JP5742479B2 - POLYMER, COMPOSITE AND METHOD FOR PRODUCING POLYMER - Google Patents
POLYMER, COMPOSITE AND METHOD FOR PRODUCING POLYMER Download PDFInfo
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- JP5742479B2 JP5742479B2 JP2011121829A JP2011121829A JP5742479B2 JP 5742479 B2 JP5742479 B2 JP 5742479B2 JP 2011121829 A JP2011121829 A JP 2011121829A JP 2011121829 A JP2011121829 A JP 2011121829A JP 5742479 B2 JP5742479 B2 JP 5742479B2
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- 229920000642 polymer Polymers 0.000 title claims description 217
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000002131 composite material Substances 0.000 title description 9
- 125000001424 substituent group Chemical group 0.000 claims description 73
- 238000007142 ring opening reaction Methods 0.000 claims description 58
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 150000002430 hydrocarbons Chemical group 0.000 claims description 18
- 239000002685 polymerization catalyst Substances 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 14
- 125000004429 atom Chemical group 0.000 claims description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- 150000002736 metal compounds Chemical class 0.000 description 24
- -1 norbornene compound Chemical class 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000005259 measurement Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 13
- 230000004927 fusion Effects 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 11
- WLCVNBXWMQMKGJ-UHFFFAOYSA-N 2-(5-bicyclo[2.2.1]hept-2-enyl)ethyl-trimethoxysilane Chemical compound C1C2C(CC[Si](OC)(OC)OC)CC1C=C2 WLCVNBXWMQMKGJ-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 150000004678 hydrides Chemical class 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 125000002524 organometallic group Chemical group 0.000 description 7
- 229920002050 silicone resin Polymers 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 239000005909 Kieselgur Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 125000005103 alkyl silyl group Chemical group 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000003624 transition metals Chemical group 0.000 description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 3
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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 group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical class ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical group C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- GCYUJISWSVALJD-UHFFFAOYSA-N 1,1-diethylcyclohexane Chemical compound CCC1(CC)CCCCC1 GCYUJISWSVALJD-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RCJMVGJKROQDCB-UHFFFAOYSA-N 1,3-dimethyl-1,3-butadiene Natural products CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical class ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
本発明は、重合体、複合体および重合体の製造方法に関し、さらに詳しくは、耐熱性および他の材料との密着性に優れるシクロオレフィンポリマー系の結晶性重合体と、その製造方法と、その重合体を用いてなる複合体に関する。 The present invention relates to a polymer, a composite, and a method for producing a polymer. More specifically, the present invention relates to a cycloolefin polymer-based crystalline polymer excellent in heat resistance and adhesion to other materials, a method for producing the same, The present invention relates to a composite using a polymer.
例えば特許文献１に記載されるようなジシクロペンタジエンの開環重合体水素化物は、いわゆるシクロオレフィンポリマーの一種であり、透明性、低複屈折性、成形加工性などに優れることから、光学用途をはじめとして、種々の用途に適用できる材料として用いられている。 For example, dicyclopentadiene ring-opening polymer hydride as described in Patent Document 1 is a kind of so-called cycloolefin polymer, and is excellent in transparency, low birefringence, molding processability, and the like. It is used as a material applicable to various uses.
特許文献１に記載されたものもそうであるように、ジシクロペンタジエンの開環重合体水素化物は、アタクチックな構造を有する非晶性の重合体として得られることが一般的である。しかし、アタクチックな構造を有する非晶性のジシクロペンタジエンの開環重合体水素化物は、その用途によっては、耐熱性、機械強度、耐溶剤性などが不十分となる場合があるものである。そこで、それらの性能を改良する手法として、ジシクロペンタジエンの開環重合体水素化物に立体規則性を有させることにより、結晶性を付与することが提案されている。 As is also the case described in Patent Document 1, the ring-opening polymer hydride of dicyclopentadiene is generally obtained as an amorphous polymer having an atactic structure. However, the amorphous dicyclopentadiene ring-opened polymer hydride having an atactic structure may have insufficient heat resistance, mechanical strength, solvent resistance and the like depending on its use. Thus, as a technique for improving these performances, it has been proposed to impart crystallinity by imparting stereoregularity to the ring-opening polymer hydride of dicyclopentadiene.
例えば、非特許文献１には、ビフェノキシ基が２つ配位した、タングステンまたはモリブデンの錯体を重合触媒として用いることにより、メソ・ダイアッドの割合が５０％を超える、すなわち、アイソタクチック構造を有する、結晶性のジシクロペンタジエンの開環重合体水素化物が得られることが開示されている。また、特許文献２および特許文献３には、窒素原子上に特定構造の置換基を有するイミド基を持つタングステン錯体を重合触媒として用いることにより、ラセモ・ダイアッドの割合が５１％以上の、すなわち、シンジオタクチック構造を有する、結晶性のジシクロペンタジエンの開環重合体水素化物が得られることが開示されている。 For example, in Non-Patent Document 1, by using a tungsten or molybdenum complex coordinated with two biphenoxy groups as a polymerization catalyst, the proportion of meso-dyad exceeds 50%, that is, has an isotactic structure. It is disclosed that a ring-opening polymer hydride of crystalline dicyclopentadiene can be obtained. In Patent Document 2 and Patent Document 3, by using a tungsten complex having an imide group having a substituent of a specific structure on a nitrogen atom as a polymerization catalyst, the ratio of racemo dyad is 51% or more, that is, It is disclosed that a crystalline ring-opening polymer hydride of dicyclopentadiene having a syndiotactic structure can be obtained.
例えば特許文献２や特許文献３に記載されるような結晶性を有するジシクロペンタジエン開環重合体水素化物は耐熱性に優れる重合体であるが、本発明者らが検討したところ、他の材料と密着させることが困難であるという性質をも有するものであることが明らかとなった。他の材料と密着性が不十分であると、他の材料との複合体を構成するための材料として適用することが困難となるので、用途の幅を広げる観点から、その改良が望まれるといえる。 For example, a dicyclopentadiene ring-opened polymer hydride having crystallinity as described in Patent Document 2 and Patent Document 3 is a polymer having excellent heat resistance. It became clear that it also has the property that it is difficult to make it adhere | attach. If the adhesion with other materials is insufficient, it will be difficult to apply as a material for forming a composite with other materials. I can say that.
そこで、本発明は、結晶性のジシクロペンタジエン開環重合体水素化物について、元来の特長である高耐熱性を維持しつつ、他の材料との密着性を改良することにより、耐熱性および他の材料との密着性に優れる、シクロオレフィンポリマー系の結晶性重合体を提供することを目的とする。 Therefore, the present invention has improved the heat resistance and the adhesiveness with other materials while maintaining the high heat resistance that is the original feature of the crystalline dicyclopentadiene ring-opened polymer hydride. An object of the present invention is to provide a cycloolefin polymer-based crystalline polymer having excellent adhesion to other materials.
本発明者らは、上記目的を達成するために、鋭意検討を行った結果、ジシクロペンタジエンの開環重合体を得るにあたり、オキシシリル基を含むノルボルネン系化合物を特定割合で共重合させた上で、それにより得られる開環重合体に水素添加を行って結晶性の重合体を得ることにより、高耐熱性などの結晶性のジシクロペンタジエン開環重合体水素化物が元来有する特長を備えながら、他の材料との密着性にも優れる重合体が得られることを見出した。本発明は、この知見に基づいて完成するに至ったものである。 As a result of intensive studies to achieve the above object, the present inventors obtained a ring-opening polymer of dicyclopentadiene after copolymerizing a norbornene compound containing an oxysilyl group at a specific ratio. By adding hydrogen to the resulting ring-opening polymer to obtain a crystalline polymer, the crystalline dicyclopentadiene ring-opening polymer hydride having high heat resistance and the like has the original characteristics The inventors have found that a polymer having excellent adhesion to other materials can be obtained. The present invention has been completed based on this finding.
かくして、本発明によれば、下記の式（１）で表される繰り返し単位Ａ９８〜９９．９９９９モル％と下記の式（２）で表される繰り返し単位Ｂ０．０００１〜２モル％とを含んでなる結晶性を有する重合体が提供される。 Thus, according to the present invention, the repeating unit A 98 to 99.9999 mol% represented by the following formula (1) and the repeating unit B 0.0001 to 2 mol% represented by the following formula (2) are included. A polymer having crystallinity is provided.
上記の重合体は、繰り返し単位Ａについてのラセモ・ダイアッドの割合が６０％以上であることが好ましい。 The polymer preferably has a racemo dyad ratio of 60% or more with respect to the repeating unit A.
上記の重合体は、融点が２５０℃以上であることが好ましい。 The polymer preferably has a melting point of 250 ° C. or higher.
また、本発明によれば、上記の重合体を成形してなる成形体に、硬化性樹脂を塗布して硬化させて得られる複合体が提供される。 Moreover, according to this invention, the composite_body | complex obtained by apply | coating and hardening a curable resin to the molded object formed by shape | molding said polymer is provided.
さらに、本発明によれば、上記の重合体の製造方法であって、重合触媒の存在下で、ジシクロペンタジエンおよび下記の式（３）で表される化合物を含んでなる単量体混合物を開環メタセシス重合した後、得られる開環重合体の炭素−炭素二重結合を水素化させる、重合体の製造方法が提供される。 Furthermore, according to the present invention, there is provided a method for producing the polymer described above, which comprises, in the presence of a polymerization catalyst, a monomer mixture comprising dicyclopentadiene and a compound represented by the following formula (3). Provided is a method for producing a polymer, in which after the ring-opening metathesis polymerization, the carbon-carbon double bond of the resulting ring-opening polymer is hydrogenated.
本発明によれば、耐熱性および他の材料との密着性に優れる、シクロオレフィンポリマー系の結晶性重合体が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the crystalline polymer of a cycloolefin polymer type | system | group excellent in heat resistance and adhesiveness with another material is provided.
本発明の重合体は、下記の式（１）で表される繰り返し単位Ａ９８〜９９．９９９９モル％と下記の式（２）で表される繰り返し単位Ｂ０．０００１〜２モル％とを含んでなり、結晶性を有する重合体である。 The polymer of the present invention includes repeating units A98 to 99.9999 mol% represented by the following formula (1) and repeating units B0.0001 to 2 mol% represented by the following formula (2). It is a polymer having crystallinity.
式（１）で表される繰り返し単位Ａは、ジシクロペンタジエンを開環重合して得られる繰り返し単位の全ての炭素−炭素二重結合を水素化することにより得ることができる繰り返し単位である。本発明の重合体における繰り返し単位Ａの含有量は、全繰り返し単位に対して、９８〜９９．９９９９モル％であることが必要であり、９８．５〜９９．９９９モル％であることが好ましく、９９．０〜９９．９９モル％であることがより好ましい。繰り返し単位Ａの含有量が少なすぎると、重合体の耐熱性が不十分となるおそれがあり、繰り返し単位Ａの含有量が多すぎると、重合体の他の材料との密着性が不十分となるおそれがある。 The repeating unit A represented by the formula (1) is a repeating unit that can be obtained by hydrogenating all the carbon-carbon double bonds of the repeating unit obtained by ring-opening polymerization of dicyclopentadiene. The content of the repeating unit A in the polymer of the present invention needs to be 98 to 99.9999 mol%, preferably 98.5 to 99.999 mol%, based on all repeating units. 99.0 to 99.99 mol% is more preferable. If the content of the repeating unit A is too small, the heat resistance of the polymer may be insufficient, and if the content of the repeating unit A is too large, the adhesion with other materials of the polymer is insufficient. There is a risk.
式（２）で表される繰り返し単位Ｂは、後述する式（３）で表される化合物を開環重合して得られる繰り返し単位について、少なくとも主鎖中の炭素−炭素二重結合を水素化し、さらに必要に応じて主鎖中以外に存在する炭素−炭素二重結合を水素化することにより得ることができる、オキシシリル基を含む繰り返し単位である。式（２）においてＲ１〜Ｒ４として示される置換基は、それぞれ独立に、水素原子；ハロゲン原子；ケイ素原子、酸素原子および窒素原子から選択される少なくとも一つの原子を含む置換基を有していてもよい炭素数１〜２０の炭化水素基；またはオキシシリル基を含む炭素数０〜２０の置換基；からなる群から選択される基であるが、少なくとも１つがオキシシリル基を含む炭素数０〜２０の置換基である必要がある。なお、Ｒ２とＲ３は互いに結合して環を形成していてもよい。 The repeating unit B represented by the formula (2) is a hydrogenation of at least a carbon-carbon double bond in the main chain of a repeating unit obtained by ring-opening polymerization of a compound represented by the formula (3) described later. Further, it is a repeating unit containing an oxysilyl group, which can be obtained by hydrogenating a carbon-carbon double bond existing outside the main chain as necessary. The substituents represented by R 1 to R 4 in Formula (2) each independently have a substituent containing at least one atom selected from a hydrogen atom; a halogen atom; a silicon atom, an oxygen atom, and a nitrogen atom. An optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substituent having 0 to 20 carbon atoms including an oxysilyl group; Must be ~ 20 substituents. R 2 and R 3 may be bonded to each other to form a ring.
式（２）においてＲ１〜Ｒ４として示される置換基となりうる、オキシシリル基を含む炭素数０〜２０の置換基は、ケイ素−酸素結合を含有する基であれば特に限定されず、例えば、アルコキシシリル基やアリーロキシシリル基などのヒドロカルビルオキシシリル基、シラノール基、シロキサン基やこれらの基を含有する炭素数０〜２０の基を挙げることができる。オキシシリル基を含む炭素数０〜２０の置換基として、特に好ましい基としては、ヒドロカルビルオキシシリル基および／またはシラノール基を含有する炭素数０〜２０の基を挙げることができ、そのなかでも下記の式（４）で表される基が特に好ましい。 The substituent having 0 to 20 carbon atoms including an oxysilyl group that can be a substituent represented by R 1 to R 4 in Formula (2) is not particularly limited as long as it is a group containing a silicon-oxygen bond. Examples thereof include hydrocarbyloxysilyl groups such as alkoxysilyl groups and aryloxysilyl groups, silanol groups, siloxane groups, and groups having 0 to 20 carbon atoms containing these groups. As a substituent having 0 to 20 carbon atoms including an oxysilyl group, particularly preferred groups include hydrocarbyloxysilyl groups and / or silanol groups having 0 to 20 carbon atoms. The group represented by the formula (4) is particularly preferable.
式（４）において、Ｒ９は単結合または炭素数１〜２０の２価の炭化水素基であればよいが、得られる重合体の他の材料との密着性を特に良好とする観点からは、炭素数１〜２０の２価の炭化水素基であることが好ましく、炭素数２〜９の２価の炭化水素基であることが特に好ましい。 In formula (4), R 9 may be a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, but from the viewpoint of particularly good adhesion to other materials of the resulting polymer. The divalent hydrocarbon group having 1 to 20 carbon atoms is preferable, and the divalent hydrocarbon group having 2 to 9 carbon atoms is particularly preferable.
式（２）においてＲ１〜Ｒ４として示される置換基となりうる、オキシシリル基を含む炭素数０〜２０の置換基以外の置換基は、水素原子；ハロゲン原子；ケイ素原子、酸素原子および窒素原子から選択される少なくとも一つの原子を含む置換基（但し、オキシシリル基を除く）を有していてもよい炭素数１〜２０の炭化水素基；からなる群から選択される基であればよいが、これらのなかでも、水素原子またはケイ素原子、酸素原子および窒素原子から選択される少なくとも一つの原子を含む置換基（但し、オキシシリル基を除く）を有していてもよい炭素数１〜２０の炭化水素基が好ましく、水素原子または炭素数１〜２０の炭化水素基がより好ましく、水素原子が最も好ましい。 Substituents other than the substituent having 0 to 20 carbon atoms including the oxysilyl group, which can be the substituents represented by R 1 to R 4 in Formula (2), are a hydrogen atom; a halogen atom; a silicon atom, an oxygen atom, and a nitrogen atom. A group selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (excluding an oxysilyl group) containing at least one atom selected from Of these, a hydrogen atom or a substituent containing at least one atom selected from a silicon atom, an oxygen atom and a nitrogen atom (excluding an oxysilyl group) optionally having 1 to 20 carbon atoms A hydrocarbon group is preferable, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms is more preferable, and a hydrogen atom is most preferable.
式（２）においてＲ１〜Ｒ４として示される置換基のうち、オキシシリル基を含む炭素数０〜２０の置換基の数は、１〜４個のいずれであってもよいが、単量体や重合体の合成を容易にする観点からは、１個または２個であることが好ましく、１個であることが特に好ましい。 Among the substituents represented by R 1 to R 4 in Formula (2), the number of the substituents having 0 to 20 carbon atoms including the oxysilyl group may be any one of 1 to 4, but the monomer From the viewpoint of facilitating the synthesis of the polymer, one or two is preferable, and one is particularly preferable.
式（２）におけるｎの数は０〜２の整数のいずれであってもよいが、単量体の合成容易性や得られる重合体の融点を適度なものとする観点からは、０または１であることが好ましく、０であることが特に好ましい。 The number of n in the formula (2) may be any integer from 0 to 2, but is 0 or 1 from the viewpoint of appropriate synthesis of the monomer and a suitable melting point of the polymer. Is preferable, and 0 is particularly preferable.
本発明の重合体における繰り返し単位Ｂの含有量は、全繰り返し単位に対して、０．０００１〜２モル％であることが必要であり、０．００１〜１．５モル％であることが好ましく、０．０１〜１．０モル％であることがより好ましい。繰り返し単位Ｂの含有量が少なすぎると、重合体の他の材料との密着性が不十分となるおそれがあり、繰り返し単位Ｂの含有量が多すぎると、重合体の耐熱性が不十分となるおそれある。なお、本発明の重合体は、繰り返し単位Ｂとして、１種の繰り返し単位のみを含むものであってもよいし、２種以上の繰り返し単位Ｂを含むものであってもよい。 The content of the repeating unit B in the polymer of the present invention is required to be 0.0001 to 2 mol%, preferably 0.001 to 1.5 mol%, based on all repeating units. More preferably, the content is 0.01 to 1.0 mol%. If the content of the repeating unit B is too small, the adhesion of the polymer to other materials may be insufficient, and if the content of the repeating unit B is too large, the heat resistance of the polymer is insufficient. There is a risk. The polymer of the present invention may contain only one type of repeating unit as the repeating unit B, or may contain two or more types of repeating unit B.
本発明の重合体は、繰り返し単位Ａおよび繰り返し単位Ｂのみからなるものであってよいが、繰り返し単位Ａおよび繰り返し単位Ｂの含有量が上記の範囲内となる限りにおいて、さらに他の繰り返し単位を含むものであってもよい。本発明の重合体に含有されうる繰り返し単位Ａおよび繰り返し単位Ｂ以外の繰り返し単位としては、ジシクロペンタジエンを開環重合することにより得られる繰り返し単位（全ての炭素−炭素二重結合が水素化されていないもの）、ジシクロペンタジエンを開環重合して得られる繰り返し単位の炭素−炭素二重結合の一部を水素化することにより得ることができる繰り返し単位、後述する式（３）で表される化合物を開環重合して得られる繰り返し単位（主鎖中の炭素−炭素二重結合が水素化されていないもの）、ジシクロペンタジエンおよび後述する式（３）で表される化合物以外の単量体に由来する繰り返し単位を挙げることができるが、これらに限定されるものではない。 The polymer of the present invention may be composed only of the repeating unit A and the repeating unit B. However, as long as the content of the repeating unit A and the repeating unit B is within the above range, other repeating units may be added. It may be included. The repeating units other than the repeating unit A and the repeating unit B that can be contained in the polymer of the present invention include repeating units obtained by ring-opening polymerization of dicyclopentadiene (all carbon-carbon double bonds are hydrogenated). A repeating unit obtainable by hydrogenating a part of the carbon-carbon double bond of the repeating unit obtained by ring-opening polymerization of dicyclopentadiene, represented by the formula (3) described later. A repeating unit obtained by ring-opening polymerization of a compound (one in which the carbon-carbon double bond in the main chain is not hydrogenated), dicyclopentadiene, and a compound other than the compound represented by formula (3) described later. Although the repeating unit derived from a monomer can be mentioned, it is not limited to these.
本発明の重合体における、繰り返し単位Ａおよび繰り返し単位Ｂ以外の繰り返し単位の含有量は、１．９９９９モル％以下であり、１．４９９モル％以下であることが好ましく、０．９９モル％以下であることがより好ましい。繰り返し単位Ａおよび繰り返し単位Ｂ以外の繰り返し単位の含有量が多すぎると、重合体の他の材料との密着性や耐熱性が不十分となるおそれある。 In the polymer of the present invention, the content of repeating units other than the repeating unit A and the repeating unit B is 1.9999 mol% or less, preferably 1.499 mol% or less, and preferably 0.99 mol% or less. It is more preferable that When there is too much content of repeating units other than the repeating unit A and the repeating unit B, there exists a possibility that adhesiveness and heat resistance with other materials of a polymer may become inadequate.
本発明の重合体における、各繰り返し単位の配列様式は、特に限定されず、ランダム、ブロック構造、テーパー構造などのいずれであってもよいが、繰り返し単位Ｂの含有量制御の観点からは、ランダムに各繰り返し単位が配列した構造を有することが好ましい。 The arrangement pattern of each repeating unit in the polymer of the present invention is not particularly limited and may be any of random, block structure, taper structure, etc., but from the viewpoint of controlling the content of repeating unit B, it is random. It is preferable to have a structure in which each repeating unit is arranged.
本発明の重合体の立体規則性の有無は、重合体が結晶性を有するものとなる限りにおいて特に限定されるものではないが、重合体に結晶性に付与して耐熱性に優れたものとする観点からは、立体規則性を有するものである（すなわち、アタクチック構造以外である）ことが好ましく、特にシンジオタクチック構造を有するものであることが好ましい。より具体的には、繰り返し単位Ａについてのラセモ・ダイアッドの割合が、６０％以上であることが好ましく、６５％以上であることがより好ましく、７０％以上であることが特に好ましい。繰り返し単位Ａについてのラセモ・ダイアッドの割合が高いものほど、すなわち、シンジオタクチック立体規則性の高いものほど、高い融点を有する耐熱性に優れた重合体となる。なお、重合体の繰り返し単位Ａについてのラセモ・ダイアッドの割合は、１３Ｃ−ＮＭＲスペクトル分析で測定し、定量することができる。具体的な定量の方法としては、オルトジクロロベンゼン−ｄ４を溶媒として、１５０℃でｉｎｖｅｒｓｅ−ｇａｔｅｄ ｄｅｃｏｕｐｌｉｎｇ法を適用して１３Ｃ−ＮＭＲ測定を行い、オルトジクロロベンゼン−ｄ４の１２７．５ｐｐｍのピークを基準シフトとして、メソ・ダイアッド由来の４３．３５ｐｐｍのシグナルと、ラセモ・ダイアッド由来の４３．４３ｐｐｍのシグナルの強度比からラセモ・ダイアッドの割合を決定する方法を挙げることができる。 The presence or absence of stereoregularity of the polymer of the present invention is not particularly limited as long as the polymer has crystallinity, but the polymer has crystallinity and is excellent in heat resistance. From this viewpoint, it is preferable to have stereoregularity (that is, other than an atactic structure), and it is particularly preferable to have a syndiotactic structure. More specifically, the ratio of the racemo dyad with respect to the repeating unit A is preferably 60% or more, more preferably 65% or more, and particularly preferably 70% or more. The higher the ratio of the racemo dyad for the repeating unit A, that is, the higher the syndiotactic stereoregularity, the higher the heat resistance polymer having the higher melting point. In addition, the ratio of the racemo dyad about the repeating unit A of a polymer can be measured and quantified by < 13 > C-NMR spectrum analysis. As a specific quantitative method, ortho-dichlorobenzene-d4 was used as a solvent and an inverse-gated decoupling method was applied at 150 ° C. to perform 13 C-NMR measurement, and a 127.5 ppm peak of orthodichlorobenzene-d4 was obtained. As a reference shift, a method of determining the ratio of racemo dyad from the intensity ratio of 43.35 ppm signal derived from meso dyad and 43.43 ppm signal derived from racemo dyad can be mentioned.
本発明の重合体は、結晶性を有するものであればよく、すなわち、常温（２３℃）を超える融点を有するものであればよい。但し、重合体の耐熱性を特に良好なものとする観点からは、２５０℃以上の融点を有するものであることが好ましく、２５５〜２９０℃の融点を有するものであることが好ましい。 The polymer of the present invention only needs to have crystallinity, that is, any polymer having a melting point exceeding normal temperature (23 ° C.). However, from the viewpoint of particularly improving the heat resistance of the polymer, the polymer preferably has a melting point of 250 ° C. or higher, and preferably has a melting point of 255 to 290 ° C.
本発明の重合体を得る方法は、結晶性を有する目的の構造の重合体が得られる方法である限りにおいて特に限定されるものではないが、以下に述べる本発明の重合体の製造方法が好適である。すなわち、本発明の重合体の製造方法は、重合触媒の存在下で、ジシクロペンタジエンおよび下記の式（３）で表される化合物を含んでなる単量体混合物を開環メタセシス重合した後、得られる開環重合体の炭素−炭素二重結合を水素化させる、重合体の製造方法である。 The method for obtaining the polymer of the present invention is not particularly limited as long as it is a method for obtaining a polymer having a target structure having crystallinity, but the method for producing the polymer of the present invention described below is preferred. It is. That is, in the method for producing a polymer of the present invention, after performing a ring-opening metathesis polymerization of a monomer mixture containing dicyclopentadiene and a compound represented by the following formula (3) in the presence of a polymerization catalyst, This is a method for producing a polymer, in which the carbon-carbon double bond of the obtained ring-opening polymer is hydrogenated.
本発明の重合体の製造方法で用いる単量体混合物は、最終的に目的とする重合体の繰り返し単位Ａを構成するための単量体として、ジシクロペンタジエンを含むものである。ジシクロペンタジエンには、エンド体およびエキソ体の立体異性体が存在するが、そのどちらも単量体として用いることが可能であり、一方の異性体を単独で用いてもよいし、エンド体およびエキソ体が任意の割合で存在する異性体混合物を用いることもできる。但し、最終的に得られる重合体の結晶性を高め、耐熱性を特に良好なものとする観点からは、一方の立体異性体の割合を高くすることが好ましく、例えば、エンド体またはエキソ体の割合が、８０％以上であることが好ましく、９０％以上であることがより好ましく、９５％以上であることが特に好ましい。なお、割合を高くする立体異性体は、合成容易性の観点から、エンド体であることが好ましい。 The monomer mixture used in the method for producing a polymer of the present invention contains dicyclopentadiene as a monomer for finally constituting the repeating unit A of the target polymer. In dicyclopentadiene, there are stereoisomers of endo and exo, both of which can be used as monomers, and either isomer may be used alone, or endo and It is also possible to use an isomer mixture in which an exo isomer is present in an arbitrary ratio. However, from the viewpoint of improving the crystallinity of the finally obtained polymer and making the heat resistance particularly good, it is preferable to increase the ratio of one stereoisomer, for example, an endo-form or an exo-form. The ratio is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. In addition, it is preferable that the stereoisomer which makes a ratio high is an end body from a viewpoint of synthetic | combination ease.
また、本発明の重合体の製造方法で用いる単量体混合物は、最終的に目的とする重合体の繰り返し単位Ｂを構成するための単量体として、式（３）で表される化合物を含むものである。式（３）においてＲ５〜Ｒ８として示される置換基は、式（２）においてＲ１〜Ｒ４として示される置換基と同様、それぞれ独立に、水素原子；ハロゲン原子；ケイ素原子、酸素原子および窒素原子から選択される少なくとも一つの原子を含む置換基を有していてもよい炭素数１〜２０の炭化水素基；またはオキシシリル基を含む炭素数０〜２０の置換基；からなる群から選択される基であるが、少なくとも１つがオキシシリル基を含む炭素数０〜２０の置換基である必要がある。なお、Ｒ６とＲ７は互いに結合して環を形成していてもよい。 In addition, the monomer mixture used in the method for producing a polymer of the present invention includes a compound represented by the formula (3) as a monomer for finally constituting the repeating unit B of the target polymer. Is included. The substituents represented by R 5 to R 8 in Formula (3) are each independently a hydrogen atom; a halogen atom; a silicon atom, an oxygen atom, as in the substituents represented by R 1 to R 4 in Formula (2). And a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent containing at least one atom selected from nitrogen atoms; or a substituent having 0 to 20 carbon atoms including an oxysilyl group; Although it is a group selected, it is necessary that at least one is a substituent having 0 to 20 carbon atoms including an oxysilyl group. R 6 and R 7 may be bonded to each other to form a ring.
式（３）においてＲ５〜Ｒ８として示される置換基として好ましい置換基は、式（２）においてＲ１〜Ｒ４として示される置換基として好ましい置換基として挙げたものと同様である。また、式（３）におけるｎの数は０〜２の整数のいずれであってもよいが、０または１であることが好ましく、０であることが特に好ましい。 Preferred substituents as substituents represented by R 5 to R 8 in formula (3) are the same as those exemplified as preferred substituents as substituents represented by R 1 to R 4 in formula (2). Moreover, although the number of n in Formula (3) may be any integer of 0 to 2, it is preferably 0 or 1, and particularly preferably 0.
式（３）で表される化合物の具体例としては、２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）エチルトリメトキシシラン、２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）メチルトリメトキシシラン、２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）メチルトリエトキシシラン、２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）メチルトリス（トリメチルシロキシ）シラン、４−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）フェニルトリメトキシシラン、２−［４−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）フェニル］エチルトリメトキシシラン、５−（トリメトキシシリルメトキシカルボニル）−ビシクロ［２．２．１］ヘプタ−２−エン、５−（３−ジメチルメトキシシリルプロポキシカルボニル）−ビシクロ［２．２．１］ヘプタ−２−エン、５−メチル−５−（３−ジメチルメトキシシリルプロポキシカルボニル）−ビシクロ［２．２．１］ヘプタ−２−エン、（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）トリメトキシシラン、（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）トリエトキシシラン、５，６−ジ（トリエトキシシリル）−ビシクロ［２．２．１］ヘプタ−５−エンを挙げることができる。なお、式（３）で表される化合物は、１種を単独で用いてもよいし、２種以上を組み合わせて用いることもできる。 Specific examples of the compound represented by the formula (3) include 2- (bicyclo [2.2.1] hept-5-en-2-yl) ethyltrimethoxysilane, 2- (bicyclo [2.2. 1] Hept-5-en-2-yl) methyltrimethoxysilane, 2- (bicyclo [2.2.1] hept-5-en-2-yl) methyltriethoxysilane, 2- (bicyclo [2. 2.1] hept-5-en-2-yl) methyltris (trimethylsiloxy) silane, 4- (bicyclo [2.2.1] hept-5-en-2-yl) phenyltrimethoxysilane, 2- [ 4- (bicyclo [2.2.1] hept-5-en-2-yl) phenyl] ethyltrimethoxysilane, 5- (trimethoxysilylmethoxycarbonyl) -bicyclo [2.2.1] hept-2- En, 5- (3-di Tilmethoxysilylpropoxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (3-dimethylmethoxysilylpropoxycarbonyl) -bicyclo [2.2.1] hept-2-ene , (Bicyclo [2.2.1] hept-5-en-2-yl) trimethoxysilane, (bicyclo [2.2.1] hept-5-en-2-yl) triethoxysilane, 5,6 Mention may be made of -di (triethoxysilyl) -bicyclo [2.2.1] hept-5-ene. In addition, the compound represented by Formula (3) may be used individually by 1 type, and can also be used in combination of 2 or more type.
本発明の重合体の製造方法では、本発明を逸脱しない範囲において、単量体混合物に、ジシクロペンタジエンおよび式（３）で表される化合物以外の単量体を含ませてもよい。ジシクロペンタジエンおよび式（３）で表される化合物以外の単量体としては、オキシシリル基を含まないノルボルネン系化合物、モノ環状オレフィン、および環状ジエン、ならびにこれらの誘導体を挙げることができる。 In the method for producing a polymer of the present invention, a monomer other than dicyclopentadiene and the compound represented by the formula (3) may be included in the monomer mixture without departing from the present invention. Examples of monomers other than dicyclopentadiene and the compound represented by formula (3) include norbornene compounds not containing an oxysilyl group, monocyclic olefins, cyclic dienes, and derivatives thereof.
本発明の重合体の製造方法で用いる単量体混合物における各単量体の組成比は、目的とする重合体の各繰り返し単位の組成比に応じて決定すればよい。 What is necessary is just to determine the composition ratio of each monomer in the monomer mixture used with the manufacturing method of the polymer of this invention according to the composition ratio of each repeating unit of the target polymer.
本発明の重合体の製造方法で用いる重合触媒は、ジシクロペンタジエンおよび式（３）で表される化合物を開環共重合させることができるものであって、最終的に目的とする重合体に結晶性を付与できるものであれば、特に限定されない。但し、最終的に目的とする重合体の耐熱性を特に良好なものとする観点からは、開環重合体にシンジオタクチック立体規則性を与えることができる重合触媒を用いることが好ましく、なかでも、下記の式（５）で表される金属化合物を含んでなる重合触媒が好適である。 The polymerization catalyst used in the method for producing a polymer of the present invention is capable of ring-opening copolymerization of dicyclopentadiene and the compound represented by the formula (3), and finally forms a target polymer. There is no particular limitation as long as crystallinity can be imparted. However, it is preferable to use a polymerization catalyst that can give syndiotactic stereoregularity to the ring-opening polymer from the viewpoint of particularly improving the heat resistance of the final polymer. A polymerization catalyst comprising a metal compound represented by the following formula (5) is preferred.
Ｍ（ＮＲ１２）Ｘ４−ａ（ＯＲ１３）ａ・Ｌｂ （５）
（式（５）中、Ｍは周期律表第６族の遷移金属原子から選択される金属原子であり、Ｒ１２は３，４，５位の少なくとも１つの位置に置換基を有していてもよいフェニル基、または−ＣＨ２Ｒ１４で表される基であり、Ｒ１３は置換基を有していてもよいアルキル基および置換基を有していてもよいアリール基から選択される基であり、Ｘはハロゲン原子、アルキル基、アリール基およびアルキルシリル基から選択される基であり、Ｌは電子供与性の中性配位子であり、ａは０または１であり、ｂは０〜２の整数である。Ｒ１４は水素原子、置換基を有していてもよいアルキル基および置換基を有していてもよいアリール基から選択される基である。）
M (NR 12 ) X 4-a (OR 13 ) a · L b (5)
(In the formula (5), M is a metal atom selected from group 6 transition metal atoms in the periodic table, and R 12 has a substituent at at least one of the 3, 4, and 5 positions. Or a group represented by —CH 2 R 14 , wherein R 13 is a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent. X is a group selected from a halogen atom, an alkyl group, an aryl group and an alkylsilyl group, L is an electron-donating neutral ligand, a is 0 or 1, and b is 0 And R 14 is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.
式（５）で表される金属化合物を構成する金属原子（式（５）中のＭ）は、周期律表第６族の遷移金属原子（クロム、モリブデン、タングステン）から選択される。なかでも、モリブデンまたはタングステンが好適に用いられ、タングステンが特に好適に用いられる。 The metal atom (M in formula (5)) constituting the metal compound represented by formula (5) is selected from group 6 transition metal atoms (chromium, molybdenum, tungsten) in the periodic table. Among these, molybdenum or tungsten is preferably used, and tungsten is particularly preferably used.
式（５）で表される金属化合物は、金属イミド結合を含んでなるものである。金属イミド結合を構成する窒素原子上の置換基（式（５）中のＲ１２）は、３，４，５位の少なくとも１つの位置に置換基を有していてもよいフェニル基、または−ＣＨ２Ｒ１４（但し、Ｒ１４は水素原子、置換基を有していてもよいアルキル基および置換基を有していてもよいアリール基から選択される基である。）で表される基である。３，４，５位の少なくとも１つの位置に置換基を有していてもよいフェニル基が有しうる置換基としては、メチル基、エチル基などのアルキル基；フッ素原子、塩素原子、臭素原子などのハロゲン原子；メトキシ基、エトキシ基、イソプロポキシ基などのアルコキシ基；などが挙げられ、さらに、３，４，５位の少なくとも２つの位置に存在する置換基が互いに結合したものであってもよい。３，４，５位の少なくとも１つの位置に置換基を有していてもよいフェニル基の具体例としては、無置換フェニル基や、４−メチルフェニル基、４−クロロフェニル基、３−メトキシフェニル基、４−シクロヘキシルフェニル基、４−メトキシフェニル基などの一置換フェニル基；３，５−ジメチルフェニル基、３，５−ジクロロフェニル基、３，４−ジメチルフェニル基、３，５−ジメトキシフェニル基などの二置換フェニル基；３，４，５−トリメチルフェニル基、３，４，５−トリクロロフェニル基などの三置換フェニル基；２−ナフチル基、３−メチル−２−ナフチル基、４−メチル−２−ナフチル基などの置換基を有していてもよい２−ナフチル基；を挙げることができる。 The metal compound represented by the formula (5) includes a metal imide bond. The substituent on the nitrogen atom constituting the metal imide bond (R 12 in the formula (5)) is a phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions, or- A group represented by CH 2 R 14 (wherein R 14 is a group selected from a hydrogen atom, an alkyl group which may have a substituent and an aryl group which may have a substituent); It is. Examples of the substituent that the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an alkyl group such as a methyl group and an ethyl group; a fluorine atom, a chlorine atom, and a bromine atom A halogen atom such as; an alkoxy group such as a methoxy group, an ethoxy group, and an isopropoxy group; and the like, and further, substituents present in at least two positions of the 3, 4, and 5 positions are bonded to each other. Also good. Specific examples of the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an unsubstituted phenyl group, a 4-methylphenyl group, a 4-chlorophenyl group, and 3-methoxyphenyl. Groups, monosubstituted phenyl groups such as 4-cyclohexylphenyl group, 4-methoxyphenyl group; 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group, 3,5-dimethoxyphenyl group Disubstituted phenyl groups such as 3,4,5-trimethylphenyl groups, 3,4,5-trichlorophenyl groups and the like; 2-naphthyl groups, 3-methyl-2-naphthyl groups, 4-methyl 2-naphthyl group which may have a substituent such as a 2-naphthyl group;
式（５）で表される金属化合物において、窒素原子上の置換基（式（５）中のＲ１２）として用いられ得る、−ＣＨ２Ｒ１４で表される基において、Ｒ１４は水素原子、置換基を有していてもよいアルキル基および置換基を有していてもよいアリール基から選択される基を表す。このＲ１４で表される基となり得る、置換基を有していてもよいアルキル基の炭素数は、特に限定されないが、通常１〜２０、好ましくは１〜１０である。また、このアルキル基は直鎖状であっても分岐状であってもよい。このアルキル基が有し得る置換基は、特に限定されないが、例えば、フェニル基、４−メチルフェニル基などの置換基を有していてもよいフェニル基；メトキシ基、エトキシ基などのアルコキシル基；を挙げることができる。 In the metal compound represented by the formula (5), in the group represented by —CH 2 R 14 that can be used as a substituent on the nitrogen atom (R 12 in the formula (5)), R 14 is a hydrogen atom. Represents a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent. The number of carbon atoms of the alkyl group which may be a substituent and can be a group represented by R 14 is not particularly limited, but is usually 1 to 20, preferably 1 to 10. The alkyl group may be linear or branched. Although the substituent which this alkyl group may have is not specifically limited, For example, the phenyl group which may have substituents, such as a phenyl group and 4-methylphenyl group; Alkoxyl groups, such as a methoxy group and an ethoxy group; Can be mentioned.
式（５）で表される金属化合物において、窒素原子上の置換基（式（５）中のＲ１２）として用いられ得る、置換基を有していてもよいアリール基としては、フェニル基、１−ナフチル基、２−ナフチル基、およびこれらの基の水素原子が他の置換基に置き換わってなるアリール基などが挙げられる。また、このアリール基の置換基としては、特に限定されないが、例えば、フェニル基、４−メチルフェニル基などの置換基を有していてもよいフェニル基；メトキシ基、エトキシ基などのアルコキシル基；を挙げることができる。 In the metal compound represented by the formula (5), an aryl group which may be used as a substituent on the nitrogen atom (R 12 in the formula (5)) and may have a substituent includes a phenyl group, Examples include 1-naphthyl group, 2-naphthyl group, and aryl groups in which hydrogen atoms of these groups are replaced with other substituents. Further, the substituent of this aryl group is not particularly limited, but for example, a phenyl group which may have a substituent such as a phenyl group or a 4-methylphenyl group; an alkoxyl group such as a methoxy group or an ethoxy group; Can be mentioned.
Ｒ１４で表される基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基などの炭素数が１〜２０のアルキル基が特に好適に用いられる。 The group represented by R 14 has 1 carbon number such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and decyl group. ˜20 alkyl groups are particularly preferably used.
式（５）で表される金属化合物は、ハロゲン原子、アルキル基、アリール基およびアルキルシリル基から選択される基を３個または４個有してなる。すなわち、式（５）において、Ｘは、ハロゲン原子、アルキル基、アリール基およびアルキルシリル基から選択される基を表す。なお、式（５）で表される金属化合物においてＸで表される基が２以上あるとき、それらの基は互いに結合していてもよい。 The metal compound represented by the formula (5) has 3 or 4 groups selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. That is, in the formula (5), X represents a group selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. In addition, when there are two or more groups represented by X in the metal compound represented by the formula (5), these groups may be bonded to each other.
Ｘで表される基となり得るハロゲン原子としては、塩素原子、臭素原子、ヨウ素原子が挙げられる。また、アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ネオペンチル基、ベンジル基、ネオフィル基などが挙げられる。アリール基としては、フェニル基、４−メチルフェニル基、２，６−ジメチルフェニル基、１−ナフチル基、２−ナフチル基などが挙げられる。アルキルシリル基としては、トリメチルシリル基、トリエチルシリル基、ｔ−ブチルジメチルシリル基などが挙げられる。 Examples of the halogen atom that can be a group represented by X include a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a benzyl group, and a neophyll group. Examples of the aryl group include a phenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group.
式（５）で表される金属化合物は、１個の金属アルコキシド結合または１個の金属アリールオキシド結合を有するものであってもよい。この金属アルコキシド結合または金属アリールオキシド結合を構成する酸素原子上の置換基（式（５）中のＲ１３）は、置換基を有していてもよいアルキル基および置換基を有していてもよいアリール基から選択される基である。このＲ１３で表される基となり得る、置換基を有していてもよいアルキル基や置換基を有していてもよいアリール基としては、前述のＲ１４で表される基におけるものと同様のものを用いることができる。 The metal compound represented by the formula (5) may have one metal alkoxide bond or one metal aryloxide bond. The substituent on the oxygen atom constituting this metal alkoxide bond or metal aryloxide bond (R 13 in formula (5)) may have an alkyl group which may have a substituent and a substituent. It is a group selected from good aryl groups. The alkyl group which may have a substituent and the aryl group which may have a substituent which can be a group represented by R 13 are the same as those in the group represented by R 14 described above. Can be used.
式（５）で表される金属化合物は、１個または２個の電子供与性の中性配位子を有するものであってもよい。この電子供与性の中性配位子（式（５）中のＬ）としては、例えば、周期律表第１４族または第１５族の原子を含有する電子供与性化合物が挙げられる。その具体例としては、トリメチルホスフィン、トリイソプロピルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィンなどのホスフィン類；ジエチルエーテル、ジブチルエーテル、１，２−ジメトキシエタン、テトラヒドロフランなどのエーテル類；トリメチルアミン、トリエチルアミン、ピリジン、ルチジンなどのアミン類；を挙げることができる。これらの中でも、エーテル類が特に好適に用いられる。 The metal compound represented by the formula (5) may have one or two electron-donating neutral ligands. Examples of the electron-donating neutral ligand (L in the formula (5)) include an electron-donating compound containing an atom of Group 14 or Group 15 of the periodic table. Specific examples thereof include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; trimethylamine, triethylamine, pyridine, And amines such as lutidine; Among these, ethers are particularly preferably used.
本発明の重合体の製造方法で用いる重合触媒として、特に好適に用いられる式（５）で表される金属化合物としては、フェニルイミド基を有するタングステン化合物（式（５）中のＭがタングステン原子で、かつ、Ｒ１２がフェニル基である化合物）を挙げることができ、その中でも、テトラクロロタングステンフェニルイミド（テトラヒドロフラン）錯体が特に好適である。 As a polymerization catalyst used in the method for producing a polymer of the present invention, a metal compound represented by the formula (5) which is particularly preferably used includes a tungsten compound having a phenylimide group (M in the formula (5) is a tungsten atom). And a compound in which R 12 is a phenyl group). Among them, a tetrachlorotungsten phenylimide (tetrahydrofuran) complex is particularly preferable.
式（５）で表される金属化合物は、第６族遷移金属のオキシハロゲン化物と、３，４，５位の少なくとも１つの位置に置換基を有していてもよいフェニルイソシアナート類、または一置換メチルイソシアナート類と、電子供与性の中性配位子（Ｌ）、および必要に応じてアルコール類、金属アルコキシド、金属アリールオキシドを混合することなど（例えば、特開平５−３４５８１７号公報に記載された方法）により合成することができる。合成された式（５）で表される金属化合物は、結晶化などにより精製・単離したものを用いてもよいし、精製することなく、触媒合成溶液をそのまま重合触媒として使用することもできる。 The metal compound represented by the formula (5) includes an oxyhalide of a Group 6 transition metal and phenyl isocyanates optionally having a substituent at at least one of the 3, 4, and 5 positions, or Mixing monosubstituted methyl isocyanates with an electron-donating neutral ligand (L) and, if necessary, alcohols, metal alkoxides, metal aryloxides (for example, JP-A-5-345817) Can be synthesized by the method described in 1). The synthesized metal compound represented by the formula (5) may be purified and isolated by crystallization or the like, or the catalyst synthesis solution can be used as a polymerization catalyst as it is without purification. .
重合触媒として用いる式（５）で表される金属化合物の使用量は、（金属化合物：用いる単量体全体）のモル比が、通常１：１００〜１：２，０００，０００、好ましくは１：５００〜１，０００，０００、より好ましくは１：１，０００〜１：５００，０００でとなる量で用いる。触媒量が多すぎると触媒除去が困難となるおそれがあり、少なすぎると十分な重合活性が得られない場合がある。 The amount of the metal compound represented by the formula (5) used as the polymerization catalyst is such that the molar ratio of (metal compound: whole monomer used) is usually from 1: 100 to 1: 2,000,000, preferably 1. : 500 to 1,000,000, more preferably 1: 1,000 to 1: 500,000. If the amount of catalyst is too large, it may be difficult to remove the catalyst. If the amount is too small, sufficient polymerization activity may not be obtained.
式（５）で表される金属化合物を重合触媒として用いるにあたっては、式（５）で表される金属化合物を単独で使用することもできるが、重合活性を高くする観点からは式（５）で表される金属化合物と有機金属還元剤とを併用することが好ましい。用いられ得る有機金属還元剤としては、炭素数１〜２０の炭化水素基を有する周期律表第１、２、１２、１３、１４族の有機金属化合物を挙げることができる。その中でも、有機リチウム、有機マグネシウム、有機亜鉛、有機アルミニウム、または有機スズが好ましく用いられ、有機アルミニウムまたは有機スズが特に好ましく用いられる。有機リチウムとしては、ｎ−ブチルリチウム、メチルリチウム、フェニルリチウムなどを挙げることができる。有機マグネシウムとしては、ブチルエチルマグネシウム、ブチルオクチルマグネシウム、ジヘキシルマグネシウム、エチルマグネシウムクロリド、ｎ−ブチルマグネシウムクロリド、アリルマグネシウムブロミドなどを挙げることができる。有機亜鉛としては、ジメチル亜鉛、ジエチル亜鉛、ジフェニル亜鉛などを挙げることができる。有機アルミニウムとしては、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、ジエチルアルミニウムクロリド、エチルアルミニウムセスキクロリド、エチルアルミニウムジクロリド、ジエチルアルミニウムエトキシド、ジイソブチルアルミニウムイソブトキシド、エチルアルミニウムジエトキシド、イソブチルアルミニウムジイソブトキシドなどを挙げることができる。有機スズとしては、テトラメチルスズ、テトラ（ｎ−ブチル）スズ、テトラフェニルスズなどを挙げることができる。有機金属還元剤の使用量は、式（５）で表される金属化合物に対して、０．１〜１００モル倍が好ましく、０．２〜５０モル倍がより好ましく、０．５〜２０モル倍が特に好ましい。使用量が少なすぎると重合活性が向上しない場合があり、多すぎると副反応が起こりやすくなるおそれがある。 In using the metal compound represented by the formula (5) as a polymerization catalyst, the metal compound represented by the formula (5) can be used alone, but from the viewpoint of increasing the polymerization activity, the formula (5) It is preferable to use together the metal compound represented by these, and an organometallic reducing agent. Examples of the organometallic reducing agent that can be used include organometallic compounds of Groups 1, 2, 12, 13, and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Among these, organic lithium, organic magnesium, organic zinc, organic aluminum, or organic tin is preferably used, and organic aluminum or organic tin is particularly preferably used. Examples of the organic lithium include n-butyl lithium, methyl lithium, and phenyl lithium. Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, and allylmagnesium bromide. Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutylaluminum isobutoxide, ethylaluminum diethoxide, isobutylaluminum diisobutoxide, etc. Can be mentioned. Examples of the organic tin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin. The amount of the organometallic reducing agent used is preferably 0.1 to 100 moles, more preferably 0.2 to 50 moles, and 0.5 to 20 moles relative to the metal compound represented by the formula (5). Double is particularly preferred. If the amount used is too small, the polymerization activity may not be improved, and if it is too much, side reactions may easily occur.
開環重合体を得るための重合反応は、通常、有機溶媒中で行う。用いる有機溶媒は、生じる開環重合体やその水素添加物が所定の条件で溶解もしくは分散させることが可能であり、重合反応や水素化反応を阻害しないものであれば、特に限定されない。有機溶媒の具体例としては、ペンタン、ヘキサン、ヘプタンなどの脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、トリメチルシクロヘキサン、エチルシクロヘキサン、ジエチルシクロヘキサン、デカヒドロナフタレン、ビシクロヘプタン、トリシクロデカン、ヘキサヒドロインデン、シクロオクタンなどの脂環族炭化水素；ベンゼン、トルエン、キシレンなどの芳香族炭化水素；ジクロロメタン、クロロホルム、１，２−ジクロロエタンなどのハロゲン系脂肪族炭化水素；クロロベンゼン、ジクロロベンゼンなどのハロゲン系芳香族炭化水素；ニトロメタン、ニトロベンゼン、アセトニトリルなどの含窒素炭化水素系溶媒；ジエチルエ−テル、テトラヒドロフランなどのエ−テル類；またはこれらの混合溶媒を挙げることができる。これらの溶媒の中でも、芳香族炭化水素、脂肪族炭化水素、脂環族炭化水素、エーテル類が好ましく用いられる。 The polymerization reaction for obtaining the ring-opened polymer is usually carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as the resulting ring-opening polymer or a hydrogenated product thereof can be dissolved or dispersed under predetermined conditions and does not inhibit the polymerization reaction or the hydrogenation reaction. Specific examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclodecane. , Hexahydroindene, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; dichloromethane, chloroform, 1,2-dichloroethane and other halogenated aliphatic hydrocarbons; chlorobenzene, dichlorobenzene, etc. Halogen-containing aromatic hydrocarbons; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; Others can be mixtures of these solvents. Among these solvents, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers are preferably used.
開環重合反応は、単量体混合物と、式（５）で表される金属化合物と、必要に応じて有機金属還元剤とを混合することにより開始することができる。これらの成分を添加する順序は、特に限定されない。例えば、単量体混合物に式（５）で表される金属化合物と有機金属還元剤との混合物を添加して混合してもよいし、有機金属還元剤に単量体混合物と式（５）で表される金属化合物との混合物を添加して混合してもよく、また、単量体混合物と有機金属還元剤との混合物に式（５）で表される金属化合物を添加して混合してもよい。また、各成分を混合するにあたっては、それぞれの成分の全量を一度に添加してもよいし、複数回に分けて添加してもよく、比較的に長い時間（例えば１分間以上）にわたって連続的に添加することもできる。 The ring-opening polymerization reaction can be started by mixing the monomer mixture, the metal compound represented by the formula (5), and, if necessary, an organometallic reducing agent. The order in which these components are added is not particularly limited. For example, a mixture of a metal compound represented by formula (5) and an organometallic reducing agent may be added to and mixed with the monomer mixture, or the monomer mixture and formula (5) may be added to the organometallic reducing agent. A mixture with a metal compound represented by the formula (5) may be added and mixed, or a metal compound represented by formula (5) may be added to and mixed with a mixture of the monomer mixture and the organometallic reducing agent. May be. Moreover, when mixing each component, the whole quantity of each component may be added at once, may be added in multiple times, and it is continuous over a comparatively long time (for example, 1 minute or more). It can also be added.
有機溶媒中の重合反応時における単量体混合物の濃度は、特に限定されないが、１〜５０重量％であることが好ましく、２〜４５重量％であることがより好ましく、３〜４０重量％が特に好ましい。単量体混合物の濃度が低すぎると重合体の生産性が悪くなるおそれがあり、高すぎる場合は重合後の溶液粘度が高すぎて、その後の水素化反応が困難となる場合がある。 The concentration of the monomer mixture during the polymerization reaction in the organic solvent is not particularly limited, but is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and 3 to 40% by weight. Particularly preferred. If the concentration of the monomer mixture is too low, the productivity of the polymer may be deteriorated. If it is too high, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction may be difficult.
重合反応系には、活性調整剤を添加してもよい。活性調整剤は、重合触媒の安定化、重合反応の速度および重合体の分子量分布を調整する目的で使用することができる。活性調整剤は、官能基を有する有機化合物であれば特に制限されないが、含酸素、含窒素、含りん有機化合物が好ましい。具体的には、ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、アニソール、フラン、テトラヒドロフランなどのエーテル類；アセトン、ベンゾフェノン、シクロヘキサノンなどのケトン類；エチルアセテートなどのエステル類；アセトニトリルベンゾニトリルなどのニトリル類；トリエチルアミン、トリイソプロピルアミン、キヌクリジン、Ｎ，Ｎ−ジエチルアニリンなどのアミン類；ピリジン、２，４−ルチジン、２，６−ルチジン、２−ｔ−ブチルピリジンなどのピリジン類；トリフェニルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフェ−ト、トリメチルホスフェ−トなどのホスフィン類；トリフェニルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフェ−ト、トリメチルホスフェ−トなどのホスフィン類；トリフェニルホスフィンオキシドなどのホスフィンオキシド類；などが挙げられるが、これらに限定されない。これらの活性調整剤は、１種を単独で、または２種以上を混合して用いることができる。添加する活性調整剤の量は、特に限定されないが、通常、重合触媒として用いる金属化合物に対して０．０１〜１００モル％の間で選択すればよい。 An activity regulator may be added to the polymerization reaction system. The activity adjusting agent can be used for the purpose of stabilizing the polymerization catalyst, adjusting the polymerization reaction rate and the molecular weight distribution of the polymer. The activity regulator is not particularly limited as long as it is an organic compound having a functional group, but is preferably an oxygen-containing, nitrogen-containing, or phosphorus-containing organic compound. Specifically, ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, furan and tetrahydrofuran; ketones such as acetone, benzophenone and cyclohexanone; esters such as ethyl acetate; nitriles such as acetonitrile benzonitrile; triethylamine , Triisopropylamine, quinuclidine, amines such as N, N-diethylaniline; pyridines such as pyridine, 2,4-lutidine, 2,6-lutidine, 2-t-butylpyridine; triphenylphosphine, tricyclohexylphosphine Phosphines such as triphenyl phosphate and trimethyl phosphate; triphenyl phosphine, tricyclohexyl phosphine, triphenyl phosphate, trimethyl phosphate - phosphines such as preparative; phosphine oxides such as triphenylphosphine oxide; but like, but not limited to. These activity regulators can be used singly or in combination of two or more. The amount of the activity regulator to be added is not particularly limited, but it is usually selected from 0.01 to 100 mol% with respect to the metal compound used as the polymerization catalyst.
また、重合反応系には、開環重合体の分子量を調整するために分子量調整剤を添加してもよい。分子量調整剤としては、１−ブテン、１−ペンテン、１−ヘキセン、１−オクテンなどのα−オレフィン類；スチレン、ビニルトルエンなどの芳香族ビニル化合物；エチルビニルエーテル、イソブチルビニルエーテル、アリルグリシジルエーテル、酢酸アリル、アリルアルコール、グリシジルメタクリレートなどの酸素含有ビニル化合物；アリルクロライドなどのハロゲン含有ビニル化合物；アクリルアミドなどの窒素含有ビニル化合物；１，4−ペンタジエン、１，４−ヘキサジエン、１，５−ヘキサジエン、１，６−ヘプタジエン、２−メチル−１，４−ペンタジエン、２，５−ジメチル−１，５−ヘキサジエンなどの非共役ジエン；１，３−ブタジエン、２−メチル−１，３−ブタジエン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、１，３−ヘキサジエンなどの共役ジエン；を挙げることができる。添加する分子量調整剤の量は目的とする分子量に応じて決定すればよいが、通常、用いる単量体混合物に対して、０．１〜５０モル％の範囲で選択すればよい。 Further, a molecular weight modifier may be added to the polymerization reaction system in order to adjust the molecular weight of the ring-opening polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, acetic acid Oxygen-containing vinyl compounds such as allyl, allyl alcohol, and glycidyl methacrylate; halogen-containing vinyl compounds such as allyl chloride; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1 , 6-heptadiene, 2-methyl-1,4-pentadiene, non-conjugated dienes such as 2,5-dimethyl-1,5-hexadiene; 1,3-butadiene, 2-methyl-1,3-butadiene, 2, 3-dimethyl-1,3-butadiene, 1, - pentadiene, a conjugated diene such as 1,3-hexadiene; can be mentioned. The amount of the molecular weight modifier to be added may be determined according to the target molecular weight, but is usually selected in the range of 0.1 to 50 mol% with respect to the monomer mixture used.
重合温度は特に制限はないが、通常、−７８℃〜＋２００℃の範囲であり、好ましくは−３０℃〜＋１８０℃の範囲である。重合時間は、特に制限はなく、反応規模にも依存するが、通常１分間から１０００時間の範囲である。 Although there is no restriction | limiting in particular in superposition | polymerization temperature, Usually, it is the range of -78 degreeC-+200 degreeC, Preferably it is the range of -30 degreeC-+180 degreeC. The polymerization time is not particularly limited and depends on the reaction scale, but is usually in the range of 1 minute to 1000 hours.
上述したような式（５）で表される金属化合物を含む開環重合触媒を用いて、上述したような条件で単量体混合物の開環重合反応を行うことにより、シンジオタクチック立体規則性を有する開環共重合体を得ることができる。水素化反応で開環共重合体のタクチシチーが変化することはないので、このシンジオタクチック立体規則性を有する開環共重合体を水素化反応に供することにより、シンジオタクチック立体規則性を有することに基づいて結晶性を有する、開環共重合体水素化物である目的の重合体を得ることができる。なお、開環重共合体のシンジオタクチック立体規則性の度合いは、重合触媒の種類を選択することなどにより、調節することが可能である。 By using the ring-opening polymerization catalyst containing the metal compound represented by the formula (5) as described above, the ring-opening polymerization reaction of the monomer mixture is performed under the conditions as described above, thereby syndiotactic stereoregularity. A ring-opening copolymer having can be obtained. Since the tacticity of the ring-opening copolymer does not change in the hydrogenation reaction, the ring-opening copolymer having syndiotactic stereoregularity is subjected to a hydrogenation reaction, thereby having syndiotactic stereoregularity. Based on the above, it is possible to obtain a target polymer which is a hydride of a ring-opening copolymer having crystallinity. Note that the degree of syndiotactic stereoregularity of the ring-opening heavy copolymer can be adjusted by selecting the type of polymerization catalyst.
水素化反応に供する開環共重合体のゲルパーミエーションクロマトグラフィーにより測定される重量平均分子量（Ｍｗ）は、特に限定されないが、ポリスチレン換算で１０，０００〜１００，０００であることが好ましく、１５，０００〜８０，０００であることがより好ましい。このような重量平均分子量を有する開環共重合体を水素化反応に供することによって、特に成形加工性と耐熱性とのバランスに優れた重合体を得ることができる。開環共重合体の重量平均分子量は、重合時に用いる分子量調整剤の添加量などを調節することにより、調節することができる。 The weight average molecular weight (Mw) measured by gel permeation chromatography of the ring-opening copolymer subjected to the hydrogenation reaction is not particularly limited, but is preferably 10,000 to 100,000 in terms of polystyrene. More preferably, it is 8,000-80,000. By subjecting the ring-opening copolymer having such a weight average molecular weight to a hydrogenation reaction, a polymer having an excellent balance between molding processability and heat resistance can be obtained. The weight average molecular weight of the ring-opening copolymer can be adjusted by adjusting the amount of the molecular weight modifier used during polymerization.
水素化反応に供する開環共重合体の分子量分布〔ゲルパーミエーションクロマトグラフィーにより測定したポリスチレン換算の数平均分子量と重量平均分子量との比（Ｍｗ／Ｍｎ）〕は、特に限定されないが、通常１．５〜４．０であり、好ましくは１．６〜３．５である。このような分子量分布を有する開環共重合体を水素化反応に供することによって、特に成形加工性に優れた重合体を得ることができる。開環共重合体の分子量分布は、重合反応時における単量体混合物の添加方法や単量体混合物の濃度により、調節することができる。 The molecular weight distribution of the ring-opening copolymer to be subjected to the hydrogenation reaction [ratio of number average molecular weight in terms of polystyrene and weight average molecular weight (Mw / Mn) measured by gel permeation chromatography] is not particularly limited, but is usually 1 0.5 to 4.0, preferably 1.6 to 3.5. By subjecting the ring-opening copolymer having such a molecular weight distribution to a hydrogenation reaction, a polymer particularly excellent in molding processability can be obtained. The molecular weight distribution of the ring-opening copolymer can be adjusted by the addition method of the monomer mixture and the concentration of the monomer mixture during the polymerization reaction.
開環共重合体の水素化反応（重合体主鎖中およびジシクロペンタジエンに由来する繰り返し単位中に存在する二重結合の水素化）は、水素化触媒の存在下で、反応系内に水素を供給することにより行うことができる。水素化触媒としては、オレフィン化合物の水素化に際して一般に使用されているものであれば使用可能であり、特に制限されないが、例えば、次のようなものが挙げられる。 The hydrogenation reaction of the ring-opening copolymer (hydrogenation of double bonds existing in the polymer main chain and in the repeating unit derived from dicyclopentadiene) is carried out in the reaction system in the presence of a hydrogenation catalyst. This can be done by supplying Any hydrogenation catalyst can be used as long as it is generally used in the hydrogenation of olefin compounds, and is not particularly limited. Examples thereof include the following.
均一系触媒としては、遷移金属化合物とアルカリ金属化合物の組み合わせからなる触媒系、例えば、酢酸コバルト／トリエチルアルミニウム、ニッケルアセチルアセトナート／トリイソブチルアルミニウム、チタノセンジクロリド／ｎ−ブチルリチウム、ジルコノセンジクロリド／ｓｅｃ−ブチルリチウム、テトラブトキシチタネート／ジメチルマグネシウムなどの組み合わせが挙げられる。さらに、ジクロロビス(トリフェニルホスフィン）パラジウム、クロロヒドリドカルボニルトリス（トリフェニルホスフィン）ルテニウム、ビス（トリシクロヘキシルホスフィン）ベンジリジンルテニウム（ＩＶ）ジクロリド、クロロトリス（トリフェニルホスフィン）ロジウムなどの貴金属錯体触媒を挙げることができる。 As the homogeneous catalyst, a catalyst system comprising a combination of a transition metal compound and an alkali metal compound, such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec- Examples include butyl lithium, tetrabutoxy titanate / dimethyl magnesium, and the like. Further, mention may be made of noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride, chlorotris (triphenylphosphine) rhodium. Can do.
不均一触媒としては、ニッケル、パラジウム、白金、ロジウム、ルテニウム、またはこれらの金属をカーボン、シリカ、ケイソウ土、アルミナ、酸化チタンなどの担体に担持させた固体触媒、例えば、ニッケル／シリカ、ニッケル／ケイソウ土、ニッケル／アルミナ、パラジウム／カーボン、パラジウム／シリカ、パラジウム／ケイソウ土、パラジウム／アルミナなどの触媒系が挙げられる。 As the heterogeneous catalyst, nickel, palladium, platinum, rhodium, ruthenium, or a solid catalyst in which these metals are supported on a support such as carbon, silica, diatomaceous earth, alumina, titanium oxide, for example, nickel / silica, nickel / Examples of the catalyst system include diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.
水素化反応は、通常、不活性有機溶媒中で行う。このような不活性有機溶媒としては、ベンゼン、トルエンなどの芳香族炭化水素；ペンタン、ヘキサンなどの脂肪族炭化水素；シクロヘキサン、デカヒドロナフタレンなどの脂環族炭化水素；テトラヒドロフラン、エチレングリコールジメチルエーテルなどのエーテル類；などが挙げられる。不活性有機溶媒は、通常は、重合反応に用いる溶媒と同じでよく、重合反応液にそのまま水素化触媒を添加して反応させればよい。 The hydrogenation reaction is usually performed in an inert organic solvent. Examples of such inert organic solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like. The inert organic solvent is usually the same as the solvent used in the polymerization reaction, and the hydrogenation catalyst may be added to the polymerization reaction solution as it is and reacted.
水素化反応は、使用する水素化触媒系によっても適する条件範囲が異なるが、反応温度は通常−２０℃〜＋２５０℃、好ましくは−１０℃〜＋２２０℃、より好ましくは０℃〜２００℃である。水素化温度が低すぎると反応速度が遅くなりすぎる場合があり、高すぎると副反応が起こる場合がある。水素圧力は、通常０．０１〜２０ＭＰａ、好ましくは０．０５〜１５ＭＰａ、より好ましくは０．１〜１０ＭＰａである。水素圧力が低すぎると水素化速度が遅くなりすぎる場合があり、高すぎると高耐圧反応装置が必要となる点において装置上の制約が生じる。反応時間は所望の水素化率とできれば特に限定されないが、通常０．１〜１０時間である。水素化反応後は、常法に従って目的の重合体を回収すればよく、重合体の回収にあたっては、ろ過などの手法により、触媒残渣を除去することができる。 Although the suitable range of conditions varies depending on the hydrogenation catalyst system used, the reaction temperature is usually -20 ° C to + 250 ° C, preferably -10 ° C to + 220 ° C, more preferably 0 ° C to 200 ° C. . If the hydrogenation temperature is too low, the reaction rate may be too slow, and if it is too high, side reactions may occur. The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, and more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may be too slow, and if it is too high, there will be restrictions on the apparatus in that a high pressure reactor is required. Although reaction time will not be specifically limited if it can be set as the desired hydrogenation rate, Usually, it is 0.1 to 10 hours. After the hydrogenation reaction, the target polymer may be recovered according to a conventional method. In recovering the polymer, the catalyst residue can be removed by a technique such as filtration.
開環共重合体の水素化反応における水素化率（水素化された主鎖二重結合の割合）は、特に限定されないが、好ましくは９８％以上、より好ましくは９９％以上、特に好ましくは９９．５％以上である。水素化率が高くなるほど、最終的に得られる重合体の耐熱性が良好なものとなる。 The hydrogenation rate (ratio of hydrogenated main chain double bonds) in the hydrogenation reaction of the ring-opening copolymer is not particularly limited, but is preferably 98% or more, more preferably 99% or more, and particularly preferably 99. .5% or more. The higher the hydrogenation rate, the better the heat resistance of the finally obtained polymer.
以上のように開環重合体を水素化反応に供して得られる重合体は、従来公知の変性反応に付して、官能基を導入したり、重合体中に含まれる官能基を他の官能基に変換したりしてもよい。また、そのような変性反応により、重合体中のオキシシリル基を他のオキシシリル基に変換することもできる。例えば、シリルオキシ基としてヒドロカルビルオキシシリル基を含む重合体は、酸などを用いた加水分解反応に供することにより、ヒドロカルビルオキシシリル基をシラノール基に変換することができる。 As described above, a polymer obtained by subjecting a ring-opening polymer to a hydrogenation reaction is subjected to a conventionally known modification reaction to introduce a functional group or to convert a functional group contained in the polymer to another functional group. Or may be converted into a group. Moreover, the oxysilyl group in a polymer can also be converted into another oxysilyl group by such modification reaction. For example, a polymer containing a hydrocarbyloxysilyl group as a silyloxy group can convert the hydrocarbyloxysilyl group into a silanol group by subjecting it to a hydrolysis reaction using an acid or the like.
例えば以上のようにして得ることができる本発明の重合体は、シクロオレフィンポリマー元来の優れた成形加工性を備え、さらに、耐熱性および他の材料との密着性が高度に改良されたものであるので、種々の用途の材料として好適に使用することができる。本発明の重合体の利用形態は特に限定されるものではないが、他の材料との密着性に優れる性質を活かす観点からは、本発明の重合体の成形体と他の材料との複合体として用いることが好ましく、なかでも、本発明の重合体を成形してなる成形体に、硬化性樹脂を塗布して硬化させて得られる複合体として用いることが好ましい。 For example, the polymer of the present invention that can be obtained as described above has excellent processability inherent to the cycloolefin polymer, and is further improved in heat resistance and adhesion to other materials. Therefore, it can be suitably used as a material for various applications. The form of use of the polymer of the present invention is not particularly limited, but from the viewpoint of utilizing the property of excellent adhesion to other materials, a composite of the molded product of the polymer of the present invention and other materials It is preferable to use as a composite obtained by applying a curable resin to a molded product obtained by molding the polymer of the present invention and curing it.
本発明の重合体の成形方法は、特に限定されないが、射出成形、押出成形、プレス成形、ブロー成形、カレンダー成形などの溶融成形法が好適である。また、成形体を得るにあたっては、必要に応じて、各種の添加剤を重合体に配合してもよい。添加剤の具体例としては、酸化防止剤、核剤、充填剤、難燃剤、難燃助剤、顔料、着色剤、帯電防止剤、可塑剤、紫外線吸収剤、光安定剤、近赤外線吸収剤、滑剤を挙げることができる。 The method for molding the polymer of the present invention is not particularly limited, but melt molding methods such as injection molding, extrusion molding, press molding, blow molding, and calendar molding are suitable. Moreover, when obtaining a molded object, you may mix | blend various additives with a polymer as needed. Specific examples of additives include antioxidants, nucleating agents, fillers, flame retardants, flame retardant aids, pigments, colorants, antistatic agents, plasticizers, ultraviolet absorbers, light stabilizers, and near infrared absorbers. And a lubricant.
複合体を得る場合に、成形体に塗布して硬化させる硬化性樹脂の例としては、硬化性シリコーン樹脂、硬化性エポキシ樹脂、硬化性エポキシシリコーン混成樹脂、硬化性アクリル樹脂、硬化性ポリイミド樹脂が挙げられる。これらの中でも、硬化性シリコーン樹脂、または硬化性エポキシ樹脂が特に好適である。硬化性樹脂の硬化方式も特に限定されず、熱硬化性、光硬化性などのいずれの方式であってもよいが、熱硬化性樹脂が特に好適である。 In the case of obtaining a composite, examples of the curable resin that is applied to the molded body and cured are curable silicone resin, curable epoxy resin, curable epoxy silicone hybrid resin, curable acrylic resin, and curable polyimide resin. Can be mentioned. Among these, a curable silicone resin or a curable epoxy resin is particularly suitable. The curing method of the curable resin is not particularly limited, and any method such as thermosetting or photocuring may be used, but a thermosetting resin is particularly preferable.
本発明の重合体の成形体と硬化性樹脂から得られる複合体の用途は特に限定されるものではないが、重合体の成形体を光反射体とし、硬化性樹脂を封止剤として、ＬＥＤを構成するために特に好適に用いられる。この場合、重合体に、酸化チタン、鉛白、亜鉛華、硫酸バリウム、硫酸カルシウム、塩基性硫酸鉛、リトポン、硫化亜鉛、チタン酸鉛、酸化ジルコニウム、バライト、炭酸バリウム、白亜、沈降性炭酸カルシウム、石コウ、炭酸マグネシウム、アルミナ、クレー、滑石粉、珪藻土などの白色顔料を添加することにより、光反射性を向上させることができる。 The use of the composite obtained from the polymer molded product of the present invention and the curable resin is not particularly limited, but the polymer molded product is used as a light reflector, the curable resin is used as a sealing agent, and the LED is used. It is particularly preferably used for constructing. In this case, the polymer is titanium oxide, white lead, zinc white, barium sulfate, calcium sulfate, basic lead sulfate, lithopone, zinc sulfide, lead titanate, zirconium oxide, barite, barium carbonate, chalk, precipitated calcium carbonate. The light reflectivity can be improved by adding white pigments such as stone kou, magnesium carbonate, alumina, clay, talc powder, and diatomaceous earth.
また、本発明の重合体は、金属との密着性にも優れるものであるので、電子回路基板やフレキシブルプリント基板などの電子部品の材料としても好適に用いることができる。本発明の重合体をこのような用途に用いる場合は、本発明の重合体の成形体と、例えば、金、銀、ニッケル、銅、アルミニウムなどの金属との複合体として用いることができる。 Moreover, since the polymer of this invention is excellent also in adhesiveness with a metal, it can be used suitably also as a material of electronic components, such as an electronic circuit board and a flexible printed circuit board. When the polymer of the present invention is used for such an application, it can be used as a composite of the molded product of the polymer of the present invention and a metal such as gold, silver, nickel, copper, and aluminum.
以下に、実施例および比較例を挙げて、本発明についてより具体的に説明する。なお、各例中の部および％は、特に断りのない限り、重量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, unless otherwise indicated, the part and% in each example are a basis of weight.
また、各例における測定や評価は、以下の方法により行った。
（１）重合体の分子量（重量平均分子量および数平均分子量）
ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）システム ＨＬＣ−８２２０（東ソー社製）で、Ｈタイプカラム（東ソー社製）を用い、テトラヒドロフランを溶媒として４０℃で測定し、ポリスチレン換算値として求めた。
（２）重合体中の各繰り返し単位の含有量
水素化前の開環重合体について１Ｈ−ＮＭＲを測定することにより得られる、オキシシリル基に由来するピーク面積およびジシクロペンタジエンを開環重合してなる繰り返し単位に由来するピーク面積に基づいて、全繰り返し単位に対するオキシシリル基を含む繰り返し単位の含有割合を求め、この割合を重合体（水素化後のもの）における繰り返し単位Ｂの含有割合とした。但し、オキシシリル基を含む繰り返し単位の含有割合が極めて小さい場合（０．０１モル％以下の場合）は、１Ｈ−ＮＭＲ測定による定量が困難であるので、重合反応後の反応溶液についてガスクロマトグラフィの測定により未反応のモノマー量を求め、その値に基づいて、全繰り返し単位に対するオキシシリル基を含む繰り返し単位の含有割合を求めた。
（３）開環重合体の水素化率
１Ｈ−ＮＭＲ測定に基づいて求めた。
（４）重合体の融点および融解熱
示差走査熱量計を用いて、１０℃／分で昇温して測定した。
（５）重合体のラセモ・ダイアッドの割合
オルトジクロロベンゼン−ｄ４を溶媒として、１５０℃でｉｎｖｅｒｓｅ−ｇａｔｅｄ ｄｅｃｏｕｐｌｉｎｇ法を適用して１３Ｃ−ＮＭＲ測定を行い、オルトジクロロベンゼン−ｄ４の１２７．５ｐｐｍのピークを基準シフトとして、メソ・ダイアッド由来の４３．３５ｐｐｍのシグナルと、ラセモ・ダイアッド由来の４３．４３ｐｐｍのシグナルの強度比に基づいて、繰り返し単位Ａ（ジシクロペンタジエンを開環重合した後、全ての炭素−炭素二重結合を水素化することにより得られた繰り返し単位）についてのラセモ・ダイアッドの割合を求めた。
（６）熱硬化性シリコーン樹脂との密着性試験
各例で得られた重合体の粉末を真空熱プレスして、３０ｍｍ×３０ｍｍ×１ｍｍの試験板を作製した。次いで、熱硬化性シリコーン樹脂（東レ・ダウコーニング社製の「ＯＥ−６６３６Ａ」と「ＯＥ−６６３６Ｂ」とを重量比１：２で混合したもの）を試験板に厚さ０．０５ｍｍで塗布し、これをオーブンに入れて１００℃で１時間加熱し、続いて１５０℃で１時間加熱することにより、熱硬化性シリコーン樹脂を硬化させた。そして、試験板上の硬化したシリコーン樹脂の膜に、カッターナイフで５ｍｍ角方眼状に３個×３個の格子状の切れ目を入れて、当該部に接着テープ（ニチバン社製、「ＮＩＣＨＩＢＡＮ セロテープ Ｎｏ．４０５」）を貼り付け、９０°剥離試験を行い、剥がれた格子の数を数えた。剥がれた格子の数が少ないものほど、密着性に優れる。
Moreover, the measurement and evaluation in each example were performed by the following methods.
(1) Molecular weight of polymer (weight average molecular weight and number average molecular weight)
Using a gel permeation chromatography (GPC) system HLC-8220 (manufactured by Tosoh Corporation), an H-type column (manufactured by Tosoh Corporation) was measured at 40 ° C. using tetrahydrofuran as a solvent, and was determined as a polystyrene equivalent value.
(2) Content of each repeating unit in the polymer Ring-opening polymerization of the peak area derived from the oxysilyl group and dicyclopentadiene obtained by measuring 1 H-NMR of the ring-opening polymer before hydrogenation Based on the peak area derived from the repeating unit, the content ratio of the repeating unit containing oxysilyl groups relative to all the repeating units was determined, and this ratio was defined as the content ratio of the repeating unit B in the polymer (after hydrogenation). . However, when the content of the repeating unit containing an oxysilyl group is extremely small (0.01 mol% or less), quantification by 1 H-NMR measurement is difficult, so the reaction solution after the polymerization reaction is subjected to gas chromatography. The amount of unreacted monomer was determined by measurement, and based on the value, the content ratio of the repeating unit containing an oxysilyl group relative to all the repeating units was determined.
(3) Hydrogenation rate of ring-opening polymer
It calculated | required based on < 1 > H-NMR measurement.
(4) Melting point of polymer and heat of fusion Using a differential scanning calorimeter, the temperature was raised at 10 ° C./min and measured.
(5) Ratio of racemo dyad of polymer Using ortho-dichlorobenzene-d4 as a solvent, an inverse-gate decoupling method was applied at 150 ° C. to perform 13 C-NMR measurement, and 127.5 ppm of orthodichlorobenzene-d4 Based on the intensity ratio of 43.35 ppm signal derived from meso dyad and 43.43 ppm signal derived from racemo dyad, with the peak as a reference shift, repeating unit A (all after ring-opening polymerization of dicyclopentadiene, The ratio of racemo dyad was determined for the repeating unit obtained by hydrogenating the carbon-carbon double bond.
(6) Adhesion Test with Thermosetting Silicone Resin The polymer powder obtained in each example was vacuum hot pressed to prepare a 30 mm × 30 mm × 1 mm test plate. Next, a thermosetting silicone resin (a mixture of “OE-6636A” and “OE-6636B” manufactured by Toray Dow Corning Co., Ltd. at a weight ratio of 1: 2) was applied to the test plate at a thickness of 0.05 mm. The thermosetting silicone resin was cured by placing it in an oven and heating at 100 ° C. for 1 hour, followed by heating at 150 ° C. for 1 hour. Then, 3 × 3 grid-like cuts are made in a 5 mm square grid shape on the cured silicone resin film on the test plate, and an adhesive tape (“NICHIBAN cello tape No. .405 "), a 90 ° peel test was performed, and the number of peeled grids was counted. The smaller the number of peeled lattices, the better the adhesion.
〔実施例１〕
充分に乾燥した後、窒素置換したガラス製耐圧反応容器に、ジシクロペンタジエン（エンド体含有率９９％以上）の７５％シクロヘキサン溶液４０部（ジシクロペンタジエンの量として３０部）と２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）エチルトリメトキシシラン０．０５５部とを仕込み、さらに、シクロヘキサン７６部および１−ヘキセン１．９部を加え、続いて、ジエチルアルミニウムエトキシドの１９％ｎ−ヘキサン溶液０．４６部を加えて攪拌した。次いで、テトラクロロタングステンフェニルイミド（テトラヒドロフラン）錯体０．１１部を２部のトルエンに溶解した溶液を加えて、５０℃に加温して開環重合反応を開始した。３時間後、少量のイソプロパノールを加えて、重合反応を停止した後、重合反応溶液を多量のイソプロパノール中に注ぎ込み、開環重合体を凝固させた。凝固した開環重合体はろ過により溶液より分離して回収した後、真空下４０℃で２０時間乾燥した。得られた開環重合体の収量は２８部（収率９３％）であった。また、得られた開環重合体については、分子量と１Ｈ−ＮＭＲの測定を行った。次いで、得られた開環重合体１０部とシクロヘキサン４４部とを耐圧反応容器に加えて攪拌し、開環重合体をシクロヘキサンに溶解させた後、クロロヒドリドカルボニルトリス（トリフェニルホスフィン）ルテニウム０．００６５部をトルエン６部に溶解させてなる水素化触媒液を添加し、水素圧４ＭＰａ、１６０℃で５時間水素化反応を行った。得られた水素化反応液を多量のイソプロピルアルコールに注いで重合体を完全に析出させ、濾別洗浄後、６０℃で２４時間減圧乾燥して、結晶性の重合体を得た。得られた重合体については、１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲおよび示差走査熱量の測定と熱硬化性シリコーン樹脂との密着性試験を行った。それぞれの測定の結果から求められた、開環重合体の水素化率は実質的に１００％（水素化されていない炭素−炭素二重結合が検出限界以下の含有率）であり、また、開環重合体の分子量、重合体中の繰り返し単位Ｂの含有量、重合体のラセモ・ダイアッドの割合、融点、および融解熱、ならびに密着性試験の結果は表１にまとめて示した。
[Example 1]
After fully drying, in a pressure-resistant reaction vessel made of nitrogen-substituted glass, 40 parts of a 75% cyclohexane solution (30 parts as the amount of dicyclopentadiene) of dicyclopentadiene (endo content 99% or more) and 2- (bicyclo [2.2.1] hept-5-en-2-yl) ethyltrimethoxysilane 0.055 parts, and further 76 parts cyclohexane and 1.9 parts 1-hexene were added, followed by diethylaluminum 0.46 parts of a 19% n-hexane solution of ethoxide was added and stirred. Next, a solution in which 0.11 part of tetrachlorotungstenphenylimide (tetrahydrofuran) complex was dissolved in 2 parts of toluene was added and heated to 50 ° C. to initiate a ring-opening polymerization reaction. After 3 hours, a small amount of isopropanol was added to stop the polymerization reaction, and then the polymerization reaction solution was poured into a large amount of isopropanol to solidify the ring-opened polymer. The solidified ring-opening polymer was separated from the solution by filtration and collected, and then dried at 40 ° C. for 20 hours under vacuum. The yield of the obtained ring-opening polymer was 28 parts (yield 93%). Also, the resulting ring-opening polymer was subjected to measurement of molecular weight and 1 H-NMR. Next, 10 parts of the obtained ring-opening polymer and 44 parts of cyclohexane were added to a pressure-resistant reaction vessel and stirred to dissolve the ring-opening polymer in cyclohexane, and then chlorohydridocarbonyltris (triphenylphosphine) ruthenium. A hydrogenation catalyst solution prepared by dissolving 0065 parts in 6 parts of toluene was added, and a hydrogenation reaction was performed at a hydrogen pressure of 4 MPa and 160 ° C. for 5 hours. The obtained hydrogenation reaction liquid was poured into a large amount of isopropyl alcohol to completely precipitate the polymer, washed by filtration and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a crystalline polymer. About the obtained polymer, the measurement of < 1 > H-NMR, < 13 > C-NMR and differential scanning calorific value, and the adhesiveness test with a thermosetting silicone resin were done. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100% (the content of unhydrogenated carbon-carbon double bonds below the detection limit). The molecular weight of the ring polymer, the content of the repeating unit B in the polymer, the ratio of the racemo dyad in the polymer, the melting point, the heat of fusion, and the results of the adhesion test are summarized in Table 1.
〔実施例２、３〕
開環重合反応における２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）エチルトリメトキシシランの使用量を、それぞれ、０．００５５部および０．０００５５部に変更したこと以外は、実施例１と同様に開環重合反応および水素化反応を行って、結晶性の実施例２および実施例３の重合体を得た。開環重合体の収量は、それぞれ、２８部（収率９３％）、３０部（収率１００％）であった。得られた開環重合体および結晶性の重合体については、実施例１と同様の測定および試験を行った。それぞれの測定の結果から求められた、開環重合体の水素化率はそれぞれ実質的に１００％であり、また、開環重合体の分子量、重合体中の繰り返し単位Ｂの含有量、重合体のラセモ・ダイアッドの割合、融点、および融解熱、ならびに密着性試験の結果は表１にまとめて示した。
[Examples 2 and 3]
The amount of 2- (bicyclo [2.2.1] hept-5-en-2-yl) ethyltrimethoxysilane used in the ring-opening polymerization reaction was changed to 0.0055 parts and 0.00055 parts, respectively. Except for the above, a ring-opening polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Example 1 to obtain crystalline polymers of Example 2 and Example 3. The yields of the ring-opening polymer were 28 parts (yield 93%) and 30 parts (yield 100%), respectively. The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opening polymer determined from the results of each measurement is substantially 100%, respectively, and the molecular weight of the ring-opening polymer, the content of the repeating unit B in the polymer, the polymer Table 1 summarizes the ratio of racemo dyad, melting point, heat of fusion, and adhesion test results.
〔実施例４〕
開環重合反応において、２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）エチルトリメトキシシランに代えて、２−［４−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）フェニル］エチルトリメトキシシラン０．０７３部を用いたこと以外は、実施例１と同様に開環重合反応および水素化反応を行って、結晶性の重合体を得た。開環重合体の収量は、３０部（収率１００％）であった。得られた開環重合体および結晶性の重合体については、実施例１と同様の測定および試験を行った。それぞれの測定の結果から求められた、開環重合体の水素化率は実質的に１００％（但し、重合体中の芳香環は水素化されずに残留した）であり、また、開環重合体の分子量、重合体中の繰り返し単位Ｂの含有量、重合体のラセモ・ダイアッドの割合、融点、および融解熱、ならびに密着性試験の結果は表１にまとめて示した。
Example 4
In the ring-opening polymerization reaction, instead of 2- (bicyclo [2.2.1] hept-5-en-2-yl) ethyltrimethoxysilane, 2- [4- (bicyclo [2.2.1] hepta A crystalline polymer is obtained by carrying out a ring-opening polymerization reaction and a hydrogenation reaction in the same manner as in Example 1 except that 0.073 part of -5-en-2-yl) phenyl] ethyltrimethoxysilane is used. Obtained. The yield of the ring-opening polymer was 30 parts (yield 100%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement was substantially 100% (however, the aromatic ring in the polymer remained without being hydrogenated). Table 1 summarizes the molecular weight of the polymer, the content of the repeating unit B in the polymer, the ratio of the racemo dyad of the polymer, the melting point, the heat of fusion, and the adhesion test results.
〔実施例５〕
開環重合反応において、２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）エチルトリメトキシシランに代えて、（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）トリメトキシシラン０．０４９部を用いたこと以外は、実施例１と同様に開環重合反応および水素化反応を行って、結晶性の重合体を得た。開環重合体の収量は、７部（収率２３％）であった。得られた開環重合体および結晶性の重合体については、実施例１と同様の測定および試験を行った。それぞれの測定の結果から求められた、開環重合体の水素化率は実質的に１００％であり、また、開環重合体の分子量、重合体中の繰り返し単位Ｂの含有量、重合体のラセモ・ダイアッドの割合、融点、および融解熱、ならびに密着性試験の結果は表１にまとめて示した。
Example 5
In the ring-opening polymerization reaction, instead of 2- (bicyclo [2.2.1] hept-5-en-2-yl) ethyltrimethoxysilane, (bicyclo [2.2.1] hept-5-ene- A crystalline polymer was obtained by carrying out a ring-opening polymerization reaction and a hydrogenation reaction in the same manner as in Example 1 except that 0.049 part of 2-yl) trimethoxysilane was used. The yield of the ring-opening polymer was 7 parts (yield 23%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%. Also, the molecular weight of the ring-opened polymer, the content of the repeating unit B in the polymer, the polymer The ratio of the racemo dyad, melting point, heat of fusion, and results of the adhesion test are summarized in Table 1.
〔実施例６〕
開環重合反応において、２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）エチルトリメトキシシランに代えて、（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）トリエトキシシラン０．０５８部を用いたこと以外は、実施例１と同様に開環重合反応および水素化反応を行って、結晶性の重合体を得た。開環重合体の収量は、９部（収率３０％）であった。得られた開環重合体および結晶性の重合体については、実施例１と同様の測定および試験を行った。それぞれの測定の結果から求められた、開環重合体の水素化率は実質的に１００％であり、また、開環重合体の分子量、重合体中の繰り返し単位Ｂの含有量、重合体のラセモ・ダイアッドの割合、融点、および融解熱、ならびに密着性試験の結果は表１にまとめて示した。
Example 6
In the ring-opening polymerization reaction, instead of 2- (bicyclo [2.2.1] hept-5-en-2-yl) ethyltrimethoxysilane, (bicyclo [2.2.1] hept-5-ene- A crystalline polymer was obtained by carrying out a ring-opening polymerization reaction and a hydrogenation reaction in the same manner as in Example 1 except that 0.058 part of 2-yl) triethoxysilane was used. The yield of the ring-opening polymer was 9 parts (yield 30%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%. Also, the molecular weight of the ring-opened polymer, the content of the repeating unit B in the polymer, the polymer The ratio of the racemo dyad, melting point, heat of fusion, and results of the adhesion test are summarized in Table 1.
〔実施例７〕
充分に乾燥した後、窒素置換したガラス製耐圧反応容器に、ジシクロペンタジエン（エンド体含有率９９％以上）の７５％シクロヘキサン溶液４０部（ジシクロペンタジエンの量として３０部）を仕込み、さらに、シクロヘキサン７３８部および１−ヘキセン１．９部を加え、５０℃に加温した。一方、テトラクロロタングステンフェニルイミド（テトラヒドロフラン）錯体１．１部を５６部のトルエンに溶解した溶液に、ジエチルアルミニウムエトキシドの１９％ｎ−ヘキサン溶液４．６部を加えて１０分間攪拌し、重合触媒液を調製し、この重合触媒液を反応器に加えて開環重合反応を開始した。その後、５０℃を保ちながら、５分毎にジシクロペンタジエン（エンド体含有率９９％以上）の７５％シクロヘキサン溶液４０部を９回添加（合計３６０部添加）した後、さらに１時間反応を継続した。続いて、２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）エチルトリメトキシシラン２．２部を加えて、さらに２時間反応を継続させた。その後、少量のイソプロパノールを加えて、重合反応を停止した後、重合反応溶液を多量のイソプロパノール中に注ぎ込み、開環重合体を凝固させた。凝固した開環重合体はろ過により溶液より分離して回収した後、真空下４０℃で２０時間乾燥した。得られた開環重合体の収量は２８７部（収率９５％）であった。得られた開環重合体については、実施例１と同様の測定を行った後、実施例１と同様にして水素化反応を行って、結晶性の重合体を得た。得られた結晶性の重合体については、実施例１と同様の測定および試験を行った。それぞれの測定の結果から求められた、開環重合体の水素化率は実質的に１００％であり、また、開環重合体の分子量、重合体中の繰り返し単位Ｂの含有量、重合体のラセモ・ダイアッドの割合、融点、および融解熱、ならびに密着性試験の結果は表１にまとめて示した。
Example 7
After fully drying, a pressure-resistant reaction vessel made of nitrogen-substituted glass was charged with 40 parts of a 75% cyclohexane solution of dicyclopentadiene (endo content 99% or more) (30 parts as the amount of dicyclopentadiene). 738 parts of cyclohexane and 1.9 parts of 1-hexene were added and heated to 50 ° C. Meanwhile, 4.6 parts of a 19% n-hexane solution of diethylaluminum ethoxide was added to a solution of 1.1 parts of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 56 parts of toluene, and the mixture was stirred for 10 minutes to polymerize. A catalyst solution was prepared, and this polymerization catalyst solution was added to the reactor to initiate a ring-opening polymerization reaction. Then, while maintaining 50 ° C, 40 parts of a 75% cyclohexane solution of dicyclopentadiene (endo content rate of 99% or more) was added 9 times (addition of 360 parts in total), and the reaction was continued for another hour. did. Subsequently, 2.2 parts of 2- (bicyclo [2.2.1] hept-5-en-2-yl) ethyltrimethoxysilane was added, and the reaction was further continued for 2 hours. Thereafter, a small amount of isopropanol was added to stop the polymerization reaction, and then the polymerization reaction solution was poured into a large amount of isopropanol to solidify the ring-opened polymer. The solidified ring-opening polymer was separated from the solution by filtration and collected, and then dried at 40 ° C. for 20 hours under vacuum. The yield of the obtained ring-opening polymer was 287 parts (yield 95%). The obtained ring-opening polymer was measured in the same manner as in Example 1, and then hydrogenated in the same manner as in Example 1 to obtain a crystalline polymer. The obtained crystalline polymer was measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%. Also, the molecular weight of the ring-opened polymer, the content of the repeating unit B in the polymer, the polymer The ratio of the racemo dyad, melting point, heat of fusion, and results of the adhesion test are summarized in Table 1.
〔実施例８〕
充分に乾燥した後、窒素置換したガラス製耐圧反応容器に、２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）エチルトリメトキシシラン２．２部を仕込み、さらに、シクロヘキサン７３８部および１−ヘキセン１．９部を加え、５０℃に加温した。一方、テトラクロロタングステンフェニルイミド（テトラヒドロフラン）錯体１．１部を５６部のトルエンに溶解した溶液に、ジエチルアルミニウムエトキシドの１９％ｎ−ヘキサン溶液４．６部を加えて１０分間攪拌し、重合触媒液を調製し、この重合触媒液を反応器に加えて開環重合反応を開始し、５０℃を保ちながら１時間反応を継続した。続いて、５分毎にジシクロペンタジエン（エンド体含有率９９％以上）の７５％シクロヘキサン溶液４０部を１０回添加（合計４００部添加）した後、さらに２時間反応を継続した。その後、少量のイソプロパノールを加えて、重合反応を停止した後、重合反応溶液を多量のイソプロパノール中に注ぎ込み、開環重合体を凝固させた。凝固した開環重合体はろ過により溶液より分離して回収した後、真空下４０℃で２０時間乾燥した。得られた開環重合体の収量は２９０部（収率９６％）であった。得られた開環重合体については、実施例１と同様の測定を行った後、実施例１と同様にして水素化反応を行って、結晶性の重合体を得た。得られた結晶性の重合体については、実施例１と同様の測定および試験を行った。それぞれの測定の結果から求められた、開環重合体の水素化率は実質的に１００％であり、また、開環重合体の分子量、重合体中の繰り返し単位Ｂの含有量、重合体のラセモ・ダイアッドの割合、融点、および融解熱、ならびに密着性試験の結果は表１にまとめて示した。
Example 8
After sufficiently drying, 2.2 parts of 2- (bicyclo [2.2.1] hept-5-en-2-yl) ethyltrimethoxysilane was charged into a glass pressure-resistant reaction vessel purged with nitrogen, 738 parts of cyclohexane and 1.9 parts of 1-hexene were added and heated to 50 ° C. Meanwhile, 4.6 parts of a 19% n-hexane solution of diethylaluminum ethoxide was added to a solution of 1.1 parts of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 56 parts of toluene, and the mixture was stirred for 10 minutes to polymerize. A catalyst solution was prepared, this polymerization catalyst solution was added to the reactor to initiate a ring-opening polymerization reaction, and the reaction was continued for 1 hour while maintaining 50 ° C. Subsequently, 40 parts of a 75% cyclohexane solution of dicyclopentadiene (endo content 99% or more) was added 10 times every 5 minutes (total 400 parts added), and the reaction was continued for another 2 hours. Thereafter, a small amount of isopropanol was added to stop the polymerization reaction, and then the polymerization reaction solution was poured into a large amount of isopropanol to solidify the ring-opened polymer. The solidified ring-opening polymer was separated from the solution by filtration and collected, and then dried at 40 ° C. for 20 hours under vacuum. The yield of the obtained ring-opening polymer was 290 parts (yield 96%). The obtained ring-opening polymer was measured in the same manner as in Example 1, and then hydrogenated in the same manner as in Example 1 to obtain a crystalline polymer. The obtained crystalline polymer was measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%. Also, the molecular weight of the ring-opened polymer, the content of the repeating unit B in the polymer, the polymer The ratio of the racemo dyad, melting point, heat of fusion, and results of the adhesion test are summarized in Table 1.
〔実施例９〕
実施例１と同様にして開環重合反応を行って得られた開環重合体１０部を、テトラヒドロフラン５０部に溶解させ、さらに１規定の塩酸水溶液１．０部を添加して８０℃にて４時間攪拌することにより、加水分解反応（トリメトキシシリル基を反応させ、トリヒドロキシシリル基とする反応）を行った。得られた開環重合体については、実施例１と同様の測定を行った後、実施例１と同様にして水素化反応を行って、結晶性の重合体を得た。得られた重合体の収量は１０部（原料の開環重合体からの収率１００％）であった。得られた結晶性の重合体については、実施例１と同様の測定および試験を行った。それぞれの測定の結果から求められた、開環重合体の水素化率は実質的に１００％であり、また、開環重合体の分子量、重合体中の繰り返し単位Ｂの含有量、重合体のラセモ・ダイアッドの割合、融点、および融解熱、ならびに密着性試験の結果は表１にまとめて示した。
Example 9
10 parts of the ring-opening polymer obtained by carrying out the ring-opening polymerization reaction in the same manner as in Example 1 was dissolved in 50 parts of tetrahydrofuran, and 1.0 part of 1N hydrochloric acid aqueous solution was further added at 80 ° C. By stirring for 4 hours, a hydrolysis reaction (reaction in which a trimethoxysilyl group was reacted to obtain a trihydroxysilyl group) was performed. The obtained ring-opening polymer was measured in the same manner as in Example 1, and then hydrogenated in the same manner as in Example 1 to obtain a crystalline polymer. The yield of the obtained polymer was 10 parts (100% yield from the raw material ring-opening polymer). The obtained crystalline polymer was measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%. Also, the molecular weight of the ring-opened polymer, the content of the repeating unit B in the polymer, the polymer The ratio of the racemo dyad, melting point, heat of fusion, and results of the adhesion test are summarized in Table 1.
〔比較例１〕
開環重合反応における２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）エチルトリメトキシシランの使用量を、２．７４部に変更したこと以外は、実施例１と同様に開環重合反応および水素化反応を行って、結晶性の重合体を得た。開環重合体の収量は、２８部（収率８７％）であった。得られた開環重合体および結晶性の重合体については、実施例１と同様の測定および試験を行った。それぞれの測定の結果から求められた、開環重合体の水素化率は実質的に１００％であり、また、開環重合体の分子量、重合体中の繰り返し単位Ｂの含有量、重合体のラセモ・ダイアッドの割合、融点、および融解熱、ならびに密着性試験の結果は表１にまとめて示した。
[Comparative Example 1]
Example 1 except that the amount of 2- (bicyclo [2.2.1] hept-5-en-2-yl) ethyltrimethoxysilane used in the ring-opening polymerization reaction was changed to 2.74 parts. Similarly, a ring-opening polymerization reaction and a hydrogenation reaction were performed to obtain a crystalline polymer. The yield of the ring-opening polymer was 28 parts (yield 87%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%. Also, the molecular weight of the ring-opened polymer, the content of the repeating unit B in the polymer, the polymer The ratio of the racemo dyad, melting point, heat of fusion, and results of the adhesion test are summarized in Table 1.
〔比較例２〕
開環重合反応において２−（ビシクロ［２．２．１］ヘプタ−５−エン−２−イル）エチルトリメトキシシランを用いなかったこと以外は、実施例１と同様に開環重合反応および水素化反応を行って、結晶性の重合体を得た。開環重合体の収量は、２９部（収率９５％）であった。得られた開環重合体および結晶性の重合体については、実施例１と同様の測定および試験を行った。それぞれの測定の結果から求められた、開環重合体の水素化率は実質的に１００％であり、また、開環重合体の分子量、重合体中の繰り返し単位Ｂの含有量、重合体のラセモ・ダイアッドの割合、融点、および融解熱、ならびに密着性試験の結果は表１にまとめて示した。
[Comparative Example 2]
The ring-opening polymerization reaction and hydrogen as in Example 1 except that 2- (bicyclo [2.2.1] hept-5-en-2-yl) ethyltrimethoxysilane was not used in the ring-opening polymerization reaction. A crystalline polymer was obtained by performing a reaction. The yield of the ring-opening polymer was 29 parts (yield 95%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%. Also, the molecular weight of the ring-opened polymer, the content of the repeating unit B in the polymer, the polymer The ratio of the racemo dyad, melting point, heat of fusion, and results of the adhesion test are summarized in Table 1.
表１に示した結果からわかるように、本発明の重合体（実施例１〜９）は、高い融点および大きな融解熱を示し、かつ、密着性試験でテープの剥離を殆ど生じさせないことから、耐熱性および他の材料との密着性に優れるものであるといえる。なかでも、繰り返し単位Ｂとして、環構造骨格とオキシシリル基とが２価の炭化水素基を介して結合してなる単位を有する重合体（実施例１〜４，７〜９）は、特に優れた密着性を示すものであるといえる。一方、繰り返し単位Ｂを含んでいても、その含有量が多すぎる重合体（比較例１）は、本発明の重合体に比して低い融点および小さな融解熱を示す、耐熱性に劣るものであり、また、繰り返し単位Ｂを含まず、オキシシリル基を含まない重合体（比較例２）は、密着性試験でテープの剥離を生じさせるものであり、本発明の重合体に比して、他の材料との密着性に劣るものであった。 As can be seen from the results shown in Table 1, the polymers of the present invention (Examples 1 to 9) exhibit a high melting point and a large heat of fusion, and hardly cause peeling of the tape in the adhesion test. It can be said that it is excellent in heat resistance and adhesion to other materials. Especially, the polymer (Examples 1-4, 7-9) which has as a repeating unit B the unit which a ring structure frame | skeleton and an oxysilyl group couple | bond together through a bivalent hydrocarbon group was excellent. It can be said that it shows adhesiveness. On the other hand, even if the repeating unit B is included, the polymer having a too large content (Comparative Example 1) exhibits a low melting point and a small heat of fusion as compared with the polymer of the present invention, and is inferior in heat resistance. In addition, the polymer not containing the repeating unit B and not containing the oxysilyl group (Comparative Example 2) causes tape peeling in the adhesion test, and is different from the polymer of the present invention. It was inferior in adhesiveness with the material.
Claims (5)
A repeating unit A9 9.0 ~99.9999 mol% of the formula (1) below, repeating units B0.0001～ 1 mol% represented by the following formula (2) (where, 1.0 mole %), And a polymer having crystallinity.
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