JPH03166204A - Styrene-based copolymer and production thereof - Google Patents
Styrene-based copolymer and production thereofInfo
- Publication number
- JPH03166204A JPH03166204A JP30787289A JP30787289A JPH03166204A JP H03166204 A JPH03166204 A JP H03166204A JP 30787289 A JP30787289 A JP 30787289A JP 30787289 A JP30787289 A JP 30787289A JP H03166204 A JPH03166204 A JP H03166204A
- Authority
- JP
- Japan
- Prior art keywords
- atom
- group
- formula
- vinyl
- styrene
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title abstract description 29
- 229920001577 copolymer Polymers 0.000 title abstract description 25
- 125000001424 substituent group Chemical group 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 229910052718 tin Inorganic materials 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 9
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract 2
- 150000002367 halogens Chemical class 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 125000005843 halogen group Chemical group 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- 125000004437 phosphorous atom Chemical group 0.000 claims description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 12
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 12
- 229910052711 selenium Inorganic materials 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 229920006249 styrenic copolymer Polymers 0.000 claims description 12
- 125000004434 sulfur atom Chemical group 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 2
- 230000005494 condensation Effects 0.000 abstract 2
- 238000009833 condensation Methods 0.000 abstract 2
- -1 acenaphthylene compound Chemical class 0.000 description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- 238000000034 method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 150000001240 acenaphthylenes Chemical class 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 5
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000003623 transition metal compounds Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 125000005287 vanadyl group Chemical group 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- BQDUQUBZHIQLPL-UHFFFAOYSA-N 1-ethenyl-2-(2-phenylphenyl)benzene Chemical group C=CC1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 BQDUQUBZHIQLPL-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 210000003739 neck Anatomy 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- HIZFJKUEOHPPMO-UHFFFAOYSA-N 1,2-dibromoacenaphthylene Chemical group C1=CC(C(Br)=C2Br)=C3C2=CC=CC3=C1 HIZFJKUEOHPPMO-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- LLNQJWMIQJLBMO-UHFFFAOYSA-N 1-ethenyl-3-(2-phenylphenyl)benzene Chemical group C=CC1=CC=CC(C=2C(=CC=CC=2)C=2C=CC=CC=2)=C1 LLNQJWMIQJLBMO-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical compound CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 2
- FMFHUEMLVAIBFI-UHFFFAOYSA-N 2-phenylethenyl acetate Chemical compound CC(=O)OC=CC1=CC=CC=C1 FMFHUEMLVAIBFI-UHFFFAOYSA-N 0.000 description 2
- VTEHXZOGYXPKKC-UHFFFAOYSA-N 5-chloroacenaphthylene Chemical group C1=CC2=CC=CC3=C2C1=CC=C3Cl VTEHXZOGYXPKKC-UHFFFAOYSA-N 0.000 description 2
- BEJCZQAOCVRCQO-UHFFFAOYSA-N 5-ethylacenaphthylene Chemical group C1=CC2=CC=CC3=C2C1=CC=C3CC BEJCZQAOCVRCQO-UHFFFAOYSA-N 0.000 description 2
- PHZMHQUNNJNUGP-UHFFFAOYSA-N 5-fluoroacenaphthylene Chemical group C1=CC2=CC=CC3=C2C1=CC=C3F PHZMHQUNNJNUGP-UHFFFAOYSA-N 0.000 description 2
- YCSMEGCHVPYSLG-UHFFFAOYSA-N 5-iodoacenaphthylene Chemical group C1=CC2=CC=CC3=C2C1=CC=C3I YCSMEGCHVPYSLG-UHFFFAOYSA-N 0.000 description 2
- LVIUNSKRWITKCI-UHFFFAOYSA-N 5-methoxyacenaphthylene Chemical group C1=CC2=CC=CC3=C2C1=CC=C3OC LVIUNSKRWITKCI-UHFFFAOYSA-N 0.000 description 2
- CQKTVYCWAAZXTJ-UHFFFAOYSA-N 5-methylacenaphthylene Chemical group C1=CC2=CC=CC3=C2C1=CC=C3C CQKTVYCWAAZXTJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- QXIOOGPOJCFNNV-UHFFFAOYSA-N CC(CCC(C)(C)C)([Ti](CCCC)(CCCC)C1C=CC=C1)C Chemical compound CC(CCC(C)(C)C)([Ti](CCCC)(CCCC)C1C=CC=C1)C QXIOOGPOJCFNNV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- KMLIQWUBQIWDRF-UHFFFAOYSA-N acenaphthylen-5-yl(trimethyl)silane Chemical group C1=CC2=CC=CC3=C2C1=CC=C3[Si](C)(C)C KMLIQWUBQIWDRF-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical group COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 2
- 125000003357 methylseleno group Chemical group [H]C([H])([H])[Se][*] 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OXHSYXPNALRSME-UHFFFAOYSA-N (4-ethenylphenyl)-trimethylsilane Chemical compound C[Si](C)(C)C1=CC=C(C=C)C=C1 OXHSYXPNALRSME-UHFFFAOYSA-N 0.000 description 1
- SGVYNSUGXGDLGL-UHFFFAOYSA-N 1,2-dichloroacenaphthylene Chemical group C1=CC(C(Cl)=C2Cl)=C3C2=CC=CC3=C1 SGVYNSUGXGDLGL-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- JGSMASRYITYKSR-UHFFFAOYSA-N 1,2-dimethylacenaphthylene Chemical group C1=CC(C(C)=C2C)=C3C2=CC=CC3=C1 JGSMASRYITYKSR-UHFFFAOYSA-N 0.000 description 1
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- CKLKILXJMRJOEK-UHFFFAOYSA-N 1,5-dimethylacenaphthylene Chemical group C1=CC(C(C)=C2)=C3C2=CC=C(C)C3=C1 CKLKILXJMRJOEK-UHFFFAOYSA-N 0.000 description 1
- UDSWRXKMHZVDEL-UHFFFAOYSA-N 1-(2-chloroethyl)-4-ethenylbenzene Chemical compound ClCCC1=CC=C(C=C)C=C1 UDSWRXKMHZVDEL-UHFFFAOYSA-N 0.000 description 1
- DYMLOKBNJOZEKB-UHFFFAOYSA-N 1-(2-ethenylphenyl)anthracene Chemical compound C=CC1=CC=CC=C1C1=CC=CC2=CC3=CC=CC=C3C=C12 DYMLOKBNJOZEKB-UHFFFAOYSA-N 0.000 description 1
- ACCQVNKVOBSQOX-UHFFFAOYSA-N 1-(2-ethenylphenyl)naphthalene Chemical compound C=CC1=CC=CC=C1C1=CC=CC2=CC=CC=C12 ACCQVNKVOBSQOX-UHFFFAOYSA-N 0.000 description 1
- HCQUQLVQRCVXRN-UHFFFAOYSA-N 1-(2-ethenylphenyl)pyrene Chemical compound C=CC1=CC=CC=C1C1=CC=C(C=C2)C3=C4C2=CC=CC4=CC=C13 HCQUQLVQRCVXRN-UHFFFAOYSA-N 0.000 description 1
- RPFQKLYATSTHMN-UHFFFAOYSA-N 1-(3-ethenylphenyl)anthracene Chemical compound C=CC1=CC=CC(C=2C3=CC4=CC=CC=C4C=C3C=CC=2)=C1 RPFQKLYATSTHMN-UHFFFAOYSA-N 0.000 description 1
- ZHEXHNNPQTUCCL-UHFFFAOYSA-N 1-(3-ethenylphenyl)naphthalene Chemical compound C=CC1=CC=CC(C=2C3=CC=CC=C3C=CC=2)=C1 ZHEXHNNPQTUCCL-UHFFFAOYSA-N 0.000 description 1
- OAQVBAHHLKPHJN-UHFFFAOYSA-N 1-(3-ethenylphenyl)phenanthrene Chemical compound C=CC1=CC=CC(C=2C3=C(C4=CC=CC=C4C=C3)C=CC=2)=C1 OAQVBAHHLKPHJN-UHFFFAOYSA-N 0.000 description 1
- CZBANWMMSOISGO-UHFFFAOYSA-N 1-(3-ethenylphenyl)pyrene Chemical compound C=CC1=CC=CC(C=2C3=CC=C4C=CC=C5C=CC(C3=C54)=CC=2)=C1 CZBANWMMSOISGO-UHFFFAOYSA-N 0.000 description 1
- XEZDTIJPXHAUGW-UHFFFAOYSA-N 1-(4-ethenylphenyl)naphthalene Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC2=CC=CC=C12 XEZDTIJPXHAUGW-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- WSVNNBLRMXALFR-UHFFFAOYSA-N 1-chloro-4-(4-ethenylphenyl)benzene Chemical group C1=CC(Cl)=CC=C1C1=CC=C(C=C)C=C1 WSVNNBLRMXALFR-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
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- QCMUCSVOOUAWSI-UHFFFAOYSA-N 1-ethenyl-2-ethoxy-4-phenylbenzene Chemical group C1=C(C=C)C(OCC)=CC(C=2C=CC=CC=2)=C1 QCMUCSVOOUAWSI-UHFFFAOYSA-N 0.000 description 1
- BVDDGHPFPXIARJ-UHFFFAOYSA-N 1-ethenyl-2-fluoro-4-phenylbenzene Chemical group C1=C(C=C)C(F)=CC(C=2C=CC=CC=2)=C1 BVDDGHPFPXIARJ-UHFFFAOYSA-N 0.000 description 1
- YNQXOOPPJWSXMW-UHFFFAOYSA-N 1-ethenyl-2-fluorobenzene Chemical compound FC1=CC=CC=C1C=C YNQXOOPPJWSXMW-UHFFFAOYSA-N 0.000 description 1
- IPCZAAPZVUICFA-UHFFFAOYSA-N 1-ethenyl-2-methoxy-4-phenylbenzene Chemical group C1=C(C=C)C(OC)=CC(C=2C=CC=CC=2)=C1 IPCZAAPZVUICFA-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- XIRPMPKSZHNMST-UHFFFAOYSA-N 1-ethenyl-2-phenylbenzene Chemical group C=CC1=CC=CC=C1C1=CC=CC=C1 XIRPMPKSZHNMST-UHFFFAOYSA-N 0.000 description 1
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- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- PDLMXGNLCRZSPL-UHFFFAOYSA-K [Cl-].C1(C=CC=C1)CO[Ti+3].[Cl-].[Cl-] Chemical compound [Cl-].C1(C=CC=C1)CO[Ti+3].[Cl-].[Cl-] PDLMXGNLCRZSPL-UHFFFAOYSA-K 0.000 description 1
- QICHYKWHJVIRAU-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC=C1)[Ti+2]CC Chemical compound [Cl-].[Cl-].C1(C=CC=C1)[Ti+2]CC QICHYKWHJVIRAU-UHFFFAOYSA-L 0.000 description 1
- RHFHQIBMFHQFJS-UHFFFAOYSA-N [O-]CC.[O-]CC.[O-]CC.CC1=C(C(=C(C1([Ti+3])C)C)C)C Chemical compound [O-]CC.[O-]CC.[O-]CC.CC1=C(C(=C(C1([Ti+3])C)C)C)C RHFHQIBMFHQFJS-UHFFFAOYSA-N 0.000 description 1
- UPLJFGURRZIASC-UHFFFAOYSA-N [Ti+3].CCCC[O-].CCCC[O-].CCCC[O-].C[C]1C(C)=C(C)C(C)=C1C Chemical compound [Ti+3].CCCC[O-].CCCC[O-].CCCC[O-].C[C]1C(C)=C(C)C(C)=C1C UPLJFGURRZIASC-UHFFFAOYSA-N 0.000 description 1
- VSZMYWHHYYUVOJ-UHFFFAOYSA-N acenaphthylen-4-yl(trimethyl)silane Chemical group C1=CC2=CC([Si](C)(C)C)=CC(C=C3)=C2C3=C1 VSZMYWHHYYUVOJ-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- KNNXFYIMEYKHBZ-UHFFFAOYSA-N as-indacene Chemical group C1=CC2=CC=CC2=C2C=CC=C21 KNNXFYIMEYKHBZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical class C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- VUYWFCITDFXAAU-UHFFFAOYSA-N ethyl 2-ethenylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=CC=C1C=C VUYWFCITDFXAAU-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002363 hafnium compounds Chemical class 0.000 description 1
- 125000002192 heptalenyl group Chemical group 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- JDQLUYWHCUWSJE-UHFFFAOYSA-N methanolate;titanium(3+) Chemical compound [Ti+3].[O-]C.[O-]C.[O-]C JDQLUYWHCUWSJE-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- MBKUHNGECMPIHH-UHFFFAOYSA-N methyl 3-ethenylbenzoate Chemical compound COC(=O)C1=CC=CC(C=C)=C1 MBKUHNGECMPIHH-UHFFFAOYSA-N 0.000 description 1
- NUMHUJZXKZKUBN-UHFFFAOYSA-N methyl 4-ethenylbenzoate Chemical compound COC(=O)C1=CC=C(C=C)C=C1 NUMHUJZXKZKUBN-UHFFFAOYSA-N 0.000 description 1
- ZBFZRXWCLMDQDF-UHFFFAOYSA-N methyl acenaphthylene-4-carboxylate Chemical group C1=CC2=CC(C(=O)OC)=CC(C=C3)=C2C3=C1 ZBFZRXWCLMDQDF-UHFFFAOYSA-N 0.000 description 1
- IJWRUFXTYOEVMB-UHFFFAOYSA-N methyl acenaphthylene-5-carboxylate Chemical group C1=CC2=CC=CC3=C2C1=CC=C3C(=O)OC IJWRUFXTYOEVMB-UHFFFAOYSA-N 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 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
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- 125000005447 octyloxy 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])O* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical group C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- 125000005582 pentacene group Chemical group 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000001828 phenalenyl group Chemical group C1(C=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 150000008301 phosphite esters Chemical group 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 125000001388 picenyl group Chemical group C1(=CC=CC2=CC=C3C4=CC=C5C=CC=CC5=C4C=CC3=C21)* 0.000 description 1
- DIJNSQQKNIVDPV-UHFFFAOYSA-N pleiadene Chemical group C1=C2[CH]C=CC=C2C=C2C=CC=C3[C]2C1=CC=C3 DIJNSQQKNIVDPV-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- FMKFBRKHHLWKDB-UHFFFAOYSA-N rubicene Chemical group C12=CC=CC=C2C2=CC=CC3=C2C1=C1C=CC=C2C4=CC=CC=C4C3=C21 FMKFBRKHHLWKDB-UHFFFAOYSA-N 0.000 description 1
- WEMQMWWWCBYPOV-UHFFFAOYSA-N s-indacene Chemical group C=1C2=CC=CC2=CC2=CC=CC2=1 WEMQMWWWCBYPOV-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 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
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- CPENQHKKFGEUJL-UHFFFAOYSA-N trimethyl-(2-phenylphenyl)silane Chemical group C[Si](C)(C)C1=CC=CC=C1C1=CC=CC=C1 CPENQHKKFGEUJL-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、電気製品，自動車部品などの素材として好適
に用いることのできる、耐熱性や戒形性等の良好なスチ
レン系共重合体およびその製造方法に関するものである
。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to a styrenic copolymer and a styrene copolymer with good heat resistance and shapeability, which can be suitably used as a material for electrical products, automobile parts, etc. The present invention relates to a manufacturing method thereof.
〔従来の技術および発明が解決しようとする課題〕電気
製品の部材や自動車部品の部材として耐熱性や成形性の
良好な樹脂が要望されている。[Prior Art and Problems to be Solved by the Invention] There is a demand for resins with good heat resistance and moldability as members for electrical products and automobile parts.
このため、主としてシンジオククチック構造を有するボ
リスチレン（特開昭６１−１０４８１８号公報．同６２
−１８７７０８号公報など）が提案されている。この主
としてジンジオタクチノク構造を有するボリスチレンは
耐熱性に優れるものの、結晶化速度が小さいため或形サ
イクルが長くなりやすいという欠点があった。For this reason, polystyrene, which mainly has a syndiocctic structure (Japanese Patent Application Laid-open No. 104818/1983.
-187708, etc.) have been proposed. Although this polystyrene mainly having a jindiotactic structure has excellent heat resistance, it has a drawback that certain cycles tend to be long due to a low crystallization rate.
本発明はこのような従来の課題を解決し、剛熱性に優れ
、しかも結晶化速度が大きく、また成形性に優れたスチ
レン系共重合体およびその効率的な製造方法を提供する
ことを目的とするものである。The purpose of the present invention is to solve these conventional problems and provide a styrenic copolymer that has excellent heat resistance, a high crystallization rate, and excellent moldability, and an efficient method for producing the same. It is something to do.
すなわち、本発明の第ｌは
一般式
〔式中、Ｒ１は水素原子．ハロゲン原子、または炭素原
子，酸素原子，窒素原子，硫黄原子，リン原子．セレン
原子，ケイ素原子および錫原子のいずれか１種以上を含
む置換基を示し、ｍは１〜３の整数を示す。但し、ｍが
複数のときは、各ＲＩは同一でも異なるものであっても
よい。〕で表わされる少なくとも一種の構造単位ＣＩ）
および一般式
（式中、Ｒ２，Ｒ３，Ｒ４は水素原子，ハロゲン原子、
または炭素原子，酸素原子，窒素原子，硫黄原子，リン
原子，セレン原子．ケイ素原子および錫原子のいずれか
１種以上を含む置換基を示し、ｎは１〜６の整数を示す
。但し、ｎが複数のときは、各Ｒ４は同一でも異なるも
のであってもよい。〕で表わされる構造単位（Ｈ）を有
し、重合度が５以上で、かつ、そのスチレン連鎖部の立
体規則性が主としてシンジオタクチノク構造であるスチ
レン系共重合体を提供するものである。That is, the first aspect of the present invention is a general formula [wherein R1 is a hydrogen atom]. Halogen atom, or carbon atom, oxygen atom, nitrogen atom, sulfur atom, or phosphorus atom. It represents a substituent containing at least one of a selenium atom, a silicon atom, and a tin atom, and m represents an integer of 1 to 3. However, when m is plural, each RI may be the same or different. ] At least one structural unit CI)
and the general formula (wherein R2, R3, R4 are hydrogen atoms, halogen atoms,
Or carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, selenium atom. It represents a substituent containing at least one of a silicon atom and a tin atom, and n represents an integer of 1 to 6. However, when n is plural, each R4 may be the same or different. ], the degree of polymerization is 5 or more, and the stereoregularity of the styrene chain portion is mainly a syndiotactic structure. .
また、本発明の第２は、触媒成分として、（Ａ）遷移金
属成分および（Ｂ）有機アル旦ニウム化合物と縮合剤と
の接触生戒物を用い、
一般式
〔式中、Ｒ１は水素原子，ハロゲン原子、または炭素原
子，酸素原子．窒素原子，硫黄原子，リン原子，セレン
原子．ケイ素原子および錫原子のいずれか１種以上を含
む置換基を示し、ｍは１〜３の整数を示す。但し、ｍが
複数のときは、各Ｒは同一でも異なるものであってもよ
い。〕で表わされる少なくとも一種のスチレン系モノー
および
一般弐
マ
（式中、Ｒ２，Ｒ３．Ｒ’は水素原子，ハロゲン原子、
または炭素原子，酸素原子，窒素原子，硫黄原子．リン
原子，セレン原子，ケイ素原子および錫原子のいずれか
１種以上を含む置換基を示し、ｎは１〜６の整数を示す
。但し、ｎが複数のときは各Ｒ４は同一でも異なるもの
であってもよい。〕で表わされるアセナフチレン系化合
物を共重合することを特徴とする、本発明の第ｌのスチ
レン系共重合体の製造方法を提供するものである。In addition, the second aspect of the present invention uses as a catalyst component a contact mixture of (A) a transition metal component and (B) an organic altanium compound with a condensing agent; , halogen atom, or carbon atom, oxygen atom. Nitrogen atom, sulfur atom, phosphorus atom, selenium atom. It represents a substituent containing at least one of a silicon atom and a tin atom, and m represents an integer of 1 to 3. However, when m is plural, each R may be the same or different. ] at least one styrenic monomer and a general monomer (wherein R2, R3.R' are hydrogen atoms, halogen atoms,
Or carbon, oxygen, nitrogen, or sulfur atoms. It represents a substituent containing at least one of a phosphorus atom, a selenium atom, a silicon atom, and a tin atom, and n represents an integer of 1 to 6. However, when n is plural, each R4 may be the same or different. The present invention provides the first method for producing a styrenic copolymer, which comprises copolymerizing an acenaphthylene compound represented by the following.
本発明におけるスチレン系共重合体は、前記一般式〔【
〕で表わされる構造単位〔■〕 （繰り返し単位）およ
び一般式（ｎ）で表わされる構造単位〔■〕 （繰り返
し単位）を有するものである。The styrenic copolymer in the present invention has the general formula [[
It has a structural unit [■] (repeating unit) represented by ] and a structural unit [■] (repeating unit) represented by general formula (n).
ここで構造単位〔Ｉ〕および（Ｉ［）中のＲ１〜Ｒ４は
、水素原子，ハロゲン原子、または炭素原子，酸素原子
２窒素原子．硫黄原子，リン原子セレン原子，ケイ素原
子および錫原子のいずれか１種以上を含む置換基を示し
ている。Here, R1 to R4 in the structural unit [I] and (I[) are hydrogen atoms, halogen atoms, carbon atoms, oxygen atoms, 2 nitrogen atoms. Indicates a substituent containing one or more of a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom, and a tin atom.
ここでハロゲン原子としては、塩素，弗素，臭素．沃素
を挙げることができる。Here, examples of halogen atoms include chlorine, fluorine, and bromine. Iodine can be mentioned.
また、炭素原子を含む置換基の具体例としてはメチル基
，エチル基，イソプロビル基，ターシャリーブチル基な
どの炭素数１〜２０のアルキル基；炭素数６〜３０のベ
ンゼン環に水素原子，ハロゲン原子，炭素原子，酸素原
子，窒素原子，硫黄原子，リン原子，セレン原子，ケイ
素原子あるいは錫原子などを含む置換基をもつアリール
基；クロロエチル基，プロモメチル基，プロモエチル基
などの炭素１〜２０のハロゲン置換アルキル基ｔヨとが
挙げられる。Further, specific examples of substituents containing carbon atoms include alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, isoprobyl group, and tertiary butyl group; hydrogen atoms in benzene rings having 6 to 30 carbon atoms; Aryl group with a substituent containing a halogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, selenium atom, silicon atom, or tin atom; a carbon 1- to chloroethyl group, bromomethyl group, promoethyl group, etc. and 20 halogen-substituted alkyl groups.
ここで炭素数６〜３０のヘンゼン環に、水素原子，ハロ
ゲン原子，炭素原子，酸素原子，窒素原子，硫黄原子，
リン原子，セレン原子．ケイ素原子あるいは錫原子など
を含む置換基をもつアリール基としては、例えばベンゼ
ン環，ナフタレン環，フエナントレン環，アントラセン
環．インデン環．アズレン環，ヘプタレン環．ビフヱニ
レン環，ａＳインダセン環，Ｓ−インダセン環，アセナ
フチレン環，フェナレン環，フルオランテン環，アセフ
ェナントレン環．アセアントリレン環．トリフェニレン
環，ナフタセン環．プレイアデン環，ピセン環，ペリレ
ン環，ペンタフェン環，ペンタセン環，ルビセン環．コ
ロセン環，ピラントレン環，オバレン環、およびこれら
のアルキル置換基（メチル基，エチル基，イソプロビル
基，ターシャリーブチル基など）．ハロゲン置換アルキ
ル基（クロロエチル基，プロモエチル基など），酸素原
子を含む置換基（メトキシ基，エトキシ基．イソプロボ
キシ基，メトキシ力ルボニル基，アセチルオキシ基など
），ケイ素原子を含む置換基（トリメチルシリル基など
），錫原子を含む置換基（トリメチルスタンニル基．ト
リブチルスタンニル基，トリフェニルスタンニル基など
），窒素原子を含む置換基（ジメチルアミノ基，ジアゾ
基，ニトロ基，シアノ基など），硫黄原子を含む置換基
（スルホン基，スルホン酸メチルエステル基，フェニル
チオ基メチルチオ基，メルカブト基など），セレン原子
を含む置換基（メチルセレノ基，フェニルセレノ基メチ
ルセレノキシル基，フエニルセレノキシル基など）１リ
ン原子を含む置換基（リン酸メチルエステル基，亜リン
酸エステル基，ジメチルホスフィノ基，ジフェニルホス
フィノ基，メチルホスフィニル基，フェニルホスフィニ
ル基など）などを任意の位置に置換したものが含まれる
。Here, in the Hensen ring having 6 to 30 carbon atoms, hydrogen atom, halogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom,
Phosphorus atom, selenium atom. Examples of the aryl group having a substituent containing a silicon atom or a tin atom include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Inden ring. Azulene ring, heptalene ring. Biphenylene ring, aS indacene ring, S-indacene ring, acenaphthylene ring, phenalene ring, fluoranthene ring, acephenanthrene ring. Aceantrylene ring. Triphenylene ring, naphthacene ring. Pleiadene ring, picene ring, perylene ring, pentaphene ring, pentacene ring, rubicene ring. Corocene ring, pyrantrene ring, obalene ring, and their alkyl substituents (methyl group, ethyl group, isoprobyl group, tert-butyl group, etc.). Halogen-substituted alkyl groups (chloroethyl group, promoethyl group, etc.), substituents containing oxygen atoms (methoxy group, ethoxy group, isoproboxy group, methoxycarbonyl group, acetyloxy group, etc.), substituents containing silicon atoms (trimethylsilyl group, etc.) ), substituents containing tin atoms (trimethylstannyl group, tributylstannyl group, triphenylstannyl group, etc.), substituents containing nitrogen atoms (dimethylamino group, diazo group, nitro group, cyano group, etc.), sulfur Substituents containing atoms (sulfone group, sulfonic acid methyl ester group, phenylthio group, methylthio group, merkabuto group, etc.), substituents containing selenium atoms (methylseleno group, phenylseleno group, methylselenoxyl group, phenylselenoxyl group, etc.) Substituents containing 1 phosphorus atom (phosphoric acid methyl ester group, phosphite group, dimethylphosphino group, diphenylphosphino group, methylphosphinyl group, phenylphosphinyl group, etc.) can be substituted at any position. Includes things that have been done.
また酸素原子を含む置換基としては、メ１−キシ基，エ
トキシ基，イソプロボキシ基，メトキシ力ルボニル基，
アシルオキシ基などが挙げられ、ケイ素原子を含む置換
基としては、トリメチルシリル基などが挙げられる。次
に、錫原子を含む置換基としては、１・リメチルスクン
ニル基，トリブチルスタンニル基，トリフェニルスクン
ニル基などがあげられる。さらに、窒素原子を含む置換
基としては、ジメチルアミノ基，ジアゾ基，二トロ基，
シアノ基などが挙げられ、硫黄原子を含む置換基として
は、スルホン基，スルホン酸メチルエステル基，フェニ
ルチオ基，メチルチオ基，メルカブト基などがあげられ
る。また、セレン原子を含む置換基としては、メチルセ
レノ基，フヱニルセレノ基，メチルセレノキシル基，フ
ェニルセレノキシル基などが挙げられ、リン原子を含む
置換基としては、リン酸メチルエステル基，亜リン酸エ
ステル基，ジメチルホスフィノ基，ジフヱニルホスフィ
ノ基，メチルホスフィニル基，フヱニルホスフィニル基
などが挙げられる。In addition, substituents containing an oxygen atom include a methoxy group, an ethoxy group, an isoproboxy group, a methoxycarbonyl group,
Examples of the substituent include an acyloxy group, and examples of the substituent containing a silicon atom include a trimethylsilyl group. Next, examples of substituents containing a tin atom include a 1.limethylscunnyl group, a tributylstannyl group, and a triphenylscunnyl group. Furthermore, substituents containing a nitrogen atom include dimethylamino group, diazo group, nitro group,
Examples include a cyano group, and examples of substituents containing a sulfur atom include a sulfone group, a sulfonic acid methyl ester group, a phenylthio group, a methylthio group, and a merkabuto group. In addition, examples of substituents containing a selenium atom include methylseleno group, phenylseleno group, methylselenoxyl group, and phenylselenoxyl group, and examples of substituents containing a phosphorus atom include methyl phosphate group and phosphite ester group. group, dimethylphosphino group, diphenylphosphino group, methylphosphinyl group, phenylphosphinyl group, etc.
また、−ａ式（１）で表わされる構造単位（１）におい
て、ｍはＩ〜３の整数であり、一般式（Ｉｒ）で表わさ
れる構造単位（ＩＩ）において、ｎは１〜６の整数であ
る。ここでｍ，ｎがそれぞれ複数のときは、ｍ個あるＲ
１またはｎ個あるＲ４は、それぞれ同じものであっても
よいし、異なるものであってもよい。Furthermore, in the structural unit (1) represented by the -a formula (1), m is an integer of I to 3, and in the structural unit (II) represented by the general formula (Ir), n is an integer of 1 to 6. It is. Here, when m and n are each plural, there are m R
The 1 or n R4's may be the same or different.
このような置換基を有する構造単位（１）の具体例とし
ては、スチレン，Ｐ−メチルスチレン，ｍ−メチルスチ
レン，Ｏ−メチルスチレン１ ２，４−ジメヂルスチレ
ン，２．５−ジメチルスチレン，３．４−ジメチルスチ
レン２ ３，５−ジメチルスチレン，Ｐ一ターシャリー
ブチルスチレンなどのアルキルスチレン；ｐ−クロロス
チレン，ｍ一クロロスヂレン，Ｏ−クｒ：Ｉｒ：Ｉスチ
レン，ｐ−プロモスチレン，ｍ−プロモスチレン，０−
フロモスチレン，Ｐ−フルオロスチレン，ｍ−フルオロ
スヂレン，Ｏ−フルオロスチレン．０−メチルｐ−フル
オロスチレンなどのハロゲン化スチレン；４−ビニルビ
フエニル，３−ビニルビフエニル，２−ビニルビフェニ
ルなどのビニルビフエニル類；１−（４−ビニルフエニ
ル）ナフタレン，２−（４−ビニルフエニル）ナフタレ
：／，１−（３−ビニルフェニル）ナフタレ７．２−（
３−ビニルフェニル）ナフタレン，１−（２−ビニルフ
エニル）ナフタレン，２−（２−ビニルフエニル）ナフ
タレンなどのビニルフェニルナフタレン類；ｌ（４−ビ
ニルフェニル）アントラセン、２−（４−ビニルフエニ
ル）アントラセン，！−（４一ビニルフェニル）アント
ラセン，１−（３−ビニルフェニル）アントラセン，２
−（３−ビニルフェニル）アントラセン，９−（３−ビ
ニルフェニル）アントラセン，１−（２−ビニルフェニ
ル）アントラセン，２−（２−ビニルフェニル）アント
ラセン，９−（２−ビニルフェニル）アントラセンなど
のビニルフェニルアントラセン［；１−（４−ビニルフ
ェニル）フエナントレン，２一（４−ビニルフェニル）
フェナントレン，３一（４−ビニルフェニル）フェナン
トレン，４一（４−ビニルフェニル）フェナントレン，
９〜（４−ビニルフェニル）フェナントレン，１一（３
−ビニルフエニル）フエナントレン，２一（３−ビニル
フェニル）フエナントレン，３一（３−ビニルフエニル
）フエナントレン，４一（３−ビニルフェニル）フェナ
ントレン，９一（３−ビニルフェニル）フェナントレン
．ｌ−（２−ビニルフェニル）フヱナントレン，２一（
２−ビニルフェニル）フェナントレン，３一（２−ビニ
ルフェニル）フエナントレン，４一（２−ビニルフェニ
ル）フエナントレン，９一（２−ビニルフェニル）フエ
ナントレンなとのビニルフヱニルフェナントレンｌ；１
−（４−ビニルフェニル）ビレン，２−（４−ビニルフ
エニル）ピレン，１−（３−ビニルフェニル）ビレン，
２一（３−ビニルフエニル）ピレン，１−（２−ビニル
フエニル）ビレン，２−（２−ビニルフェニル）ビレン
などのビニルフェニルピレン頚；４ビニルーｐ一ターフ
エニル，４−ビニルーｍ一ターフェニル，４−ビニル一
〇〜ターフエニル，３一ヒニルーｐ一ターフヱニル，３
−ビニルーｍターフヱニル，３−ビニル一〇−ターフェ
ニル，２−ビニルーｐ一ターフヱニル，２−ビニルーｍ
ターフェニル，２−ビニル一〇一ターフエニルなどのビ
ニルターフェニルｉＪｔ；４−（４−ビニルフェニル）
一ｐ一ターフェニルなどのビニルフエニルターフェニル
頬；４−ビニル−４゜−メチルビフエニル．４−ビニル
−３゜−メチルビフェニル，４−ビニル−２″−メチル
ビフエニル．２ーメチル−４−ビニルビフェニル，３−
メチルー４−ビニルビフェニルなどのビニルアルキルビ
フエニル類；４−ビニル−４“−フルオロビフエニノレ
，４−ビニル−３”−フルオロビフエニノレ，４−ビニ
ル−２゛−フルオロビフエニル，４−ビニノレー２−フ
ルオロビフエニル，４−ビニノレ−３−フノレオロビフ
ェニル，４−ビニル−４′−クロロビフエニル ４−ビ
ニル−３゜−クロロビフエニノレ，４−ビニル−２゜−
クロロビフエニル，４−ビニル−２−クロロビフエニル
，４−ビニル−３−クロロビフエニル，４−ビニル−４
゜−プロモビフェニル，４−ビニル−３“−ブロモビフ
エニノレ，４−ビニル−２ ’ − ７’ロモビフエニ
ル，４−ビニル−２−プロモビフエニル，４−ビニノレ
−３−７′ロモビフエニルなどのハロゲン化ビニノレビ
フエニル頻；４−ビニル−４゛−メトキシビフエニＪレ
，４−ビニル−３゜−メトキシビフエニノレ，４−ビニ
ル−２′−メトキシビフエニル，４−ビニノレ−２−メ
トキシビフエニル，４−ビニノレ−３−メトキシビフエ
ニル，４−ビニル−４”一エトキシビフェニル，４−ビ
ニル−３゜一エトキシビフエニル，４−ビニル−２′一
エトキシビフヱニル，４一ビニル−２−エトキシビフエ
ニル ４−ビニル３−エトキシビフエニルなどのアルコ
キシビニルビフエニル類；４−ビニル−４ −メトキシ
力ルポニルビフエニル，４−ビニル−４゛一工１−キシ
力ルポニルビフエニルなどのアルコキシ力ルボニルビニ
ルビフエニル類；４−ビニル−４ −メトキシメチルビ
フェニルなどのアルコキシアルキルビニルビフエニル類
；４−ビニル−４”一トリメチルシリルビフエニルなど
のトリアルキルシリルビニルビフエニル類；４−ビニル
−４″一トリメチルスタンニルビフェニル，４−ビニル
−４＝トリプチルスタンニルビフエニルなどのトリアル
キルスタンニルビニルビフェニル頚：４−ビニル−４゜
一トリメチルシリルメチルビフェニルなどのトリアルキ
ルシリルメチルビニルビフエニル類，４−ビニル−４゜
一トリメチルスタンニルメチルビフェニル，４−ビニル
−４゜一トリブチルスタンニルメチルビフエニルなどの
トリアルキルスクンニルメチルビニルビフェニル類など
のアリ−ルスチレン類；ｐ−クロロエチルスチレン．ｍ
クロロエチルスチレン，０−クロロエチルスチレンなど
のハロゲン置換アルキルスチレン；ｐ一メトキシスチレ
ン，ｍ−メトキシスチレン，０−メトキシスチレン，ｐ
一エトキシスチレン， ｍ −エトキシスチレン，０−
エトキシスチレンなどのアルコキシスチレン；ｐ−メト
キシカルボニルスヂレン，ｍ−メトキシカルボニルスチ
レンなどのアルコキシ力ルポニルスチレン；アセチルオ
キシスチレン，エタノイルオキシスチレン，ペンゾイル
オキシスチレンなどのアシルオキシスチレン；ｐ−ビニ
ルベンジルプロピルエーテルなどのアルキルエーテルス
チレン；ｐ一トリメチルシリルスチレンなどのアルキル
シリルスチレン；ｐ−｝リメチルスクンニルスチレン，
Ｐ−｝リプチルスタンニルスチレン，ρ一トリフエニル
スクンニルスチレンなどのアルキルスクンニルスチレン
；ビニルベンゼンスルホン酸エチル，ビニルベンジルジ
メトキシホスファイド，Ｐ−ビニルスチレンなどのビニ
ルスチレ．ン等が挙げられる。Specific examples of the structural unit (1) having such a substituent include styrene, P-methylstyrene, m-methylstyrene, O-methylstyrene 1, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3. 4-Dimethylstyrene 2 Alkyl styrenes such as 3,5-dimethylstyrene, P-tert-butylstyrene; p-chlorostyrene, m-chlorostyrene, O-kr:Ir:I styrene, p-promostyrene, m-promo Styrene, 0-
Furomostyrene, P-fluorostyrene, m-fluorostyrene, O-fluorostyrene. Halogenated styrenes such as 0-methyl p-fluorostyrene; vinylbiphenyls such as 4-vinylbiphenyl, 3-vinylbiphenyl, and 2-vinylbiphenyl; 1-(4-vinylphenyl)naphthalene, 2-(4-vinylphenyl)naphthalene: /, 1-(3-vinylphenyl)naphthalene 7.2-(
Vinylphenylnaphthalenes such as 3-vinylphenyl)naphthalene, 1-(2-vinylphenyl)naphthalene, 2-(2-vinylphenyl)naphthalene; l(4-vinylphenyl)anthracene, 2-(4-vinylphenyl)anthracene, ! -(4-vinylphenyl)anthracene, 1-(3-vinylphenyl)anthracene, 2
-(3-vinylphenyl)anthracene, 9-(3-vinylphenyl)anthracene, 1-(2-vinylphenyl)anthracene, 2-(2-vinylphenyl)anthracene, 9-(2-vinylphenyl)anthracene, etc. Vinylphenylanthracene [;1-(4-vinylphenyl)phenanthrene, 2-(4-vinylphenyl)
phenanthrene, 3-(4-vinylphenyl)phenanthrene, 4-(4-vinylphenyl)phenanthrene,
9-(4-vinylphenyl)phenanthrene, 1-(3
-vinylphenyl)phenanthrene, 2-(3-vinylphenyl)phenanthrene, 3-(3-vinylphenyl)phenanthrene, 4-(3-vinylphenyl)phenanthrene, 9-(3-vinylphenyl)phenanthrene. l-(2-vinylphenyl)phenanthrene, 2-(
2-vinylphenyl)phenanthrene, 3-(2-vinylphenyl)phenanthrene, 4-(2-vinylphenyl)phenanthrene, 9-vinylphenylphenanthrene, etc.; 1;
-(4-vinylphenyl)pyrene, 2-(4-vinylphenyl)pyrene, 1-(3-vinylphenyl)pyrene,
Vinylphenylpyrene neck, such as 2-(3-vinylphenyl)pyrene, 1-(2-vinylphenyl)pyrene, 2-(2-vinylphenyl)pyrene; 4-vinyl-p-terphenyl, 4-vinyl-m-terphenyl, 4- vinyl 10-terphenyl, 3-hinyl-p-terphenyl, 3
-vinyl-terphenyl, 3-vinyl-terphenyl, 2-vinyl-terphenyl, 2-vinyl-terphenyl
Vinyl terphenyl iJt such as terphenyl, 2-vinyl 101 terphenyl; 4-(4-vinylphenyl)
Vinyl phenyl terphenyl such as 1p-terphenyl; 4-vinyl-4°-methylbiphenyl. 4-vinyl-3゜methylbiphenyl, 4-vinyl-2''-methylbiphenyl.2-methyl-4-vinylbiphenyl, 3-
Vinylalkylbiphenyls such as methyl-4-vinylbiphenyl; 4-vinyl-4"-fluorobiphenyl, 4-vinyl-3"-fluorobiphenyl, 4-vinyl-2"-fluorobiphenyl, 4- Vinyl-2-fluorobiphenyl, 4-vinyl-3-fluorobiphenyl, 4-vinyl-4'-chlorobiphenyl 4-vinyl-3°-chlorobiphenyl, 4-vinyl-2°-
Chlorobiphenyl, 4-vinyl-2-chlorobiphenyl, 4-vinyl-3-chlorobiphenyl, 4-vinyl-4
Vinyl halides such as ゜-promobiphenyl, 4-vinyl-3"-bromobiphenyl, 4-vinyl-2'-7' lomobiphenyl, 4-vinyl-2-promobiphenyl, 4-vinyl-3-7' lomobiphenyl 4-vinyl-4'-methoxybiphenyl, 4-vinyl-3'-methoxybiphenyl, 4-vinyl-2'-methoxybiphenyl, 4-vinyl-2-methoxybiphenyl, 4 -vinyl-3-methoxybiphenyl, 4-vinyl-4''-ethoxybiphenyl, 4-vinyl-3゜-ethoxybiphenyl, 4-vinyl-2'-ethoxybiphenyl, 4-vinyl-2-ethoxybiphenyl Alkoxyvinylbiphenyl such as 4-vinyl-3-ethoxybiphenyl; alkoxyvinylbiphenyl such as 4-vinyl-4-methoxylponylbiphenyl, 4-vinyl-4-methoxylponylbiphenyl, etc. Rubonylvinylbiphenyls; alkoxyalkylvinylbiphenyls such as 4-vinyl-4-methoxymethylbiphenyl; 4-vinyl-4" trialkylsilylvinylbiphenyls such as trimethylsilylbiphenyl; 4-vinyl-4" Trialkylstannylvinylbiphenyl such as monotrimethylstannylbiphenyl, 4-vinyl-4=triptylstanylbiphenyl, etc.: Trialkylsilylmethylvinylbiphenyl such as 4-vinyl-4゜1trimethylsilylmethylbiphenyl, 4 -Arylstyrenes such as trialkylscunnylmethylvinylbiphenyls such as vinyl-4゜-trimethylstannylmethylbiphenyl, 4-vinyl-4゜-tributylstannylmethylbiphenyl; p-chloroethylstyrene. m
Halogen-substituted alkylstyrene such as chloroethylstyrene, 0-chloroethylstyrene; p-methoxystyrene, m-methoxystyrene, 0-methoxystyrene, p
monoethoxystyrene, m-ethoxystyrene, 0-
Alkoxystyrenes such as ethoxystyrene; alkoxycarbonylstyrenes such as p-methoxycarbonylstyrene and m-methoxycarbonylstyrene; acyloxystyrenes such as acetyloxystyrene, ethanoyloxystyrene, and penzoyloxystyrene; p-vinylbenzylpropyl Alkyl ether styrenes such as ethers; alkylsilylstyrenes such as p-trimethylsilylstyrene;
Alkyl stannylstyrenes such as P-}liptylstannylstyrene and ρ-triphenylstannylstyrene; vinylstyrenes such as ethyl vinylbenzenesulfonate, vinylbenzyl dimethoxy phosphide, and P-vinylstyrene. Examples include:
また、構造単位（ｎ）の具体例としては、アセナフチレ
ンあるいは１−メチルアセナフチレン，４−メチルアセ
ナフチレン，５−メチルアセナフチレン，６−メチルア
セナフチレン．ｌ，４−ジメチルアセナフチレン，１，
５−ジメチルアセナフチレン，■，６−ジメチルアセナ
フヂレン，■，８ジメチルアセナフチレン，ｌ，９−ジ
メヂルアセナフチレン，１．１０−ジメチルアセナフチ
レン，４−エチルアセナフチレン，５−エチルアセナフ
チレン，６−エチルアセナフチレン，４−ｎ一プロビル
アセナフチレン，５−ｎ−プロビルアセナフチレン，６
−ｎ−プロビルアセナフチレンなどのアルキル置換アセ
ナフチレン類；４−クロロアセナフチレン．５−クロロ
アセナフチレン，６−クロロアセナフチレン，４−プロ
モアセナフチレン，５−プロモアセナフチレン．６−プ
ロモアセナフチレン，４−ヨードアセナフチレン，５ヨ
ードアセナフチレン，６−ヨードアセナフチレン．４−
フルオロアセナフチレン，５−フルオロアセナフチレン
，６−フルオロアセナフチレン，４，５−ジクロロアセ
ナフチレン，４．６−ジクロロアセナフチレン，４．８
−ジクロロアセナフチレン ４ ９−ジクロロアセナフ
チレン，４．１０ジクロロアセナフチレン．５．６−ジ
クロロアセナフチレン，５．８−ジクロロアセナフチレ
ン９５．９−ジクロロアセナフチレン，６，８−ジクロ
ロアセナフチレン，４，５−ジブロモアセナフチレン，
４，６−ジブロモアセナフチレン．４．８ジブロモアセ
ナフチレン，４，９−ジブロモアセナフチレン，４，ｔ
ｏ−ジブロモアセナフチレン，５ ６−ジブロモアセナ
フチレン．５．８−ジブロモアセナフチレン，５，９−
ジブロモアセナフチレン，６．８ジブロモアセナフチレ
ンなとのノ＼ロゲン置換アセナフチレン頚；４−フエニ
ルアセナフヂレン，５−フエニルアセナフチレン，６−
フェニルアセナフチレンなとのアリール置換アセナフチ
レン類；４−メトキシアセナフチレン，５−メトキシア
セナフチレン，６−メトキシアセナフチレンなどのアル
コキシ置換アセナフチレン類；４−メトキシカルボニル
アセナフチレン，５−メトキシカルボニルアセナフチレ
ン，６−メトキシカルボニルアセナフチレンなどのアル
コヰシ力ルボニル置換アセナフチレン類；４−メチル力
ルポニルオキシアセナフチレン，５〜メチル力ルポニル
オキシアセナフチレン，６−メチル力ルポニルオキシア
セナフチレンなどのアジルオキシ置換アセナフチレンＵ
Ｎ ｉ ４ − トリメチルシリルアセナフチレン，５
−トリメチルシリルアセナフチレン６−トリメチルシリ
ルアセナフチレンなどのアルキルシリル置換アセナフチ
レン類ｉ４−トリ一〇プチルスクンニルアセナフチレン
，５−トリ一〇一プチルスクンニルアセナフチレン，６
−トリｎ−プチルスタンニルアセナフチレンなどのアル
キルスタンニル置換アセナフチレン頚等が挙げられる。Specific examples of the structural unit (n) include acenaphthylene, 1-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacenaphthylene, 6-methylacenaphthylene. l,4-dimethylacenaphthylene, 1,
5-dimethylacenaphthylene, ■,6-dimethylacenaphthylene, ■,8 dimethylacenaphthylene, l,9-dimethylacenaphthylene, 1.10-dimethylacenaphthylene, 4-ethylacenaphthylene, 5-ethylacenaphthylene, 6-ethylacenaphthylene, 4-n-probylacenaphthylene, 5-n-probylacenaphthylene, 6
-Alkyl-substituted acenaphthylenes such as n-probylacenaphthylene; 4-chloroacenaphthylene. 5-chloroacenaphthylene, 6-chloroacenaphthylene, 4-promoacenaphthylene, 5-promoacenaphthylene. 6-promoacenaphthylene, 4-iodoacenaphthylene, 5-iodoacenaphthylene, 6-iodoacenaphthylene. 4-
Fluoroacenaphthylene, 5-fluoroacenaphthylene, 6-fluoroacenaphthylene, 4,5-dichloroacenaphthylene, 4.6-dichloroacenaphthylene, 4.8
-dichloroacenaphthylene 4 9-dichloroacenaphthylene, 4.10 dichloroacenaphthylene. 5.6-dichloroacenaphthylene, 5.8-dichloroacenaphthylene 95.9-dichloroacenaphthylene, 6,8-dichloroacenaphthylene, 4,5-dibromoacenaphthylene,
4,6-dibromoacenaphthylene. 4.8 dibromoacenaphthylene, 4,9-dibromoacenaphthylene, 4,t
o-dibromoacenaphthylene, 5 6-dibromoacenaphthylene. 5.8-dibromoacenaphthylene, 5,9-
dibromoacenaphthylene, 6.8 dibromoacenaphthylene with a \rogen-substituted acenaphthylene neck; 4-phenylacenaphthylene, 5-phenylacenaphthylene, 6-
Aryl-substituted acenaphthylenes such as phenylacenaphthylene; alkoxy-substituted acenaphthylenes such as 4-methoxyacenaphthylene, 5-methoxyacenaphthylene, and 6-methoxyacenaphthylene; 4-methoxycarbonylacenaphthylene, 5-methoxy Carbonyl-substituted acenaphthylenes such as carbonyl acenaphthylene and 6-methoxycarbonyl acenaphthylene; 4-methyl luponyloxyacenaphthylene, 5-methyl luponyloxyacenaphthylene, 6-methyl luponyloxy Azyloxy-substituted acenaphthylene U such as acenaphthylene
N i 4-trimethylsilylacenaphthylene, 5
-Trimethylsilylacenaphthylene Alkylsilyl-substituted acenaphthylenes such as 6-trimethylsilylacenaphthylene i4-Tri10butylscunnylacenaphthylene, 5-tri101butylscunnylacenaphthylene, 6
Examples include alkylstannyl-substituted acenaphthylene necks such as -tri-n-butylstannylacenaphthylene.
なお、本発明で得られる重合体は、一般式（ｎ）で表わ
されるアセナフチレン系モノマーの共存下に、一般式〔
■〕で表わされるスチレン系七ノマーを重合させて得ら
れる重合体であり、共重合体であっても、また高度に分
散された各々の単独重合体混合物を含んでいてもよい．
また、上記構造単位（１）と（］Ｉ）は、必ずしも一種
のみを示すものではなく、二種類以上の構造単位をも示
すことから、本発明の共重合体は、二元共重合体のほか
、三元共重合体，四元共重合体等の多元共重合体をも包
含する。In addition, the polymer obtained in the present invention has the general formula [
A polymer obtained by polymerizing a styrenic heptanomer represented by (2)], and may be a copolymer or a highly dispersed mixture of each homopolymer. Furthermore, since the above structural units (1) and (]I) do not necessarily represent only one type of structural unit, but also represent two or more types of structural units, the copolymer of the present invention is a binary copolymer. In addition, it also includes multi-component copolymers such as ternary copolymers and quaternary copolymers.
ここで、本発明の第１は、構造単位（ｎ）の含量が、好
ましくは全体の０．１〜７０モル％、より好ましくは全
体のＯ．１〜４０モル％のものである。このため結晶化
温度が高く、戒形性に優れたものである。一般に構造単
位（ｎ）の含量が、全体の０．１モル％未満では結晶化
温度が低く、戒形が難しい。Here, the first aspect of the present invention is that the content of the structural unit (n) is preferably 0.1 to 70 mol% of the total, more preferably O. It is 1 to 40 mol%. Therefore, it has a high crystallization temperature and excellent shapeability. Generally, if the content of the structural unit (n) is less than 0.1 mol % of the total, the crystallization temperature is low and it is difficult to form a crystal.
本発明のスチレン系共重合体は、以上の如き構造単位（
繰り返し単位）を有し、かつ重合度が５以上のものであ
るが、さらに、そのスチレン連鎖部の立体規則性が、主
としてシンジオタクチ・ンク構造、即ちスチレンあるい
はアセナフチレン部において、炭素一炭素結合から形或
される主鎖に対して側鎖である置換フェニル基が交互に
反対方向に位置する立体構造を有するものであり、その
タクティシティーは核磁気共鳴法（ＮＭＲ法）により定
量される。The styrenic copolymer of the present invention has the above structural units (
repeating unit) and has a degree of polymerization of 5 or more, but furthermore, the stereoregularity of the styrene linkage is mainly due to the syndiotactic chain structure, that is, the styrene or acenaphthylene moiety is formed from a carbon-carbon bond. It has a three-dimensional structure in which substituted phenyl groups as side chains are alternately positioned in opposite directions with respect to a certain main chain, and its tacticity is determined by nuclear magnetic resonance (NMR).
具体的にはｌ”Ｃ−ＮＭＲ法（同位体炭素による核磁気
共鳴法スペクトル）による芳香環のＣＩ炭素シグナル，
メチン・メチレン炭素シグナルまたは、’Ｈ−ＮＭＲの
プロトンシグナルの解析による。ＮＭＲにより定量され
るタクティシティーは、連続する複数個の構成単位の存
在割合（すなわち、連続する構戒単位の相対的立体配座
関係の存在割合）、例えば２個の場合はグイアンド，３
個の場合はトリアッド，５個の場合はベンタッドによっ
て示すことができるが、本発明に言う主としてシンジオ
タクチック構造を有するとは、置換基の種類や各繰返し
単位の含有割合によってシンジオタクティシティーの度
合いは若干変動するが、スチレン系繰返し単位の連鎖に
おいて、通常は、ラセミダイアッドで７５％以上、好ま
しくは８５％以上、若しくはラセミベンタッドで３０％
以上、好ましくは５０％以上のシンジオタクティシティ
ーを有するものを示す。Specifically, the CI carbon signal of the aromatic ring by l''C-NMR method (nuclear magnetic resonance spectrum using carbon isotope),
By analysis of methine/methylene carbon signals or 'H-NMR proton signals. Tacticity quantified by NMR is defined as the abundance ratio of a plurality of consecutive structural units (i.e., the existence ratio of relative conformational relationships of consecutive structural units), for example, in the case of two, guiando, 3
In the case of 5 units, it can be indicated by a triad, and in the case of 5 units, it can be indicated by a bentad, but in the present invention, having a mainly syndiotactic structure means that the syndiotacticity depends on the type of substituents and the content ratio of each repeating unit. Although the degree varies slightly, in the chain of styrenic repeating units, it is usually at least 75% for racemic dyads, preferably at least 85% for racemic bentads, or 30% for racemic bentads.
The above refers to those having preferably syndiotacticity of 50% or more.
なお、本発明にいう主としてシンジオタクチック構造の
スチレン系共重合体は、必ずしも単一の共重合体である
必要はない。シンジオタクティシティーが上記範囲に存
する限り、アイソタクチックもしくはアククチック構造
のスチレン系共重合体との混合物や重合鎖中に組み込ま
れたものであってもよい。Note that the styrenic copolymer mainly having a syndiotactic structure as used in the present invention does not necessarily have to be a single copolymer. As long as the syndiotacticity is within the above range, it may be a mixture with a styrene copolymer having an isotactic or actuctic structure, or it may be incorporated into a polymer chain.
また、本発明のスチレン系共重合体は、分子量が異なる
ものの混合物であってもよく、重合度は少なくとも５以
上、好ましくは１０以上のものを指称する。重量平均分
子量（Ｍｗ）で言うと、好ましくは５，０００〜１００
万、さらに好ましくは１万〜８０万のものである。なお
、分子量分布に特に制限はない。Furthermore, the styrenic copolymer of the present invention may be a mixture of different molecular weights, and the degree of polymerization is at least 5 or more, preferably 10 or more. In terms of weight average molecular weight (Mw), preferably 5,000 to 100
10,000, more preferably 10,000 to 800,000. Note that there is no particular restriction on the molecular weight distribution.
上記の如き本発明の第１のスチレン系共重合体は、例え
ば本発明の第２の方法により効率的に製造することがで
きる。The first styrenic copolymer of the present invention as described above can be efficiently produced, for example, by the second method of the present invention.
上記の如き本発明の第１のスチレン系共重合体は、例え
ば本発明の第２の方法により効率的に製造することがで
きる。The first styrenic copolymer of the present invention as described above can be efficiently produced, for example, by the second method of the present invention.
すなわち、本発明の第２は、触媒或分として、（Ａ）遷
移金属成分および（Ｂ）有機アルミニウム化合物と縮合
剤との接触生成物を用い、前記一般式（ＩＴＩ）で表わ
されるスチレン系モノマーおよび酊Ｉ記一般式（ＩＶ）
で表わされるアセナフチレン系モノマーを共重合させる
ことを特徴とするものである。That is, the second aspect of the present invention uses (A) a transition metal component and (B) a contact product of an organoaluminum compound and a condensing agent as a catalyst, and a styrenic monomer represented by the general formula (ITI). and General formula (IV)
It is characterized by copolymerizing acenaphthylene monomers represented by:
換言すれば、前記一般式（ＩＩＩ）で表わされる少なく
とも一種のスチレン系七ノマーと、前記−・般式（ＩＶ
）で表わされるアセナフチレン系モノマーの二種類ある
いはそれ以上のモノマーを原料として、これらを（Ａ）
遷移金属戒分および（Ｂ）有機アルξニウム化合物と縮
合剤との接触生成物よりなる触媒の存在下に、共重合さ
せるわけである。In other words, at least one styrenic heptanomer represented by the general formula (III) and the general formula (IV
) using two or more types of acenaphthylene monomers represented by (A) as raw materials.
Copolymerization is carried out in the presence of a catalyst consisting of a transition metal component and (B) a contact product of an organic aluminum compound and a condensing agent.
ここで触媒の（Ａ）成分である遷移金属化合物としては
様々なものがあるが、好ましくは一般式
Ｍ’Ｒ’，Ｒ’ｂＲ’ｃＲ８【４−（ａ＋ｂ＋ｃｌ＋
＋ − （Ｖ）Ｍ２Ｒ’，Ｉ Ｒ”．Ｒ”＋：＋−＜ｄ
や。１， ・・・〔■〕Ｍ３Ｒ”，ＲＩ３，，
１１
０
〔■］
または
Ｍ’Ｒ １， Ｒ”Ｈ Ｒ”Ｈ− （タ・ｈ）
１ ”’１１
０
〔■〕
〔式中、Ｒ５〜Ｒｌ６は、それぞれ水素原子，ハロゲン
原子．炭素数１〜２０のアルキル基，炭素数１〜２０の
アルコキシ基，炭素数６〜２０のアリール基，炭素数６
〜２０のアリールアルキル基，炭素数６〜２０のアリー
ルオキシ基，炭素数１〜２０のアシルオキシ基，アセチ
ルアセトニル基，シクロペンタジエニル基，置換シクロ
ペンタジエニル基或いはインデニル基を示す。また、ａ
，ｂ，ｃは、それぞれ０≦ａ＋ｂ＋ｃ≦４を満たすＯ以
上の整数を示し、ｄ，ｅは、それぞれ０≦ｄ＋ｅ≦３を
満たすＯ以上の整数を示し、ｆは０≦ｆ≦２を満たすＯ
以上の整数を示し、ｇ，ｈは、それぞれ０≦ｇ ＋ ｈ
≦３を満たす０以上の整数を示す。さらに、Ｍ１ ，
Ｍ ２はチタン，ジルコニウム，ハフニウムあるいはバ
ナジウムを示し、Ｍ ：Ｉ ， ｌｖｌ４はバナジウム
を示す。〕
で表わされる遷移金属化合物から選ばれた少なくとも１
種の化合物である。これらの遷移金属化合物の中でも、
前記一般式〔■〕中のＭ１が、チタンあるいはジルコニ
ウムであるものを用いるのが好ましい。There are various transition metal compounds that are component (A) of the catalyst, but preferably the general formula M'R', R'bR'cR8[4-(a+b+cl+
+ - (V)M2R',I R".R"+:+-<d
or. 1, ... [■] M3R", RI3,, 11 0 [■] or M'R 1, R"H R"H- (ta・h)
1 '''11 0 [■] [In the formula, R5 to Rl6 are a hydrogen atom and a halogen atom, respectively. An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms , carbon number 6
-20 arylalkyl group, C6-20 aryloxy group, C1-20 acyloxy group, acetylacetonyl group, cyclopentadienyl group, substituted cyclopentadienyl group or indenyl group. Also, a
, b, c each indicate an integer greater than or equal to O that satisfies 0≦a+b+c≦4, d and e each indicate an integer greater than or equal to O that satisfies 0≦d+e≦3, and f satisfies 0≦f≦2. O
Indicates an integer greater than or equal to g, h are each 0≦g + h
Indicates an integer greater than or equal to 0 that satisfies ≦3. Furthermore, M1,
M2 represents titanium, zirconium, hafnium or vanadium, and M:I, lvl4 represents vanadium. ] At least one selected from the transition metal compounds represented by
It is a species compound. Among these transition metal compounds,
It is preferable to use a material in which M1 in the general formula [■] is titanium or zirconium.
ここで、前記式中のＲ５〜Ｒ １６で示されるもののう
ち、ハロゲン原子として具体的には塩素，臭素，沃素あ
るいは弗素がある。また、置換シクロペンタジエニル基
は、例えば炭素数１〜６のアルキル基で１個以上置換さ
れたシクロペンタジエニル基、具体的には、メチルシク
ロペンタジエニル基，１２−ジメチルシク口ペンタジエ
ニル基，ペンタメチルシク口ペンタジエニル基等である
。Here, among those represented by R5 to R16 in the above formula, specific examples of the halogen atom include chlorine, bromine, iodine, and fluorine. In addition, the substituted cyclopentadienyl group is, for example, a cyclopentadienyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, specifically, a methylcyclopentadienyl group, a 12-dimethylcyclopentadienyl group. , pentamethylcyclopentadienyl group, etc.
また、前記式中のＲ５〜Ｒ”はそれぞれ独立に水素原子
，炭素数１〜２０のアルキル基（具体的には、メチル基
，エチル基，プロピルＭ，ｎ−ブチル基，イソブチル基
，アミル基，イソアミル基オクチル基，２−エチルヘキ
シル基，炭素数１〜２０のアルコキシ基（具体的には、
メトキシ基エトキシ基，プロポキシ基，ブトキシ基，ア
ミルオキシ基，ヘキシルオキシ基，オクチルオキシ基．
２−エチルへキシルオキシ基等），炭素数６〜２０のア
リール基（具体的には、フェニル基，ナフチル基等），
炭素数６〜２０のアリールアルキル基（具体的には、ベ
ンジル基，フェネチル基，９一アントリルメチル基等）
，炭素数１〜２０のアシルオキシ基（具体的には、アセ
チルオキシ基，ステアロイルオキシ基等）であってもよ
い。これらＲ３〜Ｒｌ６は上記条件を具備する限り、同
一のものであっても、異なるものであってもよい。In addition, R5 to R'' in the above formula are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, an amyl group). , isoamyl group, octyl group, 2-ethylhexyl group, alkoxy group having 1 to 20 carbon atoms (specifically,
Methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group, octyloxy group.
2-ethylhexyloxy group, etc.), an aryl group having 6 to 20 carbon atoms (specifically, a phenyl group, a naphthyl group, etc.),
Arylalkyl group having 6 to 20 carbon atoms (specifically, benzyl group, phenethyl group, 9-anthrylmethyl group, etc.)
, or an acyloxy group having 1 to 20 carbon atoms (specifically, an acetyloxy group, a stearoyloxy group, etc.). These R3 to Rl6 may be the same or different as long as they meet the above conditions.
このような前記一般式（Ｖ）， （ＶＩ）， （■
〕または〔■］で表される遷移金属化合物のうちチタン
化合物の具体例としては、テトラメトキシチタン，テト
ラエトキシチタン，テトラーｎ−ブトキシチタン，テト
ライソブロポキシチタン，シクロペンタジエニルトリメ
チルチタン，シクロペンタジエニルトリエチルチタン．
シクロペンタジエニルトリプ口ピルチタン．シクロペン
タジエニルトリブチルチタン．メチルシクロペンタジエ
ニルトリメチルチタン．１ｌ２−ジメチルシク口ペンタ
ジエニルトリメチルチタン，ペンタメチルシクロペンク
ジエニルトリメチルチタン，ペンタメチルシク口ペンタ
ジエニルトリエチルチタン，ベンタメチルシクロペンタ
ジエニルトリブ口ビルチタン，ペンタメチルシク口ペン
タジエニルトリブチルチタン，シクロペンタジエニルメ
チルチタンジクロリド，シクロペンタジエニルエチルチ
タンジクロリド，ペンタメチルシク口ペンタジエニルメ
チルチタンジクロリド，ペンタメチルシク口ペンタジエ
ニルエチルチタンジクロリド，シクロペンタジエニルジ
メチルチタンモノクロリド，シクロペンタジエニルジエ
チルチタンモノクロリド，シクロペンタジエニルチタン
トリメトキシド，シクロペンタジエニルチタントリエト
キシド，シクロベンタジエニルチタントリプロボキシド
，シクロベンタジエニルチタントリフェノキシド．ベン
タメチルシクロベンタジエニルチタントリメトキシド，
ペンタメチルシク口ペンタジエニルチタントリエトキシ
ド，ペンタメチルシクロペンタジェニルチタントリブロ
ポキシド，ベンタメチルシクロペンタジエニルチタント
リブトキシド．ベンタメチルシクロペンタジエニルチタ
ントリフエノキシド，シクロペンタジエニルチタントリ
クロリド，ペンタメチルシク口ペンタジエニルチタン｝
ＩＪクロリド，シクロペンタジエニルメトキシチタン
クロリド，シクロペンタジエニルジメトキシチタンクロ
リド，ベンタメチルシクロペンタジエニルメトキシチタ
ンジクロリド，シクロペンタジエニルトリベンジルチタ
ン．ベンタメチルシクロベンタジエニルメチルジエトキ
シチタン．インデニルチタントリクロリド，インデニル
チタントリメトキシド，インデニルチタントリエトキシ
ド，インデニルトリメチルチタン，インデニルトリベン
ジルチタン等が挙げられる。Such general formulas (V), (VI), (■
] or [■] Among the transition metal compounds, specific examples of titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetra-n-butoxytitanium, tetraisopropoxytitanium, cyclopentadienyltrimethyltitanium, cyclopenta Dienyltriethyl titanium.
Cyclopentadienyl tripyr titanium. Cyclopentadienyltributyl titanium. Methylcyclopentadienyltrimethyltitanium. 1l2-dimethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltributyl titanium, pentamethylcyclopentadienyltributyltitanium, Cyclopentadienylmethyl titanium dichloride, cyclopentadienyl ethyl titanium dichloride, pentamethyl pentadienyl methyl titanium dichloride, pentamethyl pentadienyl ethyl titanium dichloride, cyclopentadienyl dimethyl titanium monochloride, cyclopentadienyl titanium dichloride enyl diethyl titanium monochloride, cyclopentadienyl titanium trimethoxide, cyclopentadienyl titanium triethoxide, cyclobentadienyl titanium triproxide, cyclobentadienyl titanium triphenoxide. bentamethylcyclobentadienyl titanium trimethoxide,
Pentamethylcyclopentadienyl titanium triethoxide, pentamethylcyclopentadienyl titanium tribropoxide, pentamethylcyclopentadienyl titanium tributoxide. Bentamethyl cyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium trichloride, pentamethyl cyclopentadienyl titanium}
IJ chloride, cyclopentadienylmethoxytitanium chloride, cyclopentadienyldimethoxytitanium chloride, bentamethylcyclopentadienylmethoxytitanium dichloride, cyclopentadienyltribenzyltitanium. Bentamethylcyclobentadienylmethyldiethoxytitanium. Examples include indenyl titanium trichloride, indenyl titanium trimethoxide, indenyl titanium triethoxide, indenyl trimethyl titanium, and indenyl tribenzyl titanium.
これらのチタン化合物のうち、ハロゲン原子を含まない
化合物が好適であり、特一に、上述した如き少なくとも
ｌ配位子が不飽和なπ電子系配位子であるような４配位
型のチタン化合物が好ましい。Among these titanium compounds, compounds that do not contain a halogen atom are preferred, and in particular, four-coordinated titanium compounds in which at least the l ligand is an unsaturated π-electron system ligand as described above are preferred. Compounds are preferred.
また、前記一般式（Ｖ）， （ＶＩＡ， （■〕ま
たは〔■〕で表される遷移金属化合物のうちジルコニウ
ム化合物の具体例としては、シクロペンタジエニルジル
コニウムトリメトキシド，ペンタメチルシク口ペンタジ
エニルジルコニウムトリメトキシド，シクロペンタジュ
ニルトリベンジルジルコニウム，ペンクメチルシク口ペ
ンタジエニルトリベンジルジルコニウム，ビスインデニ
ルジルコニウムジクロリド，ジルコニウムジベンジルジ
クロリド，ジルコニウムテトラベンジル，トリブトキシ
ジルコニウムクロリド，トリイソプロボキシジルコニウ
ムクロリドなどが挙げられる。Further, among the transition metal compounds represented by the general formula (V), (VIA, (■) or [■]), specific examples of zirconium compounds include cyclopentadienyl zirconium trimethoxide, pentamethyl zirconium Dienylzirconium trimethoxide, cyclopentadjunyltribenzylzirconium, penkmethylpentadienyltribenzylzirconium, bisindenylzirconium dichloride, zirconium dibenzyl dichloride, zirconium tetrabenzyl, tributoxyzirconium chloride, triisoproboxyzirconium chloride, etc. can be mentioned.
さらに、同様にハフニウム化合物の具体例としては、シ
クロベンタジエニルハフニウムトリメトキシド，ペンタ
メチルシク口ペンタジエニルハフニウムトリメトキシド
，シクロペンタジエニルトリベンジルハフニウム，ペン
タメチルシク口ペンタジエニルトリベンジルハフニウム
，ビスインデニルハフニウムジクロリド，ハフニウムジ
ベンジルクロリド，ハフニウムテトラヘンジル，トリブ
トキシハフニウムクロリド，トリイソブロボキシハフニ
ウムクロリドなどが挙げられる。Similarly, specific examples of hafnium compounds include cyclobentadienyl hafnium trimethoxide, pentamethylcyclopentadienyl hafnium trimethoxide, cyclopentadienyltribenzyl hafnium, and pentamethylcyclopentadienyltribenzyl. Examples include hafnium, bisindenylhafnium dichloride, hafnium dibenzyl chloride, hafnium tetrahendyl, tributoxyhafnium chloride, triisobroboxyhafnium chloride, and the like.
また、同様にバナジウム化合物の具体例としては、バナ
ジウムトリクロリド，バナジルトリクロリド，バナジウ
ムトリアセチルアセトナート，バナジウムテトラクロリ
ド，バナジルトリプトキシド，バナジルジクロリド，バ
ナジルビスアセチルアセトネート，バナジルトリアセチ
ルアセトネートなどが挙げられる。Similarly, specific examples of vanadium compounds include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadyl triptoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, etc. can be mentioned.
一方、本発明の第２の方法で用いる触媒の他の或分であ
る（Ｂ）有機アルξニウム化合物と縮合剤との接触生成
物は、例えば特開昭６２−１８７７０８号公報に記載さ
れたものと同種のものであるが、詳しくは下記の通りで
ある。On the other hand, the other part of the catalyst used in the second method of the present invention (B), the contact product of the organic aluminum compound and the condensing agent, is the product described in, for example, JP-A-62-187708. The details are as follows.
即ち、この接触生戒物は、各種の有機アルミニウム化合
物と縮合剤とを接触させて得られるものである。That is, this contact product is obtained by bringing various organoaluminum compounds into contact with a condensing agent.
ここで有機アルミニウム化合物としては、通常一般式
ＡＩＲ１７３
〔式中、Ｒｌ７は炭素数１〜８のアルキル基を示す。〕
で表わされる有機アルミニウム化合物、具体的にはトリ
メチルアルミニウム，トリエチルアルミニウム トリイ
ソブチルアルミニウム等のトリアルキルアルミニウムが
挙げられ、中でもトリメチルアルミニウムが好ましい。Here, the organoaluminum compound usually has the general formula AIR173 [wherein Rl7 represents an alkyl group having 1 to 8 carbon atoms]. ] Organoaluminum compounds represented by these, specifically trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, etc., are mentioned, and trimethylaluminum is especially preferred.
なお、縮合剤については、典型的には水が挙げられるが
、そのほか上記トリアルキルアルミニウムが縮合反応す
るもの、例えば硫酸銅５水塩，無機物や有機物への吸着
水など各種のものが挙げられる。As for the condensing agent, water is typically used, but various other agents that can undergo a condensation reaction with the trialkylaluminium, such as copper sulfate pentahydrate, water adsorbed on inorganic substances or organic substances, and the like can also be used.
本発明の第２において用いる触媒の（Ｂ）戒分である有
機アルξニウム化合物と縮合剤との接触生成物の代表例
としては、前記一般式Ａ／！Ｒ”，で表わされるトリア
ルキルアル旦ニウムと水との接触生戒物があるが、具体
的には
一般式
〔式中、ｐは重合度を示し、０〜５０であり、Ｒ ｌ？
は炭素数１〜８のアルキル基を示す。〕で表わされる鎖
状アルキルアミノキサンあるいは一般式
−＋−Ａ ｌ − ０−→一−−
Ｒ１７
〔式中、Ｒｌ７は前記と同じである。〕で表わされる繰
り返し単位を有する環状アルキルアルξノキサン（繰返
し単位数２〜５０）等がある。As a representative example of the contact product of the organic aluminum compound, which is the component (B) of the catalyst used in the second aspect of the present invention, and the condensing agent, the general formula A/! There is a reaction product of trialkylaldanium represented by the formula R'' and water, specifically, a compound of the general formula [where p indicates the degree of polymerization and is from 0 to 50, and R l?
represents an alkyl group having 1 to 8 carbon atoms. ] or a linear alkylaminoxane represented by the general formula -+-Al-0-→--R17 [wherein Rl7 is the same as above. ] There are cyclic alkylalkyl ξnoxanes (number of repeating units from 2 to 50) having a repeating unit represented by the following.
一ａに、トリアルキルアルミニウム等のアルキルアル旦
ニウムと水との接触生戒物は、上述の鎖状アルキルアル
ミノキサンや環状アルキルアルミノキサンとともに、未
反応のトリアルキルアルミニウム、各種の縮合生成物の
混合物、さらにはこれらが複雑に会合した分子であり、
これらはトリアルキルアルミニウムと縮合剤である水と
の接触条件によって様々な生成物となる。1a, a mixture of unreacted trialkylaluminium, various condensation products, as well as the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane, is a mixture of alkylaluminium such as trialkylaluminium and water in contact with water; Furthermore, these molecules are complexly associated,
These products form various products depending on the contact conditions between trialkylaluminum and water, which is a condensing agent.
この際のアルキルアルミニウムと縮合剤との反応は特に
限定はなく、公知の手法に準じて反応させればよい。例
えば、■有機アルミニウム化合物を有機溶剤に溶解して
おき、これを水と接触させる方法、■重合時に当初有機
アルミニウム化合物を加えておき、後に水を添加する方
法、さらには■金属塩などに含有されている結晶水、無
機物や有機物への吸着水を有機アル珈ニウム化合物と反
応させるなどの方法がある。なお、この反応は無溶媒下
でも進行するが、溶媒中で行なうことが好ましく、好適
な溶媒としては、ヘキサン，ヘブタン，デカン等の脂肪
族炭化水素あるいはベンゼントルエン，キシレン等の芳
香族炭化水素を挙げることができる。また、上記の水に
はアンモニア，エチルアミン等のア旦ン、硫化水素等の
硫黄化合物、亜燐酸エステル等の燐化合物などが２０％
程度まで含有されていてもよい。The reaction between the alkyl aluminum and the condensing agent at this time is not particularly limited, and the reaction may be carried out according to a known method. For example, ■ A method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, ■ A method in which an organoaluminum compound is initially added during polymerization and water is added later, and ■ A method in which it is contained in a metal salt, etc. There are methods such as reacting water of crystallization, water adsorbed on inorganic substances or organic substances, with an organic aluminium compound. Although this reaction proceeds without a solvent, it is preferable to conduct it in a solvent. Suitable solvents include aliphatic hydrocarbons such as hexane, hebutane, and decane, or aromatic hydrocarbons such as benzene toluene and xylene. can be mentioned. In addition, the above water contains 20% of ammonia, sulfur compounds such as ethylamine, sulfur compounds such as hydrogen sulfide, and phosphorus compounds such as phosphorous esters.
It may be contained to some extent.
本発明の第２において触媒の（Ｆｌ）戒分として用いる
有機アルミニウム化合物と縮合剤との接触生戒物（例え
ば、アルキルアルミノキサン）は、上記の接触反応の後
、含水化合物等を使用した場合には、固体残渣を濾別し
、濾液を常圧下あるいは減圧下で３０〜２００″Ｃの温
度、好ましくは４０〜１５０゜Ｃの温度で２０分〜８時
間、好ましくは３０分〜５時間の範囲で溶媒を留去しつ
つ熱処理することが好ましい。In the second aspect of the present invention, the contact reaction product (for example, alkylaluminoxane) between the organoaluminum compound and the condensing agent used as the (Fl) component of the catalyst can be The solid residue is separated by filtration, and the filtrate is heated under normal pressure or reduced pressure at a temperature of 30 to 200°C, preferably 40 to 150°C, for 20 minutes to 8 hours, preferably 30 minutes to 5 hours. It is preferable to carry out the heat treatment while distilling off the solvent.
この熱処理にあたっては、温度は各種の状況によって適
宜定めればよいが、通常は上記範囲で行なう。一般に、
３０゜Ｃ未満の温度では、効果が発現せず、また２００
゜Ｃを超えると、アルキルアルミノキサン自体の熱分解
が起こり、いずれも好ましくない。In this heat treatment, the temperature may be determined as appropriate depending on various circumstances, but it is usually carried out within the above range. in general,
At temperatures below 30°C, the effect will not be expressed, and at temperatures below 200°C.
If the temperature exceeds °C, thermal decomposition of the alkylaluminoxane itself occurs, which is not preferable.
熱処理の処理条件により反応生底物は、無色の固体又は
溶液状態で得られる。このようにして得られた生成物を
、必要に応じて炭化水素溶媒で溶解あるいは希釈して触
媒溶液として使用することができる。Depending on the treatment conditions of the heat treatment, the reaction raw material can be obtained in the form of a colorless solid or a solution. The product thus obtained can be used as a catalyst solution by dissolving or diluting it with a hydrocarbon solvent, if necessary.
このような触媒の（Ｂ）成分として用いる有機アルミニ
ウム化合物と縮合剤との接触生戒物、特にアルキルアル
ミノキサンの好適な例は、プロトン核磁気共鳴吸収法で
観測されるアルミニウムーメチル基（Ａｌ−ＣＨ３）結
合に基くメチルプロトンシグナル領域における高磁場成
分が５０％以下のものである。つまり、上記の接触生戒
物を、室温下、トルエン溶媒中でそのプロトン核磁気共
鳴（’ Ｆ｛ − Ｎ Ｍ Ｒ ）スペクトルを観測す
ると、ＡｌＣ ｝＋ ３に基くメチルプロトンシグナル
は、テトラメチルシラン（ＴＭＳ）基準において１．０
〜−０．５ｐｐｍの範囲に見られる。ＴＭＳのプロトン
シグナル（ Ｏ ｐｐｍ）がＡｊ２ ＣＨ３に基くメ
チルプロトン観測領域にあるため、このＡ ｆ − Ｃ
Ｈ ３に基くメチルプロトンシグナルを、ＴＭＳ基準
におけるトルエンのメチルプロトンシグナル２．３５ｐ
ρｍを基準にして測定し、高磁場成分（即ち、一〇．１
〜０． ５ ｐｐｍ）と他の磁場成分（即ち、１．０
＝０．１ｐｐｍ）とに分けたときに、該高磁場成分が、
全体の５０％以下、好ましくは４５〜５％のものが触媒
の（Ｂ）威分として好適に使用できる。A preferable example of the organic aluminum compound and the condensing agent used as component (B) of such a catalyst, particularly an alkylaluminoxane, is an aluminum-methyl group (Al- The high magnetic field component in the methyl proton signal region based on CH3) bond is 50% or less. In other words, when observing the proton nuclear magnetic resonance ('F{-NMR) spectrum of the above-mentioned contact compound in a toluene solvent at room temperature, the methyl proton signal based on AlC}+3 is found to be tetramethylsilane. (TMS) standard 1.0
It is found in the range of ~-0.5 ppm. Since the TMS proton signal (O ppm) is in the methyl proton observation region based on Aj2CH3, this A f - C
The methyl proton signal based on H3 was compared to the methyl proton signal of toluene at 2.35p in TMS standard.
The high magnetic field component (i.e. 10.1
~0. 5 ppm) and other magnetic field components (i.e. 1.0
= 0.1 ppm), the high magnetic field component is
50% or less of the total amount, preferably 45 to 5%, can be suitably used as the (B) component of the catalyst.
本発明の方法に用いる触媒は、前記（ＩＩ），（Ｂ）成
分を主成分とするものであり、前記の他にさらに所望に
より他の触媒威分、例えば
一般式
Ａ／！Ｒ”
Ｃ式中、Ｒ１は炭素数１〜８のアルキル基を示す。〕
で表されるトリアルキルアルミニウムや他の有機金属化
合物などを加えることもできる。The catalyst used in the method of the present invention has the above-mentioned components (II) and (B) as main components, and in addition to the above-mentioned components, other catalyst components may be added if desired, such as the general formula A/! In the formula R''C, R1 represents an alkyl group having 1 to 8 carbon atoms.] Trialkylaluminum or other organometallic compounds represented by the following can also be added.
本発明の第２では、上記のようにして得られた触媒を用
いて、スチレン系モノマーおよびアセナフチレン系七ノ
マーを共重合するが、重合方法は塊状重合，溶液重合，
懸濁重合等いずれの方法を用いてもよい。そしてこれら
の場合、溶剤としてはペンタン，ヘキサン．ヘプタンな
どの脂肪族炭化水素；シクロヘキサンなどの脂環式炭化
水素；ベンゼン，トルエン，キシレンなどの芳香族炭化
水素が用いられる。これらの中でも芳香族炭化水素が好
ましく、とりわけトルエン，キシレンが好ましい。この
場合において、モノマー／溶媒（体積比）は任意に！ｔ
沢することができる。In the second aspect of the present invention, a styrene monomer and an acenaphthylene heptanomer are copolymerized using the catalyst obtained as described above, and the polymerization method is bulk polymerization, solution polymerization,
Any method such as suspension polymerization may be used. In these cases, the solvent is pentane or hexane. Aliphatic hydrocarbons such as heptane; alicyclic hydrocarbons such as cyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene are used. Among these, aromatic hydrocarbons are preferred, with toluene and xylene being particularly preferred. In this case, the monomer/solvent (volume ratio) is arbitrary! t
It is possible to make a lot of money.
また、重合条件としては特に制限はないが、一般的には
、重合温度はＯ〜１２０゜Ｃ１好ましくは１０〜７０゜
Ｃであり、また重合時間は５分〜２４時間、好ましくは
１時間以上である。Furthermore, there are no particular restrictions on the polymerization conditions, but generally the polymerization temperature is 0 to 120°C, preferably 10 to 70°C, and the polymerization time is 5 minutes to 24 hours, preferably 1 hour or more. It is.
さらに、得られるスチレン系共重合体の分子量を調節す
るには、水素の存在下で行なうことが効果的である。Furthermore, in order to control the molecular weight of the obtained styrenic copolymer, it is effective to carry out the reaction in the presence of hydrogen.
さらに、この触媒を使用するにあたって、触媒中の（Ａ
）戒分と（Ｂ）戒分との割合は、各成分の抽頚や、原料
であるスチレン系モノマーおよびアセナフチレン系モノ
マーの種類その他の条件により異なり、一義的に定める
ことは困難であるが、通常は、触媒戒分（Ｂ）中のアル
ミニウムと、（Ａ）遷移金属或分中の遷移金属との比、
すなわち、アルミニウム／遷移金属（モル比）として、
１ −１０６（モル比）、好ましくは１０〜１０４（モ
ル比）である。Furthermore, when using this catalyst, (A
) The ratio of the (B) precept varies depending on the extraction of each component, the type of styrene monomer and acenaphthylene monomer used as raw materials, and other conditions, and it is difficult to determine it unambiguously. Usually, the ratio of aluminum in the catalyst fraction (B) to the transition metal in the transition metal fraction (A);
That is, as aluminum/transition metal (molar ratio),
1 to 106 (molar ratio), preferably 10 to 104 (molar ratio).
また原料の仕込比、すなわちスチレン系モノマー／アセ
ナフチレン系モノマー（モル比）は’１８に制限はなく
、目的物の組戒に応じて定めることができるが、好まし
くは１以上である。また、モノマーと触媒戒分（Ｂ）中
のアルミニウムとの比、すなわちモノマー合計量／アル
ミニウム（モル比）としては１〜１０６（モル比）であ
る。Further, the charging ratio of the raw materials, that is, the styrene monomer/acenaphthylene monomer (molar ratio) is not limited to '18 and can be determined depending on the composition of the target product, but is preferably 1 or more. Further, the ratio between the monomer and aluminum in the catalyst component (B), that is, the total amount of monomers/aluminum (molar ratio), is 1 to 106 (molar ratio).
さらに、原料と触媒成分の仕込みの順序は特に制限はな
く、任意の順序で行なうことができる。Furthermore, the order of charging the raw materials and catalyst components is not particularly limited and can be carried out in any order.
叙上の如くして、本発明の第１のスチレン系共重合体を
製造することができる。この共重合体は、前記の如くシ
ンジオタクティシティーの高いものであるが、重合後、
必要に応じて塩酸等を含む洗浄液で脱灰処理し、さらに
洗浄，減圧乾燥を経てメチルエチルケトン等の溶媒で洗
浄して可溶分を除去すれば、極めてシンジオタタティシ
テーの大きい高純度のスチレン系共重合体を人手するこ
とができる。The first styrenic copolymer of the present invention can be produced as described above. This copolymer has high syndiotacticity as described above, but after polymerization,
If necessary, deashing with a cleaning solution containing hydrochloric acid, etc., followed by washing and drying under reduced pressure, followed by washing with a solvent such as methyl ethyl ketone to remove soluble components, produces a highly pure styrene-based product with extremely high syndiotality. Copolymers can be prepared manually.
〔実施例］ 次に本発明を実施例により詳しく説明する。〔Example] Next, the present invention will be explained in detail with reference to examples.
実施例１
（１）メチノレアノレξノキサンの言周製アルゴン置換
した内容積５ ０ ０ ｍｌのガラス製容器にトルエン
２００ｄ，硫酸銅５水塩（ＣｕＳ○４・５Ｈｚ○） １
７．７ ｇ （７ １ミリモル）及びトリメチルアル旦
ニウム２４ｄＣ２５０ミリモル）を入れ、４０゜Ｃで８
時間反応させた。その後、固体或分を除去し、得られた
溶液からさらにトルエンを減圧留去して接触生戊物６．
７ｇを得た。このものの凝固点降下法により測定した分
子量は６１０であった。Example 1 (1) Methynoleanole ξnoxane manufactured by Kanshu Co., Ltd. In a glass container with an internal volume of 500 ml and replaced with argon, 200 d of toluene and copper sulfate pentahydrate (CuS○4.5Hz○) 1
7.7 g (71 mmol) and 250 mmol of trimethylaluminium 24dC) were added and heated at 40°C.
Allowed time to react. Thereafter, some of the solids were removed, and toluene was further distilled off under reduced pressure from the resulting solution to obtain the contact product 6.
7g was obtained. The molecular weight of this product was 610 as measured by freezing point depression method.
また． ’ Ｈ − Ｎ Ｍ Ｒ測定による高磁場戒分
、すなわち、室温下、トルエン溶媒中でそのプロトン核
磁気共鳴スペクトルを観測すると、（Ａｆ−Ｃｌｆ３）
結合に基づくメチルプロトンシグナルは、テトラメチル
シラン基準において１．０〜−０． ５ ｐｐｍの範囲
に見られる。テトラメチルシランのプロトンシグナルは
（ Ｏ ｐｐｍ）がＡ／２−ＣＨ．結合に基づくメチル
プロトンに基づく観測領域にあるため、このＡｌ−ＣＨ
３結合に基づくメチルプロトンシグナルをテトラメチル
シラン基準におけるトルエンのメチルプロトンシグナル
２． ３ ５ ｐｐｍを基準にして測定し、高磁場或分
（すなわち、一〇．１〜−０．５ｐｌｌＩｎ）と他の磁
場威分（すなわち、１．０〜−０．１ｐｐｍ）とに分け
たときに、該高磁場戒分が全体の４３％であった。Also. ' High magnetic field analysis by H-NMR measurement, that is, when observing the proton nuclear magnetic resonance spectrum in toluene solvent at room temperature, (Af-Clf3)
The methyl proton signal based on the bond ranges from 1.0 to -0.0 on the basis of tetramethylsilane. Found in the 5 ppm range. The proton signal of tetramethylsilane (O ppm) is A/2-CH. This Al-CH
2. The methyl proton signal based on the 3 bonds is the methyl proton signal of toluene based on tetramethylsilane. When measured on the basis of 35 ppm and divided into high magnetic field part (i.e. 10.1 to -0.5 pllIn) and other magnetic field part (i.e. 1.0 to -0.1 ppm) The high magnetic field precept accounted for 43% of the total.
（２）スチレンーアセナフチレン共重合体の製造アルゴ
ン雰囲気下において、乾燥した反応容器に、室温下、ト
ルエン２ｄ，トリイソブチルアルξニウム（Ｔ Ｉ Ｂ
Ａ） ２ ｘｌＯ−３モル（２モル／２一トルエン溶液
）および触媒成分（Ｂ）として上記（１）で得られたメ
チルアルミノキサン２Ｘ１０−３モル（２．６モル／ｌ
一トルエン溶液）を加え、その後、７０゜Ｃの温度に保
持した。この反応溶液に、触媒成分（Ａ）として、Ｌ２
，３，４．５−ペンタメチルシク口ペンタジエニルチタ
ニウムトリメトキシド（Ｃｐ” Ｔｉ （ＯＭｅ）ｚ
）ＩＸＩＯ−’モル（０．０１モル／２−トルエン溶液
）および合計モノマー濃度２モル＃２−トルエン溶液に
調製されたアセナフチレン・スチレン混合溶液〔アセナ
フチレン／スチレン−５／５（モノマー仕込み比）．モ
ノマー合計量１．７５Ｘ１０−’モル〕を加え、２時間
反応させた。(2) Production of styrene-acenaphthylene copolymer In a dry reaction vessel under an argon atmosphere, toluene 2d and triisobutylaluminum (T I B
A) 2 x lO-3 mol (2 mol/2-toluene solution) and 2 x 10-3 mol (2.6 mol/l) of methylaluminoxane obtained in (1) above as catalyst component (B)
1 toluene solution) was added and then maintained at a temperature of 70°C. This reaction solution was added with L2 as the catalyst component (A).
,3,4.5-pentamethylcyclopentadienyltitanium trimethoxide (Cp” Ti (OMe)z
) IXIO-' mol (0.01 mol/2-toluene solution) and acenaphthylene/styrene mixed solution prepared to a total monomer concentration of 2 mol #2-toluene solution [acenaphthylene/styrene-5/5 (monomer charge ratio). A total amount of monomers of 1.75 x 10-' mol] was added and reacted for 2 hours.
その後、メタノールー塩酸混合液に反応生戒物を注ぎ、
反応を停止、脱灰し、濾過し、メチルエチルケトンで２
回，さらにメタノールで３回洗浄した。これを減圧下で
乾燥させて、０．３４ｇのスチレン・アセナフチレン共
重合体を得た。After that, pour the reactant into the methanol-hydrochloric acid mixture,
The reaction was stopped, deashed, filtered, and diluted with methyl ethyl ketone.
Washed twice with methanol and then three times with methanol. This was dried under reduced pressure to obtain 0.34 g of styrene/acenaphthylene copolymer.
この共重合体の分子量を、ゲルパーごエーションク口マ
トグラフィ−（ｃｐｃ）により測定したところ、重量平
均分子量（Ｍｗ）は、ボリスチレン（ｐｓ）換算で１３
，０００であり、数平均分子量（Ｍｎ）はＰＳ換算で５
，４００であった。When the molecular weight of this copolymer was measured by gel permeation chromatography (CPC), the weight average molecular weight (Mw) was 13 in terms of polystyrene (ps).
,000, and the number average molecular weight (Mn) is 5 in terms of PS.
,400.
また、示差走査熱量測定（ＤＳＣ）（測定条件■３００
’Ｃ，５分間保持，■３０’Ｃまで７゜Ｃ／分で冷却（
ファーストクーリング），■３０゜Ｃ， ５分間保持
，■３ ０ ０ ’Ｃまで２０゜Ｃ／分で昇温（セカン
ドヒーティング）〕により求めた、この共重合体のガラ
ス転移点（Ｔｇ）及び融点（Ｔｍ）は、それぞれ１０６
．６゜Ｃ，２６６．６゜Ｃであり、冷却時結晶化温度（
Ｔｃ）は２３２．８゜Ｃであった。また、この共重合体
の組戒比は、赤外線吸収スペクトルの検量線法（ラジカ
ル重合により得たポリアセナフチレンと、公知の手法で
合成したシンジオタクチック構造を有するボリスチレン
を、所定量均一に混合したものを用意し、それぞれの赤
外線吸収スペクトルを測定し、６９６ｃｍ−’の吸収と
８１４ｃｍ−’の吸収のピーク強度比を求め、その混合
比と、ピーク強度比から検量線を作威し、得られた共重
合体の６９６ｃｍ−’の吸収と８１４ｃｍ−’の吸収の
ピーク強度比と、その検量線により共重合体の組成比を
決定した。）により求めたところ、アセナフチレン／ス
チレン＝３８／６２であった。これらの測定結果を第１
表に示す。In addition, differential scanning calorimetry (DSC) (measurement conditions ■300
'C, held for 5 minutes, cooled at 7°C/min to 30'C (
The glass transition point (Tg) and The melting point (Tm) is 106, respectively.
．． 6°C, 266.6°C, and the crystallization temperature during cooling (
Tc) was 232.8°C. In addition, the composition ratio of this copolymer was determined using the infrared absorption spectrum calibration curve method (polyacenaphthylene obtained by radical polymerization and boristyrene having a syndiotactic structure synthesized by a known method) were uniformly mixed in a predetermined amount. Prepare a mixture, measure the infrared absorption spectrum of each, determine the peak intensity ratio of absorption at 696 cm-' and absorption at 814 cm-', create a calibration curve from the mixture ratio and peak intensity ratio, The composition ratio of the copolymer was determined from the peak intensity ratio of the absorption at 696 cm-' and the absorption at 814 cm-' of the obtained copolymer and its calibration curve. It was 62. These measurement results are the first
Shown in the table.
なお、ＧＰＣ測定条件は以下の通りであった。Note that the GPC measurement conditions were as follows.
・装置：ウォーターズ ＡＬＣ／ＧＰＣ １５０℃・カ
ラム： ＴＳＫ Ｉ｛Ｍ−１−ＧＭ｝ｆ ６Ｘ２・流量
： １．Ｏ ｒＩｄｔ／ｓｉｎ．・温度＝１３５゜Ｃ
・ｉ媒： １．２．４− ｝リクロ口ベンゼン・流入量
：４００μｌ
また、第１図に得られた共重合体の”Ｃ−ＮＭＲ（６７
ＭＨｚ，溶媒二重クロロホルム）の測定結果を示す。・Apparatus: Waters ALC/GPC 150°C ・Column: TSK I{M-1-GM}f 6X2 ・Flow rate: 1. OrIdt/sin.・Temperature = 135°C ・I medium: 1.2.4-}licrobenzene ・Inflow amount: 400 μl In addition, "C-NMR (67
MHz, solvent (double chloroform) measurement results are shown.
Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ， ３ ， １７５（
１９７０）には、ＩＩＣ−ＮＭＲにおけるｔ４５，２ｐ
ｐｍのピークがラセミペンタッド配列に基づくフェニル
ＣＩ炭素に帰属できることが示されているが、第１図に
も１４５．２ｐｐｍの位置に鋭いピークがあることから
、このものがラセごペンタッド配列のシンジオタクチッ
ク構造を有することがわかる。Macromolecules, 3, 175 (
(1970), t45,2p in IIC-NMR
It has been shown that the peak of pm can be assigned to the phenyl CI carbon based on the racemic pentad arrangement, but since there is also a sharp peak at the position of 145.2 ppm in Figure 1, this peak can be assigned to the phenyl CI carbon based on the racemic pentad arrangement. It can be seen that it has a geeky structure.
また、第１図のＣＩのピークの半値幅から、この高分子
は、ラセミペンタッドで９０％以上であることがわかっ
た。Further, from the half-width of the CI peak in FIG. 1, it was found that this polymer was 90% or more racemic pentad.
実施例２〜５および比較例１
アセナフチレン／スチレンのモノマー仕込み比を、それ
ぞれ４／６． ３／７． ２／８． １／９． ０／１
０としたこと以外は、実施例ｌと同様に行なった。結果
を第１表に示す。Examples 2 to 5 and Comparative Example 1 The monomer charging ratio of acenaphthylene/styrene was 4/6. 3/7. 2/8. 1/9. 0/1
The same procedure as in Example 1 was carried out except that the value was set to 0. The results are shown in Table 1.
北 の の石 切
ボリスチレンとして比較例ｌで得られたシンジオタクチ
ックボリスチレン（ＳＰＳ）を用いて、ポリアセナフチ
レン（ラジカル重合により合威したもの： ＭＷ＝１１
，０００， ＭＮ＝４，５００）とのｌ昆合物のＤＳＣ
による熱挙動を実施例ｌと同様にして測定した。結果を
参考例１〜３として第２表に示す。Using the syndiotactic polystyrene (SPS) obtained in Comparative Example 1 as the stone-cut polystyrene in the north, polyacenaphthylene (synthesized by radical polymerization: MW = 11
,000, MN=4,500)
The thermal behavior was measured in the same manner as in Example 1. The results are shown in Table 2 as Reference Examples 1 to 3.
第２表
第ｌ表による重合系と、第２表による混合系による結果
を比較してみると、重合系は混合系に比べＴｃの向上，
Ｔｍの低下、Ｔｇの低下が認められ、これにより実施例
１〜５で得られた重合体は共重合体を含んでいることが
わかる。Comparing the results of the polymerization system according to Table 2, Table 1 and the mixed system according to Table 2, it is found that the polymerization system has improved Tc compared to the mixed system.
A decrease in Tm and a decrease in Tg were observed, which indicates that the polymers obtained in Examples 1 to 5 contain a copolymer.
本発明の第１の共重合体は、アセナフチレンを共重合さ
せることにより、ジンジオタクチノクボリスチレンに比
べ、結晶化速度が大きいものとなっている。従って、こ
の共重合体を用いれば射出成形等の戒形サイクルを短縮
することができる。By copolymerizing acenaphthylene, the first copolymer of the present invention has a higher crystallization rate than jindiotactic polystyrene. Therefore, by using this copolymer, molding cycles such as injection molding can be shortened.
また、この共重合体は充分な耐熱性を有している。Moreover, this copolymer has sufficient heat resistance.
それ故、本発明の第１の共屯合体は、戒形材料に極めて
有効に用いられる。Therefore, the first conjugate of the present invention can be used very effectively for forming materials.
また、本発明の第２の製造方法を用いれば、上記共重合
体を極めて効率的に製造することができる。Further, by using the second production method of the present invention, the above copolymer can be produced extremely efficiently.
第ｌ図は、本発明の実施例ｌで得られた共重合体（７）
１３Ｃ−ＮＭＲ （６ ７ＭＨｚ）測足ｆ＋’ｊ果を示
すチャートである。
才
１
区Figure 1 shows the copolymer (7) obtained in Example 1 of the present invention.
13C-NMR (67MHz) is a chart showing the results of foot measurement f+'j. Sai1 Ward
Claims (2)
原子、酸素原子、窒素原子、硫黄原子、リン原子、セレ
ン原子、ケイ素原子および錫原子のいずれか１種以上を
含む置換基を示し、ｍは１〜３の整数を示す。但し、ｍ
が複数のときは、各Ｒ＾１は同一でも異なるものであっ
てもよい。〕 で表わされる少なくとも一種の構造単位〔 I 〕および
一般式 ▲数式、化学式、表等があります▼……（II） 〔式中、Ｒ＾２、Ｒ＾３、Ｒ＾４は水素原子、ハロゲン
原子、または炭素原子、酸素原子、窒素原子、硫黄原子
、リン原子、セレン原子、ケイ素原子および錫原子のい
ずれか１種以上を含む置換基を示し、ｎは１〜６の整数
を示す。但し、ｎが複数のときは、各Ｒ＾４は同一でも
異なるものであってもよい。〕で表わされる構造単位〔
II〕を有し、重合度が５以上で、かつ、そのスチレン連
鎖部の立体規則性が主としてシンジオタクチック構造で
あるスチレン系共重合体。(1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼……(I) [In the formula, R^1 is a hydrogen atom, a halogen atom, or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, It represents a substituent containing at least one of a selenium atom, a silicon atom, and a tin atom, and m represents an integer of 1 to 3. However, m
When there is a plurality of R^1's, each R^1 may be the same or different. ] At least one structural unit [I] represented by [I] and general formula ▲ Numerical formula, chemical formula, table, etc. ▼... (II) [In the formula, R^2, R^3, R^4 are hydrogen atoms, halogen represents an atom or a substituent containing any one or more of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom, and a tin atom, and n represents an integer of 1 to 6. However, when n is plural, each R^4 may be the same or different. ] Structural unit represented by [
II], the degree of polymerization is 5 or more, and the stereoregularity of the styrene chain portion is mainly a syndiotactic structure.
）有機アルミニウム化合物と縮合剤との接触生成物を用
い、 一般式 ▲数式、化学式、表等があります▼……（III） 〔式中、Ｒ＾１は水素原子、ハロゲン原子、または炭素
原子、酸素原子、窒素原子、硫黄原子、リン原子、セレ
ン原子、ケイ素原子および錫原子のいずれか１種以上を
含む置換基を示し、ｍは１〜３の整数を示す。但し、ｍ
が複数のときは、各Ｒ＾１は同一でも異なるものであっ
てもよい。〕 で表わされる少なくとも一種のスチレン系モノマーおよ
び 一般式 ▲数式、化学式、表等があります▼……（IV） 〔式中、Ｒ＾２、Ｒ＾３、Ｒ＾４は水素原子、ハロゲン
原子、または炭素原子、酸素原子、窒素原子、硫黄原子
、リン原子、セレン原子、ケイ素原子および錫原子のい
ずれか１種以上を含む置換基を示し、ｎは１〜６の整数
を示す。但し、ｎが複数のときは各Ｒ＾４は同一でも異
なるものであってもよい。〕 で表わされるアセナフチレン系モノマーを共重合するこ
とを特徴とする請求項１記載のスチレン系共重合体の製
造方法。(2) As catalyst components, (A) transition metal component and (B
) Using the contact product of an organoaluminum compound and a condensing agent, the general formula ▲ has mathematical formulas, chemical formulas, tables, etc. ▼... (III) [In the formula, R^1 is a hydrogen atom, a halogen atom, or a carbon atom, It represents a substituent containing any one or more of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom, and a tin atom, and m represents an integer of 1 to 3. However, m
When there is a plurality of R^1's, each R^1 may be the same or different. [In the formula, R^2, R^3, R^4 are hydrogen atoms, halogen atoms, or a substituent containing any one or more of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom, and a tin atom, and n represents an integer of 1 to 6. However, when n is plural, each R^4 may be the same or different. ] The method for producing a styrenic copolymer according to claim 1, characterized in that an acenaphthylene monomer represented by the following is copolymerized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30787289A JP2834806B2 (en) | 1989-11-24 | 1989-11-24 | Styrene copolymer and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30787289A JP2834806B2 (en) | 1989-11-24 | 1989-11-24 | Styrene copolymer and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03166204A true JPH03166204A (en) | 1991-07-18 |
| JP2834806B2 JP2834806B2 (en) | 1998-12-14 |
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ID=17974179
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30787289A Expired - Fee Related JP2834806B2 (en) | 1989-11-24 | 1989-11-24 | Styrene copolymer and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP2834806B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001077192A1 (en) * | 2000-04-11 | 2001-10-18 | Nippon Steel Chemical Co., Ltd. | Aromatic oligomer, phenolic resin composition containing the same, and epoxy resin composition and cured object obtained therefrom |
-
1989
- 1989-11-24 JP JP30787289A patent/JP2834806B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001077192A1 (en) * | 2000-04-11 | 2001-10-18 | Nippon Steel Chemical Co., Ltd. | Aromatic oligomer, phenolic resin composition containing the same, and epoxy resin composition and cured object obtained therefrom |
| JP2001294623A (en) * | 2000-04-11 | 2001-10-23 | Nippon Steel Chem Co Ltd | Aromatic oligomer, phenol resin composition or epoxy resin composition compounded with the same, and its cured material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2834806B2 (en) | 1998-12-14 |
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