CA2337003A1 - Process for polymerizing a cationically polymerizable olefin - Google Patents
Process for polymerizing a cationically polymerizable olefin Download PDFInfo
- Publication number
- CA2337003A1 CA2337003A1 CA002337003A CA2337003A CA2337003A1 CA 2337003 A1 CA2337003 A1 CA 2337003A1 CA 002337003 A CA002337003 A CA 002337003A CA 2337003 A CA2337003 A CA 2337003A CA 2337003 A1 CA2337003 A1 CA 2337003A1
- Authority
- CA
- Canada
- Prior art keywords
- process defined
- group
- substituted
- radicals
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 95
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 46
- 230000000379 polymerizing effect Effects 0.000 title claims abstract description 22
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 30
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 19
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 8
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 cyclopentadienyl transition metal Chemical class 0.000 claims description 60
- 150000001450 anions Chemical class 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 36
- 150000001768 cations Chemical class 0.000 claims description 32
- 150000003254 radicals Chemical group 0.000 claims description 30
- 229910052796 boron Inorganic materials 0.000 claims description 28
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001993 dienes Chemical class 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052798 chalcogen Inorganic materials 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 150000002738 metalloids Chemical class 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 229910052696 pnictogen Inorganic materials 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 229910052752 metalloid Inorganic materials 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000005425 toluyl group Chemical group 0.000 claims description 6
- 125000005023 xylyl group Chemical group 0.000 claims description 6
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 5
- 125000005917 3-methylpentyl group Chemical group 0.000 claims description 5
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002879 Lewis base Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 150000007527 lewis bases Chemical class 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910000085 borane Inorganic materials 0.000 claims description 4
- 150000001639 boron compounds Chemical class 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- DXQXWMYUGOTNGJ-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]boron Chemical compound [B]C1=CC=C(C(F)(F)F)C=C1 DXQXWMYUGOTNGJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 claims description 2
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 claims description 2
- JTXUVHFRSRTSAT-UHFFFAOYSA-N 3,5,5-trimethylhex-1-ene Chemical compound C=CC(C)CC(C)(C)C JTXUVHFRSRTSAT-UHFFFAOYSA-N 0.000 claims description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- LTVYTYLQCJEFTH-UHFFFAOYSA-N benzyl(dimethyl)silanylium Chemical compound C[Si+](C)CC1=CC=CC=C1 LTVYTYLQCJEFTH-UHFFFAOYSA-N 0.000 claims description 2
- TVBISCWBJBKUDP-UHFFFAOYSA-N borate Chemical compound [O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] TVBISCWBJBKUDP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001638 boron Chemical class 0.000 claims description 2
- 150000001787 chalcogens Chemical class 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 150000003063 pnictogens Chemical class 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- CXKQHHJKHZXXPZ-UHFFFAOYSA-N triethylsilanylium Chemical compound CC[Si+](CC)CC CXKQHHJKHZXXPZ-UHFFFAOYSA-N 0.000 claims description 2
- VOYMPSZBODLRKS-UHFFFAOYSA-N trimethylsilanylium Chemical compound C[Si+](C)C VOYMPSZBODLRKS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims 7
- 150000001767 cationic compounds Chemical class 0.000 claims 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims 2
- DEDZSLCZHWTGOR-UHFFFAOYSA-N propylcyclohexane Chemical compound CCCC1CCCCC1 DEDZSLCZHWTGOR-UHFFFAOYSA-N 0.000 claims 2
- 125000006743 (C1-C60) alkyl group Chemical group 0.000 claims 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims 1
- 229960003750 ethyl chloride Drugs 0.000 claims 1
- 150000008282 halocarbons Chemical class 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims 1
- 229940073584 methylene chloride Drugs 0.000 claims 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims 1
- YFDAMRSZJLWUSQ-UHFFFAOYSA-N tris(2-methylphenyl)borane Chemical compound CC1=CC=CC=C1B(C=1C(=CC=CC=1)C)C1=CC=CC=C1C YFDAMRSZJLWUSQ-UHFFFAOYSA-N 0.000 claims 1
- LEIHCYASDULBKZ-UHFFFAOYSA-N tris(4-methylphenyl)borane Chemical compound C1=CC(C)=CC=C1B(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LEIHCYASDULBKZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 16
- 229920005549 butyl rubber Polymers 0.000 abstract description 9
- 125000002091 cationic group Chemical group 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000002841 Lewis acid Substances 0.000 description 8
- 150000007517 lewis acids Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SCABQASLNUQUKD-UHFFFAOYSA-N silylium Chemical class [SiH3+] SCABQASLNUQUKD-UHFFFAOYSA-N 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012683 anionic precursor Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical compound [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000004678 hydrides Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- RJUCIROUEDJQIB-GQCTYLIASA-N (6e)-octa-1,6-diene Chemical compound C\C=C\CCCC=C RJUCIROUEDJQIB-GQCTYLIASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical compound CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 description 1
- KLAWFKRMCIXRFS-UHFFFAOYSA-N 5-ethenylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C=C)CC1C=C2 KLAWFKRMCIXRFS-UHFFFAOYSA-N 0.000 description 1
- UGJBFMMPNVKBPX-UHFFFAOYSA-N 5-propan-2-ylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C(C)C)CC1C=C2 UGJBFMMPNVKBPX-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AASUFOVSZUIILF-UHFFFAOYSA-N diphenylmethanone;sodium Chemical compound [Na].C=1C=CC=CC=1C(=O)C1=CC=CC=C1 AASUFOVSZUIILF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002290 germanium Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002737 metalloid compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006216 polyvinyl aromatic Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A process for polymerizing a cationically polymerizable olefin such as a mixtrue of isoprene and isobutylene to produce butyl rubber. The process is conducted at subatmospheric pressure in the presence of a conventional cationic polymerization catalyst system. The preferred cationic polymerizati on catalyst system comprises Cp*TiMe3 and B(C6H5)3. By conducting the process i n this manner at subatmospheric pressure, a polymer having desirable molecular weight properties may be produced at a higher temperature than conventional means thereby lower capital and operating costs of the plant producing the polymer product.
Description
PROCESS FOR POLYMERIZING A CATIONICALLY
POLYMERIZABLE OLEFIN
TECHNICAL FIELD
The present invention relates to a process for polymerizing at least one canonically polymerizable olefin.
BACKGROUND ART
Cationic polymerization of olefins is known in the art.
Conventional, cationic polymerization is effected using a catalyst system comprising: (i) a Lewis acid, (ii) a tertiary alkyl initiator molecule containing a halogen, ester, ether, acid or alcohol group, and, optionally, (iii) an electron donor molecule such as ethyl acetate. Such catalysts systems have been used for the so-called "living" and "non-living" carbocationic polymerization of oleFms.
Component (ii) of the catalyst system typically is a compound having the formula:
Rz R' X
n wherein R' , RZ and R3 are a variety of alkyl or aromatic groups or combinations thereof, n is the number of initiator molecules and X is the functional group on which the Lewis acid effects a change to generate a carbocationic initiatiation site - i.e., X typically is a halogen, ester, ether, acid or alcohol group depending on the Lewis acid employed. One or two X groups per initiator molecule tends to lead to the production of substantially linear polymers, whereas three or more X groups per initiator molecule tends to lead to the production of substantially star polymers.
Catalyst systems based on halogens and/or alkyl-containing Lewis acids, such as boron trichloride and titanium tetrachloride, use various combinations S of the above components and typically have similar process characteristics.
For the so-called "living" polymerization systems, it is conventional for Lewis acid concentrations to exceed the concentration of initiator sites by 16 to 40 times in order to achieve 100 percent conversion in 30 minutes (based upon a degree of polymerization equal to 890) at -75 ° to -80°C.
Examples of the so-called "living" polymerization systems are taught in United States patents 4,929,683 and United States patent 4,910,321, the contents of each of which are incorporated herein by reference. Specifically, these patents teach the use of Lewis acids in combination with organic acids, organic esters or organic ethers to form cationic polymerization initiators that 1S also create a complex counter anion. Apparently, the complex counter anion does not assist in or cause proton elimination.
In the so-called "non-living" polymerization systems, high molecular weight polyisobutylenes are prepared practically only at low temperatures (-60 to -100°C) and at catalyst concentrations exceeding one catalyst molecule per initiator molecule. In practice, many of these catalyst systems are applicable only in certain narrow temperature regions and concentration profiles.
In recent years, a new class of catalyst systems utilizing compatible non coordinating anions in combination with cyclopentadienyl transition metal compounds (also referred to in the art as "metallocenes") has been developed.
2S See, for example, any one of:
published European patent application 0,277,003A;
published European patent application 0,277,004;
United States patent 5,198,401; and published International patent application W092/00333.
POLYMERIZABLE OLEFIN
TECHNICAL FIELD
The present invention relates to a process for polymerizing at least one canonically polymerizable olefin.
BACKGROUND ART
Cationic polymerization of olefins is known in the art.
Conventional, cationic polymerization is effected using a catalyst system comprising: (i) a Lewis acid, (ii) a tertiary alkyl initiator molecule containing a halogen, ester, ether, acid or alcohol group, and, optionally, (iii) an electron donor molecule such as ethyl acetate. Such catalysts systems have been used for the so-called "living" and "non-living" carbocationic polymerization of oleFms.
Component (ii) of the catalyst system typically is a compound having the formula:
Rz R' X
n wherein R' , RZ and R3 are a variety of alkyl or aromatic groups or combinations thereof, n is the number of initiator molecules and X is the functional group on which the Lewis acid effects a change to generate a carbocationic initiatiation site - i.e., X typically is a halogen, ester, ether, acid or alcohol group depending on the Lewis acid employed. One or two X groups per initiator molecule tends to lead to the production of substantially linear polymers, whereas three or more X groups per initiator molecule tends to lead to the production of substantially star polymers.
Catalyst systems based on halogens and/or alkyl-containing Lewis acids, such as boron trichloride and titanium tetrachloride, use various combinations S of the above components and typically have similar process characteristics.
For the so-called "living" polymerization systems, it is conventional for Lewis acid concentrations to exceed the concentration of initiator sites by 16 to 40 times in order to achieve 100 percent conversion in 30 minutes (based upon a degree of polymerization equal to 890) at -75 ° to -80°C.
Examples of the so-called "living" polymerization systems are taught in United States patents 4,929,683 and United States patent 4,910,321, the contents of each of which are incorporated herein by reference. Specifically, these patents teach the use of Lewis acids in combination with organic acids, organic esters or organic ethers to form cationic polymerization initiators that 1S also create a complex counter anion. Apparently, the complex counter anion does not assist in or cause proton elimination.
In the so-called "non-living" polymerization systems, high molecular weight polyisobutylenes are prepared practically only at low temperatures (-60 to -100°C) and at catalyst concentrations exceeding one catalyst molecule per initiator molecule. In practice, many of these catalyst systems are applicable only in certain narrow temperature regions and concentration profiles.
In recent years, a new class of catalyst systems utilizing compatible non coordinating anions in combination with cyclopentadienyl transition metal compounds (also referred to in the art as "metallocenes") has been developed.
2S See, for example, any one of:
published European patent application 0,277,003A;
published European patent application 0,277,004;
United States patent 5,198,401; and published International patent application W092/00333.
These references teach a method by which the metallocenes (biscyclopentadienyl and monocyclopentadienyl transition metal compounds) are protonated by an anionic precursor such that an alkyl/hydride group is abstracted from a transition metal to make it both cationic and charge-balanced by the non-coordinating anion.
The use of ionizing compounds not containing an active proton is also known. See, for example, any one of:
published European patent application 0,426,637A; and published European patent application 0,573,403A.
A further method of making ionic catalysts is disclosed in published European patent application 0,520,732A. Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anionic pre-cursors containing metallic oxidizing groups along with the anion groups - see, for example, published European patent application 0,495, 375A.
It is also known in the art to immobilize the cationic polymerization catalyst system on an inert support material. Methods of supporting ionic catalysts comprising metallocene cations and non-coordinating anions are described in:
published International patent application W091/09882; and published International patent application W094/03506.
Further, United States patent 5,066,741 teaches the preparation of syndiotactic polystyrene or polyvinyl aromatics) using non-coordinating anions in combination with cyclopentadienyl transition metal derivatives under coordination catalysis conditions. In United States patents 5,196,490 and 4,808,680 there is disclosed a similar procedure using an alumoxane.
Jordan, in the Journal of the American Chemical Society (1986, 108, 1718-1719) teaches that tetraphenyl boron forms stable complexes with bis(cyclopentadienyl)zirconiumdimethyl, unhindered Lewis bases such as 4,4'-dimethylbipyridine and 4-(dimethylamino) pyridine in CH3CN. This reference also teaches that tetraphenyl boron is stable in THF solution.
The polymerization of olefin monomers comprising isobutylene, including mixtures thereof with small amounts of isoprene to produce butyl rubber, present unique challenges. Specifically, as is well known in the art, since the polymerization reaction is highly exothermic, it is necessary to cool the reaction mixture to approximately -95 °C in large scale production facilities.
This requirement has remained notwithstanding advances in the art relating to the development of novel reactor designs and/or novel catalyst systems.
Thus, it would be desirable to have a novel approach to polymerization of cationically polymerizable olefins, particularly olefins such as isobutylene and mixtures thereof with diolefins (e.g., isoprene), which would allow for the polymerization reaction to be conducted under less stringent temperature regimes. It would be particularly useful if the novel approach could be readily adapted to existing production facilities.
DISCLOSURE OF THE INVENTION
It is an object of the present invention to obviate or mitigate at least one of the above-mentioned disadvantages of the prior art.
It is another object of the present invention to provide a novel process for polymerizing a cationically polymerizable olefin.
It is yet another object of the present invention to provide a novel process for polymerizing an olefin monomer comprising isobutylene.
Accordingly, in one of its aspects, the present invention provides a process for polymerizing a cationically polymerizable olefin comprising the step of polymerizing at least one cationically polymerizable olefin at a subatmospheric pressure in the presence of a cationic polymerization catalyst system.
The use of ionizing compounds not containing an active proton is also known. See, for example, any one of:
published European patent application 0,426,637A; and published European patent application 0,573,403A.
A further method of making ionic catalysts is disclosed in published European patent application 0,520,732A. Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anionic pre-cursors containing metallic oxidizing groups along with the anion groups - see, for example, published European patent application 0,495, 375A.
It is also known in the art to immobilize the cationic polymerization catalyst system on an inert support material. Methods of supporting ionic catalysts comprising metallocene cations and non-coordinating anions are described in:
published International patent application W091/09882; and published International patent application W094/03506.
Further, United States patent 5,066,741 teaches the preparation of syndiotactic polystyrene or polyvinyl aromatics) using non-coordinating anions in combination with cyclopentadienyl transition metal derivatives under coordination catalysis conditions. In United States patents 5,196,490 and 4,808,680 there is disclosed a similar procedure using an alumoxane.
Jordan, in the Journal of the American Chemical Society (1986, 108, 1718-1719) teaches that tetraphenyl boron forms stable complexes with bis(cyclopentadienyl)zirconiumdimethyl, unhindered Lewis bases such as 4,4'-dimethylbipyridine and 4-(dimethylamino) pyridine in CH3CN. This reference also teaches that tetraphenyl boron is stable in THF solution.
The polymerization of olefin monomers comprising isobutylene, including mixtures thereof with small amounts of isoprene to produce butyl rubber, present unique challenges. Specifically, as is well known in the art, since the polymerization reaction is highly exothermic, it is necessary to cool the reaction mixture to approximately -95 °C in large scale production facilities.
This requirement has remained notwithstanding advances in the art relating to the development of novel reactor designs and/or novel catalyst systems.
Thus, it would be desirable to have a novel approach to polymerization of cationically polymerizable olefins, particularly olefins such as isobutylene and mixtures thereof with diolefins (e.g., isoprene), which would allow for the polymerization reaction to be conducted under less stringent temperature regimes. It would be particularly useful if the novel approach could be readily adapted to existing production facilities.
DISCLOSURE OF THE INVENTION
It is an object of the present invention to obviate or mitigate at least one of the above-mentioned disadvantages of the prior art.
It is another object of the present invention to provide a novel process for polymerizing a cationically polymerizable olefin.
It is yet another object of the present invention to provide a novel process for polymerizing an olefin monomer comprising isobutylene.
Accordingly, in one of its aspects, the present invention provides a process for polymerizing a cationically polymerizable olefin comprising the step of polymerizing at least one cationically polymerizable olefin at a subatmospheric pressure in the presence of a cationic polymerization catalyst system.
In another of its aspects the present invention provides a process for polymerizing an olefin monomer comprising isobutylene, the process comprising the step of polymerizing the olefin monomer at a subatmospheric pressure at a temperature higher than about -80°C in the presence of a cationic polymerization catalyst system.
Thus, the present inventor has surprisingly and unexpectedly discovered that it is possible to produce useful polymers by polymerizing a cationically polymerizable olefin at a subatmospheric pressure. This discovery is especially surprising and unexpected when applied to the polymerization of an olefin comprising isobutylene, optionally containing a diolefm such as isoprene.
Specifically, the present process is applicable to the production of butyl rubber at temperatures higher than is conventional. This particular application of the process can result in significant savings in capital and operating expenses for a butyl rubber production facility.
BEST MODE FOR CARRYING OUT THE INVENTION
Thus, the present process is directed to the polymerization of at least one cationically polymerizable monomer. Of course the present process may be used to polymerize a mixture of monomers comprising the cationically polymerizable monomer. The mixture may comprise another cationically polymerizable monomer and/or another polymerizable monomer.
Preferably, the cationically polymerizable olefin is selected from the group comprising an olefin, a styrenic olefin, a heteroatom olefin and mixtures thereof.
Preferably, the olefin comprises a CZ-C3o olefin, more preferably a C2-Czo olefin. Non-limiting examples of a useful olefin may be selected from the group comprising ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, dodecyldocecene, 3-methylpentene-1, 3,5,5 trimethylhexene-1, isobutylene, 2-methyl-butene, 2-methyl-pentene, vinyl ether, vinyl carbazole and mixtures thereof.
Thus, the present inventor has surprisingly and unexpectedly discovered that it is possible to produce useful polymers by polymerizing a cationically polymerizable olefin at a subatmospheric pressure. This discovery is especially surprising and unexpected when applied to the polymerization of an olefin comprising isobutylene, optionally containing a diolefm such as isoprene.
Specifically, the present process is applicable to the production of butyl rubber at temperatures higher than is conventional. This particular application of the process can result in significant savings in capital and operating expenses for a butyl rubber production facility.
BEST MODE FOR CARRYING OUT THE INVENTION
Thus, the present process is directed to the polymerization of at least one cationically polymerizable monomer. Of course the present process may be used to polymerize a mixture of monomers comprising the cationically polymerizable monomer. The mixture may comprise another cationically polymerizable monomer and/or another polymerizable monomer.
Preferably, the cationically polymerizable olefin is selected from the group comprising an olefin, a styrenic olefin, a heteroatom olefin and mixtures thereof.
Preferably, the olefin comprises a CZ-C3o olefin, more preferably a C2-Czo olefin. Non-limiting examples of a useful olefin may be selected from the group comprising ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, dodecyldocecene, 3-methylpentene-1, 3,5,5 trimethylhexene-1, isobutylene, 2-methyl-butene, 2-methyl-pentene, vinyl ether, vinyl carbazole and mixtures thereof.
Preferably, the styrenic olefin is selected from the group comprising styrene, C,-Cbo alkyl substituted styrene and mixtures thereof. Non-limiting examples of useful styrenic olefins may be selected from the group comprising styrene, a-methyl styrene, p-chlorostyrene, p-methylstyrene and mixtures thereof.
Preferably, the heteroatom olefin is selected from the group comprising alkyl vinyl ethers, alkyl, amines, alkenyl amines and aryl amines. Non-limiting examples of useful heteroatom olefins may be selected from the group comprising methyl vinyl ether, isobutylvinyl ether, butyl vinyl ether, vinyl carbazole and mixtures thereof.
A preferred monomer comprises a mixture of isobutylene and p-methyl styrene.
In a particularly preferred embodiment, polymerization is conducted in the presence of the at least one cationically polymerizable olefin and a diene monomer. The diene monomer may be conjugated or non-conjugated.
Diolefm monomers are well known in the art and the choice thereof for use in the present process is within the purview of a person skilled in the art.
The non-conjugated diolefin can be straight chain, branched chain or cyclic hydrocarbon dioolefms having from 6 to 15 carbon atoms. Illustrative nonlimiting examples are straight chain acyclic diolefms such as 1,4-hexadiene and 1,6-octadiene, the branched chain acyclic diolefms such as 5-methylhexadiene-1,4, 7-methyl-octadiene-1,6 and 7-methyl-octadiene-1,7;
single ring alicyclic diolefms such as 1,4-cyclohexadiene and 1,5-cyclooctadiene, and mufti ring alicyclic fused and bridged ring dioolefins such as tetrahydroindene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinylidene-2-norbornene and 5-isopropylidene-2-norbornene. The conjugated diolefin is preferably selected from the group comprising 2,3-dimethyl-butadiene-1,3, isoprene, 1,3-butadiene and mixtures thereof.
As mentioned hereinabove, the present process is particularly advantageous in the preparation of butyl rubber polymers. The term "butyl rubber" as used throughout this specification is intended to denote polymers _7_ prepared by reacting a major portion, e.g., from about 70 to 99.5 parts by weight, usually 85 to 99.5 parts by weight of an isomonoolefin, such as isobutylene, with a minor portion, e.g., about 30 to 0.5 parts by weight, usually 15 to 0.5 parts by weight, of a multiolefm, e.g., a conjugated diolefin, such as isoprene or butadiene, for each 100 weight parts of these monomers reacted.
The isoolefin, in general, is a C4 to C8 compound , e.g., isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene and 4-methyl-1-pentene. The preferred monomer mixture for use in the production of butyl rubber comprises isobutylene and isoprene. Optionally, an additional olefinic termonomer such as styrene, a-methylstyrence, p-methylstyrene, chlorostyrene, pentadiene and the like may be incorporated in the butyl rubber polymer. See, for example, any one of:
United States patent 2,631,984;
United States patent 5,162,445; and United States patent 5,886,106.
The present process is conducted at subatmospheric pressure.
Preferably, the pressure at which the present process is conducted is less than about 100 kPa, more preferably less than about 90 kPa, even more preferably in the range of from about 0.00001 to about 50 kPa, even more preferably in the range of from about 0.0001 to about 40 kPa, even more preferably in the range of from about 0.0001 to about 30 kPa, most preferably in the range of from about 0.0001 to about 15 kPa.
The present process comprises the use of a cationic polymerization system.
Preferably, the cationic polymerization system comprises a reactive cation and a compatible non-coordinating anion. The reactive cation may be any cation that can react with an olefin to create a carbocationic polymerization site.
_8_ The terms "compatible non-coordinating anion" and "NCA" are used interchangeably throughout this specification and are intended to encompass an anion which either does not coordinate the cation or which is only weakly coordinated to the cation thereby remaining sufficiently labile to be displaced by an olefin monomer. Further, the term "compatible non-coordinating anion"
specifically refers to an anion which, when functioning as a stabilizing anion in the cationic polymerization system used in the present process, does not irreversibly transfer an anionic substituent or fragment thereof to the cation thereby forming a neutral byproduct or other neutral compound. Compatible non-coordinating anions are anions which are not degraded to neutrality when the initially formed complex decomposes.
Non-limiting examples of such compatible non-coordinating anions may be selected from the group comprising alkyltris(pentafluorophenyl) boron (RB(pfp)3-), tetraperfluorophenylboron (B(pfp)4-), tetraperflouro-phenylaluminum, carboranes, halogenated carboranes and the like.
For clarity, the formulae presented below depict the catalyst components in the "ionic" state. Of course, those of skill in the art will readily realize that many of these components are not stable as depicted and are obtained from a neutral stable form. For example, the species:
Me I+
CP2~.
typically does not exist in this state alone. Rather, it is formed by reacting Cp2ZrMez with another compound that will abstract an Me group. This convention of describing the components in "ionic" form is used for descriptive purposes only and should not be construed as limiting in any way.
The following references teach the neutral stable forms, and the synthesis of the cyclopentadienyl transition metal compositions and the NCA:
published International patent application WO 92/00333;
publised European patent application 0,129,368A;
published European patent application 0,551,277A
published European patent application 0,520,732A;
published European patent application 0,277,003A;
published European patent application 0,277,004A;
published European patent application 0,426,637A;
published European patent application 0,573,403A;
published European patent application 0,520,732A;
published European patent application 0,495,375A.
United States patent 5,017,714;
United States patent 5,055,438;
United States patent 5,153,157; and United States patent 5,198,401.
For a description of compounds capable of producing the ionic species in situ see either of published European patent applications 0,500,944A and 0,570,982A. These references teach in situ processes comprising the reaction of alkyl aluminum compounds with dihalosubstituted metallocene compounds prior to or with the addition of activating anionic compounds.
The neutral stable forms of the substituted carbocations and synthesis thereof are described in United States patent 4,910,321, United States patent 4,929,683 and published European patent application 0,341,012A. In general, the neutral stable form of such carbocations is typically represented by the formula:
Rz R' X
n wherein R,, RZ, and R3 are a variety of substituted or unsubstituted alkyl or aromatic groups or combinations thereof, n is the number of initiator molecules and is preferably greater than or equal to 1, even more preferably between 1 and 30, and X is the functional group on which the Lewis acid affects a change to bring about the carbocationic initiating site. This group is typically a halogen, ester, ether, alcohol or acid group depending on the Lewis acid employed.
For a discussion of stable forms of the substituted silylium and synthesis thereof, see F.A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, John Wiley and Sons, New York 1980. Likewise for stable forms of the cationic tin, germanium and lead compositions and synthesis thereof, see Dictionary of Organometallic compounds, Chapman and Hall New York 1984.
Thus, as stated hereinabove, the preferred cationic polymerization system comprises: (i) a reactive cation, and (ii) a non-coordinating anion.
A preferred class of compatible non-coordinating anions includes chemically stable, non-nucleophilic substituted anionic complexes.
With reference to the non-coordinating anion, any metal or metalloid compound may be used that is capable of forming an anionic complex which is resistant to irreversibly transferring a substituent or fragment to the cation to neutralize the cation to produce a neutral molecule. In addition, any metal or metalloid capable of forming a coordination complex which is stable in water may also be used or contained in a composition comprising the anion. Suitable metals include, but are not limited to, boron, phosphorus, silicon and the like.
Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially. In light of this, salts containing anions comprising a coordination complex containing a single boron atom are preferred.
Preferably, the non-coordinating anion has the formula:
((M') m+QI ,.. Qn~d_ wherein:
M' is a metal or metalloid;
Q, to Q~ are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, with the proviso that not more than one of Ql to Q" may be a halide radical;
m is an integer representing the formal valence charge of M;
n is the total number of ligands Q; and d is an integer greater than or equal to 1.
As set out above, it is to be understood that the anions herein are, in practice, counter balanced with a positively charged component that is removed before the anion acts with the reactive cation.
Non-limiting examples of a metal useful as M may be selected from the group comprising aluminum, gold and platinum. Non-limiting examples of a metalloid useful as M may be selected from the group comprising boron, phosphorus and silicon.
In a preferred embodiment:
M' is boron;
n=4;
Q, and QZ are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from about 6 to about 20 carbon atoms and may be linked to each other through a stable bridging group; and Q3 and Q4 are, independently, hydride radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals, hydrocarbyl- and halocarbyl-substituted organometalloid radicals, disubstituted pnictogen radicals, substituted chalcogen radicals and halide radicals, with the proviso that Q3 and Q4 will not be halide at the same time.
Non-limiting examples of boron components which may be used as NCA's may be selected from the group comprising: tetra-valent boron compounds such as tetra(phenyl)boron, tetra(p-tolyl)boron, tetra(o-tolyl)boron, tetra(pentafluorophenyl)boron, tetra(o,p-dimethylphenyl)boron, tetra(m,m-dimethylphenyl)boron, (p-tri-fluoromethylphenyl)boron and mixtures thereof.
In a particularly preferred embodiment, M = boron, n = 4, Q,, QZ and Q3 are each (C6F5) and Q4 is as defined above. Non-limiting examples of those preferred NCA's comprising boron triphenylmethyl salts where Q is a simple hydrocarbyl such as methyl, butyl, cyclohexyl, or phenyl or where Q is a polymerix hydrocarbyl of indefinite chain length such as polystyrene, polyisoprene or poly(paramethylstyrene).
Another preferred class of NCA's is the class comprising those NCA
comprising a plurality of boron atoms, including boranes and carboranes . Non-limiting examples of carborane NCA's may be selected from the group comprising: dodecaborate, decachlorodecaborate, dodecachlorododecaborate, 1-carbadecaborate,1-carbaundecaborate,1-trimethylsilyl-1-carbadecaborate and mixtures thereof. Non-limiting examples of borane and carborane complexes and salts of borane and carborane anions may be selected from the group comprising decaborane(14), 7,8-dicarbadecaborane(13), 2,7-dicarbaundecaborane(13), undecahydrido-7,8-dimethyl-7,8-dicarbaundecaborane, 6-carbadecaborate(12), 7-carbaundecaborate, 7,8-dicarbaundecaborate.
Further, NCA's comprising metallaborane anions are also useful. Non-limiting examples of such NCA's may be selected from the group comprising bis(nonahydrido-1,3-dicarbanonaborato)cobaltate(III), bis(undecahydrido-7,8-dicarbaundecaborato)ferrate(III), bis(undecahydrido-7,8-dicarbaundecaborato) cobaltate(III), bis(undecahydrido-7,8-dicarbaborato) nikelate(III), bis(nonahydrido-7, 8-dimethyl-7, 8-dicarbaundecaborato)ferrate(III), bis(tribromooctahydrido-7, 8-dicarbaundecaborato)cobaltate(III), bis(undecahydridodicarbadodecaborato)cobaltate(III), bis(undecahydrido-7-carbaundecaborato) cobaltate(III) and mixtures thereof.
The NCA compositions most preferred for use in the cationic polymerization system are those containing a tris-perfluorophenyl boron, tetrapentafluorphenyl boron anion and/or two or more tripentafluorophenyl boron anion groups covalently bonded to a central atomic molecular or polymeric complex or particle.
The other component in the preferred cationic polymerization catalyst system comprises one or more reactive cations that are selected from different classes of cations and cation sources. Some preferred classes are:
(A) cyclopentadienyl transition metal complexes and derivatives thereof;
(B) substituted carbocations;
(C) substituted silylium;
(D) compositions capable of generating a proton as further described below; and (E) cationic compositions of germanium, tin or lead.
With reference to class (A), preferred cyclopentadienyl metal derivatives may be selected from the group comprising compounds that are a mono-, bis-or tris-cyclopentadienyl derivative of a transition metal selected from Groups 4, 5 or 6 of the Periodic Table of Elements. Preferred compositions include mono- cyclopentadienyl (Mono-Cp) or bis-cyclopentadienyl (Bis-Cp) Group 4 transition metal compositions, particularly zirconium, titanium and/or hafnium compositions.
Preferred cyclopentadienyl derivatives are transition metal complexes selected from the group comprising:
(A- Cp)M+ (A _ Cp)M+ ( i PR) Xl L (Cp*)- M
(CsHs-y-Xs~
(CsHs y-xsx) (A~)y M.-X M+
R"~ \X
~~(Z-~-y>
wherein:
(A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp*;
Cp and Cp* are the same or different cyclopentadienyl rings substituted with from 0 to 5 substituent groups S, each substituent group S being, independently, a radical group selected from the group comprising hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, 10 disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to CZO ring system to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
R is a substituent on one of the cyclopentadienyl radicals which is also 15 bonded to the metal atom;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings or (CSHS_y.XSX) and JR'(Z_1_y) groups;
M is a Group 4,5, or 6 transition metal;
y is 0 or 1;
(CSHS_y_XSX) is a cyclopentadienyl ring substituted with from 0 to 5 S
radicals;
x is from 0 to 5;
JR' (Z_,_,,) is a heteroatom ligand in which J is a Group 15 element with a coordination number of three or a Group 16 element with a coordination number of 2, preferably nitrogen, phosphorus, oxygen or sulfur;
R" is a hydrocarbyl group;
X and X' are independently a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, and hydrocarbyl- and halocarbyl-substituted organometalloid radical, substituted pnictogen radical, or substituted chalcogen radicals; and L is an olefin, diolefin or aryne ligand, or a neutral Lewis base.
Other cyclopentadienyl compounds that may be used in the cationic polymerization catalyst system are described in:
published European patent application 0,551,277A;
United States patent 5,055,438;
United States patent 5,278,119;
United States patent 5,198,401; and United States patent 5,096,867.
With reference to class (B), a preferred group of reactive cations comprises carbocationic compounds having the formula:
R~
wherein R', Rz and R3, are independently hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, with the proviso that only one of R' , R2 and R3 may be hydrogen. Preferably, none of R', RZ and R3 are H. Preferably, R', R'- and R3, are independently a C, to CZO aromatic or aliphatic group. Non-limiting examples of suitable aromatic groups may be selected from the group comprising phenyl, toluyl, xylyl and biphenyl. Non-limiting examples of suitable aliphatic groups may be selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl.
With reference to class (C), a preferred group of reactive cations comprises substituted silylium cationic compounds having the formula:
R' I
R2- S~ R3 wherein R', RZ and R3, are independently hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, with the proviso that only one of R', RZ
and R3 may be hydrogen. Preferably, none of R', RZ and R3 are H. Preferably, R', R'- and R3 are, independently, a C1 to C~ aromatic or aliphatic group. More preferably, R', RZ and R3 are independently a C, to C8 alkyl group. Non-limiting examples of useful aromatic groups may be selected from the group comprising phenyl, toluyl, xylyl and biphenyl. Non-limiting examples of useful aliphatic groups may be selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl. A particularly preferred group of reactive substituted silylium cations may be selected from the group comprising trimethylsilylium, triethylsilylium and benzyldimethylsilylium. Such cations may be prepared by the exchange of the hydride group of the R'RZR3Si-H with the NCA, such as Ph3C+B(pfp)4 yielding compositions such as R'R2R3SiB(pfp)4 which in the appropriate solvent obtain the cation.
With reference to class (D), the source for the cation may be any compound that will produce a proton when combined with the non-coordinating anion or a composition containing a non-coordinating anion. Protons may be generated from the reaction of a stable carbocation salt which contains a non-coordinating, non-nucleophilic anion with water, alcohol or phenol to produce the proton and the corresponding by-product. Such reaction may be preferred in the event that the reaction of the carbocation salt is faster with the protonated additive as compared with its reaction with the olefin. Other proton generating reactants include thiols, carboxylic acids, and the like. Similar chemistries may be realized with silylium type catalysts. In another embodiment, when low molecular weight polymer product is desired an aliphatic or aromatic alcohol may be added to inhibit the polymerization.
Another method to generate a proton comprises combining a Group 1 or Group 2 metal cation, preferably lithium, with water, preferably in a wet, non-protic organic solvent, in the presence of a Lewis base that does not interfere with polymerization. A wet solvent is defined to be a hydrocarbon solvent partially or fully saturated with water. It has been observed that when a Lewis base, such as isobutylene, is present with the Group 1 or 2 metal cation and the water, a proton is generated. In a preferred embodiment the non-coordinating anion is also present in the "wet" solvent such that active catalyst is generated when the Group 1 or 2 metal cation is added.
With reference to class (E), another preferred source for the cation is substituted germanium, tin or lead cations. Preferred non-limiting examples of such cations include substances having the formula:
R' R2_ M- R3 wherein R', RZ and R3, are independently hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, and M is germanium, tin or lead with the proviso that only one of R', R' and R3 may be hydrogen. Preferably, none of R', RZ and R3 are H. Preferably, R', RZ and R3 are, independently, a C, to CZo aromatic or aliphatic group. Non-limiting examples of useful aromatic groups may be selected from the group comprising phenyl, toluyl, xylyl and biphenyl.
Non-limiting examples of useful aliphatic groups may be selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl.
A further preferred non-coordinating anion comprises a compound selected from the group comprising:
CM ~ _Z_M ~~~a_ wherein:
d is an integer greater than or equal to 1;
Z is selected from the group comprising: OR-, SR~, SeR-, NRz , PRi , AsRz , SbRi , F-, Cl', Br and I-;
R is selected from the group comprising hydrogen, C,-C4o alkyl, C,-C~
cycloalkyl, CS-C4o aryl, halogen substituted derivatives thereof and heteratom substituted derivatives thereof;
M' and M" may be the same or different and each has the formula M~Q1 ... Qn wherein:
M is a metal or metalloid;
Ql to Q~ are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, with the proviso that not more than one of Q, to Q" may be a halide radical; and n is an integer representing the formal valence charge of M.
Preferably, M is selected from the group comprising B, Al, Ga and In.
In this embodiment, the preferred non-coordinating anion is a tetra-valent boron compound. Non-limiting examples of such compounds may be selected from the group comprising tri(phenyl)boron, trip-tolyl)boron, trio-tolyl)boron, tri(pentafluorophenyl)boron, tri(o,p-dimethylphenyl)boron, tri(m,m-dimethylphenyl)boron and (p-tri-fluoromethylphenyl)boron.
Further details on the interaction of the reactive cation and the non-coordination anion of the preferred cationic polymerization system may be found in published International patent application WO 95/29940.
A particularly preferred type of cationic polymerization catalyst system is disclosed in United States patent 5,448,001. In some cases, it is possible to use the coinitiator (BRR'R") disclosed in the '001 patent as the sole component of the cationic polymerization system in the present process. This approach is particularly well suited for the production of isobutylene-based polymers such as isobutylene homopolymer and the like.
As described above, the present process is particularly well suited for the production of butyl rubber and other isobutylene-based polymers.
Specifically, it has been discovered that such rubbers and polymers having desirable physical properties may be produced at higher temperatures than conventionally used.
Thus, the present process may be conducted at a temperature higher than about -80°C, preferably at a temperature in the range of from about -80°C to about 25°C, more preferably at a temperature in the range of from about -40°C
to about 25°C, even more preferably at a temperature in the range of from about -30°C to about 25°C, even more preferably at a temperature in the range of from about -20°C to about 25°C, most preferably at a temperature in the range of from about 0°C to about 25°C.
Embodiments of the present invention will be described with reference to the following Examples which are provided for illustrative purposes only and should note be used to limit the scope of or construe the invention.
All glassware was dried by heating at 120°C for at least 12 hours before being assembled in a nitrogen filled dry box. Nitrogen was purified by passing sequentially over heated BASF catalyst and molecular sieves. Dichloromethane was dried by refluxing over calcium hydride under nitrogen, toluene by refluxing over sodium-benzophenone under nitrogen, and both solvents were freshly distilled under nitrogen immediately prior to use.
The dime monomers (isoprene (IP) or 2,3-dimethyl-1,3-butadiene, (DMBD)) were dried over molecular sieves and then distilled. Isobutylene (IB) was purified by passing through molecular sieve and barium oxide columns, and condensed into a graduated flask immersed in liquid nitrogen. The IB was allowed to melt, the volume was noted ( --- 3 to ~ 9 mL) and the IB was then refrozen by immersing in the liquid nitrogen bath. The system was evacuated to 10-' to 10-2 torr, and the IB was melted and distilled at a temperature in the range of from about -10°C to about -6.5°C (the boiling point of IB being -6.4°C at one atmosphere pressure) into the glass polymerization vessel; 6 mL
of solvent (toluene) was added to the condenser which was attached to the reactor; and the solution of IB was brought to the desired temperature (usually approximately -30°C).
Solutions of Cp*TiMe3 (Cp*= ~5-pentamethylcyclopentadienyl; Me methyl; usually 14 mg, 0.06 mmol; recrystallized from pentane) and B(C6F5)3 (usually 32 mg, 0.06 mmol; sublimed), both in 1-2 mL of solvent, were added sequentially to provide an initiator to monomer ratio of approximately 1:1500.
In some Examples, an amount of dime equivalent to --1 % (mole) of the amount of IB was added to the reaction vessel prior to the addition of initiator and co-initiator.
Solutions of olefins) and initiator system were generally stirred as long as possible under a static vacuum and at the predetermined temperature (by "static vacuum", it is meant that the system was closed at this point and the pressure essentially was the vapour pressure of PIB at the reaction temperature).
Copious amounts of polymeric materials generally began to precipitate after about 2 minutes, and reactions were terminated after 10-30 min by the addition of 5-10 mL methanol. The precipitated polymeric materials were purified of inorganic residues by dissolving in pentane or hexane and passing through a short silica column. Solvents were removed under reduced pressure and the solid, white polymers were dried at 60°C-90°C for at least two days. Control reactions were also run using just Cp*TiMe3 or B(C6F5)3.
In Table 1, there is reported the use of vacuum (where vacuum was not used, polymerization was conducted under Ar(g) at atmosphereic pressure), the presence/absence of isoprene comonomer, the polymerization temperature (T), the weight average molecular weight of the polymer product (Mw) and the polydispersity index (Mw/Mn) of the polymer product.
Table 1 Example Vacuum Comonomer T Mw, x Mw/Mn 1 No No -32C 41.3 2.0 2 Yes No -32 61.6 2.0 C
3 No Yes -30C 11.6 1.6 4 Yes Yes -30C 14.4 1.8 As will be apparent to those of skill in the art, a vacuum was not applied during polymerization in Examples 1 and 3. Accordingly, Examples 1 and 3 are provided for comparative purposes only and are not encompassed by the present invention.
The results in Table 1 support the conclusion that conducting the polymerization of isobutylene at subatmospheric pressure (Example 2) results in the production of a polymer having a higher Mw when compared to conducting the polymerization of isobutylene at atmospheric pressure (Example 1). Similarly, the results in Table 1 support the conclusion that conducting the polymerization of isobutylene/isoprene at subatmospheric pressure (Example 4) results in the production of a copolymer having a higher Mw when compared to conducting the polymerization of isobutylene/isoprene at atmospheric pressure (Example 3).
All publications, patents and patent applications referred to herein are incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety.
Preferably, the heteroatom olefin is selected from the group comprising alkyl vinyl ethers, alkyl, amines, alkenyl amines and aryl amines. Non-limiting examples of useful heteroatom olefins may be selected from the group comprising methyl vinyl ether, isobutylvinyl ether, butyl vinyl ether, vinyl carbazole and mixtures thereof.
A preferred monomer comprises a mixture of isobutylene and p-methyl styrene.
In a particularly preferred embodiment, polymerization is conducted in the presence of the at least one cationically polymerizable olefin and a diene monomer. The diene monomer may be conjugated or non-conjugated.
Diolefm monomers are well known in the art and the choice thereof for use in the present process is within the purview of a person skilled in the art.
The non-conjugated diolefin can be straight chain, branched chain or cyclic hydrocarbon dioolefms having from 6 to 15 carbon atoms. Illustrative nonlimiting examples are straight chain acyclic diolefms such as 1,4-hexadiene and 1,6-octadiene, the branched chain acyclic diolefms such as 5-methylhexadiene-1,4, 7-methyl-octadiene-1,6 and 7-methyl-octadiene-1,7;
single ring alicyclic diolefms such as 1,4-cyclohexadiene and 1,5-cyclooctadiene, and mufti ring alicyclic fused and bridged ring dioolefins such as tetrahydroindene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinylidene-2-norbornene and 5-isopropylidene-2-norbornene. The conjugated diolefin is preferably selected from the group comprising 2,3-dimethyl-butadiene-1,3, isoprene, 1,3-butadiene and mixtures thereof.
As mentioned hereinabove, the present process is particularly advantageous in the preparation of butyl rubber polymers. The term "butyl rubber" as used throughout this specification is intended to denote polymers _7_ prepared by reacting a major portion, e.g., from about 70 to 99.5 parts by weight, usually 85 to 99.5 parts by weight of an isomonoolefin, such as isobutylene, with a minor portion, e.g., about 30 to 0.5 parts by weight, usually 15 to 0.5 parts by weight, of a multiolefm, e.g., a conjugated diolefin, such as isoprene or butadiene, for each 100 weight parts of these monomers reacted.
The isoolefin, in general, is a C4 to C8 compound , e.g., isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene and 4-methyl-1-pentene. The preferred monomer mixture for use in the production of butyl rubber comprises isobutylene and isoprene. Optionally, an additional olefinic termonomer such as styrene, a-methylstyrence, p-methylstyrene, chlorostyrene, pentadiene and the like may be incorporated in the butyl rubber polymer. See, for example, any one of:
United States patent 2,631,984;
United States patent 5,162,445; and United States patent 5,886,106.
The present process is conducted at subatmospheric pressure.
Preferably, the pressure at which the present process is conducted is less than about 100 kPa, more preferably less than about 90 kPa, even more preferably in the range of from about 0.00001 to about 50 kPa, even more preferably in the range of from about 0.0001 to about 40 kPa, even more preferably in the range of from about 0.0001 to about 30 kPa, most preferably in the range of from about 0.0001 to about 15 kPa.
The present process comprises the use of a cationic polymerization system.
Preferably, the cationic polymerization system comprises a reactive cation and a compatible non-coordinating anion. The reactive cation may be any cation that can react with an olefin to create a carbocationic polymerization site.
_8_ The terms "compatible non-coordinating anion" and "NCA" are used interchangeably throughout this specification and are intended to encompass an anion which either does not coordinate the cation or which is only weakly coordinated to the cation thereby remaining sufficiently labile to be displaced by an olefin monomer. Further, the term "compatible non-coordinating anion"
specifically refers to an anion which, when functioning as a stabilizing anion in the cationic polymerization system used in the present process, does not irreversibly transfer an anionic substituent or fragment thereof to the cation thereby forming a neutral byproduct or other neutral compound. Compatible non-coordinating anions are anions which are not degraded to neutrality when the initially formed complex decomposes.
Non-limiting examples of such compatible non-coordinating anions may be selected from the group comprising alkyltris(pentafluorophenyl) boron (RB(pfp)3-), tetraperfluorophenylboron (B(pfp)4-), tetraperflouro-phenylaluminum, carboranes, halogenated carboranes and the like.
For clarity, the formulae presented below depict the catalyst components in the "ionic" state. Of course, those of skill in the art will readily realize that many of these components are not stable as depicted and are obtained from a neutral stable form. For example, the species:
Me I+
CP2~.
typically does not exist in this state alone. Rather, it is formed by reacting Cp2ZrMez with another compound that will abstract an Me group. This convention of describing the components in "ionic" form is used for descriptive purposes only and should not be construed as limiting in any way.
The following references teach the neutral stable forms, and the synthesis of the cyclopentadienyl transition metal compositions and the NCA:
published International patent application WO 92/00333;
publised European patent application 0,129,368A;
published European patent application 0,551,277A
published European patent application 0,520,732A;
published European patent application 0,277,003A;
published European patent application 0,277,004A;
published European patent application 0,426,637A;
published European patent application 0,573,403A;
published European patent application 0,520,732A;
published European patent application 0,495,375A.
United States patent 5,017,714;
United States patent 5,055,438;
United States patent 5,153,157; and United States patent 5,198,401.
For a description of compounds capable of producing the ionic species in situ see either of published European patent applications 0,500,944A and 0,570,982A. These references teach in situ processes comprising the reaction of alkyl aluminum compounds with dihalosubstituted metallocene compounds prior to or with the addition of activating anionic compounds.
The neutral stable forms of the substituted carbocations and synthesis thereof are described in United States patent 4,910,321, United States patent 4,929,683 and published European patent application 0,341,012A. In general, the neutral stable form of such carbocations is typically represented by the formula:
Rz R' X
n wherein R,, RZ, and R3 are a variety of substituted or unsubstituted alkyl or aromatic groups or combinations thereof, n is the number of initiator molecules and is preferably greater than or equal to 1, even more preferably between 1 and 30, and X is the functional group on which the Lewis acid affects a change to bring about the carbocationic initiating site. This group is typically a halogen, ester, ether, alcohol or acid group depending on the Lewis acid employed.
For a discussion of stable forms of the substituted silylium and synthesis thereof, see F.A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, John Wiley and Sons, New York 1980. Likewise for stable forms of the cationic tin, germanium and lead compositions and synthesis thereof, see Dictionary of Organometallic compounds, Chapman and Hall New York 1984.
Thus, as stated hereinabove, the preferred cationic polymerization system comprises: (i) a reactive cation, and (ii) a non-coordinating anion.
A preferred class of compatible non-coordinating anions includes chemically stable, non-nucleophilic substituted anionic complexes.
With reference to the non-coordinating anion, any metal or metalloid compound may be used that is capable of forming an anionic complex which is resistant to irreversibly transferring a substituent or fragment to the cation to neutralize the cation to produce a neutral molecule. In addition, any metal or metalloid capable of forming a coordination complex which is stable in water may also be used or contained in a composition comprising the anion. Suitable metals include, but are not limited to, boron, phosphorus, silicon and the like.
Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially. In light of this, salts containing anions comprising a coordination complex containing a single boron atom are preferred.
Preferably, the non-coordinating anion has the formula:
((M') m+QI ,.. Qn~d_ wherein:
M' is a metal or metalloid;
Q, to Q~ are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, with the proviso that not more than one of Ql to Q" may be a halide radical;
m is an integer representing the formal valence charge of M;
n is the total number of ligands Q; and d is an integer greater than or equal to 1.
As set out above, it is to be understood that the anions herein are, in practice, counter balanced with a positively charged component that is removed before the anion acts with the reactive cation.
Non-limiting examples of a metal useful as M may be selected from the group comprising aluminum, gold and platinum. Non-limiting examples of a metalloid useful as M may be selected from the group comprising boron, phosphorus and silicon.
In a preferred embodiment:
M' is boron;
n=4;
Q, and QZ are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from about 6 to about 20 carbon atoms and may be linked to each other through a stable bridging group; and Q3 and Q4 are, independently, hydride radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals, hydrocarbyl- and halocarbyl-substituted organometalloid radicals, disubstituted pnictogen radicals, substituted chalcogen radicals and halide radicals, with the proviso that Q3 and Q4 will not be halide at the same time.
Non-limiting examples of boron components which may be used as NCA's may be selected from the group comprising: tetra-valent boron compounds such as tetra(phenyl)boron, tetra(p-tolyl)boron, tetra(o-tolyl)boron, tetra(pentafluorophenyl)boron, tetra(o,p-dimethylphenyl)boron, tetra(m,m-dimethylphenyl)boron, (p-tri-fluoromethylphenyl)boron and mixtures thereof.
In a particularly preferred embodiment, M = boron, n = 4, Q,, QZ and Q3 are each (C6F5) and Q4 is as defined above. Non-limiting examples of those preferred NCA's comprising boron triphenylmethyl salts where Q is a simple hydrocarbyl such as methyl, butyl, cyclohexyl, or phenyl or where Q is a polymerix hydrocarbyl of indefinite chain length such as polystyrene, polyisoprene or poly(paramethylstyrene).
Another preferred class of NCA's is the class comprising those NCA
comprising a plurality of boron atoms, including boranes and carboranes . Non-limiting examples of carborane NCA's may be selected from the group comprising: dodecaborate, decachlorodecaborate, dodecachlorododecaborate, 1-carbadecaborate,1-carbaundecaborate,1-trimethylsilyl-1-carbadecaborate and mixtures thereof. Non-limiting examples of borane and carborane complexes and salts of borane and carborane anions may be selected from the group comprising decaborane(14), 7,8-dicarbadecaborane(13), 2,7-dicarbaundecaborane(13), undecahydrido-7,8-dimethyl-7,8-dicarbaundecaborane, 6-carbadecaborate(12), 7-carbaundecaborate, 7,8-dicarbaundecaborate.
Further, NCA's comprising metallaborane anions are also useful. Non-limiting examples of such NCA's may be selected from the group comprising bis(nonahydrido-1,3-dicarbanonaborato)cobaltate(III), bis(undecahydrido-7,8-dicarbaundecaborato)ferrate(III), bis(undecahydrido-7,8-dicarbaundecaborato) cobaltate(III), bis(undecahydrido-7,8-dicarbaborato) nikelate(III), bis(nonahydrido-7, 8-dimethyl-7, 8-dicarbaundecaborato)ferrate(III), bis(tribromooctahydrido-7, 8-dicarbaundecaborato)cobaltate(III), bis(undecahydridodicarbadodecaborato)cobaltate(III), bis(undecahydrido-7-carbaundecaborato) cobaltate(III) and mixtures thereof.
The NCA compositions most preferred for use in the cationic polymerization system are those containing a tris-perfluorophenyl boron, tetrapentafluorphenyl boron anion and/or two or more tripentafluorophenyl boron anion groups covalently bonded to a central atomic molecular or polymeric complex or particle.
The other component in the preferred cationic polymerization catalyst system comprises one or more reactive cations that are selected from different classes of cations and cation sources. Some preferred classes are:
(A) cyclopentadienyl transition metal complexes and derivatives thereof;
(B) substituted carbocations;
(C) substituted silylium;
(D) compositions capable of generating a proton as further described below; and (E) cationic compositions of germanium, tin or lead.
With reference to class (A), preferred cyclopentadienyl metal derivatives may be selected from the group comprising compounds that are a mono-, bis-or tris-cyclopentadienyl derivative of a transition metal selected from Groups 4, 5 or 6 of the Periodic Table of Elements. Preferred compositions include mono- cyclopentadienyl (Mono-Cp) or bis-cyclopentadienyl (Bis-Cp) Group 4 transition metal compositions, particularly zirconium, titanium and/or hafnium compositions.
Preferred cyclopentadienyl derivatives are transition metal complexes selected from the group comprising:
(A- Cp)M+ (A _ Cp)M+ ( i PR) Xl L (Cp*)- M
(CsHs-y-Xs~
(CsHs y-xsx) (A~)y M.-X M+
R"~ \X
~~(Z-~-y>
wherein:
(A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp*;
Cp and Cp* are the same or different cyclopentadienyl rings substituted with from 0 to 5 substituent groups S, each substituent group S being, independently, a radical group selected from the group comprising hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, 10 disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to CZO ring system to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
R is a substituent on one of the cyclopentadienyl radicals which is also 15 bonded to the metal atom;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings or (CSHS_y.XSX) and JR'(Z_1_y) groups;
M is a Group 4,5, or 6 transition metal;
y is 0 or 1;
(CSHS_y_XSX) is a cyclopentadienyl ring substituted with from 0 to 5 S
radicals;
x is from 0 to 5;
JR' (Z_,_,,) is a heteroatom ligand in which J is a Group 15 element with a coordination number of three or a Group 16 element with a coordination number of 2, preferably nitrogen, phosphorus, oxygen or sulfur;
R" is a hydrocarbyl group;
X and X' are independently a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, and hydrocarbyl- and halocarbyl-substituted organometalloid radical, substituted pnictogen radical, or substituted chalcogen radicals; and L is an olefin, diolefin or aryne ligand, or a neutral Lewis base.
Other cyclopentadienyl compounds that may be used in the cationic polymerization catalyst system are described in:
published European patent application 0,551,277A;
United States patent 5,055,438;
United States patent 5,278,119;
United States patent 5,198,401; and United States patent 5,096,867.
With reference to class (B), a preferred group of reactive cations comprises carbocationic compounds having the formula:
R~
wherein R', Rz and R3, are independently hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, with the proviso that only one of R' , R2 and R3 may be hydrogen. Preferably, none of R', RZ and R3 are H. Preferably, R', R'- and R3, are independently a C, to CZO aromatic or aliphatic group. Non-limiting examples of suitable aromatic groups may be selected from the group comprising phenyl, toluyl, xylyl and biphenyl. Non-limiting examples of suitable aliphatic groups may be selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl.
With reference to class (C), a preferred group of reactive cations comprises substituted silylium cationic compounds having the formula:
R' I
R2- S~ R3 wherein R', RZ and R3, are independently hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, with the proviso that only one of R', RZ
and R3 may be hydrogen. Preferably, none of R', RZ and R3 are H. Preferably, R', R'- and R3 are, independently, a C1 to C~ aromatic or aliphatic group. More preferably, R', RZ and R3 are independently a C, to C8 alkyl group. Non-limiting examples of useful aromatic groups may be selected from the group comprising phenyl, toluyl, xylyl and biphenyl. Non-limiting examples of useful aliphatic groups may be selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl. A particularly preferred group of reactive substituted silylium cations may be selected from the group comprising trimethylsilylium, triethylsilylium and benzyldimethylsilylium. Such cations may be prepared by the exchange of the hydride group of the R'RZR3Si-H with the NCA, such as Ph3C+B(pfp)4 yielding compositions such as R'R2R3SiB(pfp)4 which in the appropriate solvent obtain the cation.
With reference to class (D), the source for the cation may be any compound that will produce a proton when combined with the non-coordinating anion or a composition containing a non-coordinating anion. Protons may be generated from the reaction of a stable carbocation salt which contains a non-coordinating, non-nucleophilic anion with water, alcohol or phenol to produce the proton and the corresponding by-product. Such reaction may be preferred in the event that the reaction of the carbocation salt is faster with the protonated additive as compared with its reaction with the olefin. Other proton generating reactants include thiols, carboxylic acids, and the like. Similar chemistries may be realized with silylium type catalysts. In another embodiment, when low molecular weight polymer product is desired an aliphatic or aromatic alcohol may be added to inhibit the polymerization.
Another method to generate a proton comprises combining a Group 1 or Group 2 metal cation, preferably lithium, with water, preferably in a wet, non-protic organic solvent, in the presence of a Lewis base that does not interfere with polymerization. A wet solvent is defined to be a hydrocarbon solvent partially or fully saturated with water. It has been observed that when a Lewis base, such as isobutylene, is present with the Group 1 or 2 metal cation and the water, a proton is generated. In a preferred embodiment the non-coordinating anion is also present in the "wet" solvent such that active catalyst is generated when the Group 1 or 2 metal cation is added.
With reference to class (E), another preferred source for the cation is substituted germanium, tin or lead cations. Preferred non-limiting examples of such cations include substances having the formula:
R' R2_ M- R3 wherein R', RZ and R3, are independently hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, and M is germanium, tin or lead with the proviso that only one of R', R' and R3 may be hydrogen. Preferably, none of R', RZ and R3 are H. Preferably, R', RZ and R3 are, independently, a C, to CZo aromatic or aliphatic group. Non-limiting examples of useful aromatic groups may be selected from the group comprising phenyl, toluyl, xylyl and biphenyl.
Non-limiting examples of useful aliphatic groups may be selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl.
A further preferred non-coordinating anion comprises a compound selected from the group comprising:
CM ~ _Z_M ~~~a_ wherein:
d is an integer greater than or equal to 1;
Z is selected from the group comprising: OR-, SR~, SeR-, NRz , PRi , AsRz , SbRi , F-, Cl', Br and I-;
R is selected from the group comprising hydrogen, C,-C4o alkyl, C,-C~
cycloalkyl, CS-C4o aryl, halogen substituted derivatives thereof and heteratom substituted derivatives thereof;
M' and M" may be the same or different and each has the formula M~Q1 ... Qn wherein:
M is a metal or metalloid;
Ql to Q~ are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, with the proviso that not more than one of Q, to Q" may be a halide radical; and n is an integer representing the formal valence charge of M.
Preferably, M is selected from the group comprising B, Al, Ga and In.
In this embodiment, the preferred non-coordinating anion is a tetra-valent boron compound. Non-limiting examples of such compounds may be selected from the group comprising tri(phenyl)boron, trip-tolyl)boron, trio-tolyl)boron, tri(pentafluorophenyl)boron, tri(o,p-dimethylphenyl)boron, tri(m,m-dimethylphenyl)boron and (p-tri-fluoromethylphenyl)boron.
Further details on the interaction of the reactive cation and the non-coordination anion of the preferred cationic polymerization system may be found in published International patent application WO 95/29940.
A particularly preferred type of cationic polymerization catalyst system is disclosed in United States patent 5,448,001. In some cases, it is possible to use the coinitiator (BRR'R") disclosed in the '001 patent as the sole component of the cationic polymerization system in the present process. This approach is particularly well suited for the production of isobutylene-based polymers such as isobutylene homopolymer and the like.
As described above, the present process is particularly well suited for the production of butyl rubber and other isobutylene-based polymers.
Specifically, it has been discovered that such rubbers and polymers having desirable physical properties may be produced at higher temperatures than conventionally used.
Thus, the present process may be conducted at a temperature higher than about -80°C, preferably at a temperature in the range of from about -80°C to about 25°C, more preferably at a temperature in the range of from about -40°C
to about 25°C, even more preferably at a temperature in the range of from about -30°C to about 25°C, even more preferably at a temperature in the range of from about -20°C to about 25°C, most preferably at a temperature in the range of from about 0°C to about 25°C.
Embodiments of the present invention will be described with reference to the following Examples which are provided for illustrative purposes only and should note be used to limit the scope of or construe the invention.
All glassware was dried by heating at 120°C for at least 12 hours before being assembled in a nitrogen filled dry box. Nitrogen was purified by passing sequentially over heated BASF catalyst and molecular sieves. Dichloromethane was dried by refluxing over calcium hydride under nitrogen, toluene by refluxing over sodium-benzophenone under nitrogen, and both solvents were freshly distilled under nitrogen immediately prior to use.
The dime monomers (isoprene (IP) or 2,3-dimethyl-1,3-butadiene, (DMBD)) were dried over molecular sieves and then distilled. Isobutylene (IB) was purified by passing through molecular sieve and barium oxide columns, and condensed into a graduated flask immersed in liquid nitrogen. The IB was allowed to melt, the volume was noted ( --- 3 to ~ 9 mL) and the IB was then refrozen by immersing in the liquid nitrogen bath. The system was evacuated to 10-' to 10-2 torr, and the IB was melted and distilled at a temperature in the range of from about -10°C to about -6.5°C (the boiling point of IB being -6.4°C at one atmosphere pressure) into the glass polymerization vessel; 6 mL
of solvent (toluene) was added to the condenser which was attached to the reactor; and the solution of IB was brought to the desired temperature (usually approximately -30°C).
Solutions of Cp*TiMe3 (Cp*= ~5-pentamethylcyclopentadienyl; Me methyl; usually 14 mg, 0.06 mmol; recrystallized from pentane) and B(C6F5)3 (usually 32 mg, 0.06 mmol; sublimed), both in 1-2 mL of solvent, were added sequentially to provide an initiator to monomer ratio of approximately 1:1500.
In some Examples, an amount of dime equivalent to --1 % (mole) of the amount of IB was added to the reaction vessel prior to the addition of initiator and co-initiator.
Solutions of olefins) and initiator system were generally stirred as long as possible under a static vacuum and at the predetermined temperature (by "static vacuum", it is meant that the system was closed at this point and the pressure essentially was the vapour pressure of PIB at the reaction temperature).
Copious amounts of polymeric materials generally began to precipitate after about 2 minutes, and reactions were terminated after 10-30 min by the addition of 5-10 mL methanol. The precipitated polymeric materials were purified of inorganic residues by dissolving in pentane or hexane and passing through a short silica column. Solvents were removed under reduced pressure and the solid, white polymers were dried at 60°C-90°C for at least two days. Control reactions were also run using just Cp*TiMe3 or B(C6F5)3.
In Table 1, there is reported the use of vacuum (where vacuum was not used, polymerization was conducted under Ar(g) at atmosphereic pressure), the presence/absence of isoprene comonomer, the polymerization temperature (T), the weight average molecular weight of the polymer product (Mw) and the polydispersity index (Mw/Mn) of the polymer product.
Table 1 Example Vacuum Comonomer T Mw, x Mw/Mn 1 No No -32C 41.3 2.0 2 Yes No -32 61.6 2.0 C
3 No Yes -30C 11.6 1.6 4 Yes Yes -30C 14.4 1.8 As will be apparent to those of skill in the art, a vacuum was not applied during polymerization in Examples 1 and 3. Accordingly, Examples 1 and 3 are provided for comparative purposes only and are not encompassed by the present invention.
The results in Table 1 support the conclusion that conducting the polymerization of isobutylene at subatmospheric pressure (Example 2) results in the production of a polymer having a higher Mw when compared to conducting the polymerization of isobutylene at atmospheric pressure (Example 1). Similarly, the results in Table 1 support the conclusion that conducting the polymerization of isobutylene/isoprene at subatmospheric pressure (Example 4) results in the production of a copolymer having a higher Mw when compared to conducting the polymerization of isobutylene/isoprene at atmospheric pressure (Example 3).
All publications, patents and patent applications referred to herein are incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety.
Claims (65)
1. A process for polymerizing a cationically polymerizable olefin comprising the step of polymerizing at least one cationically polymerizable olefin at a subatmospheric pressure in the presence of a cationic polymerization catalyst system.
2. The process defined in claim 1, wherein said step of polymerizing is conducted at a temperature higher than about -80°C.
3. The process defined in claim 1, wherein said step of polymerizing is conducted at a temperature in the range of from about -80°C to about 25°C.
4. The process defined in claim 1, wherein said step of polymerizing is conducted at a temperature in the range of from about -40°C to about 25°C.
5. The process defined in claim 1, wherein said step of polymerizing is conducted at a temperature in the range of from about -30° C to about 25°C.
6. The process defined in claim 1, wherein said step of polymerizing is conducted at a temperature in the range of from about -20°C to about 25°C.
7. The process defined in claim 1, wherein said step of polymerizing is conducted at a temperature in the range of from about 0°C to about 25°C.
8. The process defined in any one of claims 1-7, wherein the subatmospheric pressure is less than about 100 kPa.
9. The process defined in any one of claims 1-7, wherein the subatmospheric pressure is less than about 90 kPa.
10. The process defined in any one of 1-7, wherein the subatmospheric pressure is in the range of from about 0.00001 to about 50 kPa.
11. The process defined in any one of claims 1-7, wherein the subatmospheric pressure is in the range of from about 0.0001 to about 40 kPa.
12. The process defined in any one of claims 1-7, wherein the subatmospheric pressure is in the range of from about 0.0001 to about 30 kPa.
13. The process defined in any one of claims 1-7, wherein the subatmospheric pressure is in the range of from about 0.0001 to about 15 kPa.
14. The process defined in any one of claims 1-13, wherein the cationic polymerization system comprises: (i) a reactive cation, and (ii) a non-coordinating anion.
15. The process defined in claim 14, wherein the reactive cation comprises a cyclopentadienyl transition metal complex.
16. The process defined in claim 15, wherein the transition metal complex comprises a compound selected from the group comprising:
wherein:
(A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp*;
Cp and Cp* are the same or different cyclopentadienyl rings substituted with from 0 to 5 substituent groups S, each substituent group S being, independently, a radical group selected from the group comprising hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C20 ring system to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
R is a substituent on one of the cyclopentadienyl radicals which is also bonded to the metal atom;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings or (C5H5-y-x S x) and JR'(z-1-y) groups;
M is a Group 4,5, or 6 transition metal;
y is 0 or 1;
(C5H5-y-x S x) is a cyclopentadienyl ring substituted with from 0 to 5 S
radicals;
x is from 0 to 5;
JR'(z-1-y) is a heteroatom ligand in which J is a Group 15 element with a coordination number of three or a Group 16 element with a coordination number of 2, preferably nitrogen, phosphorus, oxygen or sulfur;
R" is a hydrocarbyl group;
X and X1 are independently a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, and hydrocarbyl- and halocarbyl-substituted organometalloid radical, substituted pnictogen radical, or substituted chalcogen radicals; and L is an olefin, diolefin or aryne ligand, or a neutral Lewis base.
wherein:
(A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp*;
Cp and Cp* are the same or different cyclopentadienyl rings substituted with from 0 to 5 substituent groups S, each substituent group S being, independently, a radical group selected from the group comprising hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C20 ring system to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
R is a substituent on one of the cyclopentadienyl radicals which is also bonded to the metal atom;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings or (C5H5-y-x S x) and JR'(z-1-y) groups;
M is a Group 4,5, or 6 transition metal;
y is 0 or 1;
(C5H5-y-x S x) is a cyclopentadienyl ring substituted with from 0 to 5 S
radicals;
x is from 0 to 5;
JR'(z-1-y) is a heteroatom ligand in which J is a Group 15 element with a coordination number of three or a Group 16 element with a coordination number of 2, preferably nitrogen, phosphorus, oxygen or sulfur;
R" is a hydrocarbyl group;
X and X1 are independently a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, and hydrocarbyl- and halocarbyl-substituted organometalloid radical, substituted pnictogen radical, or substituted chalcogen radicals; and L is an olefin, diolefin or aryne ligand, or a neutral Lewis base.
17. The process defined in claim 14, wherein the reactive cation comprises a cationic compound having the formula:
wherein R1, R2 and R3 are, independently, hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, with the proviso that only one of R1, R2 and R3 may be hydrogen.
wherein R1, R2 and R3 are, independently, hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, with the proviso that only one of R1, R2 and R3 may be hydrogen.
18. The process defined in claim 17, wherein none of R1, R2 and R3 are H.
19. The process defined in claim 17, wherein R1, R2 and R3 are, independently, a C5 to C20 aromatic or a C1 to C20 aliphatic group.
20. The process defined in claim 19, wherein the aromatic group is selected from the group comprising phenyl, toluyl, xylyl and biphenyl.
21. The process defined in claim 19, wherein the aliphatic group is selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3- and 3,5,5-trimethylhexyl.
22. The process defined in claim 14, wherein the reactive cation comprises a cationic compound having the formula:
wherein R1, R2 and R3 are, independently, hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, with the proviso that only one of R1, R2 and R3 may be hydrogen.
wherein R1, R2 and R3 are, independently, hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, with the proviso that only one of R1, R2 and R3 may be hydrogen.
23. The process defined in claim 22, wherein none of R1, R2 and R3 are H.
24. The process defined in claim 22, wherein R1, R2 and R3 are, independently, a C5 to C20 aromatic or a C1 to C20 aliphatic group.
25. The process defined in claim 22, wherein R1 , R2 and R3 are, independently, a C4 to C8 alkyl group.
26. The process defined in claim 24, wherein the aromatic group is selected from the group comprising phenyl, toluyl, xylyl and biphenyl.
27. The process defined in claim 24, wherein the aliphatic group is selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl.
28. The process defined in claim 14, wherein the reactive cation comprises a cationic compound selected from the group comprising trimethylsilylium, triethylsilylium and benzyldimethylsilylium.
29. The process defined in claim 14, wherein the reactive cation comprises a cationic compound having the formula:
wherein R1, R2 and R3 are, independently, hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, and M is germanium, tin or lead with the proviso that only one of R1, R2 and R3 may be hydrogen.
wherein R1, R2 and R3 are, independently, hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, and M is germanium, tin or lead with the proviso that only one of R1, R2 and R3 may be hydrogen.
30. The process defined in claim 29, wherein none of R1, R2 and R3 are H.
31. The process defined in claim 29, wherein R1, R2 and R3 are, independently, a C5 to C50 aromatic or a C1 to C20 aliphatic group.
32. The process defined in claim 31, wherein the aromatic group is selected from the group comprising phenyl, toluyl, xylyl and biphenyl.
33. The process defined in claim 31, wherein the aliphatic group is selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl.
34. The process defined in any one of claims 14-33, wherein the non-coordinating anion has the formula:
[(M') m+Q1 ... Q n ]d-wherein:
M' is a metal or metalloid;
Q1 to Q n are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, with the proviso that not more than one of Q1 to Q n may be a halide radical;
m is an integer representing the formal valence charge of M;
n is the total number of ligands Q; and d is an integer greater than or equal to 1.
[(M') m+Q1 ... Q n ]d-wherein:
M' is a metal or metalloid;
Q1 to Q n are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, with the proviso that not more than one of Q1 to Q n may be a halide radical;
m is an integer representing the formal valence charge of M;
n is the total number of ligands Q; and d is an integer greater than or equal to 1.
35. The process defined in claim 34, wherein the metal is selected from the group comprising aluminum, gold and platinum.
36. The process defined in claim 34, wherein the metalloid is selected from the the group comprising boron, phosphorus and silicon.
37. The process defined in claim 34, wherein M' is boron;
n=4;
Q1 and Q2 are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from about 6 to about 20 carbon atoms and may be linked to each other through a stable bridging group; and Q3 and Q4 are, independently, hydride radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals, hydrocarbyl- and halocarbyl-substituted organometalloid radicals, disubstituted pnictogen radicals, substituted chalcogen radicals and halide radicals, with the proviso that Q3 and Q4 are not halide at the same time.
n=4;
Q1 and Q2 are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from about 6 to about 20 carbon atoms and may be linked to each other through a stable bridging group; and Q3 and Q4 are, independently, hydride radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals, hydrocarbyl- and halocarbyl-substituted organometalloid radicals, disubstituted pnictogen radicals, substituted chalcogen radicals and halide radicals, with the proviso that Q3 and Q4 are not halide at the same time.
38. The process defined in claim 37, wherein:
M' is boron;
n=4;
Q1, Q2 and Q3 are each (C6F5); and Q4 is as defined above.
M' is boron;
n=4;
Q1, Q2 and Q3 are each (C6F5); and Q4 is as defined above.
39. The process defined in any one of claims 14-33, wherein the non-coordinating anion comprises a compound selected from the group comprising:
[M1-Z-M"]d-wherein:
d is an integer greater than or equal to 1;
Z is selected from the group comprising: OR-, SR-, SeR-, NR2-, PR2-, AsR2-, SbR2-, F-, Cl-, Br- and I-;
R is selected from the group comprising hydrogen, C1-C40 alkyl, C1-C40 cycloalkyl, C5-C40 aryl, halogen substituted derivatives thereof and heteratom substituted derivatives thereof;
M' and M" may be the same or different and each has the formula M(Q1 ... Q n) wherein:
M is a metal or metalloid;
Q1 to Q n are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, with the proviso that not more than one of Q1 to Q n may be a halide radical; and n is an integer representing the formal valence charge of M.
[M1-Z-M"]d-wherein:
d is an integer greater than or equal to 1;
Z is selected from the group comprising: OR-, SR-, SeR-, NR2-, PR2-, AsR2-, SbR2-, F-, Cl-, Br- and I-;
R is selected from the group comprising hydrogen, C1-C40 alkyl, C1-C40 cycloalkyl, C5-C40 aryl, halogen substituted derivatives thereof and heteratom substituted derivatives thereof;
M' and M" may be the same or different and each has the formula M(Q1 ... Q n) wherein:
M is a metal or metalloid;
Q1 to Q n are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, with the proviso that not more than one of Q1 to Q n may be a halide radical; and n is an integer representing the formal valence charge of M.
40. The process defined in claim 39, wherein M is selected from the group comprising B, Al, Ga and In.
41. The process defined in any one of claims 14-33, wherein the non-coordinating anion is a tetra-valent boron compound.
42. The process defined in claim 41, wherein the tetra-valent boron compound is selected from the group comprising tri(phenyl)boron, tri(p-tolyl)boron, tri(o-tolyl)boron, tri(pentafluorophenyl)boron, tri(o,p-dimethylphenyl)boron, tri(m,m-dimethylphenyl)boron and (p-tri-fluoromethylphenyl)boron.
43. The process defined in any one of claims 14-33, wherein the non-coordinating anion is selected from the group comprising boranes and carboranes.
44. The process defined in any one of claims 14-33, wherein the non-coordinating anion is selected from the group comprising dodecaborate, decachlorodecaborate, dodecachlorododecaborate, 1-carbadecaborate, 1-carbaundecaborate, 1-trimethylsilyl-1-carbadecaborate.
45. The process defined in any one of claims 14-33, wherein the non-coordinating anion is selected from the group comprising decaborane(14), 7,8-dicarbadecaborane(13), 2,7-dicarbaundecaborane(13), undecahydrido-7,8-dimethyl-7,8-dicarbaundecaborane, 6-carbadecaborate(12), 7-carbaundecaborate and 7,8-dicarbaundecaborate.
46. The process defined in any one of claims 14-33, wherein the non-coordinating anion comprises a metalloborane anion selected from the group comprising bis(nonahydrido-1,3-dicarbanonaborato)cobaltate(III), bis(undecahydrido-7,8-dicarbaundecaborato)ferrate(III), bis(undecahydrido-7,8-dicarbaundecaborato) cobaltate(III), bis(undecahydrido-7,8-dicarbaborato) nikelate(III), bis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborato)ferrate(III), bis(tribromooctahydrido-7,8-dicarbaundecaborato)cobaltate(III), bis(undecahydridodicarba-dodecaborato)cobaltate(III) and bis(undecahydrido-7-carbaundecaborato) cobaltate(III).
47. The process defined in any one of claims 1-46, wherein said step of polymerizing is conducted under substantially anhydrous conditions.
48. The process defined in any one of claims 1-47, wherein said step of polymerizing is conducted in the substantial absence of a diluent.
49. The process defined in any one of claims 1-47, wherein said step of polymerizing is conducted in the presence of a diluent.
50. The process defined in claim 49, wherein the diluent is selected from the group comprising polar diluents, non-polar diluents and mixtures thereof.
51. The process defined in claim 49, wherein the diluent is selected from the group comprising haloaromatic compounds, hexane, heptane, halogenated hydrocarbons and mixtures thereof.
52. The process defined in claim 49, wherein the diluent is selected from the group comprising methyl cyclohexane, ethyl cyclohexane, propyl cyclohexane, chlorobenzene, bromobenzene, fluorobenzene, iodobenzene, methyl chloride, methylene chloride, ethyl chloride, propyl chloride, butyl chloride, chloroform and mixtures thereof.
53. The process defined in any one of claims 1-52, wherein at least one cationically polymerizable olefin is selected from the group comprising an olefin, a styrenic olefin, a heteroatom olefin and mixtures thereof.
54. The process defined in claim 53, wherein the olefin comprises a C2-C30 olefin.
55. The process defined in claim 53, wherein the olefin comprises a C2-C20 olefin.
56. The process defined in claim 53, wherein the olefin is selected from the group comprising ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, dodecyldocecene, 3-methylpentene-1, 3,5,5-trimethylhexene-1, isobutylene, 2-methyl-butene, 2-methyl-pentene, vinyl ether, vinyl carbazole and mixtures thereof.
57. The process defined in claim 53, wherein the styrenic olefin is selected from the group comprising styrene, C1-C60 alkyl substituted styrene and mixtures thereof.
58. The process defined in claim 53, wherein the styrenic olefin is selected from the group comprising styrene, .alpha.-methyl styrene, p-chlorostyrene and p-methylstyrene and mixtures thereof.
59. The process defined in claim 53, wherein the heteroatom olefin is selected from the group comprising alkyl vinyl ethers, alkyl, amines, alkenyl amines and aryl amines.
60. The process defined in claim 53, wherein the heteroatom olefin is selected from the group comprising methyl vinyl ether, isobutylvinyl ether, butyl vinyl ether, vinyl carbazole and mixtures thereof.
61. The process defined in any one of claims 1-52, wherein the at least one cationically polymerizable olefin comprises a mixture of isobutylene and p-methyl styrene.
62. The process defined in any one of claims 1-60, wherein said step of polymerization is conducted in the presence of the at least one cationically polymerizable olefin and a diene monomer.
63. The process defined in claim 62, wherein the diene monomer is conjugated.
64. The process defined in any one of claims 1-60, wherein the at least one cationically polymerizable olefin comprises a mixture of isobutylene and isoprene.
65. The process defined in claim 62, wherein the diene monomer is unconjugated.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9327698P | 1998-07-17 | 1998-07-17 | |
| US60/093,276 | 1998-07-17 | ||
| PCT/CA1999/000644 WO2000004061A1 (en) | 1998-07-17 | 1999-07-16 | Process for polymerizing cationically polymerizable olefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2337003A1 true CA2337003A1 (en) | 2000-01-27 |
Family
ID=22238075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002337003A Abandoned CA2337003A1 (en) | 1998-07-17 | 1999-07-16 | Process for polymerizing a cationically polymerizable olefin |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1124865A1 (en) |
| JP (1) | JP2002520453A (en) |
| CN (1) | CN1309670A (en) |
| AU (1) | AU4597799A (en) |
| CA (1) | CA2337003A1 (en) |
| HK (1) | HK1039951A1 (en) |
| WO (1) | WO2000004061A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7699962B2 (en) | 2004-06-23 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Processes utilizing extractive distillation |
| US7781547B2 (en) | 2004-06-25 | 2010-08-24 | Exxonmobil Chemical Patents Inc. | Reactor systems for use in polymerization processes |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2332203A1 (en) * | 2001-01-24 | 2002-07-24 | Bayer Inc. | Process for making high molecular weight isobutylene polymers |
| CA2360611C (en) * | 2001-10-30 | 2010-08-17 | Bayer Inc. | Transition metal-free initiator for the preparation of isobutylene-based polymers |
| CA2368724C (en) | 2002-01-21 | 2011-06-14 | Bayer Inc. | Process for preparing isobutylene-based polymers |
| US7232872B2 (en) * | 2002-12-20 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Polymerization processes |
| WO2004058827A1 (en) * | 2002-12-20 | 2004-07-15 | Exxonmobil Chemical Patents Inc. | Polymerization processes |
| EP1578806B1 (en) * | 2002-12-20 | 2013-05-22 | ExxonMobil Chemical Patents Inc. | Polymerization processes |
| JP4441487B2 (en) * | 2002-12-20 | 2010-03-31 | エクソンモービル・ケミカル・パテンツ・インク | Polymerization process |
| US7196149B2 (en) | 2003-04-17 | 2007-03-27 | The University Of Akron | Polymerization of i-butane in hydrocarbon media using bis(borane) co-initiators |
| US7202317B2 (en) | 2003-04-17 | 2007-04-10 | The University Of Akron | Polymerization of i-butene in hydrocarbon media using bis(borane) co-initiators |
| CA2441079C (en) | 2003-09-16 | 2012-04-24 | Bayer Inc. | Process for production of butyl rubber |
| JP5017102B2 (en) | 2004-06-15 | 2012-09-05 | エクソンモービル・ケミカル・パテンツ・インク | ELASTOMER COMPOSITION, AIR BARRIER, AND METHOD FOR PRODUCING THEM |
| CA2578679A1 (en) | 2006-03-14 | 2007-09-14 | Lanxess Inc. | Polymerization process using zinc halide initiators |
| US7629397B2 (en) | 2006-06-23 | 2009-12-08 | Exxonmobil Chemical Patents Inc. | Phase separation process utilizing a hydrofluorocarbon |
| US8148450B2 (en) | 2006-06-23 | 2012-04-03 | Exxonmobil Chemical Patents Inc. | Process to produce a hydrocarbon rubber cement utilizing a hydrofluorocarbon diluent |
| US7402636B1 (en) | 2007-03-23 | 2008-07-22 | Exxonmobil Chemical Patents Inc | Method and apparatus for decreasing polymer deposition |
| US7981991B2 (en) | 2007-04-20 | 2011-07-19 | Exxonmobil Chemical Patents Inc. | Separation of polymer slurries |
| CN103588918B (en) * | 2013-11-07 | 2016-03-30 | 济南开发区星火科学技术研究院 | A kind of preparation method of isoprene-isobutylene rubber |
| KR20190116949A (en) * | 2018-04-05 | 2019-10-15 | 주식회사 엘지화학 | Highly reactive butene oligomer having improved processability and method for producing the same |
| CN113527556B (en) * | 2021-01-12 | 2022-05-24 | 福州大学 | Process for the catalytic preparation of vinyl ether polymers |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391629A (en) * | 1987-01-30 | 1995-02-21 | Exxon Chemical Patents Inc. | Block copolymers from ionic catalysts |
| IL85097A (en) * | 1987-01-30 | 1992-02-16 | Exxon Chemical Patents Inc | Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes |
| PL276385A1 (en) * | 1987-01-30 | 1989-07-24 | Exxon Chemical Patents Inc | Method for polymerization of olefines,diolefins and acetylene unsaturated compounds |
| US5066741A (en) * | 1990-03-22 | 1991-11-19 | The Dow Chemical Company | Process for preparation of syndiotactic vinyl aromatic polymers |
| US5635573A (en) * | 1992-12-01 | 1997-06-03 | Exxon Chemical Patents Inc. | Method for preparing alpha-olefin/cycloolefin copolymers |
| US6008307A (en) * | 1994-04-28 | 1999-12-28 | Exxon Chemical Patents Inc | Process for producing olefin polymers using cationic catalysts |
-
1999
- 1999-07-16 CA CA002337003A patent/CA2337003A1/en not_active Abandoned
- 1999-07-16 CN CN99808778A patent/CN1309670A/en active Pending
- 1999-07-16 WO PCT/CA1999/000644 patent/WO2000004061A1/en not_active Application Discontinuation
- 1999-07-16 EP EP99928976A patent/EP1124865A1/en not_active Withdrawn
- 1999-07-16 JP JP2000560166A patent/JP2002520453A/en active Pending
- 1999-07-16 AU AU45977/99A patent/AU4597799A/en not_active Abandoned
-
2002
- 2002-02-19 HK HK02101200.2A patent/HK1039951A1/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7699962B2 (en) | 2004-06-23 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Processes utilizing extractive distillation |
| US7781547B2 (en) | 2004-06-25 | 2010-08-24 | Exxonmobil Chemical Patents Inc. | Reactor systems for use in polymerization processes |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002520453A (en) | 2002-07-09 |
| CN1309670A (en) | 2001-08-22 |
| EP1124865A1 (en) | 2001-08-22 |
| HK1039951A1 (en) | 2002-05-17 |
| AU4597799A (en) | 2000-02-07 |
| WO2000004061A1 (en) | 2000-01-27 |
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