Polymers substantially free of long chain branching

• US 7,582,715 B2
• Filed: 12/19/2003
• Issued: 09/01/2009
• Est. Priority Date: 12/20/2002
• Status: Expired due to Fees

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Chung, David Yen-Lung, Milner, Scott Thomas, Shaffer, Timothy Daniel
• Primary Examiner(s): RABAGO, ROBERTO
• Application Number:
  US10/538,965
• Publication Number:
  US 20060094847A1
• Time in Patent Office: 2,083 Days
• Field of Search: 526/90, 526/131, 526/206, 526/226, 526/339, 526/335, 525/232
• US Class Current: 526/335
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 2/002 Scale prevention in a polymerisation reactor or its auxiliary parts
• CPC Class Codes: C08F 2/06 Organic solvent
• CPC Class Codes: C08F 2/14 Organic medium
• CPC Class Codes: C08F 210/12 with conjugated diolefins, e.g. butyl rubber
• CPC Class Codes: C08F 236/08 Isoprene
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/04 Broad molecular weight distribution, i.e. Mw/Mn > 6
• CPC Class Codes: C08F 4/00 Polymerisation catalysts
• CPC Class Codes: C08F 4/06 Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
• CPC Class Codes: C08F 4/12 of boron, aluminium, gallium, indium, thallium or rare earths
• CPC Class Codes: C08F 4/52 selected from boron, aluminium, gallium, indium, thallium or rare earths C08F4/14 takes precedence

Abstract

The invention relates to new polymerization processes including diluents including hydrofluorocarbons and their use to produce novel polymers substantially free of long chain branching. In particular, the invention relates to copolymers of an isoolefin, preferably isobutylene, and a multiolefin, preferably a conjugated diene, more preferably isoprene, substantially free of long chain branching.

Claims

1. A copolymer comprising an isoolefin and a multiolefin, the copolymer being substantially free of long chain branching;

wherein the copolymer has a g′

_vis.avg. greater than or equal to 0.978 as determined by triple detection SEC.

2. The copolymer of claim 1, wherein the multiolefin is a conjugated diene.

3. The copolymer of claim 1, wherein the multiolefin content is greater than 0.5 wt %.

4. A copolymer comprising isobutylene and isoprene, the copolymer being substantially free of long chain branching;

wherein the copolymer has a g′

_vis.avg. greater than or equal to 0.978 as determined by triple detection SEC.

5. The copolymer of claim 4, wherein the isoprene content is greater than 0.5 wt %.

22. The copolymer of claim 4, wherein the copolymer is halogenated to form a halogenated copolymer.

23. The copolymer of claim 4, wherein the copolymer has a Mw of greater than 10,000.

24. The copolymer of claim 4, wherein the copolymer has a MWD from about 2 to 5.

25. A blend comprising the copolymer of claim 4 and a secondary rubber independently from the group consisting of at least one of natural rubber, polyisoprene rubber, poly(styrene-co-butadiene) rubber (SBR), polybutadiene rubber (BR), poly(isoprene-co-butadiene) rubber (IBR), styrene-isoprene-butadiene rubber (SIBR), ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), polysulfide, isobutylene/cyclopentadiene copolymer rubber, isobutylene/methyl cyclopentadiene copolymer rubber, nitrile rubber, propylene oxide polymers, star-branched butyl rubber and halogenated star-branched butyl rubber, brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutylene rubber, star-branched brominated butyl (polyisobutylene/isoprene copolymer) rubber;

poly(isobutylene-co-p-methylstyrene) and halogenated poly(isobutylene-co-p-methylstyrene), halogenated poly(isobutylene-co-isoprene-co-p-methylstyrene), poly(isobutylene-co-isoprene-co-styrene), halogenated poly(isobutylene-co-isoprene-co-styrene), poly(isobutylene-co-isoprene-co-α

-methylstyrene) halogenated poly(isobutylene-co-isoprene-co-α

-methylstyrene), and mixtures thereof.

26. The copolymer of claim 4, wherein the copolymer has a g′

_vis.avg. from greater than or equal to 0.980 as determined by triple detection SEC.

6. A copolymer produced by the process comprising contacting an isoolefin, a multiolefin, one or more Lewis acid(s), one or more initiator(s), and a diluent comprising one or more hydrofluorocarbon(s) (HFC'"'"'s);

wherein the copolymer is substantially free of long chain branching and wherein the copolymer has a g′

_vis.avg. greater than or equal to 0.978 as determined by triple detection SEC.

7. The copolymer of claim 6, wherein the multiolefin is a conjugated diene.

8. The copolymer of claim 6, wherein the multiolefin content is greater than 0.5 wt %.

9. The copolymer of claim 6, wherein one or more hydrofluorocarbon(s) is represented by the formula:

C_xH_yF_z wherein x is an integer from 1 to 40 and y and z are integers of one or more.

10. The copolymer of claim 9, wherein x is from 1 to 10.

11. The copolymer of claim 6, wherein the one or more hydrofluorocarbon(s) is independently selected from the group consisting of fluoromethane;

difluoromethane;

trifluoromethane;

fluoroethane;

1,1-difluoroethane;

1,2-difluoroethane;

1,1,1-trifluoroethane;

1,1,2-trifluoroethane;

1,1,1,2-tetrafluoroethane;

1,1,2,2-tetrafluoroethane;

1,1,1,2,2-pentafluoroethane;

1-fluoropropane;

2-fluoropropane;

1,1-difluoropropane;

1,2-difluoropropane;

1,3-difluoropropane;

2,2-difluoropropane;

1,1,1-trifluoropropane;

1,1,2-trifluoropropane;

1,1,3-trifluoropropane;

1,2,2-trifluoropropane;

1,2,3-trifluoropropane;

1,1,1,2-tetrafluoropropane;

1,1,1,3-tetrafluoropropane;

1,1,2,2-tetrafluoropropane;

1,1,2,3-tetrafluoropropane;

1,1,3,3-tetrafluoropropane;

1,2,2,3-tetrafluoropropane;

1,1,1,2,2-pentafluoropropane;

1,1,1,2,3-pentafluoropropane;

1,1,1,3,3-pentafluoropropane;

1,1,2,2,3-pentafluoropropane;

1,1,2,3,3-pentafluoropropane;

1,1,1,2,2,3-hexafluoropropane;

1,1,1,2,3,3-hexafluoropropane;

1,1,1,3,3,3-hexafluoropropane;

1,1,1,2,2,3,3-heptafluoropropane;

1,1,1,2,3,3,3-heptafluoropropane;

1-fluorobutane;

2-fluorobutane;

1,1-difluorobutane;

1,2-difluorobutane;

1,3-difluorobutane;

1,4-difluorobutane;

2,2-difluorobutane;

2,3-difluorobutane;

1,1,1-trifluorobutane;

1,1,2-trifluorobutane;

1,1,3-trifluorobutane;

1,1,4-trifluorobutane;

1,2,2-trifluorobutane;

1,2,3-trifluorobutane;

1,3,3-trifluorobutane;

2,2,3-trifluorobutane;

1,1,1,2-tetrafluorobutane;

1,1,1,3-tetrafluorobutane;

1,1,1,4-tetrafluorobutane;

1,1,2,2-tetrafluorobutane;

1,1,2,3-tetrafluorobutane;

1,1,2,4-tetrafluorobutane;

1,1,3,3-tetrafluorobutane;

1,1,3,4-tetrafluorobutane;

1,1,4,4-tetrafluorobutane;

1,2,2,3-tetrafluorobutane;

1,2,2,4-tetrafluorobutane;

1,2,3,3-tetrafluorobutane;

1,2,3,4-tetrafluorobutane;

2,2,3,3-tetrafluorobutane;

1,1,1,2,2-pentafluorobutane;

1,1,1,2,3-pentafluorobutane;

1,1,1,2,4-pentafluorobutane;

1,1,1,3,3-pentafluorobutane;

1,1,1,3,4-pentafluorobutane;

1,1,1,4,4-pentafluorobutane;

1,1,2,2,3-pentafluorobutane;

1,1,2,2,4-pentafluorobutane;

1,1,2,3,3-pentafluorobutane;

1,1,2,4,4-pentafluorobutane;

1,1,3,3,4-pentafluorobutane;

1,2,2,3,3-pentafluorobutane;

1,2,2,3,4-pentafluorobutane;

1,1,1,2,2,3-hexafluorobutane;

1,1,1,2,2,4-hexafluorobutane;

1,1,1,2,3,3-hexafluorobutane, 1,1,1,2,3,4-hexafluorobutane;

1,1,1,2,4,4-hexafluorobutane;

1,1,1,3,3,4-hexafluorobutane;

1,1,1,3,4,4-hexafluorobutane;

1,1,1,4,4,4-hexafluorobutane;

1,1,2,2,3,3-hexafluorobutane;

1,1,2,2,3,4-hexafluorobutane;

1,1,2,2,4,4-hexafluorobutane;

1,1,2,3,3,4-hexafluorobutane;

1,1,2,3,4,4-hexafluorobutane;

1,2,2,3,3,4-hexafluorobutane;

1,1,1,2,2,3,3-heptafluorobutane;

1,1,1,2,2,4,4-heptafluorobutane;

1,1,1,2,2,3,4-heptafluorobutane;

1,1,1,2,3,3,4-heptafluorobutane;

1,1,1,2,3,4,4-heptafluorobutane;

1,1,1,2,4,4,4-heptafluorobutane;

1,1,1,3,3,4,4-heptafluorobutane;

1,1,1,2,2,3,3,4-octafluorobutane;

1,1,1,2,2,3,4,4-octafluorobutane;

1,1,1,2,3,3,4,4-octafluorobutane;

1,1,1,2,2,4,4,4-octafluorobutane;

1,1,1,2,3,4,4,4-octafluorobutane;

1,1,1,2,2,3,3,4,4-nonafluorobutane;

1,1,1,2,2,3,4,4,4-nonafluorobutane;

1-fluoro-2-methylpropane;

1,1-difluoro-2-methylpropane;

1,3-difluoro-2-methylpropane;

1,1,1-trifluoro-2-methylpropane;

1,1,3-trifluoro-2-methylpropane;

1,3-difluoro-2-(fluoromethyl)propane;

1,1,1,3-tetrafluoro-2-methylpropane;

1,1,3,3-tetrafluoro-2-methylpropane;

1,1,3-trifluoro-2-(fluoromethyl)propane;

1,1,1,3,3-pentafluoro-2-methylpropane;

1,1,3,3-tetrafluoro-2-(fluoromethyl)propane;

1,1,1,3-tetrafluoro-2-(fluoromethyl)propane;

fluorocyclobutane;

1,1-difluorocyclobutane;

1,2-difluorocyclobutane;

1,3-difluorocyclobutane;

1,1,2-trifluorocyclobutane;

1,1,3-trifluorocyclobutane;

1,2,3-trifluorocyclobutane;

1,1,2,2-tetrafluorocyclobutane;

1,1,3,3-tetrafluorocyclobutane;

1,1,2,2,3-pentafluorocyclobutane;

1,1,2,3,3-pentafluorocyclobutane;

1,1,2,2,3,3-hexafluorocyclobutane;

1,1,2,2,3,4-hexafluorocyclobutane;

1,1,2,3,3,4-hexafluorocyclobutane;

1,1,2,2,3,3,4-heptafluorocyclobutane;

vinyl fluoride;

1,1-difluoroethene;

1,2-difluoroethene;

1,1,2-trifluoroethene;

1-fluoropropene, 1,1-difluoropropene;

1,2-difluoropropene;

1,3-difluoropropene;

2,3-difluoropropene;

3,3-difluoropropene;

1,1,2-trifluoropropene;

1,1,3-trifluoropropene;

1,2,3-trifluoropropene;

1,3,3-trifluoropropene;

2,3,3-trifluoropropene;

3,3,3-trifluoropropene;

1-fluoro-1-butene;

2-fluoro-1-butene;

3-fluoro-1-butene;

4-fluoro-1-butene;

1,1-difluoro-1-butene;

1,2-difluoro-1-butene;

1,3-difluoropropene;

1,4-difluoro-1-butene;

2,3-difluoro-1-butene;

2,4-difluoro-1-butene;

3,3-difluoro-1-butene;

3,4-difluoro-1-butene;

4,4-difluoro-1-butene;

1,1,2-trifluoro-1-butene;

1,1,3-trifluoro-1-butene;

1,1,4-trifluoro-1-butene;

1,2,3-trifluoro-1-butene;

1,2,4-trifluoro-1-butene;

1,3,3-trifluoro-1-butene;

1,3,4-trifluoro-1-butene;

1,4,4-trifluoro-1-butene;

2,3,3-trifluoro-1-butene;

2,3,4-trifluoro-1-butene;

2,4,4-trifluoro-1-butene;

3,3,4-trifluoro-1-butene;

3,4,4-trifluoro-1-butene;

4,4,4-trifluoro-1-butene;

1,1,2,3-tetrafluoro-1-butene;

1,1,2,4-tetrafluoro-1-butene;

1,1,3,3-tetrafluoro-1-butene;

1,1,3,4-tetrafluoro-1-butene;

1,1,4,4-tetrafluoro-1-butene;

1,2,3,3-tetrafluoro-1-butene;

1,2,3,4-tetrafluoro-1-butene;

1,2,4,4-tetrafluoro-1-butene;

1,3,3,4-tetrafluoro-1-butene;

1,3,4,4-tetrafluoro-1-butene;

1,4,4,4-tetrafluoro-1-butene;

2,3,3,4-tetrafluoro-1-butene;

2,3,4,4-tetrafluoro-1-butene;

2,4,4,4-tetrafluoro-1-butene;

3,3,4,4-tetrafluoro-1-butene;

3,4,4,4-tetrafluoro-1-butene;

1,1,2,3,3-pentafluoro-1-butene;

1,1,2,3,4-pentafluoro-1-butene;

1,1,2,4,4-pentafluoro-1-butene;

1,1,3,3,4-pentafluoro-1-butene;

1,1,3,4,4-pentafluoro-1-butene;

1,1,4,4,4-pentafluoro-1-butene;

1,2,3,3,4-pentafluoro-1-butene;

1,2,3,4,4-pentafluoro-1-butene;

1,2,4,4,4-pentafluoro-1-butene;

2,3,3,4,4-pentafluoro-1-butene;

2,3,4,4,4-pentafluoro-1-butene;

3,3,4,4,4-pentafluoro-1-butene;

1,1,2,3,3,4-hexafluoro-1-butene;

1,1,2,3,4,4-hexafluoro-1-butene;

1,1,2,4,4,4-hexafluoro-1-butene;

1,2,3,3,4,4-hexafluoro-1-butene;

1,2,3,4,4,4-hexafluoro-1-butene;

2,3,3,4,4,4-hexafluoro-1-butene;

1,1,2,3,3,4,4-heptafluoro-1-butene;

1,1,2,3,4,4,4-heptafluoro-1-butene;

1,1,3,3,4,4,4-heptafluoro-1-butene;

1,2,3,3,4,4,4-heptafluoro-1-butene;

1-fluoro-2-butene;

2-fluoro-2-butene;

1,1-difluoro-2-butene;

1,2-difluoro-2-butene;

1,3-difluoro-2-butene;

1,4-difluoro-2-butene;

2,3-difluoro-2-butene;

1,1,1-trifluoro-2-butene;

1,1,2-trifluoro-2-butene;

1,1,3-trifluoro-2-butene;

1,1,4-trifluoro-2-butene;

1,2,3-trifluoro-2-butene;

1,2,4-trifluoro-2-butene;

1,1,1,2-tetrafluoro-2-butene;

1,1,1,3-tetrafluoro-2-butene;

1,1,1,4-tetrafluoro-2-butene;

1,1,2,3-tetrafluoro-2-butene;

1,1,2,4-tetrafluoro-2-butene;

1,2,3,4-tetrafluoro-2-butene;

1,1,1,2,3-pentafluoro-2-butene;

1,1,1,2,4-pentafluoro-2-butene;

1,1,1,3,4-pentafluoro-2-butene;

1,1,1,4,4-pentafluoro-2-butene;

1,1,2,3,4-pentafluoro-2-butene;

1,1,2,4,4-pentafluoro-2-butene;

1,1,1,2,3,4-hexafluoro-2-butene;

1,1,1,2,4,4-hexafluoro-2-butene;

1,1,1,3,4,4-hexafluoro-2-butene;

1,1,1,4,4,4-hexafluoro-2-butene;

1,1,2,3,4,4-hexafluoro-2-butene;

1,1,1,2,3,4,4-heptafluoro-2-butene;

1,1,1,2,4,4,4-heptafluoro-2-butene; and

mixtures thereof.

12. The copolymer of claim 6, wherein the diluent comprises from 15 to 100 volume % HFC based upon the total volume of the diluent.

13. The copolymer of claim 6, wherein the diluent further comprises a hydrocarbon, a non-reactive olefin, and/or an inert gas.

14. The copolymer of claim 6, wherein the diluent further comprises a halogenated hydrocarbon other than an HFC.

15. The copolymer of claim 6, wherein the one or more Lewis acid(s) is represented by a formula selected from the group consisting of

MX₄ 

 

a)

wherein M is a Group 4, 5, or 14 metal; and

each X is a halogen;

MR_nX_4-n 

 

b)

wherein M is Group 4, 5, or 14 metal;

each R is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4; and

each X is a halogen;

M(RO)_nR′

_mX₄-(m+n) 

 

c)

wherein M is Group 4, 5, or 14 metal;

each RO is a monovalent C₁ to C₃₀ hydrocarboxy radical independently selected from the group consisting of an alkoxy, aryloxy, arylalkoxy, alkylaryloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4;

m is an integer from 0 to 4, wherein the sum of n and m is not more than 4; and

each X is a halogen; and

M(RC═

OO)_nR′

_mX_4-(m+n) 

 

d)

wherein M is Group 4, 5, or 14 metal;

each RC═

OO is a monovalent C₂ to C₃₀ hydrocarbacyl radical independently selected from the group consisting of an alkacyloxy, arylacyloxy, arylalkylacyloxy, alkylarylacyloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4;

m is an integer from 0 to 4, wherein the sum of n and m is not more than 4; and

each X is a halogen.

16. The copolymer of claim 6, wherein the one or more Lewis acid(s) is represented by a formula selected from the group consisting of:

MOX₃ 

 

a)

wherein M is a Group 5 metal; and

each X is a halogen;

MX₃;

 

 

b)

wherein M is a Group 13 metal; and

each X is a halogen;

MR_nX_3-n 

 

c)

wherein M is a Group 13 metal;

each R is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 1 to 3; and

each X is a halogen;

M(RO)_nR′

_mX_3-(m+n) 

 

d)

wherein M is a Group 13 metal;

each RO is a monovalent C₁ to C₃₀ hydrocarboxy radical independently selected from the group consisting of an alkoxy, aryloxy, arylalkoxy, alkylaryloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 3;

m is an integer from 0 to 3, wherein the sum of n and m is from 1 to 3; and

each X is a halogen; and

M(RC═

OO)_nR′

_mX_3-(m+n);

 

 

e)

wherein M is a Group 13 metal;

each RC═

OO is a monovalent hydrocarbacyl radical independently selected from the group independently selected from the C₂ to C₃₀ group consisting of an alkacyloxy, arylacyloxy, arylalkylacyloxy, alkylarylacyloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 3;

m is a integer from 0 to 3, wherein the sum of n and m is from 1 to 3; and

each X is a halogen.

17. The copolymer of claim 6, wherein the one or more Lewis acid(s) is represented by a formula selected from the group consisting of:

MX_y 

 

a)

wherein M is a Group 15 metal;

each X is a halogen; and

y is 3, 4 or 5;

MR_nX_y-n;

 

 

b)

wherein M is a Group 15 metal;

each R is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4;

y is 3, 4 or 5, wherein n is less than y; and

each X is a halogen;

M(RO)_nR′

_mX_y-(m+n);

 

 

c)

wherein M is a Group 15 metal,

each RO is a monovalent C₁ to C₃₀ hydrocarboxy radical independently selected from the group consisting of an alkoxy, aryloxy, arylalkoxy, alkylaryloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4;

m is an integer from 0 to 4;

y is 3, 4 or 5, wherein the sum of n and m is less than y; and

each X is a halogen; and

M(RC═

OO)_nR′

_mX_y-(m+n);

 

 

d)

wherein M is a Group 15 metal;

each RC═

OO is a monovalent C₂ to C₃₀ hydrocarbacyloxy radical independently selected from the group consisting of an alkacyloxy, arylacyloxy, arylalkylacyloxy, alkylarylacyloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4;

m is an integer from 0 to 4;

y is 3, 4 or 5, wherein the sum of n and m is less than y; and

each X is a halogen.

18. The copolymer of claim 6, wherein the one or more initiator(s) comprise a hydrogen halide, a carboxylic acid, a carboxylic acid halide, a sulfonic acid, an alcohol, a phenol, a polymeric halide, a tertiary alkyl halide, a tertiary aralkyl halide, a tertiary alkyl ester, a tertiary aralkyl ester, a tertiary alkyl ether, a tertiary aralkyl ether, an alkyl halide, an aryl halide, an alkylaryl halide or an arylalkylacid halide.

19. The copolymer of claim 6, wherein the one or more initiator(s) further comprise a weakly-coordinating anion.

20. The copolymer of claim 6, wherein the one or more initiator(s) comprise greater than 30 ppm water (based upon weight).

21. The copolymer of claim 6, wherein the contacting further comprises contacting one or more monomer(s) independently selected from the group consisting of olefins, alpha-olefins, disubstituted olefins, isoolefins, conjugated dienes, non-conjugated dienes, styrenics, substituted styrenics, and vinyl ethers.