CN101100489B - 使用卤化锌引发剂的聚合方法 - Google Patents
使用卤化锌引发剂的聚合方法 Download PDFInfo
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- CN101100489B CN101100489B CN2007101421544A CN200710142154A CN101100489B CN 101100489 B CN101100489 B CN 101100489B CN 2007101421544 A CN2007101421544 A CN 2007101421544A CN 200710142154 A CN200710142154 A CN 200710142154A CN 101100489 B CN101100489 B CN 101100489B
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- zinc
- isoolefin
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- zinc halide
- polymer
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- 239000011701 zinc Substances 0.000 title claims abstract description 39
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 36
- 239000003999 initiator Substances 0.000 title claims abstract description 25
- -1 zinc halide Chemical class 0.000 title abstract description 28
- 238000006116 polymerization reaction Methods 0.000 title abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 239000012190 activator Substances 0.000 claims abstract description 10
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 8
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 7
- 229920001519 homopolymer Polymers 0.000 claims abstract description 6
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 26
- 239000000203 mixture Substances 0.000 description 25
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 19
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 9
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 8
- KPJKMUJJFXZGAX-UHFFFAOYSA-N 2-chloropropan-2-ylbenzene Chemical compound CC(C)(Cl)C1=CC=CC=C1 KPJKMUJJFXZGAX-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229940050176 methyl chloride Drugs 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GTIVDIGFCBZLEE-UHFFFAOYSA-M [Cl-].CC[Zn+] Chemical compound [Cl-].CC[Zn+] GTIVDIGFCBZLEE-UHFFFAOYSA-M 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 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 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- BOGRNZQRTNVZCZ-AATRIKPKSA-N (3e)-3-methylpenta-1,3-diene Chemical compound C\C=C(/C)C=C BOGRNZQRTNVZCZ-AATRIKPKSA-N 0.000 description 1
- BOGRNZQRTNVZCZ-UHFFFAOYSA-N 1,2-dimethyl-butadiene Natural products CC=C(C)C=C BOGRNZQRTNVZCZ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- JLSUFZZPRVNDIW-UHFFFAOYSA-N 1-ethenylcyclohexa-1,3-diene Chemical compound C=CC1=CC=CCC1 JLSUFZZPRVNDIW-UHFFFAOYSA-N 0.000 description 1
- QAACSRQBSSDJML-UHFFFAOYSA-N 1H-indene 1-methylcyclopenta-1,3-diene Chemical compound C1C=CC2=CC=CC=C12.CC1=CC=CC1 QAACSRQBSSDJML-UHFFFAOYSA-N 0.000 description 1
- DZPCYXCBXGQBRN-UHFFFAOYSA-N 2,5-Dimethyl-2,4-hexadiene Chemical compound CC(C)=CC=C(C)C DZPCYXCBXGQBRN-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- XNUNYHQZMMREQD-UHFFFAOYSA-N 2-methylhepta-1,6-diene Chemical compound CC(=C)CCCC=C XNUNYHQZMMREQD-UHFFFAOYSA-N 0.000 description 1
- SLQMKNPIYMOEGB-UHFFFAOYSA-N 2-methylhexa-1,5-diene Chemical compound CC(=C)CCC=C SLQMKNPIYMOEGB-UHFFFAOYSA-N 0.000 description 1
- DRWYRROCDFQZQF-UHFFFAOYSA-N 2-methylpenta-1,4-diene Chemical compound CC(=C)CC=C DRWYRROCDFQZQF-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
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- AQYKIROTAGYYQK-UHFFFAOYSA-N 5,5-dimethyl-3-methylidenehex-1-ene Chemical compound CC(C)(C)CC(=C)C=C AQYKIROTAGYYQK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 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 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 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 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 125000004968 halobutyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 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 description 1
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012035 limiting reagent Substances 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 description 1
- 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 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- GQIJYUMTOUBHSH-IJIVKGSJSA-N piperyline Chemical compound C=1C=C2OCOC2=CC=1/C=C/C=C/C(=O)N1CCCC1 GQIJYUMTOUBHSH-IJIVKGSJSA-N 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
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- 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
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- 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
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
- C08F10/10—Isobutene
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
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- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
- C08F110/10—Isobutene
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- 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
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
Abstract
一种使用卤化锌引发剂的异烯烃阳离子聚合方法。将卤化锌引发剂添加到异烯烃在适合溶剂(优选卤代烃溶剂)中的溶液中。聚合反应通常在高至足以使卤化锌引发剂溶解在该溶液中的温度下进行。烷基卤活化剂可任选使用并且优选在卤化锌引发剂之前添加到该溶液中。多烯烃可任选地存在于该溶液中。该方法特别用于形成异烯烃均聚物和异烯烃与多烯烃共聚物如丁基橡胶。
Description
技术领域
本发明涉及使用卤化锌引发剂的异烯烃和任选多烯烃的阳离子聚合。更具体地说,本发明涉及使用卤化锌引发剂和任选的烷基卤共引发剂阳离子聚合异丁烯和异戊二烯形成丁基橡胶聚合物的方法。
背景技术
聚(异丁烯-共-异戊二烯),或IIR,是一种通常被称作丁基橡胶的合成弹性体,从十九世纪四十年代以来就通过异丁烯与少量异戊二烯(1-2mol%)的无规阳离子共聚合制备。由于它的分子结构,IIR具有优越的气密性、高损耗模量、氧化稳定度和持久的抗疲劳性。
丁基橡胶是异烯烃和一种或多种作为共聚单体的多烯烃的共聚物,优选多烯烃是共轭多烯烃。商品化丁基橡胶包括异烯烃主体部分和不超过2.5摩尔%的少量共轭多烯烃。
通常使用适合的聚合溶剂例如氯代甲烷和Friedel-Crafts催化剂如三氯化铝作为聚合引发剂,以淤浆法制备丁基橡胶或丁基聚合物。氯代甲烷具有的优势在于三氯化铝这一相对便宜的Friedel-Crafts催化剂溶解于其中,同样异丁烯和异戊二烯共聚单体也溶解于其中。此外,丁基橡胶聚合物不溶于氯代甲烷并作为细粒从溶液中沉淀出来。通常在大约-90℃至-100℃的温度下进行聚合。参见美国专利US 2,356,128和Ullmanns Encyclopedia of IndustrialChemistry,卷A23,1993,第288-295页。低聚合温度用于获得足够高的用于橡胶用途的分子量。
已发现可有效作为异烯烃聚合催化剂的其它化合物包括与阳离子生成剂结合的有机金属化合物,例如C5Me5TiMe3/B(C6F5)3(WO-00/04061-A1)、Cp2AlMe/B(C6F5)3(US-5,703,182)、和二茂锆与相关的具有B(C6F5)3或CPh3[B(C6F5)4]的络合物的组合(WO-95/29940-A1,DE-A1-198 36663),Song,X.;Thornton-Pett,M.;Bochmann,M.Organometallics 1998,17,1004,Carr,A.G.;Dawson,D.M.;Bochmann,M.Macromol.Rapid Commun.1998,19,205。
Nuyken与M.Bohnenpoll合作(Chem.Eur.J.2004,10,6323)公开了一种基于非配位硼酸盐阴离子的[Mn(NCMe)6]2+盐的体系,其在室温下是活性的:
该体系在+30℃下于IB/CH2Cl2中操作,但在≤0℃不显示活性。聚合通常很慢(IB均聚需55-110h),从而对其机理存在一些疑问。IB均聚物和共聚物的分子量Mn=8,000-10,000。在较高的IP进料下,转化率迅速降低。
锌化合物通常不用作异烯烃聚合催化剂。的确,ZnCl2在存在或不存在烷基卤活化剂(如Me3CCl或MeCoCl)时,和在纯异丁烯或在异丁烯/一氯甲烷混合物中使用时,证明是非活性的,并且得不到聚合物。然而最近,Bochmann和他的合作者申请了一件关于使用Zn(C6F5)2/ButCl体系进行IB均聚-和IB/IP共聚的专利(加拿大专利申请2,441,079,2003年9月16日申请)。在此之前锌从未用作阳离子聚合引发剂。该专利教导了该***拥有特别好的共聚特性并使IB/IP共聚物在纯IB溶液(无溶剂)中形成。聚合物具有高达15mol-%的IP,凝胶含量很少。然而,监测Zn(C6F5)2与叔丁基氯(tBuCl)的反应总是发现大量的与不溶的沉淀在一起的C6F5H。此外,Zn(C6F5)2在工业规模方法中使用是昂贵的,因此,而要寻找一种低廉的替代品。
因此,仍然存在使用锌基引发剂改善聚合方法的需要。
发明内容
根据本发明,提供了一种使用锌基引发剂的异烯烃单体阳离子聚合方法,该方法包括:提供异烯烃单体在卤代烃溶剂中的溶液;向溶液中添加包括烷基或芳基卤化锌的锌基引发剂;和使含锌基引发剂的溶液反应以形成包含异烯烃的聚合物。
聚合反应可以在足以使卤化锌引发剂溶解在溶液中的高温下进行。可任选使用烷基卤活化剂并且优选在卤化锌引发剂之前添加到溶液中。多烯烃可任选与异烯烃存在于溶液中并可参与反应以与异烯烃形成共聚物。该异烯烃可包括异丁烯,多烯烃可包括异戊二烯,和聚合物可包括丁基橡胶。
用于本发明方法中的卤化锌引发剂表现出在溶剂中溶解度高和成本低的优势。
现在将更完全地描述本发明更多的特征和它的优选实施方案。
具体实施方式
本发明涉及异烯烃均聚物和异烯烃、多烯烃和任选的其它可共聚单体的共聚物。在一个优选的实施方案中,共聚物为丁基橡胶聚合物。术语“丁基聚合物”、“丁基橡胶”和“丁基橡胶聚合物”在整个说明书中可互换使用,意指通过占主体的异烯烃单体与少部分多烯烃单体反应制备的聚合物。
该方法不局限于特定的异烯烃。然而,优选4至16个碳原子范围内的异烯烃,特别是4-8个碳原子的异烯烃,如异丁烯、2-甲基-1-丁烯、3-甲基-1-丁烯、2-甲基-2-丁烯、4-甲基-1-戊烯和它们的混合物。最优选异丁烯。
当多烯烃存在于反应混合物中时,该方法不局限于特定的多烯烃。可以使用任何本领域技术人员已知的可与异烯烃共聚的多烯烃。优选4-14个碳原子范围的多烯烃。优选的C4至C14多烯烃包括C4至C10的共轭二烯烃。适合的多烯烃的一些具体非限制性实例包括异戊二烯、丁二烯、2-甲基丁二烯、2,4-二甲基丁二烯、戊间二烯、3-甲基-1,3-戊二烯、2,4-己二烯、2-新戊基丁二烯、2-甲基-1,5-己二烯、2,5-二甲基-2,4-己二烯、2-甲基-1,4-戊二烯、2-甲基-1,6-庚二烯、环戊二烯、甲基环戊二烯、环己二烯、1-乙烯基-环己二烯和它们的混合物。特别优选使用异戊二烯。
可以从只包括异烯烃单体的混合物获得聚合物。也可从大约70至99.5重量份的C4至C8异烯烃单体和大约30至大约0.5重量份的C4至C14多烯烃单体的混合物获得聚合物。更优选,从包括大约80至大约99.5重量份的C4至C8异烯烃单体和大约20至大约0.5重量份的C4至C14多烯烃单体的混合物获得聚合物。从包括大约97至大约99.5重量份的异丁烯和大约3至大约0.5重量份的异戊二烯的混合物获得本发明最优选的聚合物。
本领域技术人员将认识到可以包括一种任选的第三单体以生产丁基三元共聚物。例如,单体混合物中可以包括苯乙烯类单体,优选高达单体混合物的大约15%重量的含量。优选的苯乙烯类单体可选自对甲基苯乙烯、苯乙烯、α-甲基苯乙烯、对氯苯乙烯、对甲氧基苯乙烯、环戊二烯、甲基环戊二烯茚、茚的衍生物和它们的混合物。最优选的苯乙烯类单体可选自苯乙烯、对甲基苯乙烯和它们的混合物。其它合适的可共聚的第三共聚单体对本领域技术人员是显而易见的。
生产含异烯烃的聚合物特别是丁基橡胶聚合物的适合的聚合方法对本领域技术人员是已知的,并在美国专利US 2,356,128中进一步描述。通常,该方法包括把单体混合物溶于适合的溶剂中。溶剂通常为有机液体。适用于工业丁基橡胶聚合的有机液体包括惰性C1至C4卤代烃和它们的混合物、C5至C8脂肪烃、C5至C8环烃、一种或多种卤代烃和一种或多种脂肪烃的混合物和一种或多种卤代烃和一种或多种环烃的混合物。优选的惰性有机液体或溶剂的实例包括戊烷、己烷、庚烷和它们彼此或与卤代烃如氯甲烷和/或二氯甲烷等的混合物。最优选的有机液体是选自氯甲烷、二氯甲烷和它们的混合物的卤代烃。
本发明的锌基引发剂包括二价卤化锌路易斯酸,优选其溶于纯IB或IB与适合有机溶剂的混合物。尽管氯化锌(ZnCl2)是一种可适用作引发剂的普通卤化锌,但它不溶于纯IB或IB/溶剂的混合物。因此,优选的卤化锌包括可溶的有机卤化锌,更优选烷基或芳基卤化锌,然而更优选短链烷基卤化锌。因为锌是二价的,除了卤基,只存在一个烷基或芳基。优选卤化锌不包括烷氧化物。尽管也可以使用溴,然而优选的卤素为氯。优选的卤化锌的实例包括下式化合物:
R-Zn-X (1)
其中,
R是甲基、乙基、丙基或丁基;和
X是Cl、Br或I。
向单体混合物中进一步添加活化剂或共引发剂是有利的。只要共引发剂化合物不有害地影响聚合反应,本发明不局限于任何特定的共引发剂/活化剂。优选通式为HX,RX,R3CX或RCOX的活化剂,式中每个R独立地为C1至C50的烃基,其可以是线性、支链或环状,可以在碳链上包含一个或多个非碳原子;如甲基、乙基、正丙基、正丁基、仲丁基、叔丁基、戊基、己基、辛基、壬基、癸基、十二烷基、枯基、3-甲基戊基、2,4,4-三甲基戊基和3,5,5-三甲基己基;每个X是卤素,优选氯、溴或碘。优选的共引发剂是Me3CCl、tBuCl、枯基氯、TMP-2-氯、MeCOCl、和Me3CBr。最优选的是tBuCl和枯基氯。
优选锌化合物与共引发剂的摩尔比为1∶0.1至1∶10的范围,最优选的比例为1∶1至1∶3的范围。
乙基氯化锌(EtZnCl)是一种特别优选的锌基引发剂,它在IB与卤代烃溶剂二氯甲烷(CH2Cl2)的混合物中呈现良好的溶解度,但在纯IB中的溶解度有限。EtZnCl是一种氯桥四聚物。该固体在室温下溶于有机溶剂。EtZnCl/ButCl体系对IB聚合和IB/IP共聚显现出良好的活性。因为在该体系中即使原位产生的ZnCl2在-78℃不溶于IB/CH2Cl2混合物,该体系在≥-35℃的温度也显示出最好的活性。然而,EtZnCl/枯基氯体系具有提高的低温溶解度,并在-78℃下至-90℃或更低的温度下显示出良好的聚合活性。因此,优选在-100℃至40℃范围,更优选在-90℃至35℃的范围,然而更优选在-80℃至35℃的范围,甚至更优选在-70℃至35℃的范围,更加优选在-60℃至35℃的范围,然而甚至更优选在-50℃至35℃的范围,然而更加优选在-35℃至35℃的范围的温度,和0.1到4巴范围的压力下聚合单体。
与间歇式反应器相比,使用连续反应器可对该方法具有积极的影响。优选地,在至少一个具有0.1m3和100m3之间、更优选在1m3和10m3之间体积的连续反应器中实施该方法。
如果聚合连续进行,优选该方法进行时具有至少以下进料流:
I)溶剂/稀释剂(优选二氯甲烷)+异烯烃(优选异丁烯)+多烯烃(如果存在,优选二烯,如异戊二烯);和
II)卤化锌化合物(优选乙基氯化锌)。
烷基卤活化剂(如果存在)可以预先溶解在溶剂中或与单体一起或在加入单体之后添加到溶剂中。优选在添加卤化锌引发剂之前加入烷基卤活化剂。
卤化锌引发体系可用于生产IB均聚物或IB与二烯单体的共聚物。当二烯单体为异戊二烯时,IB与IP的共聚物是丁基橡胶。IB均聚物具有在25,000至500,000范围的分子量(Mn),IB/IP共聚物具有在15,000至500,000范围的分子量。
由本发明方法产生的包括残余双键的聚合物可以是卤化方法的起始原料,以便生产卤丁基聚合物。可以根据Rubber Technology,3rd Ed.,Edited byMaurice Morton,Kluwer Academic Publishers,pp.297-300和该文献引用的参考所描述的方法进行溴化或氯化。
本发明中的共聚物理论上适合于各种模塑物的生产,特别是轮胎组分和工业橡胶制品,如塞子、阻尼元件、仿形件(profiles)、薄膜、涂层。用于此目的的聚合物是纯物质形式或与其它橡胶如NR、BR、HNBR、NBR、SBR、EPDM或氟橡胶的混合物。这些胶料的制备对本领域技术人员是已知的。在大多数情况下,把碳黑作为填料添加并且使用硫基硫化体系。也可使用过氧化物基硫化体系,特别是当聚合物含有至少4mol%的衍生自至少一种多烯烃单体的重复单元时。至于配混和硫化,参考Encyclopedia of Polymer Science and Engineering,第4卷,S.66 et seq.(配混)和第17卷,S.666 et seq.(硫化)。胶料的硫化过程通常在100℃至200℃范围、优选130℃至180℃的温度(任选在10至200巴范围的压力下)实施。
以下实施例用于说明本发明。
实施例
实施例1:用于IB均聚的EtZnCl体系
在-78℃把IB(9ml)压缩至刻度容器中。注入预先冷却的二氯甲烷,以装满22ml的总反应体积。在-78℃下制备二氯甲烷中的tBuCl储备溶液(100μmol/mlCH2Cl2)。把适量tBuCl的等分试样添加至反应器中,继之以添加固体EtZnCl。在此温度下,白色固体不发生变化。然而,当把该混合物加热到-35℃(经内部热电偶测量)时,固体完全溶解。使用过量的EtZnCl,tBuCl作为限制试剂用于控制反应速率。用甲醇终止反应,在60℃下干燥直到恒重。结果见表1-4。
密封体系并加热至表中显示的设定温度。对于20℃的反应,内部压力计算为2巴。一分钟(混合物达到反应起始临界温度-35℃需要的时间)后溶液变得非常浑浊。再冷却至-78℃只产生微量聚合物(操作例(run)637)。这表明包括在聚合反应中的锌类物质在-78℃是不溶的。然而,如果为了避免IB挥发而密封体系,则在室温(操作例639)下达到非常高的转化率。由此制得的聚合物显示的Mn值为25-47×103。使用高浓度的tBuCl(操作例654-655),在反应三十分钟后产生数量接近的转化率。降低温度提高了聚合物的分子量。达到了高达 的分子量。
表3:EtZnCl/tBuCl浓度对IB均聚的影响
条件:溶剂=CH2Cl2,V总量=31mL,[IB]0=5.03M,反应时间=30分钟,T=20℃。
表4:使用EtZnCl的IB均聚的温度依从关系
条件:溶剂=CH2Cl2,V总量=22mL,[IB]0=5.03M,[EtZnCl]=9.1×10-3M,[tBuCl]=4.5×10-3M,反应时间=30分。
实施例2:用于IB-IP共聚的具有
t
BuCl的EtZnCl体系
举例说明了在20℃EtZnCl/ButCl体系引发IB和IP共聚的能力。实验步骤与实施例1使用的相似,使用IB和IP单体的混合物代替IB单体。使用的IP单体体积如表5所示,IB单体体积是需要组成9mL总体积的余量部分。
表5:使用EtZnCl/tBuCl的IB-IP共聚
条件:溶剂=CH2Cl2,V总量=22mL,[IB]0=5.03M,[EtZnCl]=[tBuCl]=13.6×10-3M
高达3.8mol-%IP结合到共聚物中,其呈现大约16-22,000的分子量Mn。转化率随IP浓度的增加而降低。
实施例3:用于IB-IP共聚的具有枯基氯的EtZnCl体系
接下来是与实施例2相似的实验步骤,用枯基氯代替tBuCl作为活化剂和在-78℃进行聚合反应。结果如表6所示。
表6:使用EtZnCl/枯基氯的IB-IP共聚
条件:VCH2Cl2=20mL,VIB=10mL,[EtZnCl]=1.6×10-3M,[枯基氯]=1.3×10-3高达5.7mol-%IP结合到共聚物中,其呈现大约122,000-149,000的分子量Mn。转化率随着IP浓度的增加而降低。在不同的实验条件下,共聚物无疑可以结合更高量的IP。
Claims (7)
1.使用锌基引发剂的异烯烃单体阳离子聚合方法,该方法包括:
a)提供异烯烃单体在卤代烃溶剂中的溶液;
b)向溶液中添加包括式R-Zn-X的化合物的锌基引发剂,式中R为甲基、乙基、丙基或丁基,X为Cl、Br或I;和
c)使含该锌基引发剂的溶液反应以生成包含异烯烃的聚合物。
2.根据权利要求1的方法,其中所述方法进一步包括在加入锌基引发剂之前在溶剂中添加烷基卤活化剂。
3.根据权利要求1或2的方法,其中所述聚合物是异烯烃均聚物。
4.根据权利要求1或2的方法,其中所述溶液进一步包括一种多烯烃单体,其含量为溶液中单体总量的1-15mol%。
5.根据权利要求4的方法,其中聚合物是异烯烃和多烯烃单体的共聚物。
6.根据权利要求3的方法制备的聚合物。
7.根据权利要求4的方法制备的聚合物。
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EP0920909A1 (en) * | 1994-03-31 | 1999-06-09 | Exxon Chemical Patents Inc. | Supported lewis acid catalysts for hydrocarbon conversion reactions |
CN1654487A (zh) * | 2003-09-16 | 2005-08-17 | 兰塞克斯公司 | 丁基橡胶的制备方法 |
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US2356128A (en) | 1939-10-20 | 1944-08-22 | Jasco Inc | Mixed olefinic polymerization process and product |
IT953490B (it) * | 1972-03-11 | 1973-08-10 | Snam Progetti | Procedimento per la polimerizzazio ne e copolimerzzazione dell isobu tilene |
SU792901A1 (ru) * | 1978-06-05 | 1997-03-10 | В.Д. Петрова | Способ получения бутилкаучука |
US6008307A (en) | 1994-04-28 | 1999-12-28 | Exxon Chemical Patents Inc | Process for producing olefin polymers using cationic catalysts |
DE19603331A1 (de) | 1996-01-31 | 1997-08-07 | Bayer Ag | Verfahren zur Herstellung von Polyisoolefinen mittels neuer Initiatorsysteme vom Metallocen-Typ |
ATE239737T1 (de) | 1997-08-21 | 2003-05-15 | Crompton Corp | Blockierte merkaptosilane als kupplungsmittel für gefüllte kautschukzusammensetzung |
AU4597799A (en) | 1998-07-17 | 2000-02-07 | Bayer Inc. | Process for polymerizing cationically polymerizable olefin |
DE19836663A1 (de) | 1998-08-13 | 2000-02-17 | Bayer Ag | Verfahren zur Herstellung von Polyisoolefinen mittels neuer Initiatorsysteme vom Metallocen-Typ |
CA2293149A1 (en) | 1999-12-24 | 2001-06-24 | Bayer Inc. | Elastomeric butyl compounds with improved chemical bonding between the butyl elastomer and the filler |
KR20020046165A (ko) | 2000-12-12 | 2002-06-20 | 빌프리더 하이더 | 타이어 트레드용 고무 조성물 |
CA2339056A1 (en) | 2001-03-02 | 2002-09-02 | Bayer Inc. | Filled elastomeric compositions |
JP2005513178A (ja) * | 2001-12-10 | 2005-05-12 | エクソンモービル・ケミカル・パテンツ・インク | エラストマー組成物 |
WO2004058836A1 (en) * | 2002-12-20 | 2004-07-15 | Exxonmobil Chemical Patents Inc. | Polymers with new sequence distributions |
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2007
- 2007-02-15 CA CA002578679A patent/CA2578679A1/en not_active Abandoned
- 2007-02-22 US US11/709,487 patent/US7851577B2/en not_active Expired - Fee Related
- 2007-02-23 SG SG200701295-8A patent/SG136040A1/en unknown
- 2007-02-27 TW TW096106759A patent/TW200738756A/zh unknown
- 2007-02-27 JP JP2007047122A patent/JP5586824B2/ja not_active Expired - Fee Related
- 2007-03-08 DE DE602007008491T patent/DE602007008491D1/de active Active
- 2007-03-08 AT AT07004769T patent/ATE478098T1/de not_active IP Right Cessation
- 2007-03-08 EP EP07004769A patent/EP1834964B1/en not_active Not-in-force
- 2007-03-13 CN CN2007101421544A patent/CN101100489B/zh not_active Expired - Fee Related
- 2007-03-13 RU RU2007109105/04A patent/RU2497833C9/ru not_active IP Right Cessation
- 2007-03-13 KR KR1020070024373A patent/KR20070093847A/ko active IP Right Grant
Patent Citations (3)
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US3965078A (en) * | 1971-11-26 | 1976-06-22 | Snam Progetti S.P.A. | Procedure for the production of polymers and copolymers of isobutylene |
EP0920909A1 (en) * | 1994-03-31 | 1999-06-09 | Exxon Chemical Patents Inc. | Supported lewis acid catalysts for hydrocarbon conversion reactions |
CN1654487A (zh) * | 2003-09-16 | 2005-08-17 | 兰塞克斯公司 | 丁基橡胶的制备方法 |
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TW200738756A (en) | 2007-10-16 |
SG136040A1 (en) | 2007-10-29 |
EP1834964A3 (en) | 2007-12-12 |
JP5586824B2 (ja) | 2014-09-10 |
EP1834964A2 (en) | 2007-09-19 |
JP2007246902A (ja) | 2007-09-27 |
CN101100489A (zh) | 2008-01-09 |
CA2578679A1 (en) | 2007-09-14 |
ATE478098T1 (de) | 2010-09-15 |
RU2007109105A (ru) | 2008-09-20 |
US7851577B2 (en) | 2010-12-14 |
EP1834964B1 (en) | 2010-08-18 |
RU2497833C9 (ru) | 2014-07-20 |
DE602007008491D1 (de) | 2010-09-30 |
RU2497833C2 (ru) | 2013-11-10 |
US20070238843A1 (en) | 2007-10-11 |
KR20070093847A (ko) | 2007-09-19 |
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