 2347501A1 CA 002347501 A CA002347501 A CA 002347501A CA 2347501 A CA2347501 A CA 2347501A CA 2347501 A1 CA2347501 A1 CA 2347501A1
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Prior art keywords
interpolymer
alpha
olefin
weight
ethylene
Prior art date
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Granted
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CA002347501A
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French (fr)
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CA2347501C (en
Inventor
Larry Duane Cady
Morgan Mark Hughes
Michael Kenneth Laughner
Larry Alan Meiske
Deepak Rasiklal Parikh
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Dow Global Technologies LLC
Original Assignee
Larry Duane Cady
Morgan Mark Hughes
Michael Kenneth Laughner
Larry Alan Meiske
Deepak Rasiklal Parikh
Du Pont Dow Elastomers L.L.C.
Dupont Performance Elastomers L.L.C.
Wenben Inc.
Dow Global Technologies Inc.
Dow Global Technologies Llc
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Application filed by Larry Duane Cady, Morgan Mark Hughes, Michael Kenneth Laughner, Larry Alan Meiske, Deepak Rasiklal Parikh, Du Pont Dow Elastomers L.L.C., Dupont Performance Elastomers L.L.C., Wenben Inc., Dow Global Technologies Inc., Dow Global Technologies Llc filed Critical Larry Duane Cady
Publication of CA2347501A1 publication Critical patent/CA2347501A1/en
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Publication of CA2347501C publication Critical patent/CA2347501C/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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • 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
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/903—Monomer polymerized in presence of transition metal containing catalyst and hydrocarbon additive affecting polymer properties of catalyst activity
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

Shear-thinning ethylene/.alpha.-olefin and ethylene/.alpha.-olefin/diene monomer interpolymers that do not include a traditional branch-inducing monomer such as norbornadiene are prepared at an elevated temperature in an atmosphere that has little or no hydrogen using a constrained geometry complex catalyst and an activating cocatalyst.

Claims (25)

1. A shear thinning ethylene/.alpha.-olefin interpolymer, the interpolymer having polymerized therein ethylene, at least one .alpha.-olefin monomer and, optionally, at least one dime monomer and being characterized by a Processing Rheology Ratio (PRR) of at least four, where PRR = (interpolymer Viscosity measured at 190°C with a shear rate of 0.1 rad/sec)/( interpolymer Viscosity measured at 190°C with a shear rate of 100 rad/sec) +
[3.82 - interpolymer Mooney Viscosity (ML1.,@ 125°C)] x 0.3.
2. The interpolymer of Claim 1, wherein the interpolymer has (a) a weight ratio of ethylene to .alpha.-olefin within a range of from 90:10 to 10:90, the .alpha.-olefin being a C3-20 .alpha.-olefin and (b) a diene monomer content within a range of from 0 to 25 percent by weight, based on interpolymer weight.
3. The interpolymer of Claim 1, wherein the interpolymer has a Mooney Viscosity (ML1+4 at 125°C) within a range of from 0.5 to about 200.
4. The interpolymer of Claim 1, wherein the interpolymer has a molecular weight distribution (Mw/Mn) of at least 2Ø
5. The interpolymer of Claim 4, wherein the molecular weight distribution is at least 2.5 and the PRR
is at least 8.
6. The interpolymer of Claim 1, wherein the interpolymer is an EAODM interpolymer with a molecular weight distribution of at least 2.3, a Mooney Viscosity (ML1+4 at 125°C) of at least 15 and a PRR of at least 20.
7. The interpolymer of Claim 1, wherein the interpolymer is an ethylene/octene-1 copolymer with a molecular weight distribution of at least 2.3, a Mooney Viscosity (ML1+4 at 125°C) of at least 5.
8. The interpolymer of Claim 2, wherein the alpha-olefin is selected from the group consisting of propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, styrene, p-methyl styrene and mixtures thereof, and the optional dime monomer is selected from the group consisting of 5-ethylidene-2-norbornene, 5-vinylidene-2-norbornene, 5-methylene-2-norbornene, 1,4-hexadiene, 1,3-pentadiene, 7-methyl-1,6-octadiene, 1,3-butadiene, 4-methyl-1,3-pentadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,5-heptadiene and mixtures thereof.
9. The interpolymer of Claim 2, further comprising a PRR enhancing amount of an additional dime monomer, the additional diene monomer being selected from the group consisting of dicyclopentadiene, norbornadiene, 1,7-octadiene, and 1,9-decadiene.
10. A process for preparing ethylene/.alpha.-olefin interpolymer of Claim 1, the process comprising:
contacting ethylene, at least one .alpha.-olefin monomer and, optionally, at least one dime monomer with a catalyst and an activating cocatalyst under conditions sufficient to attain an ethylene conversion of at least 60 weight percent, the conditions including a temperature of at least 70°C and, optionally, in the presence of an effective amount of hydrogen, the amount being sufficient to maintain an interpolymer PRR of at least 4, the catalyst being a constrained geometry metal complex
11. The process of Claim 10, wherein the amount of hydrogen is greater than 0 mole percent, but less than 0.10 mole percent, based upon total monomer content plus hydrogen content.
12. The process of Claim 10, wherein the amount of hydrogen is greater than 0 mole percent, but less than 0.05 mole percent, based upon total monomer content plus hydrogen content.
13. The process of Claim 10, wherein the catalyst is selected from the group consisting of (t-butyl-amido)-dimethyl(~5-2-methyl-s-indacen-1-yl)silane-titanium (IV) dimethyl, (t-butylamido)-dimethyl-(~5-2-methyl-s-indacen-1-yl)silane-titanium (II) 1,3-pentadiene and (t-butylamido)dimethyl-(~5-2- methyl-s-indacen-1-yl )silanetitanium (II) 2,4-hexadiene or a Group B catalyst selected from (t-butylamido)-dimethyl(~5-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butyl-amido)-dimethyl(~5-2,3-dimethyl-s-indacen-1-yl)silanetitanium (IV) dimethyl and mixtures thereof.
14. The process of Claim 10, wherein the activating cocatalyst is trispentafluorophenyl borane.
15. The process of Claim 10, wherein the interpolymer has an ethylene content of from 20 to 95 weight percent (wt%), an .alpha.-olefin content of from 80 to 5 wt%, the .alpha.-olefin being a C3-20 .alpha.-olefin and, optionally a diene monomer content within a range of from 0 to 25 percent by weight, all percentages based on interpolymer weight and totaling 100 wt%.
16. The process of Claim 10, wherein the interpolymer is amorphous.
17. The process of Claim 10, wherein the interpolymer is at least partially crystalline and the temperature is at least 80°C and the ethylene conversion is at least 80%.
18. An article of manufacture having at least one portion thereof fabricated from a composition that comprises the interpolymer of Claim 1.
19. The article of claim 18, wherein the article is selected from the group consisting of wire and cable components, electrical insulation, belts, hoses, tubes, gaskets, membranes, molded goods, extruded parts, automotive parts, adhesives, tire walls and tires.
20. The article of Claim 18, wherein the composition further comprises at least one additive selected from the group consisting of fillers, fibers, plasticizers, oils, colorants, stabilizers, foaming agents, retarders, accelerators, and cross-linking agents.
21. An polymer blend composition, the composition comprising more than 50 parts by weight of a crystalline polyolefin resin and less than 50 parts by weight of the interpolymer of Claim 1, the total amount of crystalline polyolefin resin and interpolymer being 100 parts by weight.
22. A thermoplastic vulcanizate composition, the composition comprising from 60 to less than 10 parts by weight of a crystalline polyolefin resin and from 40 to more than 90 parts by weight of the interpolymer of Claim 1 wherein the interpolymer is at least partially cross-linked such that the composition has a gel content of at least 70 %, based on interpolymer weight, the total amount of crystalline polyolefin resin and interpolymer being 100 parts by weight.
23. The composition of Claim 21 or 22, wherein the crystalline polyolefin resin is a polypropylene homopolymer, a copolymer of propylene with an .alpha.-olefin selected from the group consisting of ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 2-methyl-1-propene or 4-methyl-1-pentene, or a blend of a polypropylene homopolymer and a propylene/.alpha.-olefin copolymer or a mixture thereof.
24. The composition of Claim 23, wherein the .alpha.-olefin is ethylene.
25. An article of manufacture fabricated from the composition of any of Claims 21-24.
CA2347501A 1998-11-02 1999-11-02 Shear thinning ethylene/.alpha.-olefin interpolymers and their preparation Expired - Lifetime CA2347501C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10656998P 1998-11-02 1998-11-02
US60/106,569 1998-11-02
PCT/US1999/025637 WO2000026268A1 (en) 1998-11-02 1999-11-02 SHEAR THINNING ETHYLENE/α-OLEFIN INTERPOLYMERS AND THEIR PREPARATION

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CA2347501A1 true CA2347501A1 (en) 2000-05-11
CA2347501C CA2347501C (en) 2010-03-23

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US (1) US7750104B2 (en)
EP (2) EP1159320B1 (en)
JP (3) JP5276757B2 (en)
KR (1) KR100623106B1 (en)
CN (1) CN1134467C (en)
AT (1) ATE495205T1 (en)
AU (1) AU1241600A (en)
BR (1) BR9915199B1 (en)
CA (1) CA2347501C (en)
DE (1) DE69943133D1 (en)
ES (2) ES2666708T3 (en)
MX (1) MXPA01004337A (en)
WO (1) WO2000026268A1 (en)

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