JPH04288308A - Functional isobutylene polymer and production thereof - Google Patents
Functional isobutylene polymer and production thereofInfo
- Publication number
- JPH04288308A JPH04288308A JP10885491A JP10885491A JPH04288308A JP H04288308 A JPH04288308 A JP H04288308A JP 10885491 A JP10885491 A JP 10885491A JP 10885491 A JP10885491 A JP 10885491A JP H04288308 A JPH04288308 A JP H04288308A
- Authority
- JP
- Japan
- Prior art keywords
- group
- isobutylene
- formula
- hydrocarbon group
- lewis acid
- 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.)
- Pending
Links
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 150000001993 dienes Chemical class 0.000 claims abstract description 16
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 11
- 239000002841 Lewis acid Substances 0.000 claims abstract description 9
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 9
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 9
- 150000001336 alkenes Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 5
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910015844 BCl3 Inorganic materials 0.000 description 5
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 5
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910003074 TiCl4 Inorganic materials 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- GMGYODAMPOELNZ-MDZDMXLPSA-N (5e)-deca-1,5,9-triene Chemical compound C=CCC\C=C\CCC=C GMGYODAMPOELNZ-MDZDMXLPSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- SRNQAQUOOIZPJL-UHFFFAOYSA-N 1,3,5-tris(2-chloropropan-2-yl)benzene Chemical compound CC(C)(Cl)C1=CC(C(C)(C)Cl)=CC(C(C)(C)Cl)=C1 SRNQAQUOOIZPJL-UHFFFAOYSA-N 0.000 description 1
- GWRGEEAABGHXBR-UHFFFAOYSA-N 1,4-bis(2-chloropropan-2-yl)benzene Chemical compound CC(C)(Cl)C1=CC=C(C(C)(C)Cl)C=C1 GWRGEEAABGHXBR-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-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
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-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
- UCKITPBQPGXDHV-UHFFFAOYSA-N 7-methylocta-1,6-diene Chemical compound CC(C)=CCCCC=C UCKITPBQPGXDHV-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 229910021553 Vanadium(V) chloride Inorganic materials 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- ZPECUSGQPIKHLT-UHFFFAOYSA-N bis(ethenyl)-dimethoxysilane Chemical compound CO[Si](OC)(C=C)C=C ZPECUSGQPIKHLT-UHFFFAOYSA-N 0.000 description 1
- QRHCILLLMDEFSD-UHFFFAOYSA-N bis(ethenyl)-dimethylsilane Chemical compound C=C[Si](C)(C)C=C QRHCILLLMDEFSD-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MAYIDWCWWMOISO-UHFFFAOYSA-N dichloro-bis(ethenyl)silane Chemical compound C=C[Si](Cl)(Cl)C=C MAYIDWCWWMOISO-UHFFFAOYSA-N 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- NUFVQEIPPHHQCK-UHFFFAOYSA-N ethenyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C=C NUFVQEIPPHHQCK-UHFFFAOYSA-N 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 for example Polymers 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
- PKRKCDBTXBGLKV-UHFFFAOYSA-N tris(ethenyl)-methylsilane Chemical compound C=C[Si](C)(C=C)C=C PKRKCDBTXBGLKV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、官能基を有するイソブ
チレン系重合体及びその製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an isobutylene polymer having a functional group and a method for producing the same.
【０００２】0002
【従来の技術・発明が解決しようとする課題】末端官能
性ポリマー、例えば分子両末端に水酸基等が導入された
ポリマーは、ポリウレタン、接着剤、改質剤、コーティ
ング剤、シーリング剤等の原料等として有用である。こ
のようなポリマーの一種である、例えば末端官能性イソ
ブチレン系ポリマーの製造法としては、１，４−ビス（
α−クロロイソプロピル）ベンゼン（以下「ｐ−ＤＣＣ
」と記す）を開始剤兼連鎖移動剤とし、且つＢＣｌ３
を触媒としてイソブチレンをカチオン重合させるイニフ
ァー法（米国特許第４２７６３９４ 号明細書）が知ら
れている。更にかかるイニファー法で得られる重合直後
あるいは精製後の両末端に塩素原子を有するイソブチレ
ン系ポリマーに、重合触媒のＢＣｌ３ 以外に、更にＴ
ｉＣｌ４ を追加した後にアリルトリメチルシランと反
応させることにより両末端にアリル基を有するポリマー
に変換されることが知られている （特開昭６３−１０
５００５号公報） 。[Prior Art/Problems to be Solved by the Invention] Terminal functional polymers, for example, polymers in which hydroxyl groups, etc. are introduced at both ends of the molecule, are used as raw materials for polyurethane, adhesives, modifiers, coating agents, sealants, etc. It is useful as As a method for producing one type of such polymer, for example, a terminally functional isobutylene polymer, 1,4-bis(
α-chloroisopropyl)benzene (hereinafter “p-DCC”)
) is used as an initiator and chain transfer agent, and BCl3
The Inifer method (US Pat. No. 4,276,394) is known, in which isobutylene is cationically polymerized using as a catalyst. Furthermore, in addition to BCl3 as a polymerization catalyst, T is added to the isobutylene polymer having chlorine atoms at both ends immediately after polymerization or after purification, which is obtained by the Inifer method.
It is known that by adding iCl4 and then reacting with allyltrimethylsilane, it is converted into a polymer having allyl groups at both ends (JP-A-63-10
Publication No. 5005).
【０００３】しかしながら、上記の方法に従えば、重合
触媒 （ＢＣｌ３ ） とアリル化の際の触媒 （Ｔｉ
Ｃｌ４ ）が異なるという問題があった。更に該イニフ
ァー法では、高価なＢＣｌ３ が触媒として用いられて
いるが、触媒として安価なＴｉＣｌ４ を用いて上記イ
ニファー法を適用すると、ＢＣｌ３ を用いる場合に比
し、副反応による生成物がさらに増大するという問題が
ある。本発明の目的は、重合体の側鎖又は主鎖の末端に
官能基 （特にオレフィン基）を導入し、イソブチレン
系重合体を低コストで、しかもワンポットで製造し得る
方法を提供することにある。However, if the above method is followed, the polymerization catalyst (BCl3) and the allylation catalyst (Ti
There was a problem that Cl4) was different. Furthermore, in the Inifer method, expensive BCl3 is used as a catalyst, but if the Inifer method is applied using inexpensive TiCl4 as a catalyst, the amount of products due to side reactions will further increase compared to when BCl3 is used. There is a problem. An object of the present invention is to provide a method for producing an isobutylene polymer at low cost and in one pot by introducing a functional group (especially an olefin group) into the end of the side chain or main chain of the polymer. .
【０００４】0004
【課題を解決するための手段】即ち、本発明は、イソブ
チレンを含有するカチオン重合性モノマーと非共役ジエ
ンとをルイス酸の存在下に共重合させて得られる官能基
を有するイソブチレン系重合体及びその製造法に係る。
本明細書において、イソブチレンを含有するカチオン重
合性モノマーとは、イソブチレンのみからなるモノマー
に限定されるものではなく、イソブチレンの５０重量％
（以下単に「％」と記す） 以下をイソブチレンと共
重合し得るカチオン重合性モノマーで置換したモノマー
を意味する。[Means for Solving the Problems] That is, the present invention provides an isobutylene-based polymer having a functional group obtained by copolymerizing a cationically polymerizable monomer containing isobutylene and a non-conjugated diene in the presence of a Lewis acid; It pertains to its manufacturing method. In this specification, the cationic polymerizable monomer containing isobutylene is not limited to a monomer consisting only of isobutylene, but is 50% by weight of isobutylene.
(Hereinafter, simply referred to as "%") It means a monomer in which the following is substituted with a cationically polymerizable monomer that can be copolymerized with isobutylene.
【０００５】イソブチレンと共重合し得るカチオン重合
性モノマーとしては、例えば炭素数３〜１２のオレフィ
ン類、共役ジエン類、ビニルエーテル類、芳香族ビニル
化合物類、ビニルシラン類等が挙げられる。これらの中
でも炭素数３〜１２のオレフィン類及び共役ジエン類等
が好ましい。前記イソブチレンと共重合し得るカチオン
重合性モノマーの具体例としては、例えばプロピレン、
１−ブテン、２−ブテン、２−メチル−１−ブテン、３
−メチル−２−ブテン、ペンテン、４−メチル−１−ペ
ンテン、ヘキセン、ビニルシクロヘキサン、ブタジエン
、イソプレン、シクロペンタジエン、メチルビニルエー
テル、エチルビニルエーテル、イソブチルビニルエーテ
ル、スチレン、α−メチルスチレン、ジメチルスチレン
、モノクロロスチレン、ジクロロスチレン、β−ピネン
、インデン、ビニルトリクロロシラン、ビニルメチルジ
クロロシラン、ビニルジメチルクロロシラン、ビニルジ
メチルメトキシシラン、ビニルトリメチルシラン、ジビ
ニルジクロロシラン、ジビニルジメトキシシラン、ジビ
ニルジメチルシラン、１， ３−ジビニル−１， １，
３， ３−テトラメチルジシロキサン、トリビニルメ
チルシラン、テトラビニルシラン， γ−メタクリロイ
ルオキシプロピルトリメトキシシラン、γ−メタクリロ
イルオキシプロピルメチルジメトキシシラン等が挙げら
れる。
これらの中で、例えばプロピレン、１−ブテン、２−ブ
テン、スチレン、ブタジエン、イソプレン、シクロペン
タジエン等が好適である。これらイソブチレンと共重合
し得るカチオン重合性モノマーは、１種単独でイソブチ
レンと併用してもよいし、２種以上で併用してもよい。Examples of cationically polymerizable monomers that can be copolymerized with isobutylene include olefins having 3 to 12 carbon atoms, conjugated dienes, vinyl ethers, aromatic vinyl compounds, and vinyl silanes. Among these, olefins having 3 to 12 carbon atoms and conjugated dienes are preferred. Specific examples of the cationic polymerizable monomer that can be copolymerized with the isobutylene include propylene,
1-butene, 2-butene, 2-methyl-1-butene, 3
-Methyl-2-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexane, butadiene, isoprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene , dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl- 1, 1,
Examples include 3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane. Among these, propylene, 1-butene, 2-butene, styrene, butadiene, isoprene, cyclopentadiene and the like are preferred. These cationic polymerizable monomers that can be copolymerized with isobutylene may be used alone or in combination with isobutylene.
【０００６】本発明に用いる非共役ジエンとは、一般式
（３）The non-conjugated diene used in the present invention has the general formula (3)
【化３】
〔式中、Ｒ１ 、Ｒ２ 及びＲ３ は、同一又は異なっ
て水素原子又は炭素数１〜８のアルキル基を示す。Ｒ７
、Ｒ８ 及びＲ９ は、同一又は異なって水素原子、
メチル基又はエチル基を示す。Ｑは 炭素数１〜３０
の２価の有機基を示す。〕で表わされる化合物を意味す
る。本発明では、前記一般式 （３）に該当する限り従
来公知のものを広く使用でき、例えば１，４−ペンタジ
エン、１，５−ヘキサジエン、１，６−ヘプタジエン、
１，７−オクタジエン、１，８−ノナジエン、１，９−
デカジエン、１，１９−ドデカジエン、２−メチル−２
，７−オクタジエン、２，６−ジメチル−１，５−ペプ
タジエン、１，５，９−デカトリエン等が挙げられる。
これらの中でも、得られる共重合体の官能基の活性の点
から、α，ω−ジエンである、１，４−ペンタジエン、
１，５−ヘキサジエン、１，６−ヘプタジエン、１，７
−オクタジエン、１，８−ノナジエン、１，９−デカジ
エン、１，１９−ドデカジエン等が好ましい。embedded image [In the formula, R1, R2 and R3 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R7
, R8 and R9 are the same or different hydrogen atoms,
Indicates a methyl group or an ethyl group. Q is carbon number 1-30
represents a divalent organic group. ] means a compound represented by In the present invention, a wide variety of conventionally known compounds can be used as long as they meet the general formula (3), such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene,
1,7-octadiene, 1,8-nonadiene, 1,9-
Decadiene, 1,19-dodecadiene, 2-methyl-2
, 7-octadiene, 2,6-dimethyl-1,5-peptadiene, 1,5,9-decatriene and the like. Among these, from the viewpoint of the activity of the functional group of the resulting copolymer, α,ω-diene, 1,4-pentadiene,
1,5-hexadiene, 1,6-heptadiene, 1,7
-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,19-dodecadiene and the like are preferred.
【０００７】本発明に用いるルイス酸は触媒として使用
される成分であり、ＭＸ’ｎ（Ｍは金属原子、Ｘ’はハ
ロゲン原子）で表わされるもの、例えばＡｌＣｌ３ 、
ＳｎＣｌ４ 、ＴｉＣｌ４ 、ＶＣｌ５ 、ＦｅＣｌ３
、ＢＦ３ 等及びＥｔ２ ＡｌＣｌ、ＥｔＡｌＣｌ２
等の有機アルミニウム化合物等が挙げられるが、これ
らに限定されるものではない。これらのルイス酸のうち
、ＳｎＣｌ４ 、ＴｉＣｌ４ 、Ｅｔ２ ＡｌＣｌ、Ｅ
ｔＡｌＣｌ２等が好ましい。前記ルイス酸の使用量は、
イソブチレンと共重合させる非共役ジエンに対して、０
．１ 〜１０倍が好ましく、更に好ましくは０．２ 〜
５倍とするのがよい。The Lewis acid used in the present invention is a component used as a catalyst, and is represented by MX'n (M is a metal atom, X' is a halogen atom), such as AlCl3,
SnCl4, TiCl4, VCl5, FeCl3
, BF3 etc. and Et2 AlCl, EtAlCl2
Examples include organoaluminum compounds such as, but are not limited to. Among these Lewis acids, SnCl4, TiCl4, Et2 AlCl, E
tAlCl2 and the like are preferred. The amount of the Lewis acid used is
For non-conjugated dienes copolymerized with isobutylene, 0
．． 1 to 10 times is preferable, more preferably 0.2 to 10 times
It is better to increase it by 5 times.
【０００８】本発明では更に反応系内に開始剤を存在さ
せるのが好ましい。かかる開始剤としては、通常系中に
微量残存する水分等のプロトン源が有効に利用できる他
、例えば、開始剤兼連鎖移動剤が好適に使用できる。
本発明に利用できる開始剤兼連鎖移動剤としては、例え
ば一般式（２）In the present invention, it is preferable that an initiator is further present in the reaction system. As such an initiator, a proton source such as moisture that normally remains in a small amount in the system can be effectively used, and, for example, an initiator and chain transfer agent can be suitably used. As the initiator and chain transfer agent that can be used in the present invention, for example, general formula (2)
【化４】
〔式中、Ｘはハロゲン原子、ＲＣＯＯ−基（Ｒは１価の
有機基、以下同じ）又はＲＯ−基を示す。Ｒ６ は多価
芳香環基又は置換もしくは非置換の多価脂肪族炭化水素
基を示す。Ｒ４ 及びＲ５ は、同一又は異なって水素
原子又は置換もしくは非置換の１価の炭化水素基を示す
。但しＲ６ が多価脂肪族炭化水素基の場合には、Ｒ４
及びＲ５ は同時に水素原子ではない。〕で表わされ
る基を有する有機化合物が挙げられる。かかる有機化合
物の具体例としては、例えば、一般式（４）：
ＡＹｎ （４）〔
式中、Ａは１〜４個の芳香環を有する基を示す。Ｙは一
般式（５）：embedded image [wherein, X represents a halogen atom, an RCOO- group (R is a monovalent organic group, the same applies hereinafter) or an RO- group. R6 represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R4 and R5 are the same or different and represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R6 is a polyvalent aliphatic hydrocarbon group, R4
and R5 are not hydrogen atoms at the same time. ] Examples include organic compounds having a group represented by the following. Specific examples of such organic compounds include general formula (4): AYn (4) [
In the formula, A represents a group having 1 to 4 aromatic rings. Y is general formula (5):
【化５】
（式中、Ｒ１０及びＲ１１は、同一又は異なって水素原
子又は炭素数１〜２０の１価の炭化水素基を示す。Ｘは
Ｆ、Ｃｌ、Ｂｒ、Ｉの如きハロゲン原子、ＲＣＯＯ−基
又はＲＯ−基を示す。）で示される芳香環に結合した基
を示す。ｎは１〜６の整数を示す。〕で表わされる化合
物、一般式（６）：
ＢＺｍ （６
）〔式中、Ｂは炭素数４〜４０の炭化水素基を示す。Ｚ
は第３級炭素原子に結合したハロゲン原子、ＲＣＯＯ−
基又はＲＯ−基を示す。ｍは１〜４の整数を示す。〕で
表わされる化合物及びα−ハロスチレン単位を有するオ
リゴマー等が挙げられるが、これらに限定されるもので
はない。これらの化合物は単独で用いてもよいし、２種
以上併用してもよい。(In the formula, R10 and R11 are the same or different and represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. X is a halogen atom such as F, Cl, Br, I, RCOO - group or RO- group.) represents a group bonded to an aromatic ring. n represents an integer of 1 to 6. ], a compound represented by the general formula (6): BZm (6
) [In the formula, B represents a hydrocarbon group having 4 to 40 carbon atoms. Z
is a halogen atom bonded to a tertiary carbon atom, RCOO-
or RO- group. m represents an integer of 1 to 4. ] and oligomers having α-halostyrene units, but are not limited thereto. These compounds may be used alone or in combination of two or more.
【０００９】一般式（４）で表わされる化合物における
１〜４個の芳香環を有する基であるＡは、縮合反応によ
り形成されたものでもよく、非縮合系のものでもよい。
このような芳香環を有する基の具体例としては、例えば
１〜６価のフェニル基、ビフェニル基、ナフタレン基、
アントラセン基、フェナンスレン基、ピレン基、Ｐｈ−
（ＣＨ２ ）Ｌ −Ｐｈ基（Ｐｈはフェニル基、Ｌ は
１〜１０の整数）等が挙げられ、これらの芳香環を有す
る基は炭素数１〜２０の直鎖及び（又は）枝分れの脂肪
族炭化水素基や、水酸基、エーテル基、ビニル基等の官
能基を有する基で置換されていてもよい。A, which is a group having 1 to 4 aromatic rings in the compound represented by the general formula (4), may be formed by a condensation reaction or may be a non-condensed group. Specific examples of groups having such aromatic rings include monovalent to hexavalent phenyl groups, biphenyl groups, naphthalene groups,
anthracene group, phenanthrene group, pyrene group, Ph-
(CH2)L-Ph group (Ph is a phenyl group, L is an integer of 1 to 10), etc., and these aromatic ring-containing groups are linear and/or branched groups having 1 to 20 carbon atoms. It may be substituted with an aliphatic hydrocarbon group or a group having a functional group such as a hydroxyl group, an ether group, or a vinyl group.
【００１０】一方、一般式（６）で表わされる化合物に
おけるＺは、第３級炭素原子に結合したＦ、Ｃｌ、Ｂｒ
、Ｉの如きハロゲン原子、ＲＣＯＯ−基又はＲＯ−基で
あり、一般式（６）におけるＢは炭素数４〜４０の炭化
水素基の脂肪族炭化水素基であり、好ましくは脂肪族炭
化水素基であり、この炭素数が４未満になるとハロゲン
原子、ＲＣＯＯ−基又はＲＯ−基の結合する炭素が第３
級炭素原子でなくなり、重合が進みにくくなって使用す
るのに適さなくなる。開始剤兼連鎖移動剤として用いる
ことができるα−ハロスチレン単位を有するオリゴマー
としては、例えばα−クロロスチレンのオリゴマーや、
α−クロロスチレンとこれと共重合し得る単量体とを共
重合させたオリゴマー等が挙げられる。On the other hand, Z in the compound represented by the general formula (6) is F, Cl, Br bonded to the tertiary carbon atom.
, I is a halogen atom, RCOO- group or RO- group, and B in general formula (6) is an aliphatic hydrocarbon group of a hydrocarbon group having 4 to 40 carbon atoms, preferably an aliphatic hydrocarbon group. When the number of carbon atoms is less than 4, the carbon to which the halogen atom, RCOO- group or RO- group is bonded becomes the tertiary carbon.
It is no longer a class carbon atom, and polymerization becomes difficult to proceed, making it unsuitable for use. Examples of oligomers having α-halostyrene units that can be used as initiators and chain transfer agents include α-chlorostyrene oligomers,
Examples include oligomers obtained by copolymerizing α-chlorostyrene and monomers that can be copolymerized therewith.
【００１１】本発明の方法において、一般式（２）で表
わされる結合状態のハロゲン原子、ＲＣＯＯ−基、又は
ＲＯ−基を２個以上有する化合物、又は一般式（１）で
表される結合状態のハロゲン原子、ＲＣＯＯ−基又はＲ
Ｏ−基と他の反応性官能基とを有する化合物を開始剤兼
連鎖移動剤として用いると、その官能化度を高くできる
ので非常に有効である。前記開始剤兼連鎖移動剤の具体
例としては、例えば[0011] In the method of the present invention, a compound having two or more halogen atoms, RCOO- groups, or RO- groups in a bonded state represented by general formula (2), or a bonded state represented by general formula (1) halogen atom, RCOO- group or R
The use of a compound having an O-group and other reactive functional groups as an initiator and chain transfer agent is very effective because the degree of functionalization can be increased. Specific examples of the initiator and chain transfer agent include, for example:
【化６】
α−クロロスチレンのオリゴマーのようなハロゲン原子
含有有機化合物又はＲＣＯＯ−基含有有機化合物が挙げ
られるが、これらに限定されるものではない。これら化
合物の中で好ましいものとしては、embedded image Examples include, but are not limited to, halogen atom-containing organic compounds such as α-chlorostyrene oligomers or RCOO-group-containing organic compounds. Among these compounds, preferred are:
【化７】
のような安定な炭素陽イオンを生成し易い−Ｃ（ＣＨ３
）２ Ｃｌ又は−Ｃ（ＣＨ３ ）２ Ｂｒを有するハ
ロゲン原子含有有機化合物や、-C(CH3
)2Cl or -C(CH3)2Br, a halogen atom-containing organic compound,
【化８】 のようなＣＨ３ ＣＯＯ−基含有有機化合物や、[Chemical formula 8] CH3 COO- group-containing organic compounds such as
【化９
】
のようなＣＨ３ Ｏ−基含有有機化合物等が挙げられる
。[C9
] CH3 O- group-containing organic compounds, etc. may be mentioned.
【００１２】これらの化合物は、開始剤兼連鎖移動剤と
して使用される成分であり、本発明では、１種又は２種
以上混合して用いられる。また、これらの化合物の使用
量又は残存水分量を調節することにより、得られるポリ
マーの分子量をコントロールすることができる。本発明
では、前記の化合物を、通常イソブチレンを含有するカ
チオン重合性モノマーに対して、０．０１〜２０％程度
、好ましくは０．１ 〜１０％程度の割合で使用するの
がよい。本発明において、重合溶媒としては、例えば脂
肪族炭化水素、ハロゲン化炭化水素等の炭化水素溶媒等
が用いられる。この中でもハロゲン化炭化水素が好まし
く、塩素原子を有する塩素化炭化水素がより好ましい。
かかる脂肪族炭化水素の具体例としては、ペンタン、ヘ
キサン等を、またハロゲン化炭化水素の具体例としては
、クロロメタン、クロロエタン、塩化メチレン、１，１
−ジクロロエタン、クロロホルム、１，２−ジクロロエ
タン等を例示できる。これらは、１種単独で、又は２種
以上混合して使用される。更には少量の他の溶媒、例え
ば酢酸エチル等の酢酸エステルや、ニトロエタン等のニ
トロ基を有する有機化合物を併用してもよい。These compounds are components used as initiators and chain transfer agents, and in the present invention, they are used singly or in combination of two or more. Furthermore, by adjusting the amount of these compounds used or the amount of residual water, the molecular weight of the resulting polymer can be controlled. In the present invention, the above-mentioned compound is preferably used in a proportion of about 0.01 to 20%, preferably about 0.1 to 10%, based on the cationically polymerizable monomer containing isobutylene. In the present invention, the polymerization solvent used is, for example, a hydrocarbon solvent such as an aliphatic hydrocarbon or a halogenated hydrocarbon. Among these, halogenated hydrocarbons are preferred, and chlorinated hydrocarbons having a chlorine atom are more preferred. Specific examples of such aliphatic hydrocarbons include pentane, hexane, etc., and specific examples of halogenated hydrocarbons include chloromethane, chloroethane, methylene chloride, 1,1
Examples include -dichloroethane, chloroform, and 1,2-dichloroethane. These may be used alone or in combination of two or more. Furthermore, a small amount of other solvents, such as acetic esters such as ethyl acetate, or organic compounds having a nitro group such as nitroethane, may be used in combination.
【００１３】本発明の方法を実施するに際しては、特に
制限がなく、従来の重合方法を広く適用できる。例えば
１つの容器に重合溶媒、モノマー、非共役ジエン、触媒
、必要に応じて開始剤兼連鎖移動剤等を順次仕込んでい
くバッチ法でもよいし、重合溶媒、モノマー、非共役ジ
エン、触媒、必要に応じて開始剤兼連鎖移動剤等をある
系内に連続的に仕込みながら反応させ、更に取出される
連続法でもよい。本発明の製造法において、重合温度と
しては＋１０〜−８０℃程度が好ましく、更に好ましく
は０〜−４０℃程度とするのがよく、重合時間は、通常
０．５ 〜１２０ 分程度、好ましくは１〜６０分程度
である。また重合時のモノマー濃度としては、０．１〜
８モル／リットル程度が好ましく、０．５ 〜５モル／
リットル程度がより好ましい。[0013] When carrying out the method of the present invention, there are no particular restrictions, and conventional polymerization methods can be widely applied. For example, a batch method may be used in which the polymerization solvent, monomer, non-conjugated diene, catalyst, and if necessary an initiator and chain transfer agent are sequentially charged into one container, or the polymerization solvent, monomer, non-conjugated diene, catalyst, and the necessary Depending on the situation, a continuous method may be used in which an initiator/chain transfer agent and the like are continuously introduced into a certain system to react and then taken out. In the production method of the present invention, the polymerization temperature is preferably about +10 to -80°C, more preferably about 0 to -40°C, and the polymerization time is usually about 0.5 to 120 minutes, preferably about It takes about 1 to 60 minutes. In addition, the monomer concentration during polymerization is 0.1 to
It is preferably about 8 mol/liter, and 0.5 to 5 mol/liter.
More preferably about liters.
【００１４】更に本発明において、上記カチオン重合性
モノマーの重合反応の前に重合系中に加える非共役ジエ
ンは、用いるポリマーのモル数に対して０．０１〜１倍
モルを加えて均一になるように撹拌することが好ましい
。本発明では、後の取り扱い易さからメタノール等のア
ルコール類の添加により重合反応を停止させるのが好ま
しいが、特にこれに限定されるものではなく、従来の慣
用手段のいずれも適用でき、また、特に停止反応を改め
て行なう必要もない。Furthermore, in the present invention, the non-conjugated diene added to the polymerization system before the polymerization reaction of the cationically polymerizable monomer is made uniform by adding 0.01 to 1 times the number of moles of the polymer used. It is preferable to stir the mixture as follows. In the present invention, it is preferable to stop the polymerization reaction by adding an alcohol such as methanol for ease of later handling, but the present invention is not particularly limited to this, and any conventional commonly used means can be applied. There is no particular need to perform the termination reaction again.
【００１５】かくしてイソブチレンモノマー単位を主体
とする数平均分子量が５００ 〜５００，０００ の共
重合体であって、１分子当り少なくとも１．０５個の一
般式（１）[0015] Thus, a copolymer having a number average molecular weight of 500 to 500,000, which is mainly composed of isobutylene monomer units, and has at least 1.05 units of the general formula (1) per molecule.
【化１０】
で表わされるオレフィン基を共重合体の側鎖又は主鎖の
末端に有するイソブチレン系重合体が製造される。An isobutylene polymer having an olefin group represented by the following formula at the end of the side chain or main chain of the copolymer is produced.
【００１６】[0016]
【発明の効果】本発明の方法によれば、非共役ジエンの
種類及び使用量をコントロールすることにより、官能基
含量の異なる共重合体をワンポットで簡便に得ることが
できる。また、共役ジエンを用いた場合のように、主鎖
中に１，４−付加によるオレフィン基の残存もないため
、高い耐候性等が期待できる。こうして得られた共重合
体は、そのまま架橋硬化物の原料として用いられる他、
その官能基を水酸基、アミノ基、アルコキシシリル基、
ハイドロジェンシリル基等へ変換することができる。ま
た、本発明では、開始剤兼連鎖移動剤を用いなくても、
１分子に１．０５個以上の活性なオレフィン基を導入す
ることができる。According to the method of the present invention, copolymers having different functional group contents can be easily obtained in one pot by controlling the type and amount of nonconjugated diene used. In addition, unlike when a conjugated diene is used, no olefin group remains in the main chain due to 1,4-addition, so high weather resistance etc. can be expected. The copolymer thus obtained can be used as it is as a raw material for crosslinked cured products, as well as
The functional group is hydroxyl group, amino group, alkoxysilyl group,
It can be converted to hydrogensilyl group, etc. In addition, in the present invention, even without using an initiator and chain transfer agent,
1.05 or more active olefin groups can be introduced into one molecule.
【００１７】[0017]
【実施例】次に実施例を掲げて、本発明をより一層明ら
かにするが、実施例により本発明は何ら限定されるもの
ではない。
実施例１
１００ｍｌの耐圧ガラス製オートクレーブに撹拌用羽根
、三方コック及び真空ラインを取付けて、真空ラインで
真空に引きながら重合容器を１００℃で１時間加熱する
ことにより乾燥させ、室温まで冷却後三方コックを用い
て窒素で常圧に戻した。その後、三方コックの一方から
窒素を流しながら、注射器を用いてオートクレーブに水
素化カルシウム処理により乾燥させた主溶媒である塩化
メチレン４０ｍｌを導入した。次いで蒸留、精製した１
，９−デカジエン２０ｍｍｏｌを添加し、更にトリキュ
ミルクロリド（ＴＣＣ：前記の化合物Ａ）３ｍｍｏｌを
溶解させた塩化メチレン溶液（１０ｍｌ）を添加した。
次に、酸化バリウムを充填したカラムを通過させること
により脱水したイソブチレンが７ｇ入っているニードル
バルブ付耐圧ガラス製液化ガス採取管を三方コックに接
続した後、容器本体を−７０℃のドライアイス−アセト
ンバスに浸漬し、重合容器内部を撹拌しながら１時間冷
却した。冷却後、真空ラインにより内部を減圧にした後
、ニードルバルブを開け、イソブチレンを耐圧ガラス製
液化ガス採取管から重合容器に導入した。その後三方コ
ックの一方から窒素を流すことにより常圧に戻し、更に
撹拌下に１時間冷却を続け、重合容器内を−３０℃まで
昇温した。[Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples in any way. Example 1 A 100 ml pressure-resistant glass autoclave was equipped with a stirring blade, a three-way cock, and a vacuum line, and the polymerization container was dried by heating it at 100°C for 1 hour while being evacuated with the vacuum line, and after cooling to room temperature, the three-way cock was heated. The pressure was returned to normal pressure with nitrogen using a cock. Thereafter, 40 ml of methylene chloride, the main solvent, which had been dried by calcium hydride treatment, was introduced into the autoclave using a syringe while nitrogen was flowing through one of the three-way cocks. Then distilled and purified 1
, 20 mmol of 9-decadiene were added, and a methylene chloride solution (10 ml) in which 3 mmol of tricumyl chloride (TCC: the above-mentioned compound A) was dissolved was further added. Next, a pressure-resistant glass liquefied gas sampling tube with a needle valve containing 7 g of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock, and the container body was placed in dry ice at -70°C. The polymerization container was immersed in an acetone bath and cooled for 1 hour while stirring the inside of the polymerization container. After cooling, the pressure inside the reactor was reduced using a vacuum line, the needle valve was opened, and isobutylene was introduced into the polymerization container from a pressure-resistant glass liquefied gas collection tube. Thereafter, the pressure was returned to normal pressure by flowing nitrogen through one of the three-way cocks, and cooling was continued for 1 hour while stirring, and the temperature inside the polymerization vessel was raised to -30°C.
【００１８】次に、ＴｉＣｌ４ ３．２ｇ（１０ミリモ
ル）を注射器を用いて三方コックから添加して重合を開
始させ、６０分経過した時点で予め０℃以下に冷却して
おいたメタノールを添加することにより、反応を完結さ
せた。その後、反応混合物をナス型フラスコに取出し、
未反応のイソブチレン、塩化メチレン、１，９−デカジ
エン及びメタノールを留去し、残ったポリマーを１００
ｍｌのｎ−ヘキサンに溶解後、中性になるまでこの溶液
の水洗を繰返した。その後、このｎ−ヘキサン溶液を２
０ｍｌまで濃縮し、３００ｍｌのアセトンにこの濃縮溶
液を注ぎ込むことによりポリマーを沈澱分離させた。こ
のようにして得られたポリマーを再び１００ｍｌのｎ−
ヘキサンに溶解させ、無水硫酸マグネシウムで乾燥させ
、濾過し、ｎ−ヘキサンを減圧留去することにより、イ
ソブチレン系ポリマーを得た。得られたポリマーの収量
より収率を算出すると共に、Ｍｎ及びＭｗ／ＭｎをＧＰ
Ｃ法により、また末端構造を １Ｈ−ＮＭＲ（３００Ｍ
Ｈｚ）法により各構造に帰属するプロトンの共鳴信号の
強度を測定、比較することにより求めた。結果を表２に
示す。Next, 3.2 g (10 mmol) of TiCl4 is added using a syringe through a three-way cock to initiate polymerization, and after 60 minutes, methanol that has been cooled in advance to below 0° C. is added. This completed the reaction. After that, the reaction mixture was taken out into an eggplant-shaped flask,
Unreacted isobutylene, methylene chloride, 1,9-decadiene and methanol were distilled off, and the remaining polymer was
After dissolving in ml of n-hexane, this solution was washed with water repeatedly until it became neutral. Then, add this n-hexane solution to 2
The polymer was precipitated and separated by concentrating to 0 ml and pouring this concentrated solution into 300 ml of acetone. The polymer thus obtained was again added to 100 ml of n-
An isobutylene polymer was obtained by dissolving it in hexane, drying over anhydrous magnesium sulfate, filtration, and distilling off n-hexane under reduced pressure. The yield is calculated from the yield of the obtained polymer, and Mn and Mw/Mn are calculated by GP.
The terminal structure was also determined by 1H-NMR (300M
It was determined by measuring and comparing the intensities of the resonance signals of protons belonging to each structure using the Hz) method. The results are shown in Table 2.
【００１９】実施例２〜７
開始剤兼連鎖移動剤の有無、非共役ジエンの種類や使用
量及び重合触媒を表１に示すように変更した以外は、実
施例１と同様にしてポリマーを製造し、評価した。結果
を表２に併せて示す。
比較例１
非共役ジエンを使用しない以外は、実施例１と同様にし
てポリマーを製造して評価した。結果を表２に併せて示
す。Examples 2 to 7 Polymers were produced in the same manner as in Example 1, except that the presence or absence of an initiator and chain transfer agent, the type and amount of non-conjugated diene used, and the polymerization catalyst were changed as shown in Table 1. and evaluated. The results are also shown in Table 2. Comparative Example 1 A polymer was produced and evaluated in the same manner as in Example 1, except that no non-conjugated diene was used. The results are also shown in Table 2.
【表１】[Table 1]
【表２】[Table 2]
【図１】図１は、実施例１で得られたイソブチレン系重
合体のＩＲスペクトル図である。FIG. 1 is an IR spectrum diagram of the isobutylene polymer obtained in Example 1.
【図２】図２は、実施例１で得られたイソブチレン系重
合体の １Ｈ−ＮＭＲスペクトル図（３００ＭＨｚ）で
ある。FIG. 2 is a 1H-NMR spectrum (300 MHz) of the isobutylene polymer obtained in Example 1.
Claims (4)
性モノマーと非共役ジエンとをルイス酸の存在下に共重
合させて得られる官能基を有するイソブチレン系重合体
。1. An isobutylene-based polymer having a functional group obtained by copolymerizing a cationically polymerizable monomer containing isobutylene and a non-conjugated diene in the presence of a Lewis acid.
る数平均分子量が５００〜５００，０００の共重合体で
あって、１分子当り少なくとも１．０５個の一般式（１
）： 【化１】 〔式中、Ｒ１ 、Ｒ２ 及びＲ３ は、同一又は異なっ
て水素原子又は炭素数１〜８のアルキル基を示す。〕で
表わされるオレフィン基を共重合体の側鎖又は主鎖の末
端に有する請求項１記載の重合体。2. A copolymer mainly composed of isobutylene monomer units and having a number average molecular weight of 500 to 500,000, wherein each molecule contains at least 1.05 units of the general formula (1
): [Formula 1] [In the formula, R1, R2 and R3 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 2. The polymer according to claim 1, which has an olefin group represented by the following at the end of the side chain or main chain of the copolymer.
性モノマーと非共役ジエンとをルイス酸の存在下に共重
合させることを特徴とする請求項１記載のイソブチレン
系重合体の製造法。3. The method for producing an isobutylene polymer according to claim 1, which comprises copolymerizing a cationically polymerizable monomer containing isobutylene and a nonconjugated diene in the presence of a Lewis acid.
剤兼連鎖移動剤である一般式（２）： 【化２】 〔式中、Ｘはハロゲン原子、ＲＣＯＯ−基（Ｒは１価の
有機基、以下同じ）又はＲＯ−基を示す。Ｒ６ は多価
芳香環基又は置換もしくは非置換の多価脂肪族炭化水素
基を示す。Ｒ４ 及びＲ５ は、同一又は異なって水素
原子又は置換もしくは非置換の１価の炭化水素基を示す
。但しＲ６ が多価脂肪族炭化水素基の場合には、Ｒ４
及びＲ５ は同時に水素原子ではない。〕で表わされ
る基を有する有機化合物を更に存在させる請求項３記載
の製造法。[Claim 4] General formula (2) which is an initiator and chain transfer agent together with a Lewis acid in the polymerization reaction system: [In the formula, X is a halogen atom, an RCOO- group (R is a monovalent represents an organic group (the same applies hereinafter) or an RO- group. R6 represents a polyvalent aromatic ring group or a substituted or unsubstituted polyvalent aliphatic hydrocarbon group. R4 and R5 are the same or different and represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R6 is a polyvalent aliphatic hydrocarbon group, R4
and R5 are not hydrogen atoms at the same time. 4. The manufacturing method according to claim 3, further comprising an organic compound having a group represented by the following formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10885491A JPH04288308A (en) | 1990-04-16 | 1991-04-13 | Functional isobutylene polymer and production thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10102990 | 1990-04-16 | ||
| JP2-101029 | 1990-11-29 | ||
| JP10885491A JPH04288308A (en) | 1990-04-16 | 1991-04-13 | Functional isobutylene polymer and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04288308A true JPH04288308A (en) | 1992-10-13 |
Family
ID=26441959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10885491A Pending JPH04288308A (en) | 1990-04-16 | 1991-04-13 | Functional isobutylene polymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04288308A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006501333A (en) * | 2002-10-03 | 2006-01-12 | バイエル・インク． | Peroxide-curable compounds based on butyl-like polymers that do not contain aliphatic conjugated dienes in the composition |
| JP4819360B2 (en) * | 2002-10-03 | 2011-11-24 | ランクセス・インク． | Butyl rubber adhesive compound |
-
1991
- 1991-04-13 JP JP10885491A patent/JPH04288308A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006501333A (en) * | 2002-10-03 | 2006-01-12 | バイエル・インク． | Peroxide-curable compounds based on butyl-like polymers that do not contain aliphatic conjugated dienes in the composition |
| JP4800620B2 (en) * | 2002-10-03 | 2011-10-26 | ランクセス・インク． | Peroxide-curable compounds based on butyl-like polymers that do not contain aliphatic conjugated dienes in the composition |
| JP4819360B2 (en) * | 2002-10-03 | 2011-11-24 | ランクセス・インク． | Butyl rubber adhesive compound |
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