Polymerization processes

• US 7,214,750 B2
• Filed: 12/19/2003
• Issued: 05/08/2007
• Est. Priority Date: 12/20/2002
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Webb, Robert Norman, McDonald, Michael Francis, Milner, Scott Thomas, Shaffer, Timothy Daniel
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US10/539,015
• Publication Number:
  US 20060111522A1
• Time in Patent Office: 1,236 Days
• Field of Search: 526/64, 526/206, 526/237, 526/135, 526/339, 526/347, 526/348.7
• US Class Current: 526/206
• 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 processes to produce polymers utilizing bayonette cooled slurry reactor systems and diluents including hydrofluorocarbons.

Claims

1. A process to produce polymers comprising contacting one or more monomer(s), a catalyst system comprising one or more Lewis Acid(s) and an initiator, and a diluent comprising one or more hydrofluorocarbon(s) (HFC'"'"'s) in a reactor comprising a bayonette.

2. The process of claim 1, wherein the process is a slurry polymerization process and the reactor is a tubular reactor.

3. The process of claim 1, wherein the reactor further comprises a vertical cylindrical housing, an upper part, and a lower part.

4. The process of claim 3, wherein the reactor further comprises connecting pipes for delivery of the catalyst system in the lower part, and connecting pipes for the removal of the polymer in the upper part.

5. The process of claim 1, wherein the reactor further comprises a shaft with blade mixers mounted along the height of the shaft.

6. The process of claim 1, wherein the bayonette comprises a plurality of tubes.

7. The process of claim 6, wherein the tubes comprise sectors.

8. The process of claim 1, wherein the bayonette comprises tube disks and tube baffles.

9. The process of claim 8, wherein the tube baffles comprise spaces between the sectors.

10. The process of claim 8, wherein the tube baffles comprise holes.

11. The process of claim 8, wherein the reactor comprises a catalyst system delivery tube comprising an open end, the open end located in the space between the tube baffles.

12. The process of claim 11, wherein the open end of the catalyst system delivery tube is angled in a downward direction toward a mixer.

13. The process of claim 8, wherein the reactor comprises one or more catalyst system delivery tube(s) comprising open ends.

14. The process of claim 13, wherein at least one open end is angled in a downward direction toward a mixer.

15. The process of claim 1, wherein the reactor comprises a mixer located adjacent to a tube baffle.

16. The process of claim 1, wherein the one or more monomer(s) comprise isobutylene and isoprene.

18. The process of claim 1, 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.

19. The process of claim 18, wherein x is from 1 to 10.

20. The process of claim 18, wherein x is from 1 to 6.

21. The process of claim 18, wherein x is from 1 to 3.

22. The process of claim 1, 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-nentafluoropronane;

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 and mixtures thereof.

23. The process of claim 1, wherein the one or more hydrofluorocarbon(s) is independently selected from monofluoromethane, difluoromethane, trifluoromethane, monofluoroethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,2, pentafluoroethane, and mixtures thereof.

24. The process of claims claim 1, wherein the diluent comprises from 15 to 100 volume % HFC based upon the total volume of the diluent.

25. The process of claim 1, wherein the diluent comprises from 20 to 100 volume % HFC based upon the total volume of the diluent.

26. The process of claim 1, wherein the diluent comprises from 25 to 100 volume % HFC based upon the total volume of the diluent.

27. The process of claim 1, wherein the diluent further comprises a hydrocarbon, a non-reactive olefin, and/or an inert gas.

28. The process of claim 27, wherein the hydrocarbon is a halogenated hydrocarbon other than an HFC.

29. The process of claim 28, wherein the halogenated hydrocarbon is methyl chloride.

30. The process of claim 1, wherein the one or more Lewis acid(s) is represented by the formula MX₄;

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

each X is a halogen.

31. The process of claim 1, wherein the one or more Lewis acid(s) is represented by the formula MR_nX_4-n;

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 3; and

each X is a halogen.

32. The process of claim 1, wherein the one or more Lewis acid(s) is represented by the formula M(RO)_nR′

_mX<sub>4−

(m+n)</sub>;

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 3;

m is an integer from 0 to 3, wherein the sum of n and m is not more than 3; and

each X is a halogen.

33. The process of claim 1, wherein the one or more Lewis acid(s) is represented by the formula M(RC═

OO)_nR′

_mX<sub>4−

(m+n)</sub>;

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 3;

m is an integer from 0 to 3, wherein the sum of n and m is not more than 3; and

each X is a halogen.

34. The process of claim 1, wherein the one or more Lewis acid(s) is represented by the formula MOX₃;

wherein M is a Group 5 metal; and

each X is a halogen.

35. The process of claim 1, wherein the one or more Lewis acid(s) is represented by the formula MX₃;

wherein M is a Group 13 metal; and

each X is a halogen.

36. The process of 29 claim 1, wherein the one or more Lewis acid(s) is represented by the formula MR_nX₃₋

n;

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 2; and

each X is a halogen.

37. The process of any claim 1, wherein the one or more Lewis acid(s) is represented by the formula M(RO)_nR′

_mX<sub>3−

(m+n)</sub>;

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 2;

m is an integer from 0 to 2, wherein the sum of n and m is from 1 to 2; and

each X is a halogen.

38. The process of claim 1, wherein the one or more Lewis acid(s) is represented by the formula M(RC═

OO)_nR′

<sub>ml X3−

(m+n)</sub>;

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 2;

m is a integer from 0 to 2, wherein the sum of n and m is from 1 to 2; and

each X is a halogen.

39. The process of claim 1, wherein the one or more Lewis acid(s) is represented by the formula MX_y;

wherein M is a Group 15 metal;

each X is a halogen; and

y is 3, 4 or 5.

40. The process of claim 1, wherein the one or more Lewis acid(s) is represented by the formula MR_nX_y−

n;

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.

41. The process of claim 1, wherein the one or more Lewis acid(s) is represented by the formula M(RO)_nR′

_mX<sub>y−

(m+n)</sub>;

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.

42. The process of claim 1, wherein the one or more Lewis acid(s) is represented by the formula M(RC═

OO)_nR′

_mX<sub>y−

(m+n)</sub>;

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.

43. The process of claim 1, wherein the one or more Lewis acid(s) are independently selected from the group consisting of titanium tetrachloride, titanium tetrabromide, vanadium tetrachloride, tin tetrachloride, zirconium tetrachloride, titanium bromide trichloride, titanium dibromide dichloride, vanadium bromide trichloride, tin chloride trifluoride, benzyltitanium trichloride, dibenzyltitanium dichloride, benzylzirconium trichloride, dibenzylzirconium dibromide, methyltitanium trichloride, dimethyltitanium difluoride, dimethyltin dichloride, phenylvanadium trichloride, methoxytitanium trichloride, n-butoxytitanium trichloride, di(isopropoxy)titanium dichloride, phenoxytitanium tribromide, phenylmethoxyzirconium trifluoride, methyl methoxytitanium dichloride, methyl methoxytin dichloride, benzyl isopropoxyvanadium dichloride, acetoxytitanium trichloride, benzoylzirconium tribromide, benzoyloxytitanium trifluoride, isopropoyloxytin trichloride, methyl acetoxytitanium dichloride, benzyl benzoyloxyvanadium chloride, vanadium oxytrichloride, aluminum trichloride, boron trifluoride, gallium trichloride, indium trifluoride, ethylaluminum dichloride, methylaluminum dichloride, benzylaluminum dichloride, isobutylgallium dichloride, diethylaluminum chloride, dimethylaluminum chloride, ethylaluminum sesquichloride, methylaluminum sesquichloride, trimethylaluminum, triethylaluminum, methoxyaluminum dichloride, ethoxyaluminum dichloride, 2,6-di-tert-butylphenoxyaluminum dichloride, methoxy methylaluminum chloride, 2,6-di-tert-butylphenoxy methylaluminum chloride, isopropoxygallium dichloride, phenoxy methylindium fluoride, acetoxyaluminum dichloride, benzoyloxyaluminum dibromide, benzoyloxygallium difluoride, methyl acetoxyaluminum chloride, isopropoyloxyindium trichloride, antimony hexachloride, antimony hexafluoride, arsenic pentafluoride, antimony chloride pentafluoride, arsenic trifluoride, bismuth trichloride arsenic fluoride tetrachloride, tetraphenylantimony chloride, triphenylantimony dichloride, tetrachloromethoxyantimony, dimethoxytrichloroantimony, dichloromethoxyarsine, chlorodimethoxyarsine, difluoromethoxyarsine, acetatotetrachloroantimony, (benzoato) tetrachloroantimony, and bismuth acetate chloride.

44. The process of claim 1, wherein the one or more Lewis acid(s) is independently selected from the group consisting of aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, methylaluminum dichloride, methylaluminum sesquichloride, dimethylaluminum chloride, boron trifluoride, and titanium tetrachloride.

45. The process of claim 1, wherein the Lewis acid is not a compound represented by formula MX₃, where M is a group 13 metal, X is a halogen.

46. The process of claim 1, wherein the catalyst system further comprises 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.

47. The process of claim 1, wherein the one or more initiator(s) is independently selected from the group consisting of HCl, H₂O, methanol, (CH₃)₃CCl, C₆H₅C(CH₃)₂Cl, (2-Chloro-2,4,4-trimethylpentane) and 2-chloro-2-methylpropane.

48. The process of claim 1, wherein the one or more initiator(s) is independently selected from the group consisting of hydrogen chloride, hydrogen bromide, hydrogen iodide, acetic acid, propanoic acid, butanoic acid;

cinnamic acid, benzoic acid, 1-chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, p-chlorobenzoic acid, p-fluorobenzoic acid, acetyl chloride, acetyl bromide, cinnamyl chloride, benzoyl chloride, benzoyl bromide, trichloroacetylchloride, trifluoroacetylchloride, p-fluorobenzoylchloride, methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonyl chloride, methanesulfonyl bromide, trichloromethanesulfonyl chloride, trifluoromethanesulfonyl chloride, p-toluenesulfonyl chloride, methanol, ethanol, propanol, 2-propanol, 2-methylpropan-2-ol, cyclohexanol, benzyl alcohol, phenol, 2-methylphenol, 2,6-dimethylphenol, p-chlorophenol, p-fluorophenol, 2,3,4,5,6-pentafluorophenol, and 2-hydroxynaphthalene.

49. The process of claim 1, wherein the one or more initiator(s) is independently selected from the group consisting of 2-chloro-2,4,4-trimethylpentane;

2-bromo-2,4,4-trimethylpentane;

2-chloro-2-methylpropane;

2-bromo-2-methylpropane;

2-chloro-2,4,4,6,6-pentamethylheptane;

2-bromo-2,4,4,6,6-pentamethylheptane;

1-chloro-1-methylethylbenzene;

1-chloroadamantane;

1-chloroethylbenzene;

1,4-bis(1-chloro-1-methylethyl)benzene;

5-tert-butyl-1,3-bis(1-chloro-1-methylethyl)benzene;

2-acetoxy-2,4,4-trimethylpentane;

2-benzoyloxy-2,4,4-trimethylpentane;

2-acetoxy-2-methylpropane;

2-benzoyloxy-2-methylpropane;

2-acetoxy-2,4,4,6,6-pentamethylheptane;

2-benzoyl-2,4,4,6,6-pentamethylheptane;

1-acetoxy-1-methylethylbenzene;

1-aceotxyadamantane;

1-benzoyloxyethylbenzene;

1,4-bis(1-acetoxy-1-methylethyl)benzene;

5-tert-butyl-1,3-bis(1-acetoxy-1-methylethyl)benzene;

2-methoxy-2,4,4-trimethylpentane;

2-isopropoxy-2,4,4-trimethylpentane;

2-methoxy-2-methylpropane;

2-benzyloxy-2-methylpropane;

2-methoxy-2,4,4,6,6-pentamethylheptane;

2-isopropoxy-2,4,4,6,6-pentamethylheptane;

1-methoxy-1-methylethylbenzene;

1-methoxyadamantane;

1-methoxyethylbenzene;

1,4-bis(1-methoxy-1-methylethyl)benzene;

5-tert-butyl-1,3-bis(1-methoxy-1-methylethyl)benzene, and 1,3,5-tris(1-chloro-1-methylethyl)benzene.

50. The process of claim 1, wherein the catalyst system comprises a weakly-coordinating anion.

51. The process of claim 1, wherein the one or more initiator(s) comprises greater than 30 ppm water (based upon weight).

52. The process of claim 1, wherein the one or more monomer(s) is independently selected from the group consisting of olefins, alpha-olefins, disubstituted olefins, isoolefins, conjugated dienes, non-conjugated dienes, styrenics, substituted styrenics, and vinyl ethers.

53. The process of claim 1, wherein the one or more monomer(s) is independently selected from the group consisting of isobutylene, styrene, para-alkylstyrene, para-methylstyrene, alpha-methyl styrene, divinylbenzene, diisopropenylbenzene, isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-pentene, isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, β

-pinene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, methyl cyclopentadiene, piperylene, methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.

54. The process of claim 1, wherein the one or more monomer(s) comprise at least 80 wt % isobutylene based upon the total weight of the one or more monomer(s).

55. The process of claim 1, wherein the polymerization temperature is from 15°

C. to −

100°

C.

56. The process of claim 1, wherein the polymerization temperature is from −

30°

C. to −

70°

C.

57. The process of claim 1, wherein the polymerization temperature is from −

40°

C. to −

60°

C.

58. The process of claim 1 wherein the one or more monomers comprises an isoolefin.

59. The process of claim 58 wherein the one or more monomers further comprises a multiolefin.

60. The process of claim 59 wherein the isoolefin is isobutylene and the multiolelin is isoprene.

61. The process of claim 1 wherein the one or more monomers comprises an isoolefin and an alkylstyrene.

62. The process of claim 61 wherein the alkylstyrene is p-methylstyrene.

63. The process of claim 1, wherein the one or more monomer(s) is independently selected from the group consisting of olefins, alpha-olefins, isoolefins, dienes, styrenics, and substituted styrenics.

64. The process of claim 1, wherein the one or more monomer(s) is independently selected from the group consisting of isobutylene, styrene, para-alkylstyrene, para-methylstyrene, alpha-methyl styrene, divinylbenzene, diisopropenylbenzene, isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-pentene, isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, β

-pinene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, methyl cyclopentadiene, and piperylene.

17. A process to produce polymers comprising contacting one or more monomer(s), a catalyst system comprising one or more Lewis Acid and an initiator, and a diluent comprising one or more hydrofluorocarbon(s) (HFC'"'"'s) in a reactor comprising a bayonette, wherein the one or more monomer(s) comprise isobutylene and para-methylstyrene.