TW201311656A - 組成物及聚合物 - Google Patents
組成物及聚合物 Download PDFInfo
- Publication number
- TW201311656A TW201311656A TW101126222A TW101126222A TW201311656A TW 201311656 A TW201311656 A TW 201311656A TW 101126222 A TW101126222 A TW 101126222A TW 101126222 A TW101126222 A TW 101126222A TW 201311656 A TW201311656 A TW 201311656A
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- TW
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- Prior art keywords
- bis
- compound
- phosphine
- ketone
- group
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 239
- 229920000642 polymer Polymers 0.000 title claims description 44
- -1 ether compound Chemical class 0.000 claims abstract description 595
- 150000001875 compounds Chemical class 0.000 claims abstract description 164
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 117
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 79
- 239000011574 phosphorus Substances 0.000 claims abstract description 65
- 125000001033 ether group Chemical group 0.000 claims abstract description 58
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 42
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 65
- 229910052796 boron Inorganic materials 0.000 claims description 65
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 39
- 125000004437 phosphorous atom Chemical group 0.000 claims description 33
- 125000001931 aliphatic group Chemical group 0.000 claims description 30
- 125000000524 functional group Chemical group 0.000 claims description 28
- 230000000379 polymerizing effect Effects 0.000 claims description 28
- 125000000468 ketone group Chemical group 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 150000004294 cyclic thioethers Chemical group 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 15
- 150000002576 ketones Chemical class 0.000 claims description 15
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 6
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 150000002118 epoxides Chemical class 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 156
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 139
- 241000208340 Araliaceae Species 0.000 description 123
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 123
- 235000003140 Panax quinquefolius Nutrition 0.000 description 123
- 235000008434 ginseng Nutrition 0.000 description 123
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 105
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 104
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 102
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 99
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 93
- 150000001335 aliphatic alkanes Chemical class 0.000 description 92
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 89
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 66
- 238000006116 polymerization reaction Methods 0.000 description 66
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 58
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 54
- 239000001273 butane Substances 0.000 description 53
- 239000001294 propane Substances 0.000 description 53
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 50
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 47
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 42
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 37
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 34
- 238000007086 side reaction Methods 0.000 description 33
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 28
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 26
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 26
- 229910052717 sulfur Inorganic materials 0.000 description 24
- 239000011593 sulfur Substances 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 23
- 239000007983 Tris buffer Substances 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 150000003553 thiiranes Chemical group 0.000 description 23
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 22
- IHBZSURDEONQJT-UHFFFAOYSA-N 4,5-diethyl-3,4-dihydro-2H-phosphole Chemical compound C(C)C1C(=PCC1)CC IHBZSURDEONQJT-UHFFFAOYSA-N 0.000 description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 21
- QRVUWACBZWBGNC-UHFFFAOYSA-N 4,5-dimethyl-3,4-dihydro-2H-phosphole Chemical compound CC1C(=PCC1)C QRVUWACBZWBGNC-UHFFFAOYSA-N 0.000 description 19
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 18
- 125000004149 thio group Chemical group *S* 0.000 description 18
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- ZKBNEEKDPSHBAE-UHFFFAOYSA-N 4,5-dicyclohexyl-3,4-dihydro-2H-phosphole Chemical compound C1(CCCCC1)C1C(=PCC1)C1CCCCC1 ZKBNEEKDPSHBAE-UHFFFAOYSA-N 0.000 description 15
- QSROMOSCKXVFTE-UHFFFAOYSA-N 4,5-dipropyl-3,4-dihydro-2H-phosphole Chemical compound C(CC)C1C(=PCC1)CCC QSROMOSCKXVFTE-UHFFFAOYSA-N 0.000 description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 15
- AGGOQVIFHWJDPG-UHFFFAOYSA-N 4,5-diphenyl-3,4-dihydro-2H-phosphole Chemical compound C1(=CC=CC=C1)C1C(=PCC1)C1=CC=CC=C1 AGGOQVIFHWJDPG-UHFFFAOYSA-N 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- 238000004821 distillation Methods 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- IDASTKMEQGPVRR-UHFFFAOYSA-N cyclopenta-1,3-diene;zirconium(2+) Chemical group [Zr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 IDASTKMEQGPVRR-UHFFFAOYSA-N 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 13
- 229920003986 novolac Polymers 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 12
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 12
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical group 0.000 description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 12
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 12
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 11
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical compound C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 11
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 11
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 239000004914 cyclooctane Substances 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexane-2,3-dione Chemical compound CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 description 10
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 10
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical compound C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 description 10
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000012965 benzophenone Substances 0.000 description 9
- 235000010290 biphenyl Nutrition 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 229910052720 vanadium Inorganic materials 0.000 description 9
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 9
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 8
- FJPGAMCQJNLTJC-UHFFFAOYSA-N 2,3-Heptanedione Chemical compound CCCCC(=O)C(C)=O FJPGAMCQJNLTJC-UHFFFAOYSA-N 0.000 description 8
- ZJKDOHKAWORXOB-UHFFFAOYSA-N 2-(trioxidanyl)octane Chemical compound CCCCCCC(C)OOO ZJKDOHKAWORXOB-UHFFFAOYSA-N 0.000 description 8
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- 239000004305 biphenyl Substances 0.000 description 8
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 8
- PWVDFPINYKVAFM-UHFFFAOYSA-N fluoren-4-one Chemical compound C1=CC=CC2=C3C(=O)C=CC=C3C=C21 PWVDFPINYKVAFM-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 8
- RTPIKNDFJYHOKH-UHFFFAOYSA-N nonane-4,5-dione Chemical compound CCCCC(=O)C(=O)CCC RTPIKNDFJYHOKH-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 125000003944 tolyl group Chemical group 0.000 description 8
- CVZGUJMLZZTPKH-UHFFFAOYSA-N 1.2-Dipropionyl-aethan Natural products CCC(=O)CCC(=O)CC CVZGUJMLZZTPKH-UHFFFAOYSA-N 0.000 description 7
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- WEEPLAUJNANUQB-UHFFFAOYSA-N decane-4,6-dione Chemical compound CCCCC(=O)CC(=O)CCC WEEPLAUJNANUQB-UHFFFAOYSA-N 0.000 description 7
- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 7
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 7
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 7
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 6
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 6
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 6
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 6
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 6
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 6
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 6
- XCBBNTFYSLADTO-UHFFFAOYSA-N 2,3-Octanedione Chemical compound CCCCCC(=O)C(C)=O XCBBNTFYSLADTO-UHFFFAOYSA-N 0.000 description 6
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 6
- WWNSDHGGFVEVHV-UHFFFAOYSA-N 2-methyl-2-(trioxidanyl)octane Chemical compound CC(OOO)(CCCCCC)C WWNSDHGGFVEVHV-UHFFFAOYSA-N 0.000 description 6
- KVFQMAZOBTXCAZ-UHFFFAOYSA-N 3,4-Hexanedione Chemical compound CCC(=O)C(=O)CC KVFQMAZOBTXCAZ-UHFFFAOYSA-N 0.000 description 6
- AXKCWJABFZJNJO-UHFFFAOYSA-N 3-ethyl-3-(trioxidanyl)nonane Chemical compound C(C)C(OOO)(CCCCCC)CC AXKCWJABFZJNJO-UHFFFAOYSA-N 0.000 description 6
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- WRRUPSPIVUVXHZ-UHFFFAOYSA-N CCCCCCCCC(CCCSCC1OC1)C(OC)(OC)OC Chemical compound CCCCCCCCC(CCCSCC1OC1)C(OC)(OC)OC WRRUPSPIVUVXHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical class [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- HLPUHEJQIIHQDF-UHFFFAOYSA-N cyclodecane-1,2-dione Chemical compound O=C1CCCCCCCCC1=O HLPUHEJQIIHQDF-UHFFFAOYSA-N 0.000 description 6
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/06—Polythioethers from cyclic thioethers
- C08G75/08—Polythioethers from cyclic thioethers from thiiranes
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
本發明揭示含有下述者之組成物:(A)選自由含有2個以上醚基的醚化合物、三價磷化合物、及酮化合物所成群組中至少1種的化合物,與(B)三鹵化硼,與(C)環硫化合物。
Description
本發明是關於一種含有環硫化合物(episulfide)之組成物及由該組成物獲得之聚合物。
環硫化合物使用在塑膠之原料化合物、接著劑、藥劑、殺蟲劑、除草劑等廣範領域中。
環硫化合物經聚合所形成的塑膠,由於具有所謂的高折射率、高阿貝數(Abbe number)、高耐熱性及高強度之特性,因此尤其是近年,在光學材料領域中,作為具有比以往更優異的性能的材料使用。
環硫化合物,由於聚合性高,因此作為接著劑時,作為與以往一般使用的環氧化合物相比具有更優異的速硬化性的接著劑使用。
作為使環硫化合物聚合之方法之一者,可以列舉使用聚合觸媒的方法,到目前為止,已有好幾種方法之提案。
例如專利文獻1揭示使用3價有機膦化合物、含有胺基之有機化合物或是此等之鹽的方法。又,專利文獻2揭示使用各種鎓鹽(onium salt)作為能量線感受性陽離子聚合起始劑的方法。再者,非專利文獻1揭示使用卟啉鋅錯合物的方法,非專利文獻2揭示使用硫醇化合物與1,8-二氮雜二環[5.4.0]十一碳-7-烯之鹽的方法,非專利文獻3揭示使用具有鋅或鎘作為中心金屬之金屬硫醇鹽(thiolate)化合物之方法。
[專利文獻1]日本特開2001-288177號公報
[專利文獻2]日本特開2011-063776號公報
[非專利文獻1] Macromolecules 1990, 23, 3887-3892.
[非專利文獻2] Macromolecules 1999, 32, 4485-4487.
[非專利文獻3] J. Chem. Soc. C 1969, 2087-2092.
然而,專利文獻1所記載之3價有機膦化合物,與環硫基反應,會產生脫硫反應,而有無法得到所期望之聚合物的情形。又,含有胺基之有機化合物,在可以最容易調製與環硫化合物之組成物的常溫條件中,由於與環硫基之反應急劇地發生,故有組成物之安定性低的情形。再者,急劇地發生與環硫基之反應,故會有發生副反應之情形。又,此等之鹽,含有鹵化陰離子,該陰離子會引起副反應,成為防礙所期望之聚合的原因。
專利文獻2所記載之鎓鹽是為了具有吸收特定能量線之構造而設計之複雜的分子,為了製造,必需要經多階段之步驟,故有成為高價化合物之傾向。因此,前述鎓鹽與環硫化合物的組成物,必然有成本變高的傾向。
非專利文獻1所記載的卟啉鋅錯合物,在可以最容易調製與環硫化合物的組成物之常溫條件中,會急劇地發生
與環硫基之反應,故有組成物安定性低的情形。再者,與環硫基的反應急劇地發生,會有產生副反應的情形。又,合成卟啉化合物及其錯合物的方法很複雜,為了製造,必需要經多階段之步驟,故有成為高價化合物之傾向。因此,含有前述卟啉鋅錯合物之組成物,必定會有成本變高之傾向。再者,前述卟啉鋅錯合物,含有鋅原子,從近年受注目的降低環境負荷之觀點而言,得到比較不佳的組成物。
非專利文獻2所記載之硫醇化合物與1,8-二氮雜二環[5.4.0]十一碳-7-烯之鹽,由於價廉並且是可以容易調製之鹽,故為有用的聚合觸媒。然而,此鹽在可以最容易調製與環硫化合物之組成物之常溫條件中,與環硫基的反應會急劇地發生,故會有組成物安定性低的情形。再者,此鹽,由於急劇地發生與環硫基之反應,故會有發生副反應的情形。
非專利文獻3所記載的金屬硫醇鹽化合物,在可以最容易調製與環硫化合物的組成物之常溫條件中,與環硫基之反應會急劇地發生,故會有組成物安定性低的情形,再者,此金屬硫醇鹽化合物與環硫基之反應會急劇地發生,故有產生副反應的情形。又,會有從在聚合物中存在之金屬-硫鍵結產生分解反應之可能性,故聚合物之耐候性有下降之傾向。另外,上述聚合觸媒含有金屬,從近年受注目的降低環境負荷之觀點而言,得到比較不佳的組成物。
在此,本發明是有鑑於上述事實而成者,目的是提供在室溫的安定性優異,同時,有充分高的聚合性,聚合時
副反應少的組成物,以及,由該組成物所得到之聚合物。
本發明是有關下述者。
[1]一種組成物,含有:(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種的化合物,與(B)三鹵化硼,與(C)環硫化合物。
[2]如[1]項所記載之組成物,其中,前述醚化合物之醚基數是2至8。
[3]如[1]項所記載之組成物,其中,前述醚化合物之碳原子數是3至50。
[4]如[1]項所記載之組成物,其中,前述三價磷化合物是以下述式(1)所示之化合物。
[5]如[4]項所記載之組成物,其中,式(1)中,a為1,R1、R2、及R3全部為芳香族烴基,R1、R2、及R3之中至少1個為經取代之芳香族烴基。
[6]如[4]項所記載之組成物,其中,前述三價磷化合物之碳原子數為4至52。
[7]如[4]項所記載之組成物,其中,式(1)中,a為1至4。
[8]如[1]項所記載之組成物,其中,前述酮化合物為下述式(2)、(3)或是(4)所示之化合物。
[9]如[8]項所記載之組成物,其中,式(2)中,a為2時,2個酮基間之碳原子數為2至20。
[10]如[8]項所記載之組成物,其中,前述酮化合物之碳原子數為3至31。
[11]如[8]項所記載之組成物,其中,前述酮化合物之酮基數為1至8。
[12]如[1]項所記載之組成物,其中,前述(A)選自由含有2個以上醚基的醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與前述(B)三鹵化硼之至少一部份形成錯合物。
[13]如[1]項所記載之組成物,其中,下述式(5)所示,表
示前述(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與前述(B)三鹵化硼之比率的指標α為1至1000。
指標α=(α e+α p+α k)/α b (5)
α e:前述醚化合物之醚基的物質量(mol)
α p:前述三價磷化合物中所含有之三價磷原子的物質量(mol)
α k:前述酮化合物之酮基的物質量(mol)
α b:前述三鹵化硼的物質量(mol)。
[14]如[13]項所記載之組成物,其中,α p/α b為10以下。
[15]如[1]項所記載之組成物,其中,前述三鹵化硼為選自由三氟化硼、三氯化硼、及三溴化硼所成群組中至少1種的化合物。
[16]如[1]項所記載之組成物,其中,前述環硫化合物為只具有3員環硫醚結構作為聚合性官能基的化合物。
[17]如[1]項所記載之組成物,其中,前述三鹵化硼之物質量(mol),與前述環硫化合物中所含有之環硫基之物質量(mol)的比為1:10至1:100000。
[18]如[1]項所記載之組成物,其中,前述環硫化合物之環硫當量為65至700g/mol。
[19]如[1]項所記載之組成物,其中,前述環硫化合物具有下述式(6)、(7)、(8)或是(9)所示之部分結構。
[20]一種聚合物,係將[1]項所記載之組成物中的前述環硫化合物聚合而形成者。
[21]一種製造聚合物之方法,將[1]項所記載之組成物中的前述環硫化合物,藉由加熱及/或是能量線照射而聚合。
[22]一種聚合物,係將含有環硫化合物之組成物中的前述環硫化合物聚合而形成者,其中,乙烯基鍵結之含量以該聚合物之全體質量當作基準為2質量%以下。
[23]一種聚合物,係將含有環硫化合物之組成物中之前述環硫化合物聚合而形成者,其中,硼原子之含量以該聚合物之全體質量當作基準為1至6500ppm。
[24]一種聚合物,係將含有環硫化合物之組成物中的前述環硫化合物聚合而形成者,其中,磷原子之含量以該聚合物之全體質量當作基準為1至14000ppm。
依本發明,可以提供在室溫的安定性優異,同時,有充分高的聚合性,聚合時之副反應少之組成物,及,由該組成物所得到之聚合物。
以下詳細說明本發明的實施形態(以下,稱為「本實施形態」)。但本發明並不侷限於以下之本實施形態,在此主旨之範圍內可以進行各種變形並實施。
本實施形態中相關的組成物含有:(A)選自由含有2個以上醚基之醚化合物(以下,依情形稱為「成分(A-1)」)、三價磷化合物(以下,依情形稱為「成分(A-2)」)、及酮化合物(以下,依情形稱為「成分(A-3)」)所成群組中至少1種之化合物,與(B)三鹵化硼(以下,依情形稱為「成分(B)」),與(C)環硫化合物(以下,依情形稱為「成分(C)」)。
以下,詳細說明在組成物中所含有之(A)、(B)、(C)成分及其他的成分。
本實施形態之成分(A-1)是含有2個以上醚基之醚化合物。作為成分(A-1)者,可以單獨使用1種之含有2個以上醚基的醚化合物,也可以使用組合複數種之含有2個以上醚基之醚化合物。
(A-1)醚化合物之醚基數,從在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向而言,醚基數是以2以上為佳。從在大氣下調整組成物之際,有可以更抑制(A-1)醚化合物與(B)三鹵化硼之至少一部份所形成的錯合物之變質,且更提高組成物安定性的傾向而言,醚基數是以3以上為較佳。由同樣之觀點而言,醚基數以4以上為更佳。
(A-1)醚化合物之醚基數,從有變得容易取得,且可以更抑制組成物之成本,且經濟性更優良之傾向而言,醚基數是以20以下為佳。由同樣之觀點而言,醚基數是以10以下為較佳。從在調整組成物之際,有可以更抑制未溶解物之殘留,且可得均勻性更優良之組成物之傾向而言,醚基數是以8以下為更佳。從有可以提高組成物聚合性之傾向而言,醚基數是以6以下為特佳。
(A-1)醚化合物之碳原子數,從在將(C)環硫化合物聚合之際,有可以更抑制副反應之傾向而言,碳原子數是以3以上為佳。從有(A-1)醚化合物之蒸氣壓變更高,且更提
高處理性之傾向而言,碳原子數是以4以上為較佳。由同樣之觀點而言,碳原子數是以6以上為更佳。
(A-1)醚化合物之碳原子數,從有變得容易取得,且可以更抑制組成物之成本,且經濟性更優良之傾向而言,碳原子數是以50以下為佳。由同樣之觀點而言,碳原子數是以30以下為較佳。從在調整組成物之際,有可以更抑制未溶解物之殘留,且可得均勻性更優良的組成物之傾向而言,碳原子數是以24以下為更佳。由同樣之觀點而言,碳原子數是以12以下為特佳。
(A-1)醚化合物之結構是鏈狀、分枝狀或是環狀結構之任何一種皆可,但從提高(A-1)醚化合物與(B)三鹵化硼之結合力,作為組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向而言,是以鏈狀或是環狀結構為佳。由同樣之觀點而言,(A-1)醚化合物是以具有環狀結構為更佳。
若具體例示(A-1)醚化合物,則可以列舉:含有2個以上醚基之鏈狀醚化合物、分枝狀醚化合物、環狀醚化合物等。此等可以單獨使用,也可以組合複數種而使用。
作為含有2個以上醚基之鏈狀醚化合物(以下,稱為「鏈狀醚化合物」)者,例示下述式(10)所示者。
式中,R40及R41各自獨立地表示鏈狀之脂肪族或是芳香
族烴基。m1表示1以上之數,以1至20為佳。n1表示1以上之數,以1至9為佳。
上述式(10)所示之化合物之中,從有變得容易取得,且可以更抑制組成物之成本,且經濟性更優良之傾向,在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,以選自以下之群組中至少1種之化合物為佳。
甲醛二甲基縮醛、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丙基醚、乙二醇二丁基醚、乙二醇二戊基醚、乙二醇二己基醚、乙二醇二苄基醚、二甲氧基丙烷、二乙氧基丙烷、二丙氧基丙烷、二丁氧基丙烷、二甲氧基苯基丙烷、二甲氧基丁烷、二乙氧基丁烷、二丙氧基丁烷、二丁氧基丁烷、二甲氧基苯基丁烷、二甲氧基戊烷、二乙氧基戊烷、二丙氧基戊烷、二丁氧基戊烷、二甲氧基苯基戊烷、二甲氧基己烷、二乙氧基己烷、二丙氧基己烷、二丁氧基己烷、二甲氧基苯基己烷、二甲氧基庚烷、二乙氧基庚烷、二丙氧基庚烷、二丁氧基庚烷、二甲氧基苯基庚烷、二甲氧基辛烷、二乙氧基辛烷、二丙氧基辛烷、二丁氧基辛烷、二甲氧基苯基辛烷、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、二乙二醇二戊基醚、二乙二醇二己基醚、三乙二醇二甲基醚、三乙二醇二乙基醚、三乙二醇二丙基醚、三乙二醇二丁基醚、四乙二醇二甲基醚、四乙二醇二乙基醚、四乙二醇二丙基醚、
四乙二醇二丁基醚、聚乙二醇二甲基醚、聚乙二醇二乙基醚、聚乙二醇二丙基醚、聚乙二醇二丁基醚、聚乙二醇二戊基醚、聚乙二醇二己基醚、三氧雜十一烷、三氧雜十三烷、三氧雜十五烷、三氧雜十七烷、四氧雜十二烷、四氧雜十四烷、四氧雜十六烷、1,14-雙(2-萘氧基)-3,6,9,12-四氧雜十四烷、聚三亞甲基醚二醇二甲基醚、聚三亞甲基醚二醇二乙基醚、聚三亞甲基醚二醇二丙基醚、聚三亞甲基醚二醇二丁基醚、聚四亞甲基醚二醇二甲基醚、聚四亞甲基醚二醇二乙基醚、聚四亞甲基醚二醇二丙基醚、聚四亞甲基醚二醇二丁基醚。
鏈狀醚化合物,較佳是選自以下之群組中至少1種之化合物。
乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚、乙二醇二己基醚、二甲氧基丙烷、二乙氧基丙烷、二丁氧基丙烷、二甲氧基丁烷、二乙氧基丁烷、二丁氧基丁烷、二甲氧基己烷、二乙氧基己烷、二丁氧基己烷、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丁基醚、三乙二醇二甲基醚、三乙二醇二乙基醚、三乙二醇二丁基醚、四乙二醇二甲基醚、四乙二醇二乙基醚、四乙二醇二丁基醚、三氧雜十一烷、三氧雜十三烷。
鏈狀醚化合物,更佳是選自以下之群組中至少1種之化合物。
乙二醇二乙基醚、乙二醇二丁基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丁基醚、三乙二醇二
甲基醚、三乙二醇二乙基醚、三乙二醇二丁基醚。
作為含有2個以上醚基之分枝狀醚化合物(以下,稱為「分枝狀醚化合物」)者,例示下述式(11)所示者。
式中,R50表示氫原子或者是鏈狀、分枝狀、環狀之脂肪族或者是取代或是無取代之芳香族烴基。R51、R52及R53分別獨立地表示鏈狀、分枝狀、環狀之烴基,形成分枝結構之碳原子彼此可以藉由脂肪族或者是取代或是無取代之芳香族烴而連結。m2表示1以上之數,以1至20為佳,n2表示1以上之數,以1至9為佳。
上述式(11)所示之化合物之中,從有變得容易取得,且可以更抑制組成物之成本,且經濟性更優良之傾向,在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,以選自以下之群組中至少1種之化合物為佳。
丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二丙基醚、丙二醇二丁基醚、丙二醇二戊基醚、丙二醇二己基醚、丙二醇二甲氧基苯基醚、聚丙二醇二甲基醚、聚丙二醇二乙基醚、聚丙二醇二丙基醚、聚丙二醇二丁基醚、聚丙二醇二戊基醚、聚丙二醇二己基醚、聚丙二醇二甲氧基苯基醚、甲基二氧雜己烷、甲基二氧雜庚烷、甲基二氧雜辛烷、甲
基二氧雜壬烷、甲基二氧雜癸烷、甲基二氧雜十一烷、甲基二氧雜十二烷、甲基二氧雜十三烷、甲基二氧雜十四烷、甲基二氧雜十五烷、甲基二氧雜十六烷、二甲基二氧雜己烷、二甲基二氧雜庚烷、二甲基二氧雜辛烷、二甲基二氧雜壬烷、二甲基二氧雜癸烷、二甲基二氧雜十一烷、二甲基二氧雜十二烷、二甲基二氧雜十三烷、二甲基二氧雜十四烷、二甲基二氧雜十五烷、二甲基二氧雜十六烷、三甲基二氧雜己烷、三甲基二氧雜庚烷、三甲基二氧雜辛烷、三甲基二氧雜壬烷、三甲基二氧雜癸烷、三甲基二氧雜十一烷、三甲基二氧雜十二烷、三甲基二氧雜十三烷、三甲基二氧雜十四烷、三甲基二氧雜十五烷、三甲基二氧雜十六烷、乙基二氧雜己烷、乙基二氧雜庚烷、乙基二氧雜辛烷、乙基二氧雜壬烷、乙基二氧雜癸烷、乙基二氧雜十一烷、乙基二氧雜十二烷、乙基二氧雜十三烷、乙基二氧雜十四烷、乙基二氧雜十五烷、乙基二氧雜十六烷、二乙基二氧雜己烷、二乙基二氧雜庚烷、二乙基二氧雜辛烷、二乙基二氧雜壬烷、二乙基二氧雜癸烷、二乙基二氧雜十一烷、二乙基二氧雜十二烷、二乙基二氧雜十三烷、二乙基二氧雜十四烷、二乙基二氧雜十五烷、二乙基二氧雜十六烷、三乙基二氧雜己烷、三乙基二氧雜庚烷、三乙基二氧雜辛烷、三乙基二氧雜壬烷、三乙基二氧雜癸烷、三乙基二氧雜十一烷、三乙基二氧雜十二烷、三乙基二氧雜十三烷、三乙基二氧雜十四烷、三乙基二氧雜十五烷、三乙基二氧雜十六烷、
丙基二氧雜己烷、丙基二氧雜庚烷、丙基二氧雜辛烷、丙基二氧雜壬烷、丙基二氧雜癸烷、丙基二氧雜十一烷、丙基二氧雜十二烷、丙基二氧雜十三烷、丙基二氧雜十四烷、丙基二氧雜十五烷、丙基二氧雜十六烷、二丙基二氧雜己烷、二丙基二氧雜庚烷、二丙基二氧雜辛烷、二丙基二氧雜壬烷、二丙基二氧雜癸烷、二丙基二氧雜十一烷、二丙基二氧雜十二烷、二丙基二氧雜十三烷、二丙基二氧雜十四烷、二丙基二氧雜十五烷、二丙基二氧雜十六烷、三丙基二氧雜己烷、三丙基二氧雜庚烷、三丙基二氧雜辛烷、三丙基二氧雜壬烷、三丙基二氧雜癸烷、三丙基二氧雜十一烷、三丙基二氧雜十二烷、三丙基二氧雜十三烷、三丙基二氧雜十四烷、三丙基二氧雜十五烷、三丙基二氧雜十六烷、丁基二氧雜己烷、丁基二氧雜庚烷、丁基二氧雜辛烷、丁基二氧雜壬烷、丁基二氧雜癸烷、丁基二氧雜十一烷、丁基二氧雜十二烷、丁基二氧雜十三烷、丁基二氧雜十四烷、丁基二氧雜十五烷、丁基二氧雜十六烷、二丁基二氧雜己烷、二丁基二氧雜庚烷、二丁基二氧雜辛烷、二丁基二氧雜壬烷、二丁基二氧雜癸烷、二丁基二氧雜十一烷、二丁基二氧雜十二烷、二丁基二氧雜十三烷、二丁基二氧雜十四烷、二丁基二氧雜十五烷、二丁基二氧雜十六烷、三丁基二氧雜己烷、三丁基二氧雜庚烷、三丁基二氧雜辛烷、三丁基二氧雜壬烷、三丁基二氧雜癸烷、三丁基二氧雜十一烷、三丁基二氧雜十二烷、三丁基二氧雜十三烷、三丁基二氧雜十四烷、三丁基二氧雜十五烷、三丁基
二氧雜十六烷、甲基三氧雜壬烷、甲基三氧雜癸烷、甲基三氧雜十一烷、甲基三氧雜十二烷、甲基三氧雜十三烷、甲基三氧雜十四烷、甲基三氧雜十五烷、甲基三氧雜十六烷、二甲基三氧雜壬烷、二甲基三氧雜癸烷、二甲基三氧雜十一烷、二甲基三氧雜十二烷、二甲基三氧雜十三烷、二甲基三氧雜十四烷、二甲基三氧雜十五烷、二甲基三氧雜十六烷、三甲基三氧雜壬烷、三甲基三氧雜癸烷、三甲基三氧雜十一烷、三甲基三氧雜十二烷、三甲基三氧雜十三烷、三甲基三氧雜十四烷、三甲基三氧雜十五烷、三甲基三氧雜十六烷、乙基三氧雜壬烷、乙基三氧雜癸烷、乙基三氧雜十一烷、乙基三氧雜十二烷、乙基三氧雜十三烷、乙基三氧雜十四烷、乙基三氧雜十五烷、乙基三氧雜十六烷、二乙基三氧雜壬烷、二乙基三氧雜癸烷、二乙基三氧雜十一烷、二乙基三氧雜十二烷、二乙基三氧雜十三烷、二乙基三氧雜十四烷、二乙基三氧雜十五烷、二乙基三氧雜十六烷、三乙基三氧雜壬烷、三乙基三氧雜癸烷、三乙基三氧雜十一烷、三乙基三氧雜十二烷、三乙基三氧雜十三烷、三乙基三氧雜十四烷、三乙基三氧雜十五烷、三乙基三氧雜十六烷、丙基三氧雜壬烷、丙基三氧雜癸烷、丙基三氧雜十一烷、丙基三氧雜十二烷、丙基三氧雜十三烷、丙基三氧雜十四烷、丙基三氧雜十五烷、丙基三氧雜十六烷、二丙基三氧雜壬烷、二丙基三氧雜癸烷、二丙基三氧雜十一烷、二丙基三氧雜十二烷、二丙基三氧雜十三烷、二丙基三氧雜十
四烷、二丙基三氧雜十五烷、二丙基三氧雜十六烷、三丙基三氧雜壬烷、三丙基三氧雜癸烷、三丙基三氧雜十一烷、三丙基三氧雜十二烷、三丙基三氧雜十三烷、三丙基三氧雜十四烷、三丙基三氧雜十五烷、三丙基三氧雜十六烷、丁基三氧雜壬烷、丁基三氧雜癸烷、丁基三氧雜十一烷、丁基三氧雜十二烷、丁基三氧雜十三烷、丁基三氧雜十四烷、丁基三氧雜十五烷、丁基三氧雜十六烷、二丁基三氧雜壬烷、二丁基三氧雜癸烷、二丁基三氧雜十一烷、二丁基三氧雜十二烷、二丁基三氧雜十三烷、二丁基三氧雜十四烷、二丁基三氧雜十五烷、二丁基三氧雜十六烷、三丁基三氧雜壬烷、三丁基三氧雜癸烷、三丁基三氧雜十一烷、三丁基三氧雜十二烷、三丁基三氧雜十三烷、三丁基三氧雜十四烷、三丁基三氧雜十五烷、三丁基三氧雜十六烷、甲基四氧雜十二烷、甲基四氧雜十三烷、甲基四氧雜十四烷、甲基四氧雜十五烷、甲基四氧雜十六烷、二甲基四氧雜十二烷、二甲基四氧雜十三烷、二甲基四氧雜十四烷、二甲基四氧雜十五烷、二甲基四氧雜十六烷、三甲基四氧雜十二烷、三甲基四氧雜十三烷、三甲基四氧雜十四烷、三甲基四氧雜十五烷、三甲基四氧雜十六烷、乙基四氧雜十二烷、乙基四氧雜十三烷、乙基四氧雜十四烷、乙基四氧雜十五烷、乙基四氧雜十六烷、二乙基四氧雜十二烷、二乙基四氧雜十三烷、二乙基四氧雜十四烷、二乙基四氧雜十五烷、二乙基四氧雜十六烷、三乙基四氧雜十二烷、三乙基四氧雜十三烷、三乙基四氧雜十四烷、三乙基四氧
雜十五烷、三乙基四氧雜十六烷、丙基四氧雜十二烷、丙基四氧雜十三烷、丙基四氧雜十四烷、丙基四氧雜十五烷、丙基四氧雜十六烷、二丙基四氧雜十二烷、二丙基四氧雜十三烷、二丙基四氧雜十四烷、二丙基四氧雜十五烷、二丙基四氧雜十六烷、三丙基四氧雜十二烷、三丙基四氧雜十三烷、三丙基四氧雜十四烷、三丙基四氧雜十五烷、三丙基四氧雜十六烷、丁基四氧雜十二烷、丁基四氧雜十三烷、丁基四氧雜十四烷、丁基四氧雜十五烷、丁基四氧雜十六烷、二丁基四氧雜十二烷、二丁基四氧雜十三烷、二丁基四氧雜十四烷、二丁基四氧雜十五烷、二丁基四氧雜十六烷、三丁基四氧雜十二烷、三丁基四氧雜十三烷、三丁基四氧雜十四烷、三丁基四氧雜十五烷、三丁基四氧雜十六烷。
分枝狀醚化合物較佳是選自以下之群組中至少1種之化合物。
丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二丁基醚、聚丙二醇二甲基醚、聚丙二醇二乙基醚、聚丙二醇二丁基醚、甲基二氧雜己烷、甲基二氧雜庚烷、甲基二氧雜辛烷、甲基二氧雜壬烷、甲基二氧雜癸烷、甲基二氧雜十一烷、甲基二氧雜十二烷、甲基二氧雜十三烷、甲基二氧雜十四烷、甲基二氧雜十五烷、甲基二氧雜十六烷、二甲基二氧雜己烷、二甲基二氧雜庚烷、二甲基二氧雜辛烷、二甲基二氧雜壬烷、二甲基二氧雜癸烷、二甲基二氧雜十一烷、二甲基二氧雜十二烷、二甲基二氧雜十三烷、二甲基二氧
雜十四烷、二甲基二氧雜十五烷、二甲基二氧雜十六烷、乙基二氧雜癸烷、乙基二氧雜十一烷、乙基二氧雜十二烷、乙基二氧雜十三烷、乙基二氧雜十四烷、乙基二氧雜十五烷、乙基二氧雜十六烷、二乙基二氧雜己烷、二乙基二氧雜庚烷、二乙基二氧雜辛烷、二乙基二氧雜壬烷、二乙基二氧雜癸烷、二乙基二氧雜十一烷、二乙基二氧雜十二烷、二乙基二氧雜十三烷、二乙基二氧雜十四烷、二乙基二氧雜十五烷、二乙基二氧雜十六烷、甲基三氧雜壬烷、甲基三氧雜癸烷、甲基三氧雜十一烷、甲基三氧雜十二烷、甲基三氧雜十三烷、甲基三氧雜十四烷、甲基三氧雜十五烷、甲基三氧雜十六烷、二甲基三氧雜壬烷、二甲基三氧雜癸烷、二甲基三氧雜十一烷、二甲基三氧雜十二烷、二甲基三氧雜十三烷、二甲基三氧雜十四烷、二甲基三氧雜十五烷、二甲基三氧雜十六烷、乙基三氧雜壬烷、乙基三氧雜癸烷、乙基三氧雜十一烷、乙基三氧雜十二烷、乙基三氧雜十三烷、乙基三氧雜十四烷、乙基三氧雜十五烷、乙基三氧雜十六烷、二乙基三氧雜壬烷、二乙基三氧雜癸烷、二乙基三氧雜十一烷、二乙基三氧雜十二烷、二乙基三氧雜十三烷、二乙基三氧雜十四烷、二乙基三氧雜十五烷、二乙基三氧雜十六烷、甲基四氧雜十二烷、甲基四氧雜十三烷、甲基四氧雜十四烷、甲基四氧雜十五烷、甲基四氧雜十六烷、二甲基四氧雜十二烷、二甲基四氧雜十三烷、二甲基四氧雜十四烷、二甲基四氧雜十五烷、二甲基四氧雜十六烷、乙基四氧雜十二烷、乙
基四氧雜十三烷、乙基四氧雜十四烷、乙基四氧雜十五烷、乙基四氧雜十六烷、二乙基四氧雜十二烷、二乙基四氧雜十三烷、二乙基四氧雜十四烷、二乙基四氧雜十五烷、二乙基四氧雜十六烷。
分枝狀醚化合物更佳是選自以下之群組中至少1種之化合物。
丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二丁基醚、甲基二氧雜己烷、甲基二氧雜庚烷、甲基二氧雜辛烷、甲基二氧雜壬烷、甲基二氧雜癸烷、甲基三氧雜壬烷、甲基三氧雜癸烷、甲基四氧雜十四烷。
作為含有2個以上醚基之環狀醚化合物(以下,稱為「環狀醚化合物」)者,例示下述式(12)所示者。
上述式(12)中,R60及R61表示:氫原子或者是鏈狀、分枝狀、環狀之脂肪族或者是取代或是無取代之芳香族烴基。又,形成環狀結構之碳原子彼此可以藉由脂肪族或是芳香族烴而連結。m3表示1以上之數,以1至20為佳。n3表示2以上之數,以2至10為佳。
上述式(12)所示之化合物之中,從有變得容易取得,且可以更抑制組成物之成本,且經濟性更優良之傾向,在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚
合,且更提高組成物安定性之傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,以選自以下之群組中至少1種之化合物為佳。
1,3-二氧雜環戊烷(1,3-dioxolane)、1,3-二烷、1,4-二烷、甲基-1,3-二烷、二甲基-1,3-二烷、三甲基-1,3-二烷、四甲基-1,3-二烷、五甲基-1,3-二烷、六甲基-1,3-二烷、七甲基-1,3-二烷、八甲基-1,3-二烷、乙基-1,3-二烷、二乙基-1,3-二烷、三乙基-1,3-二烷、四乙基-1,3-二烷、五乙基-1,3-二烷、六乙基-1,3-二烷、七乙基-1,3-二烷、八乙基-1,3-二烷、丙基-1,3-二烷、二丙基-1,3-二烷、三丙基-1,3-二烷、四丙基-1,3-二烷、五丙基-1,3-二烷、六丙基-1,3-二烷、七丙基-1,3-二烷、八丙基-1,3-二烷、丁基-1,3-二烷、二丁基-1,3-二烷、三丁基-1,3-二烷、四丁基-1,3-二烷、五丁基-1,3-二烷、六丁基-1,3-二烷、七丁基-1,3-二烷、八丁基-1,3-二烷、甲基-1,4-二烷、二甲基-1,4-二烷、三甲基-1,4-二烷、四甲基-1,4-二烷、五甲基-1,4-二烷、六甲基-1,4-二烷、七甲基-1,4-二烷、八甲基-1,4-二烷、乙基-1,4-二烷、二乙基-1,4-二烷、三乙基-1,4-二烷、四乙基-1,4-二烷、五乙基-1,4-二烷、六乙基-1,4-二烷、七乙基-1,4-二烷、八乙基-1,4-二烷、丙基-1,4-二烷、二丙基-1,4-二烷、三丙基-1,4-二烷、
四丙基-1,4-二烷、五丙基-1,4-二烷、六丙基-1,4-二烷、七丙基-1,4-二烷、八丙基-1,4-二烷、丁基-1,4-二烷、二丁基-1,4-二烷、三丁基-1,4-二烷、四丁基-1,4-二烷、五丁基-1,4-二烷、六丁基-1,4-二烷、七丁基-1,4-二烷、八丁基-1,4-二烷、三烷(trioxane)、二氧雜環庚烷、三氧雜環庚烷、二氧雜環辛烷、三氧雜環辛烷、四氧雜環辛烷、二氧雜環壬烷、三氧雜環壬烷、四氧雜環壬烷、二氧雜環癸烷、三氧雜環癸烷、四氧雜環癸烷、五氧雜環癸烷、12-冠-4、苯并-12-冠-4、二苯并-12-冠-4、萘并-12-冠-4、二萘并-12-冠-4、2,2’-聯萘基-12-冠-4、15-冠-5、苯并-15-冠-5、二苯并-15-冠-5、萘并-15-冠-5、二萘并-15-冠-5、2,3-萘并-15-冠-5、18-冠-6、苯并-18-冠-6、二苯并-18-冠-6、萘并-18-冠-6、二萘并-18-冠-6、二環己烷并-18-冠-6、24-冠-8、苯并-24-冠-8、二苯并-24-冠-8、萘并-24-冠-8、二萘并-24-冠-8、二環己烷并-24-冠-8、30-冠-10、苯并-30-冠-10、二苯并-30-冠-10、萘并-30-冠-10、二萘并-30-冠-10、二環己烷并-30-冠-10。
環狀醚化合物較佳是選自以下之群組中至少1種之化合物。
1,3-二烷、1,4-二烷、甲基-1,3-二烷、二甲基-1,3-二烷、四甲基-1,3-二烷、乙基-1,3-二烷、二乙基-1,3-二烷、四乙基-1,3-二烷、甲基-1,4-二烷、二甲基-1,4-二烷、四甲基-1,4-二烷、乙基-1,4-
二烷、二乙基-1,4-二烷、四乙基-1,4-二烷、二氧雜環庚烷、三氧雜環庚烷、二氧雜環辛烷、三氧雜環辛烷、四氧雜環辛烷、二氧雜環壬烷、三氧雜環壬烷、四氧雜環壬烷、二氧雜環癸烷、12-冠-4、苯并-12-冠-4、15-冠-5、苯并-15-冠-5、18-冠-6、苯并-18-冠-6。
環狀醚化合物更佳是選自以下之群組中至少1種之化合物。
1,3-二烷、1,4-二烷、12-冠-4、苯并-12-冠-4、15-冠-5、18-冠-6。
本實施形態之成分(A-2)是在分子內含有三價磷原子之化合物。作為成分(A-2)者,可以單獨使用1種之三價磷化合物,也可以組合複數種之三價磷化合物而使用。
從有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,(A-2)三價磷化合物是以下述式(1)所示之化合物為佳。
式中,a表示1以上之數。
R1表示碳原子數1至33之鏈狀、分枝狀或是環狀之脂肪族烴基,取代或是無取代之芳香族烴基,或者是取代或是無取代之金屬茂基。
R2及R3各自獨立地表示碳原子數1至33之鏈狀、分枝狀或
是環狀之脂肪族烴基,或者是取代或是無取代之芳香族烴基。
R1與R2,R1與R3或者是R2與R3可以連結。
a為2以上之情形,存在複數個之R2及R3可以相同也可以不同。
R2彼此或是R3彼此可以連結。
上述式(1)中,R1、R2及R3未連結的情形中,若具體地例示R1、R2及R3,則可以列舉以下者。
甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基、二十三烷基、二十四烷基、二十五烷基、二十六烷基、二十七烷基、二十八烷基、二十九烷基、三十烷基、三十一烷基、三十二烷基等脂肪族烴基(此等基可以是直鏈狀、分枝狀或是環狀),取代或是無取代之苯基、萘基、蒽基等芳香族烴基,以及,取代或是無取代之二茂鐵基、二茂釩基、二茂鉻基、二茂鈷基、二茂鎳基、二茂鋯基、二茂鈦基、二茂釕基、二茂鉿基等金屬茂基。
式(1)中,R1與R2、R1與R3、R2與R3、R2彼此或是R3彼此連結之情形,若具體例示R1、R2及R3,則可以列舉以下。
亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、伸十一基、伸十二基、
伸十三基、伸十四基、伸十五基、伸十六基、伸十七基、伸十八基、伸十九基、伸二十基、伸二十一基、伸二十二基、伸二十三基、伸二十四基、伸二十五基、伸二十六基、伸二十七基、伸二十八基、伸二十九基、伸三十基、伸三十一基、伸三十二基等脂肪族烴基(此等基可以是直鏈狀、分枝狀或是環狀),以及,取代或是無取代之伸苯基、伸萘基、伸蒽基等芳香族烴基。
上述式(1)中,a為1,R1、R2、R3皆為芳香族烴基之情形,從有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性的傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,以R1、R2及R3之中至少1個是經取代之芳香族烴基為佳。由同樣之觀點而言,以R1、R2及R3之中2個以上為經取代之芳香族烴基為更佳。從有變得容易取得,且可以更抑制組成物之成本,且經濟性更優良的傾向而言,以R1、R2、R3皆為經取代之芳香族烴基為更佳。
構成經取代之芳香族烴基之取代基並無特別限定,可為電子供與性基(例如,可以列舉:OR基、OCOR基、NR2基、NHCOR基、烷基等,R表示脂肪族烴基、芳香族烴基)、電子吸引性基(可以列舉:CF3基、CCl3基、NO2基、CN基、CHO基、COR基、CO2R基、SO2R基、SO3R基等。又,R表示脂肪族烴基、芳香族烴基)之任何一種。
構成經取代之芳香族烴基之取代基為電子供與性基之情形,有可以更抑制(C)環硫化合物之聚合,且更提高組成
物安定性之傾向,為更佳。構成經取代之芳香族烴基之取代基為電子吸引性基之情形,在聚合(C)環硫化合物之際,有可以更抑制副反應發生之傾向,為更佳。
構成經取代之芳香族烴基之取代基的數量是1以上。從有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,取代基之數量是以2以上為更佳。
構成經取代之芳香族烴基之取代基的數量,從在調整組成物之際,有可以更抑制未溶解物之殘留,且可得到均勻性更優良之組成物的傾向而言,以9以下為佳。從有取得變容易,且可以更抑制組成物之成本,且經濟性更優良之傾向而言,取代基之數量是以5以下為較佳。由同樣之觀點而言,取代基之數量是以3以下為更佳。
(A-2)三價磷化合物中所含有的碳原子數,從在聚合(C)環硫化合物之際,有可以更抑制副反應的傾向而言,以3以上為佳。從在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向而言,碳原子數是以4以上為較佳。從有(A-2)三價磷化合物之蒸氧壓變為更高,且處理性更提高之傾向而言,碳原子數是以6以上為更佳。由同樣之觀點而言,碳原子數是以9以上為特佳。
(A-2)三價磷化合物中所含有之碳原子數,從有取得變容易,且可以更抑制組成物之成本,且經濟性更優良之傾
向而言,以52以下為佳。由同樣之觀點而言,碳原子數是以34以下為較佳。從在調整組成物之際,有可以更抑制未溶解物之殘留,且可得到均勻性更優良之組成物之傾向而言,碳原子數是以28以下為更佳。由同樣之觀點而言,碳原子數是以24以下為特佳。
(A-2)三價磷化合物中所含有之三價磷原子數,從在室溫下調整組成物之際,成為有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性的傾向而言,以1以上為佳。由同樣之觀點而言,三價磷原子數是以2以上為較佳。
(A-2)三價磷化合物中所含有之三價磷原子數,從有取得變容易,且可以更抑制組成物之成本,且優良經濟性之傾向而言,以8以下為佳。由同樣之觀點而言,磷原子數是以4以下為較佳。從在調整組成物之際,有可以抑制未溶解物之殘留,且可得到均勻性優良之組成物之傾向而言,三價磷原子數是以3以下為更佳。
若具體例示成分(A-2),則可以列舉:含有1個三價磷原子的三價磷化合物、含有2個三價磷原子的三價磷化合物,含有3個以上三價磷原子的三價磷化合物等。此等可以單獨使用,也可以組合複數種而使用。
含有1個三價磷原子的三價磷化合物,只要是含有1個三價磷原子的化合物即可而無特別的限定,具體而言,可以列舉上述式(1)中,a為1所示之化合物。
含有1個三價磷原子的三價磷化合物之中,從有變得
容易取得,且可以更抑制組成物之成本,且經濟性更優良之傾向,在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且組成物安定性更提高的傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,以選自以下之群組中至少1種之化合物為佳。
三甲基膦、三乙基膦、三-正-丙基膦、三異丙基膦、三環丙基膦、三(甲基環丙基)膦、三-正-丁基膦、三異丁基膦、三-二級-丁基膦、三-三級-丁基膦、三環丁基膦、三(甲基環丁基)膦、三(甲基丁基)膦、三(二甲基丁基)膦、三(乙基丁基)膦、三(二乙基丁基)膦、三戊基膦、三環戊基膦、三(甲基環戊基)膦、三(甲基戊基)膦、三(二甲基戊基)膦、三(乙基戊基)膦、三(二乙基戊基)膦、三己基膦、三環己基膦、三(甲基環己基)膦、三(甲基己基)膦、三(二甲基己基)膦、三(乙基己基)膦、三(二乙基己基)膦、三庚基膦、三環庚基膦、三(甲基環庚基)膦、三(甲基庚基)膦、三(二甲基庚基)膦、三(乙基庚基)膦、三(二乙基庚基)膦、三辛基膦、三環辛基膦、三(甲基環辛基)膦、三(甲基辛基)膦、三(二甲基辛基)膦、三(乙基辛基)膦、三(二乙基辛基)膦、三壬基膦、三環壬基膦、三(甲基環壬基)膦、三(甲基壬基)膦、三(二甲基壬基)膦、三(乙基壬基)膦、三(二乙基壬基)膦、三癸基膦、三環癸基膦、三(甲基環癸基)膦、三(甲基癸基)膦、三(二甲基癸基)膦、三(乙基癸基)膦、三(二乙基癸基)膦、三(十一烷基)膦、三(甲基十一烷基)膦、三(乙基十一烷基)膦、三(十二烷基)膦、三(甲基十二
烷基)膦、三(乙基十二烷基)膦、三(十三烷基)膦、三(甲基十三烷基)膦、三(乙基十三烷基)膦、三(十四烷基)膦、三(甲基十四烷基)膦、三(乙基十四烷基)膦、三(十五烷基)膦、三(甲基十五烷基)膦、三(乙基十五烷基)膦、三(十六烷基)膦、三(甲基十六烷基)膦、三(乙基十六烷基)膦、三(十七烷基)膦、三(甲基十七烷基)膦、三(乙基十七烷基)膦、三(十八烷基)膦、三(甲基十八烷基)膦、三(乙基十八烷基)膦、三(十九烷基)膦、三(甲基十九烷基)膦、三(乙基十九烷基)膦、三(二十烷基)膦、三(二十一烷基)膦、三(二十二烷基)膦、三(二十三烷基)膦、三(二十四烷基)膦、三(二十五烷基)膦、三(二十六烷基)膦、三(二十七烷基)膦、三(二十八烷基)膦、三(二十九烷基)膦、三(三十烷基)膦、三苯基膦、三(甲基苯基)膦、三(乙基苯基)膦、三(丙基苯基)膦、三(丁基苯基)膦、三(甲氧基苯基)膦、三(二甲基胺基苯基)膦、三(三氟甲基苯基)膦、三(硝基苯基)膦、三(氰基苯基)膦、三(乙醯基苯基)膦、三(氟苯基)膦、三(二甲基苯基)膦、三(二乙基苯基)膦、三(二丙基苯基)膦、三(二丁基苯基)膦、三(二甲氧基苯基)膦、三[雙(二甲基胺基)苯基]膦、三[雙(三氟甲基)苯基]膦、三(二硝基苯基)膦、三(二氰基苯基)膦、三(二乙醯基苯基)膦、三(二氟苯基)膦、三(三甲基苯基)膦、三(三乙基苯基)膦、三(三丙基苯基)膦、三(三丁基苯基)膦、三(三甲氧基苯基)膦、三[參(二甲基胺基)苯基]膦、三[參(三氟甲基)苯基]膦、三(三硝基苯基)膦、三(三
氰基苯基)膦、三(三乙醯基苯基)膦、三(五氟苯基)膦、三苄基膦、三萘基膦、三(甲基萘基)膦、三(乙基萘基)膦、三(丙基萘基)膦、三(丁基萘基)膦、三蒽基膦;二乙基甲基膦、二丙基甲基膦、二丁基甲基膦、二戊基甲基膦、二己基甲基膦、二環己基甲基膦、二辛基甲基膦、二苯基甲基膦、二(甲基苯基)甲基膦、二(丁基苯基)甲基膦、二(二甲基苯基)甲基膦、二(二丙基苯基)甲基膦、二(二丁基苯基)甲基膦、二(三甲基苯基)甲基膦、二(三丁基苯基)甲基膦、二萘基甲基膦、二甲基乙基膦、二丙基乙基膦、二丁基乙基膦、二戊基乙基膦、二己基乙基膦、二環己基乙基膦、二辛基乙基膦、二苯基乙基膦、二(甲基苯基)乙基膦、二(丁基苯基)乙基膦、二(二甲基苯基)乙基膦、二(二丁基苯基)乙基膦、二(三甲基苯基)乙基膦、二(三丁基苯基)乙基膦、二萘基乙基膦、二甲基丙基膦、二乙基丙基膦、二丁基丙基膦、二戊基丙基膦、二己基丙基膦、二環己基丙基膦、二辛基丙基膦、二苯基丙基膦、二(甲基苯基)丙基膦、二(丁基苯基)丙基膦、二(二甲基苯基)丙基膦、二(二丁基苯基)丙基膦、二(三甲基苯基)丙基膦、二(三丁基苯基)丙基膦、二萘基丙基膦、二甲基丁基膦、二乙基丁基膦、二丙基丁基膦、二戊基丁基膦、二己基丁基膦、二環己基丁基膦、二辛基丁基膦、二苯基丁基膦、二(甲基苯基)丁基膦、二(丁基苯基)丁基膦、二(二甲基苯基)丁基膦、二(二丁基苯基)丁基膦、二(三甲基苯基)丁基膦、二(三丁基苯基)丁基膦、二萘基丁基膦、二甲基戊基膦、二乙基
戊基膦、二丙基戊基膦、二丁基戊基膦、二己基戊基膦、二環己基戊基膦、二辛基戊基膦、二苯基戊基膦、二(甲基苯基)戊基膦、二(丁基苯基)戊基膦、二(二甲基苯基)戊基膦、二(二丁基苯基)戊基膦、二(三甲基苯基)戊基膦、二(三丁基苯基)戊基膦、二萘基戊基膦、二甲基己基膦、二乙基己基膦、二丙基己基膦、二丁基己基膦、二戊基己基膦、二環己基己基膦、二辛基己基膦、二苯基己基膦、二(甲基苯基)己基膦、二(丁基苯基)己基膦、二(二甲基苯基)己基膦、二(二丁基苯基)己基膦、二(三甲基苯基)己基膦、二(三丁基苯基)己基膦、二萘基己基膦、二甲基環己基膦、二乙基環己基膦、二丙基環己基膦、二丁基環己基膦、二戊基環己基膦、二己基環己基膦、二辛基環己基膦、二苯基環己基膦、二(甲基苯基)環己基膦、二(丁基苯基)環己基膦、二(二甲基苯基)環己基膦、二(二丁基苯基)環己基膦、二(三甲基苯基)環己基膦、二(三丁基苯基)環己基膦、二萘基環己基膦、二甲基辛基膦、二乙基辛基膦、二丙基辛基膦、二異丙基辛基膦、二丁基辛基膦、二戊基辛基膦、二己基辛基膦、二環己基辛基膦、二苯基辛基膦、二(甲基苯基)辛基膦、二(丁基苯基)辛基膦、二(二甲基苯基)辛基膦、二(二丁基苯基)辛基膦、二(三甲基苯基)辛基膦、二(三丁基苯基)辛基膦、二萘基辛基膦、二甲基苯基膦、二乙基苯基膦、二丙基苯基膦、二環丙基苯基膦、二丁基苯基膦、二戊基苯基膦、二己基苯基膦、
二環己基苯基膦、二辛基苯基膦、二(甲基苯基)苯基膦、二(丙基苯基)苯基膦、二(丁基苯基)苯基膦、二(甲氧基苯基)苯基膦、雙[(二甲基胺基)苯基]苯基膦、雙[(三氟甲基)苯基]苯基膦、二(硝基苯基)苯基膦、二(氰基苯基)苯基膦、二(乙醯基苯基)苯基膦、二(五氟苯基)苯基膦、二(二甲基苯基)苯基膦、二(二丙基苯基)苯基膦、二(二丁基苯基)苯基膦、二(二甲氧基苯基)苯基膦、二[雙(二甲基胺基)苯基]苯基膦、二[雙(三氟甲基)苯基]苯基膦、雙(二硝基苯基)苯基膦、雙(二氰基苯基)苯基膦、雙(二乙醯基苯基)苯基膦、二(三甲基苯基)苯基膦、二(三丙基苯基)苯基膦、二(三丁基苯基)苯基膦、二(三甲氧基苯基)苯基膦、二[參(二甲基胺基)苯基]苯基膦、二[參(三氟甲基)苯基]苯基膦、雙(三硝基苯基)苯基膦、雙(三氰基苯基)苯基膦、雙(三乙醯基苯基)苯基膦、(甲基苯基)二甲基膦、(甲基苯基)二乙基膦、(甲基苯基)二丙基膦、(甲基苯基)二環丙基膦、(甲基苯基)二丁基膦、(甲基苯基)二戊基膦、(甲基苯基)二己基膦、(甲基苯基)二環己基膦、(甲基苯基)二辛基膦、(甲基苯基)二苯基膦、(甲基苯基)二(丙基苯基)膦、(甲基苯基)二(丁基苯基)膦、(甲基苯基)二(二甲基苯基)膦、(甲基苯基)二(二丙基苯基)膦、(甲基苯基)二(二丁基苯基)膦、(甲基苯基)二(三甲基苯基)膦、(甲基苯基)二(三丙基苯基)膦、(甲基苯基)二(三丁基苯基)膦、(甲氧基苯基)二苯基膦、(二甲基胺基)苯基二苯基膦、(三氟甲基)苯基二苯基膦、(硝基苯基)二苯基膦、(氰基苯基)二苯
基膦、(乙醯基苯基)二苯基膦、(五氟苯基)二苯基膦、(二甲氧基苯基)二苯基膦、[雙(二甲基胺基)苯基]二苯基膦、[雙(三氟甲基)苯基]二苯基膦、(二硝基苯基)二苯基膦、(二氰基苯基)二苯基膦、(二乙醯基苯基)二苯基膦、(三甲氧基苯基)二苯基膦、[參(二甲基胺基)苯基]二苯基膦、[參(三氟甲基)苯基]二苯基膦、(三硝基苯基)二苯基膦、(三氰基苯基)二苯基膦、(三乙醯基苯基)二苯基膦、二(甲氧基苯基)(甲基苯基)膦、雙[(二甲基胺基)苯基](甲基苯基)膦、雙[(三氟甲基)苯基](甲基苯基)膦、二(硝基苯基)(甲基苯基)膦、二(氰基苯基)(甲基苯基)膦、二(乙醯基苯基)(甲基苯基)膦、二(五氟苯基)(甲基苯基)膦、二(二甲氧基苯基)(甲基苯基)膦、二[雙(二甲基胺基)苯基](甲基苯基)膦、二[雙(三氟甲基)苯基](甲基苯基)膦、雙(二硝基苯基)(甲基苯基)膦、雙(二氰基苯基)(甲基苯基)膦、雙(二乙醯基苯基)(甲基苯基)膦、二(三甲氧基苯基)(甲基苯基)膦、二[參(二甲基胺基)苯基](甲基苯基)膦、二[參(三氟甲基)苯基](甲基苯基)膦、雙(三硝基苯基)(甲基苯基)膦、雙(三氰基苯基)(甲基苯基)膦、雙(三乙醯基苯基)(甲基苯基)膦、(二甲基苯基)二甲基膦、(二甲基苯基)二乙基膦、(二甲基苯基)二丙基膦、(二甲基苯基)二環丙基膦、(二甲基苯基)二丁基膦、(二甲基苯基)二戊基膦、(二甲基苯基)二己基膦、(二甲基苯基)二環己基膦、(二甲基苯基)二辛基膦、(二甲基苯基)二苯基膦、(二甲基苯基)二(甲基苯基)膦、(二甲基苯基)二(丙基苯基)膦、(二甲基
苯基)二(丁基苯基)膦、(二甲基苯基)二(二甲基苯基)膦、(二甲基苯基)二(二丙基苯基)膦、(二甲基苯基)二(二丁基苯基)膦、(二甲基苯基)二(三甲基苯基)膦、(二甲基苯基)二(三丙基苯基)膦、(二甲基苯基)二(三丁基苯基)膦、二(甲氧基苯基)(二甲基苯基)膦、雙[(二甲基胺基)苯基](二甲基苯基)膦、雙[(三氟甲基)苯基](二甲基苯基)膦、二(硝基苯基)(二甲基苯基)膦、二(氰基苯基)(二甲基苯基)膦、二(乙醯基苯基)(二甲基苯基)膦、二(五氟苯基)(二甲基苯基)膦、二(二甲氧基苯基)(二甲基苯基)膦、二[雙(二甲基胺基)苯基](二甲基苯基)膦、二[雙(三氟甲基)苯基](二甲基苯基)膦、雙(二硝基苯基)(二甲基苯基)膦、雙(二氰基苯基)(二甲基苯基)膦、雙(二乙醯基苯基)(二甲基苯基)膦、二(三甲氧基苯基)(二甲基苯基)膦、二[參(二甲基胺基)苯基](二甲基苯基)膦、二[參(三氟甲基)苯基](二甲基苯基)膦、雙(三硝基苯基)(二甲基苯基)膦、雙(三氰基苯基)(二甲基苯基)膦、雙(三乙醯基苯基)(二甲基苯基)膦、(三甲基苯基)二甲基膦、(三甲基苯基)二乙基膦、(三甲基苯基)二丙基膦、(三甲基苯基)二環丙基膦、(三甲基苯基)二丁基膦、(三甲基苯基)二戊基膦、(三甲基苯基)二己基膦、(三甲基苯基)二環己基膦、(三甲基苯基)二辛基膦、(三甲基苯基)二苯基膦、(三甲基苯基)二(甲基苯基)膦、(三甲基苯基)二(丙基苯基)膦、(三甲基苯基)二(丁基苯基)膦、(三甲基苯基)二(二甲基苯基)膦、(三甲基苯基)二(二
丙基苯基)膦、(三甲基苯基)二(二丁基苯基)膦、(三甲基苯基)二(三丙基苯基)膦、(三甲基苯基)二(三丁基苯基)膦、二(甲氧基苯基)(三甲基苯基)膦、雙[(二甲基胺基)苯基](三甲基苯基)膦、雙[(三氟甲基)苯基](三甲基苯基)膦、二(硝基苯基)(三甲基苯基)膦、二(氰基苯基)(三甲基苯基)膦、二(乙醯基苯基)(三甲基苯基)膦、二(五氟苯基)(三甲基苯基)膦、二(二甲氧基苯基)(三甲基苯基)膦、二[雙(二甲基胺基)苯基](三甲基苯基)膦、二[雙(三氟甲基)苯基](三甲基苯基)膦、雙(二硝基苯基)(三甲基苯基)膦、雙(二氰基苯基)(三甲基苯基)膦、雙(二乙醯基苯基)(三甲基苯基)膦、二(三甲氧基苯基)(三甲基苯基)膦、二[參(二甲基胺基)苯基](三甲基苯基)膦、二[參(三氟甲基)苯基](三甲基苯基)膦、雙(三硝基苯基)(三甲基苯基)膦、雙(三氰基苯基)(三甲基苯基)膦、雙(三乙醯基苯基)(三甲基苯基)膦、(三丙基苯基)二甲基膦、(三丙基苯基)二乙基膦、(三丙基苯基)二丙基膦、(三丙基苯基)二環丙基膦、(三丙基苯基)二丁基膦、(三丙基苯基)二戊基膦、(三丙基苯基)二己基膦、(三丙基苯基)二環己基膦、(三丙基苯基)二辛基膦、(三丙基苯基)二苯基膦、(三丙基苯基)二(甲基苯基)膦、(三丙基苯基)二(丙基苯基)膦、(三丙基苯基)二(丁基苯基)膦、(三丙基苯基)二(二甲基苯基)膦、(三丙基苯基)二(二丙基苯基)膦、(三丙基苯基)二(二丁基苯基)膦、(三丙基苯基)二(三甲基苯基)膦、(三丙基苯基)二(三丁基苯基)
膦、(三丁基苯基)二甲基膦、(三丁基苯基)二乙基膦、(三丁基苯基)二丙基膦、(三丁基苯基)二環丙基膦、(三丁基苯基)二丁基膦、(三丁基苯基)二戊基膦、(三丁基苯基)二己基膦、(三丁基苯基)二環己基膦、(三丁基苯基)二辛基膦、(三丁基苯基)二苯基膦、(三丁基苯基)二(甲基苯基)膦、(三丁基苯基)二(丙基苯基)膦、(三丁基苯基)二(丁基苯基)膦、(三丁基苯基)二(二甲基苯基)膦、(三丁基苯基)二(二丙基苯基)膦、(三丁基苯基)二(二丁基苯基)膦、(三丁基苯基)二(三甲基苯基)膦、(三丁基苯基)二(三丙基苯基)膦、二甲基萘基膦、二乙基萘基膦、二丙基萘基膦、二環丙基萘基膦、二丁基萘基膦、二戊基萘基膦、二己基萘基膦、二環己基萘基膦、二辛基萘基膦、二苯基萘基膦、二(甲基苯基)萘基膦、二(丙基苯基)萘基膦、二(丁基苯基)萘基膦、二(二甲基苯基)萘基膦、二(二丙基苯基)萘基膦、二(二丁基苯基)萘基膦、二(三甲基苯基)萘基膦、二(三丙基苯基)萘基膦、二(三丁基苯基)萘基膦、甲基乙基丙基膦、甲基乙基丁基膦、甲基乙基戊基膦、甲基乙基戊基膦、甲基乙基己基膦、甲基乙基環己基膦、甲基乙基辛基膦、甲基乙基苯基膦、甲基乙基(甲基苯基)膦、甲基乙基(丙基苯基)膦、甲基乙基(丁基苯基)膦、甲基乙基(二甲基苯基)膦、甲基乙基(二丙基苯基)膦、甲基乙基(二丁基苯基)膦、甲基乙基(三甲基苯基)膦、甲基乙基(三丙基苯基)膦、甲基乙基(三丁基苯基)膦、甲基乙基萘基膦、甲基己基環己基
膦、甲基己基辛基膦、甲基己基苯基膦、甲基己基(甲基苯基)膦、甲基己基(丁基苯基)膦、甲基己基(二甲基苯基)膦、甲基己基(二丁基苯基)膦、甲基己基(三甲基苯基)膦、甲基己基(三丁基苯基)膦、甲基環己基辛基膦、甲基環己基苯基膦、甲基環己基(甲基苯基)膦、甲基環己基(丁基苯基)膦、甲基環己基(二甲基苯基)膦、甲基環己基(二丁基苯基)膦、甲基環己基(三甲基苯基)膦、甲基環己基(三丁基苯基)膦、甲基環己基萘基膦、甲基苯基(甲基苯基)膦、甲基苯基(丁基苯基)膦、甲基苯基(二甲基苯基)膦、甲基苯基(二丁基苯基)膦、甲基苯基(三甲基苯基)膦、甲基苯基(三丁基苯基)膦、甲基苯基萘基膦、甲基(二甲基苯基)(二丁基苯基)膦、甲基(二甲基苯基)(三甲基苯基)膦、甲基(二甲基苯基)(三丁基苯基)膦、甲基(二甲基苯基)蒽基膦、甲基(三甲基苯基)(三丁基苯基)膦、丁基乙基戊基膦、丁基乙基己基膦、丁基乙基環己基膦、丁基乙基辛基膦、丁基乙基苯基膦、丁基乙基(甲基苯基)膦、丁基乙基(丁基苯基)膦、丁基乙基(二甲基苯基)膦、丁基乙基(二丁基苯基)膦、丁基乙基(三甲基苯基)膦、丁基乙基(三丁基苯基)膦、丁基乙基萘基膦、乙基己基環己基膦、乙基己基辛基膦、乙基己基苯基膦、乙基己基(甲基苯基)膦、乙基己基(丁基苯基)膦、乙基己基(二甲基苯基)膦、乙基己基(二丁基苯基)膦、乙基己基(三甲基苯基)膦、乙基己基(三丁基苯基)膦、乙基己基萘基膦、乙基環己基辛基膦、乙基環己基苯基膦、乙基環己基(甲基苯基)
膦、乙基環己基(丁基苯基)膦、乙基環己基(二甲基苯基)膦、乙基環己基(二丁基苯基)膦、乙基環己基(三甲基苯基)膦、乙基環己基(三丁基苯基)膦、乙基苯基(甲基苯基)膦、乙基苯基(丁基苯基)膦、乙基苯基(二甲基苯基)膦、乙基苯基(二丁基苯基)膦、乙基苯基(三甲基苯基)膦、乙基苯基(三丁基苯基)膦、乙基苯基萘基膦、乙基(甲基苯基)(丁基苯基)膦、乙基(甲基苯基)(二甲基苯基)膦、乙基(甲基苯基)(二丁基苯基)膦、乙基(甲基苯基)(三甲基苯基)膦、乙基(甲基苯基)(三丁基苯基)膦、乙基(二甲基苯基)(二丁基苯基)膦、乙基(二甲基苯基)(三甲基苯基)膦、乙基(二甲基苯基)(三丁基苯基)膦、乙基(三甲基苯基)(三丁基苯基)膦、丙基己基環己基膦、丙基己基辛基膦、丙基己基苯基膦、丙基己基(甲基苯基)膦、丙基己基(丁基苯基)膦、丙基己基(二甲基苯基)膦、丙基己基(二丁基苯基)膦、丙基己基(三甲基苯基)膦、丙基己基(三丁基苯基)膦、丙基環己基辛基膦、丙基環己基苯基膦、丙基環己基(甲基苯基)膦、丙基環己基(丁基苯基)膦、丙基環己基(二甲基苯基)膦、丙基環己基(二丁基苯基)膦、丙基環己基(三甲基苯基)膦、丙基環己基(三丁基苯基)膦、丙基(甲基苯基)(二甲基苯基)膦、丙基(甲基苯基)(二丁基苯基)膦、丙基(甲基苯基)(三甲基苯基)膦、丙基(甲基苯基)(三丁基苯基)膦、丙基(二甲基苯基)(二丁基苯基)膦、丙基(二甲基苯基)(三甲基苯基)膦、丙基(二甲基苯基)(三丁基苯基)膦、丙基(三甲基苯基)(三丁基苯基)膦、丁
基己基環己基膦、丁基己基辛基膦、丁基己基苯基膦、丁基己基(甲基苯基)膦、丁基己基(丁基苯基)膦、丁基己基(二甲基苯基)膦、丁基己基(二丁基苯基)膦、丁基己基(三甲基苯基)膦、丁基己基(三丁基苯基)膦、丁基環己基辛基膦、丁基環己基苯基膦、丁基環己基(甲基苯基)膦、丁基環己基(丁基苯基)膦、丁基環己基(二甲基苯基)膦、丁基環己基(二丁基苯基)膦、丁基環己基(三甲基苯基)膦、丁基環己基(三丁基苯基)膦、丁基環己基萘基膦、丁基苯基(甲基苯基)膦、丁基苯基(丁基苯基)膦、丁基苯基(二甲基苯基)膦、丁基苯基(二丁基苯基)膦、丁基苯基(三甲基苯基)膦、丁基苯基(三丁基苯基)膦、丁基(甲基苯基)(丁基苯基)膦、丁基(甲基苯基)(二甲基苯基)膦、丁基(甲基苯基)(二丁基苯基)膦、丁基(甲基苯基)(三甲基苯基)膦、丁基(甲基苯基)(三丁基苯基)膦、丁基(甲基苯基)蒽基膦、丁基(二甲基苯基)(二丁基苯基)膦、丁基(二甲基苯基)(三甲基苯基)膦、丁基(二甲基苯基)(三丁基苯基)膦、丁基(三甲基苯基)(三丁基苯基)膦、戊基己基辛基膦、戊基己基苯基膦、戊基己基(甲基苯基)膦、戊基己基(丁基苯基)膦、戊基己基(二甲基苯基)膦、戊基己基(二丁基苯基)膦、戊基己基(三甲基苯基)膦、戊基己基(三丁基苯基)膦、戊基環己基辛基膦、戊基環己基苯基膦、戊基環己基(甲基苯基)膦、戊基環己基(丁基苯基)膦、戊基環己基(二甲基苯基)膦、戊基環己基(二丁基苯基)膦、戊基環己基(三甲基苯基)膦、戊基環己基(三丁基苯基)膦、戊基苯基(甲基
苯基)膦、戊基苯基(丁基苯基)膦、戊基苯基(二甲基苯基)膦、戊基苯基(二丁基苯基)膦、戊基苯基(三甲基苯基)膦、戊基苯基(三丁基苯基)膦、戊基苯基萘基膦、戊基(甲基苯基)(丁基苯基)膦、戊基(甲基苯基)(二甲基苯基)膦、戊基(甲基苯基)(二丁基苯基)膦、戊基(甲基苯基)(三甲基苯基)膦、戊基(甲基苯基)(三丁基苯基)膦、戊基(二甲基苯基)(二丁基苯基)膦、戊基(二甲基苯基)(三甲基苯基)膦、戊基(二甲基苯基)(三丁基苯基)膦、戊基(三甲基苯基)(三丁基苯基)膦、己基環己基辛基膦、己基環己基苯基膦、己基環己基(甲基苯基)膦、己基環己基(丁基苯基)膦、己基環己基(二甲基苯基)膦、己基環己基(二丁基苯基)膦、己基環己基(三甲基苯基)膦、己基環己基(三丁基苯基)膦、己基苯基(甲基苯基)膦、己基苯基(丁基苯基)膦、己基苯基(二甲基苯基)膦、己基苯基(二丁基苯基)膦、己基苯基(三甲基苯基)膦、己基苯基(三丁基苯基)膦、己基苯基萘基膦、己基(甲基苯基)(丁基苯基)膦、己基(甲基苯基)(二甲基苯基)膦、己基(甲基苯基)(二丁基苯基)膦、己基(甲基苯基)(三甲基苯基)膦、己基(甲基苯基)(三丁基苯基)膦、己基(二甲基苯基)(二丁基苯基)膦、己基(二甲基苯基)(三甲基苯基)膦、己基(二甲基苯基)(三丁基苯基)膦、己基(三甲基苯基)(三丁基苯基)膦、環己基苯基(甲基苯基)膦、環己基苯基(丁基苯基)膦、環己基苯基(二甲基苯基)膦、環己基苯基(二丁基苯基)膦、環己基苯基(三甲基苯基)膦、環己基苯基(三丁基苯基)膦、環己基苯基萘基
膦、環己基(甲基苯基)(丁基苯基)膦、環己基(甲基苯基)(二甲基苯基)膦、環己基(甲基苯基)(二丁基苯基)膦、環己基(甲基苯基)(三甲基苯基)膦、環己基(甲基苯基)(三丁基苯基)膦、環己基(二甲基苯基)(二丁基苯基)膦、環己基(二甲基苯基)(三甲基苯基)膦、環己基(二甲基苯基)(三丁基苯基)膦、環己基(三甲基苯基)(三丁基苯基)膦、辛基苯基(甲基苯基)膦、辛基苯基(丁基苯基)膦、辛基苯基(二甲基苯基)膦、辛基苯基(二丁基苯基)膦、辛基苯基(三甲基苯基)膦、辛基苯基(三丁基苯基)膦、辛基苯基萘基膦、辛基(甲基苯基)(丁基苯基)膦、辛基(甲基苯基)(二甲基苯基)膦、辛基(甲基苯基)(二丁基苯基)膦、辛基(甲基苯基)(三甲基苯基)膦、辛基(甲基苯基)(三丁基苯基)膦、辛基(二甲基苯基)(二丁基苯基)膦、辛基(二甲基苯基)(三甲基苯基)膦、辛基(二甲基苯基)(三丁基苯基)膦、辛基(三甲基苯基)(三丁基苯基)膦、辛基(三丁基苯基)蒽基膦、苯基(甲基苯基)(丙基苯基)膦、苯基(甲基苯基)(丁基苯基)膦、苯基(甲基苯基)(二甲基苯基)膦、苯基(甲基苯基)(二丙基苯基)膦、苯基(甲基苯基)(二丁基苯基)膦、苯基(甲基苯基)(三甲基苯基)膦、苯基(甲基苯基)(三丙基苯基)膦、苯基(甲基苯基)(三丁基苯基)膦、苯基(甲基苯基)苄基膦、苯基(甲基苯基)萘基膦、苯基(二甲基苯基)(二丙基苯基)膦、苯基(二甲基苯基)(三甲基苯基)膦、苯基(二甲基苯基)(三丙基苯基)膦、苯基(二甲基苯基)(三丁基苯基)膦、苯基(三甲基苯基)(三丙基苯基)膦、苯基(三甲基
苯基)(三丁基苯基)膦、苯基(三甲基苯基)苄基膦、苯基(三甲基苯基)萘基膦、苯基(三丙基苯基)(三丁基苯基)膦、(甲基苯基)(二甲基苯基)(二丙基苯基)膦、(甲基苯基)(二甲基苯基)(二丁基苯基)膦、(甲基苯基)(二甲基苯基)(三甲基苯基)膦、(甲基苯基)(二甲基苯基)(三丙基苯基)膦、(甲基苯基)(二甲基苯基)(三丁基苯基)膦、(甲基苯基)(三甲基苯基)(三丙基苯基)膦、(甲基苯基)(三甲基苯基)(三丁基苯基)膦、(甲基苯基)(三甲基苯基)萘基膦、(甲基苯基)(三丙基苯基)(三丁基苯基)膦、(二甲基苯基)(三甲基苯基)(三丙基苯基)膦、(二甲基苯基)(三甲基苯基)(三丁基苯基)膦、(二甲基苯基)(三甲基苯基)苄基膦、(二甲基苯基)(三甲基苯基)萘基膦、(二甲基苯基)(三丙基苯基)(三丁基苯基)膦、(三甲基苯基)(三丙基苯基)(三丁基苯基)膦、金剛烷基二甲基膦、金剛烷基二乙基膦、金剛烷基二丙基膦、金剛烷基二環丙基膦、金剛烷基二丁基膦、金剛烷基二戊基膦、金剛烷基二己基膦、金剛烷基二環己基膦、金剛烷基二辛基膦、金剛烷基二苯基膦、金剛烷基二(甲基苯基)膦、金剛烷基二(丁基苯基)膦、金剛烷基二(二甲基苯基)膦、金剛烷基二(二丁基苯基)膦、金剛烷基二(三甲基苯基)膦、金剛烷基二(三丁基苯基)膦、金剛烷基二苄基膦、金剛烷基二萘基膦、二金剛烷基甲基膦、二金剛烷基乙基膦、二金剛烷基丙基膦、二金剛烷基環丙基膦、二金剛烷基丁基膦、二金剛烷基戊基膦、二金剛烷基己基膦、
二金剛烷基環己基膦、二金剛烷基辛基膦、二金剛烷基苯基膦、二金剛烷基(甲基苯基)膦、二金剛烷基(丁基苯基)膦、二金剛烷基(二甲基苯基)膦、二金剛烷基(二丁基苯基)膦、二金剛烷基(三甲基苯基)膦、二金剛烷基(三丁基苯基)膦、二金剛烷基苄基膦、二金剛烷基萘基膦、三金剛烷基膦、2-[二(三級-丁基)膦基]-1,1’-聯苯、2-(二環己基膦基)-1,1’-聯苯、2-(二環己基膦基)-2’-甲基-1,1’-聯苯、1-甲基-2,5-二甲基磷雜環戊烷(1-methyl-2,5-dimethylphospholane)、1-乙基-2,5-二甲基磷雜環戊烷、1-丙基-2,5-二甲基磷雜環戊烷、1-丁基-2,5-二甲基磷雜環戊烷、1-戊基-2,5-二甲基磷雜環戊烷、1-己基-2,5-二甲基磷雜環戊烷、1-環己基-2,5-二甲基磷雜環戊烷、1-辛基-2,5-二甲基磷雜環戊烷、1-苯基-2,5-二甲基磷雜環戊烷、1-甲基苯基-2,5-二甲基磷雜環戊烷、1-丁基苯基-2,5-二甲基磷雜環戊烷、1-二甲基苯基-2,5-二甲基磷雜環戊烷、1-二丁基苯基-2,5-二甲基磷雜環戊烷、1-三甲基苯基-2,5-二甲基磷雜環戊烷、1-三丁基苯基-2,5-二甲基磷雜環戊烷、1-苄基-2,5-二甲基磷雜環戊烷、1-甲基-2,5-二乙基磷雜環戊烷、1-乙基-2,5-二乙基磷雜環戊烷、1-丙基-2,5-二乙基磷雜環戊烷、1-丁基-2,5-二乙基磷雜環戊烷、1-戊基-2,5-二乙基磷雜環戊烷、1-己基-2,5-二乙基磷雜環戊烷、1-環己基-2,5-二乙基磷雜環戊烷、1-辛基-2,5-二乙基磷雜環戊烷、1-苯基-2,5-二乙基磷雜環戊烷、1-甲基苯基-2,5-二乙基磷雜環戊烷、1-丁基苯基-2,5-
二乙基磷雜環戊烷、1-二甲基苯基-2,5-二乙基磷雜環戊烷、1-二丁基苯基-2,5-二乙基磷雜環戊烷、1-三甲基苯基-2,5-二乙基磷雜環戊烷、1-三丁基苯基-2,5-二乙基磷雜環戊烷、1-苄基-2,5-二乙基磷雜環戊烷、1-甲基-2,5-二丙基磷雜環戊烷、1-乙基-2,5-二丙基磷雜環戊烷、1-丙基-2,5-二丙基磷雜環戊烷、1-丁基-2,5-二丙基磷雜環戊烷、1-戊基-2,5-二丙基磷雜環戊烷、1-己基-2,5-二丙基磷雜環戊烷、1-環己基-2,5-二丙基磷雜環戊烷、1-辛基-2,5-二丙基磷雜環戊烷、1-苯基-2,5-二丙基磷雜環戊烷、1-甲基苯基-2,5-二丙基磷雜環戊烷、1-丁基苯基-2,5-二丙基磷雜環戊烷、1-二甲基苯基-2,5-二丙基磷雜環戊烷、1-二丁基苯基-2,5-二丙基磷雜環戊烷、1-三甲基苯基-2,5-二丙基磷雜環戊烷、1-三丁基苯基-2,5-二丙基磷雜環戊烷、1-苄基-2,5-二丙基磷雜環戊烷、1-甲基-2,5-二丁基磷雜環戊烷、1-乙基-2,5-二丁基磷雜環戊烷、1-丙基-2,5-二丁基磷雜環戊烷、1-丁基-2,5-二丁基磷雜環戊烷、1-戊基-2,5-二丁基磷雜環戊烷、1-己基-2,5-二丁基磷雜環戊烷、1-環己基-2,5-二丁基磷雜環戊烷、1-辛基-2,5-二丁基磷雜環戊烷、1-苯基-2,5-二丁基磷雜環戊烷、1-甲基苯基-2,5-二丁基磷雜環戊烷、1-丁基苯基-2,5-二丁基磷雜環戊烷、1-二甲基苯基-2,5-二丁基磷雜環戊烷、1-二丁基苯基-2,5-二丁基磷雜環戊烷、1-三甲基苯基-2,,5-二丁基磷雜環戊烷、1-三丁基苯基-2,5-二丁基磷雜環戊烷、1-苄基-2,5-二丁基磷雜環戊烷、
1-甲基-2,5-二己基磷雜環戊烷、1-乙基-2,5-二己基磷雜環戊烷、1-丙基-2,5-二己基磷雜環戊烷、1-環丙基-2,5-二己基磷雜環戊烷、1-丁基-2,5-二己基磷雜環戊烷、1-戊基-2,5-二己基磷雜環戊烷、1-己基-2,5-二己基磷雜環戊烷、1-環己基-2,5-二己基磷雜環戊烷、1-辛基-2,5-二己基磷雜環戊烷、1-苯基-2,5-二己基磷雜環戊烷、1-甲基苯基-2,5-二己基磷雜環戊烷、1-丁基苯基-2,5-二己基磷雜環戊烷、1-二甲基苯基-2,5-二己基磷雜環戊烷、1-二丁基苯基-2,5-二己基磷雜環戊烷、1-三甲基苯基-2,5-二己基磷雜環戊烷、1-三丁基苯基-2,5-二己基磷雜環戊烷、1-苄基-2,5-二己基磷雜環戊烷、1-甲基-2,5-二環己基磷雜環戊烷、1-乙基-2,5-二環己基磷雜環戊烷、1-丙基-2,5-二環己基磷雜環戊烷、1-環丙基-2,5-二環己基磷雜環戊烷、1-丁基-2,5-二環己基磷雜環戊烷、1-戊基-2,5-二環己基磷雜環戊烷、1-己基-2,5-二環己基磷雜環戊烷、1-環己基-2,5-二環己基磷雜環戊烷、1-辛基-2,5-二環己基磷雜環戊烷、1-苯基-2,5-二環己基磷雜環戊烷、1-甲基苯基-2,5-二環己基磷雜環戊烷、1-丁基苯基-2,5-二環己基磷雜環戊烷、1-二甲基苯基-2,5-二環己基磷雜環戊烷、1-二丁基苯基-2,5-二環己基磷雜環戊烷、1-三甲基苯基-2,5-二環己基磷雜環戊烷、1-三丁基苯基-2,5-二環己基磷雜環戊烷、1-苄基-2,5-二環己基磷雜環戊烷、1-甲基-2,5-二苯基磷雜環戊烷、1-乙基-2,5-二苯基磷雜環戊烷、1-丙基-2,5-二苯基磷雜環戊烷、1-環丙基-2,5-
二苯基磷雜環戊烷、1-丁基-2,5-二苯基磷雜環戊烷、1-戊基-2,5-二苯基磷雜環戊烷、1-己基-2,5-二苯基磷雜環戊烷、1-環己基-2,5-二苯基磷雜環戊烷、1-辛基-2,5-二苯基磷雜環戊烷、1-苯基-2,5-二苯基磷雜環戊烷、1-甲基苯基-2,5-二苯基磷雜環戊烷、1-丁基苯基-2,5-二苯基磷雜環戊烷、1-二甲基苯基-2,5-二苯基磷雜環戊烷、1-二丁基苯基-2,5-二苯基磷雜環戊烷、1-三甲基苯基-2,5-二苯基磷雜環戊烷、1-三丁基苯基-2,5-二苯基磷雜環戊烷、1-苄基-2,5-二苯基磷雜環戊烷、1-甲基-2,5-二(甲基苯基)磷雜環戊烷、1-乙基-2,5-二(甲基苯基)磷雜環戊烷、1-丙基-2,5-二(甲基苯基)磷雜環戊烷、1-丁基-2,5-二(甲基苯基)磷雜環戊烷、1-戊基-2,5-二(甲基苯基)磷雜環戊烷、1-己基-2,5-二(甲基苯基)磷雜環戊烷、1-環己基-2,5-二(甲基苯基)磷雜環戊烷、1-辛基-2,5-二(甲基苯基)磷雜環戊烷、1-苯基-2,5-二(甲基苯基)磷雜環戊烷、1-甲基苯基-2,5-二(甲基苯基)磷雜環戊烷、1-丁基苯基-2,5-二(甲基苯基)磷雜環戊烷、1-二甲基苯基-2,5-二(甲基苯基)磷雜環戊烷、1-二丁基苯基-2,5-二(甲基苯基)磷雜環戊烷、1-三甲基苯基-2,5-二(甲基苯基)磷雜環戊烷、1-三丁基苯基-2,5-二(甲基苯基)磷雜環戊烷、1-苄基-2,5-二(甲基苯基)磷雜環戊烷、1-甲基-2,5-二(甲氧基苯基)磷雜環戊烷、1-甲基-2,5-二(二甲基胺基)苯基磷雜環戊烷、1-甲基-2,5-二(三氟甲基)苯基磷雜環戊烷、1-甲基-2,5-二(硝基苯基)磷雜環戊烷、1-甲基-2,5-二(氰
基苯基)磷雜環戊烷、1-甲基-2,5-二(乙醯基苯基)磷雜環戊烷、1-甲基-2,5-二(五氟苯基)磷雜環戊烷、1-磷雜雙環[3.3.3]十一烷(phosphatrane)。
含有1個三價磷原子之三價磷化合物,較佳是選自以下之群組中至少1種之化合物。
三甲基膦、三乙基膦、三-正-丙基膦、三異丙基膦、三環丙基膦、三-正-丁基膦、三異丁基膦、三-二級-丁基膦、三-三級-丁基膦、三環丁基膦、三戊基膦、三環戊基膦、三己基膦、三環己基膦、三庚基膦、三環庚基膦、三辛基膦、三環辛基膦、三苯基膦、三(甲基苯基)膦、三(甲氧基苯基)膦、三(二甲基胺基苯基)膦、三(三氟甲基苯基)膦、三(氟苯基)膦、三(二甲基苯基)膦、三(二甲氧基苯基)膦、三[雙(二甲基胺基)苯基]膦、三[雙(三氟甲基)苯基]膦、三(二氟苯基)膦、三(三甲基苯基)膦、三(三甲氧基苯基)膦、三[參(二甲基胺基)苯基]膦、三[參(三氟甲基)苯基]膦、三(五氟苯基)膦、三苄基膦、二乙基甲基膦、二丙基甲基膦、二丁基甲基膦、二己基甲基膦、二環己基甲基膦、二苯基甲基膦、二甲基乙基膦、二丙基乙基膦、二丁基乙基膦、二己基乙基膦、二環己基乙基膦、二苯基乙基膦、二甲基丙基膦、二乙基丙基膦、二丁基丙基膦、二己基丙基膦、二環己基丙基膦、二苯基丙基膦、二甲基丁基膦、二乙基丁基膦、二丙基丁基膦、二戊基丁基膦、二己基丁基膦、二環己基丁基膦、二苯基丁基膦、二丁基戊基膦、二環己基戊基膦、二苯基戊基膦、二乙基環己基膦、
二丁基環己基膦、二苯基環己基膦、二甲基苯基膦、二乙基苯基膦、二丙基苯基膦、二丁基苯基膦、二己基苯基膦、二環己基苯基膦、二辛基苯基膦、二(甲基苯基)苯基膦、二(甲氧基苯基)苯基膦、雙[(二甲基胺基)苯基]苯基膦、雙[(三氟甲基)苯基]苯基膦、二(硝基苯基)苯基膦、二(氰基苯基)苯基膦、二(乙醯基苯基)苯基膦、二(五氟苯基)苯基膦、二(三甲氧基苯基)苯基膦、二[參(二甲基胺基)苯基]苯基膦、二[參(三氟甲基)苯基]苯基膦、雙(三硝基苯基)苯基膦、雙(三氰基苯基)苯基膦、雙(三乙醯基苯基)苯基膦、(甲氧基苯基)二苯基膦、(甲基苯基)二苯基膦、(甲氧基苯基)二苯基膦、(二甲基胺基)苯基二苯基膦、(三氟甲基)苯基二苯基膦、(硝基苯基)二苯基膦、(氰基苯基)二苯基膦、(乙醯基苯基)二苯基膦、(五氟苯基)二苯基膦、(三甲氧基苯基)二苯基膦、[參(二甲基胺基)苯基]二苯基膦、[參(三氟甲基)苯基]二苯基膦、(三硝基苯基)二苯基膦、(三氰基苯基)二苯基膦、(三乙醯基苯基)二苯基膦、二金剛烷基丁基膦、二金剛烷基苄基膦、2-[二(三級-丁基)膦基]-1.1’-聯苯、2-(二環己基膦基)-1,1’-聯苯、2-(二環己基膦基)-2’-甲基-1,1’-聯苯。
含有1個三價磷原子之三價磷化合物,更佳是選自以下之群組中至少1種之化合物。
三乙基膦、三-正-丙基膦、三異丙基膦、三-正-丁基膦、三異丁基膦、三-三級-丁基膦、三環戊基膦、三環己基膦、三辛基膦、三(甲基苯基)膦、三(甲氧基苯基)膦、
三(三氟甲基苯基)膦、三(氟苯基)膦、三(二甲基苯基)膦、三(二甲氧基苯基)膦、三[雙(三氟甲基)苯基]膦、三(五氟苯基)膦、二丁基甲基膦、二環己基乙基膦、二丙基丁基膦、二環己基丁基膦、二丁基戊基膦、二丁基環己基膦、二環己基苯基膦、2-(二環己基膦基)-1,1’-聯苯、2-(二環己基膦基)-2’-甲基-1,1’-聯苯。
作為含有2個三價磷原子之三價磷化合物者,只要是含有2個三價磷原子之化合物即可,而無特別限定者,具體而言,可以列舉上述式(1)中,a為2所示者。
含有2個三價磷原子之三價磷化合物之中,從有變得容易取得,且可以更抑制組成物之成本,且經濟性更優異之傾向,在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,以選自以下之群組中至少1種之化合物為佳。
雙(二甲基膦基)甲烷、雙(二乙基膦基)甲烷、雙(二丙基膦基)甲烷、雙(二丁基膦基)甲烷、雙(二戊基膦基)甲烷、雙(二己基膦基)甲烷、雙(二環己基膦基)甲烷、雙(二庚基膦基)甲烷、雙(二辛基膦基)甲烷、雙(二苯基膦基)甲烷、雙[二(甲基苯基)膦基]甲烷、雙[二(丁基苯基)膦基]甲烷、雙[二(二甲基苯基)膦基]甲烷、雙[二(二丁基苯基)膦基]甲烷、雙[二(三甲基苯基)膦基]甲烷、雙[二(三丁基苯基)膦基]甲烷、雙(二苄基膦基)甲烷、雙(二萘基膦基)
甲烷、雙[二(甲氧基苯基)膦基]甲烷、雙{二[(二甲基胺基)苯基]膦基}甲烷、雙{二[(三氟甲基)苯基]膦基}甲烷、雙[二(硝基苯基)膦基]甲烷、雙[二(氰基苯基)膦基]甲烷、雙[二(乙醯基苯基)膦基]甲烷、雙[二(五氟苯基)膦基]甲烷、雙[二(二甲氧基苯基)膦基]甲烷、雙{二[二(三氟甲基)苯基]膦基}甲烷、雙[二(三甲氧基苯基)膦基]甲烷、雙{二[三(三氟甲基)苯基]膦基}甲烷、雙(二甲基膦基)乙烷、雙(二乙基膦基)乙烷、雙(二丙基膦基)乙烷、雙(二丁基膦基)乙烷、雙(二環丁基膦基)乙烷、雙(二戊基膦基)乙烷、雙(二己基膦基)乙烷、雙(二環己基膦基)乙烷、雙(二庚基膦基)乙烷、雙(二辛基膦基)乙烷、雙(二苯基膦基)乙烷、雙[二(甲基苯基)膦基]乙烷、雙[二(丁基苯基)膦基]乙烷、雙[二(二甲基苯基)膦基]乙烷、雙[二(二丁基苯基)膦基]乙烷、雙[二(三甲基苯基)膦基]乙烷、雙[二(三丁基苯基)膦基]乙烷、雙(二苄基膦基)乙烷、雙(二萘基膦基)乙烷、雙[二(甲氧基苯基)膦基]乙烷、雙{二[(二甲基胺基)苯基]膦基}乙烷、雙{二[(三氟甲基)苯基]膦基}乙烷、雙[二(硝基苯基)膦基]乙烷、雙[二(氰基苯基)膦基]乙烷、雙[二(乙醯基苯基)膦基]乙烷、雙[二(五氟苯基)膦基]乙烷、雙[二(二甲氧基苯基)膦基]乙烷、雙{二[二(三氟甲基)苯基]膦基}乙烷、雙[二(三甲氧基苯基)膦基]乙烷、雙{二[三(三氟甲基)苯基]膦基}乙烷、雙(二甲基膦基)丙烷、雙(二乙基膦基)丙烷、雙(二丙基膦基)丙烷、雙(二丁基膦基)丙烷、雙(二環丁基膦基)丙烷、
雙(二戊基膦基)丙烷、雙(二己基膦基)丙烷、雙(二環己基膦基)丙烷、雙(二庚基膦基)丙烷、雙(二辛基膦基)丙烷、雙(二苯基膦基)丙烷、雙[二(甲基苯基)膦基]丙烷、雙[二(丁基苯基)膦基]丙烷、雙[二(二甲基苯基)膦基]丙烷、雙[二(二丁基苯基)膦基]丙烷、雙[二(三甲基苯基)膦基]丙烷、雙[二(三丁基苯基)膦基]丙烷、雙(二苄基膦基)丙烷、雙(二萘基膦基)丙烷、雙[二(甲氧基苯基)膦基]丙烷、雙{二[(二甲基胺基)苯基]膦基}丙烷、雙{二[(三氟甲基)苯基]膦基}丙烷、雙[二(硝基苯基)膦基]丙烷、雙[二(氰基苯基)膦基]丙烷、雙[二(乙醯基苯基)膦基]丙烷、雙[二(五氟苯基)膦基]丙烷、雙[二(二甲氧基苯基)膦基]丙烷、雙{二[二(三氟甲基)苯基]膦基}丙烷、雙[二(三甲氧基苯基)膦基]丙烷、雙{二[三(三氟甲基)苯基]膦基}丙烷、雙(二甲基膦基)丁烷、雙(二乙基膦基)丁烷、雙(二丙基膦基)丁烷、雙(二丁基膦基)丁烷、雙(二環丁基膦基)丁烷、雙(二戊基膦基)丁烷、雙(二己基膦基)丁烷、雙(二環己基膦基)丁烷、雙(二庚基膦基)丁烷、雙(二辛基膦基)丁烷、雙(二苯基膦基)丁烷、雙[二(甲基苯基)膦基]丁烷、雙[二(丁基苯基)膦基]丁烷、雙[二(二甲基苯基)膦基]丁烷、雙[二(二丁基苯基)膦基]丁烷、雙[二(三甲基苯基)膦基]丁烷、雙[二(三丁基苯基)膦基]丁烷、雙(二苄基膦基)丁烷、雙(二萘基膦基)丁烷、雙[二(甲氧基苯基)膦基]丁烷、雙{二[(二甲基胺基)苯基]膦基}丁烷、雙{二[(三氟甲基)苯基]膦基}丁烷、雙[二(硝基苯基)膦基]丁烷、雙[二(氰基苯基)膦基]
丁烷、雙[二(乙醯基苯基)膦基]丁烷、雙[二(五氟苯基)膦基]丁烷、雙[二(二甲氧基苯基)膦基]丁烷、雙{二[二(三氟甲基)苯基]膦基}丁烷、雙[二(三甲氧基苯基)膦基]丁烷、雙{二[三(三氟甲基)苯基]膦基}丁烷、雙(二甲基膦基)戊烷、雙(二乙基膦基)戊烷、雙(二丙基膦基)戊烷、雙(二丁基膦基)戊烷、雙(二環丁基膦基)戊烷、雙(二戊基膦基)戊烷、雙(二己基膦基)戊烷、雙(二環己基膦基)戊烷、雙(二庚基膦基)戊烷、雙(二辛基膦基)戊烷、雙(二苯基膦基)戊烷、雙[二(甲基苯基)膦基]戊烷、雙[二(丁基苯基)膦基]戊烷、雙[二(二甲基苯基)膦基]戊烷、雙[二(二丁基苯基)膦基]戊烷、雙[二(三甲基苯基)膦基]戊烷、雙[二(三丁基苯基)膦基]戊烷、雙(二苄基膦基)戊烷、雙(二萘基膦基)戊烷、雙(二甲基膦基)環戊烷、雙(二乙基膦基)環戊烷、雙(二丙基膦基)環戊烷、雙(二丁基膦基)環戊烷、雙(二環丁基膦基)環戊烷、雙(二戊基膦基)環戊烷、雙(二己基膦基)環戊烷、雙(二環己基膦基)環戊烷、雙(二庚基膦基)環戊烷、雙(二辛基膦基)環戊烷、雙(二苯基膦基)環戊烷、雙[二(甲基苯基)膦基]環戊烷、雙[二(丁基苯基)膦基]環戊烷、雙[二(二甲基苯基)膦基]環戊烷、雙[二(二丁基苯基)膦基]環戊烷、雙[二(三甲基苯基)膦基]環戊烷、雙[二(三丁基苯基)膦基]環戊烷、雙(二苄基膦基)環戊烷、雙(二萘基膦基)環戊烷、雙(二甲基膦基)己烷、雙(二乙基膦基)己烷、雙(二丙基膦基)己烷、雙(二丁基膦基)己烷、雙(二環丁基膦基)己烷、
雙(二戊基膦基)己烷、雙(二己基膦基)己烷、雙(二環己基膦基)己烷、雙(二庚基膦基)己烷、雙(二辛基膦基)己烷、雙(二苯基膦基)己烷、雙[二(甲基苯基)膦基]己烷、雙[二(丁基苯基)膦基]己烷、雙[二(二甲基苯基)膦基]己烷、雙[二(二丁基苯基)膦基]己烷、雙[二(三甲基苯基)膦基]己烷、雙[二(三丁基苯基)膦基]己烷、雙(二苄基膦基)己烷、雙(二萘基膦基)己烷、雙(二甲基膦基)環己烷、雙(二乙基膦基)環己烷、雙(二丙基膦基)環己烷、雙(二丁基膦基)環己烷、雙(二環丁基膦基)環己烷、雙(二戊基膦基)環己烷、雙(二己基膦基)環己烷、雙(二環己基膦基)環己烷、雙(二庚基膦基)環己烷、雙(二辛基膦基)環己烷、雙(二苯基膦基)環己烷、雙[二(甲基苯基)膦基]環己烷、雙[二(丁基苯基)膦基]環己烷、雙[二(二甲基苯基)膦基]環己烷、雙[二(二丁基苯基)膦基]環己烷、雙[二(三甲基苯基)膦基]環己烷、雙[二(三丁基苯基)膦基]環己烷、雙(二苄基膦基)環己烷、雙(二萘基膦基)環己烷、雙(二甲基膦基)辛烷、雙(二乙基膦基)辛烷、雙(二丙基膦基)辛烷、雙(二丁基膦基)辛烷、雙(二環丁基膦基)辛烷、雙(二戊基膦基)辛烷、雙(二己基膦基)辛烷、雙(二環己基膦基)辛烷、雙(二庚基膦基)辛烷、雙(二辛基膦基)辛烷、雙(二苯基膦基)辛烷、雙[二(甲基苯基)膦基]辛烷、雙[二(丁基苯基)膦基]辛烷、雙[二(二甲基苯基)膦基]辛烷、雙[二(二丁基苯基)膦基]辛烷、雙[二(三甲基苯基)膦基]辛烷、雙[二(三丁基苯基)膦基]辛烷、雙(二苄基膦基)辛烷、
雙(二萘基膦基)辛烷、雙(二甲基膦基)苯、雙(二乙基膦基)苯、雙(二丙基膦基)苯、雙(二丁基膦基)苯、雙(二環丁基膦基)苯、雙(二戊基膦基)苯、雙(二己基膦基)苯、雙(二環己基膦基)苯、雙(二庚基膦基)苯、雙(二辛基膦基)苯、雙(二苯基膦基)苯、雙[二(甲基苯基)膦基]苯、雙[二(丁基苯基)膦基]苯、雙[二(二甲基苯基)膦基]苯、雙[二(二丁基苯基)膦基]苯、雙[二(三甲基苯基)膦基]苯、雙[二(三丁基苯基)膦基]苯、雙(二苄基膦基)苯、雙(二萘基膦基)苯、雙[二(甲氧基苯基)膦基]苯、雙{二[(二甲基胺基)苯基]膦基}苯、雙{二[(三氟甲基)苯基]膦基}苯、雙[二(硝基苯基)膦基]苯、雙[二(氰基苯基)膦基]苯、雙[二(乙醯基苯基)膦基]苯、雙[二(五氟苯基)膦基]苯、雙[二(二甲氧基苯基)膦基]苯、雙{二[二(三氟甲基)苯基]膦基}苯、雙[二(三甲氧基苯基)膦基]苯、雙{二[三(三氟甲基)苯基]膦基}苯、雙(二甲基膦基)萘、雙(二乙基膦基)萘、雙(二丙基膦基)萘、雙(二丁基膦基)萘、雙(二環丁基膦基)萘、雙(二戊基膦基)萘、雙(二己基膦基)萘、雙(二環己基膦基)萘、雙(二庚基膦基)萘、雙(二辛基膦基)萘、雙(二苯基膦基)萘、雙[二(甲基苯基)膦基]萘、雙[二(丁基苯基)膦基]萘、雙[二(二甲基苯基)膦基]萘、雙[二(二丁基苯基)膦基]萘、雙[二(三甲基苯基)膦基]萘、雙[二(三丁基苯基)膦基]萘、雙(二苄基膦基)萘、雙(二萘基膦基)萘、雙(二甲基膦基)二茂鐵、雙(二乙基膦基)二茂鐵、雙(二丙基膦基)二茂鐵、雙(二
丁基膦基)二茂鐵、雙(二戊基膦基)二茂鐵、雙(二己基膦基)二茂鐵、雙(二環己基膦基)二茂鐵、雙(二庚基膦基)二茂鐵、雙(二辛基膦基)二茂鐵、雙(二苯基膦基)二茂鐵、雙[二(甲基苯基)膦基]二茂鐵、雙[二(丁基苯基)膦基]二茂鐵、雙[二(二甲基苯基)膦基]二茂鐵、雙[二(二丁基苯基)膦基]二茂鐵、雙[二(三甲基苯基)膦基]二茂鐵、雙[二(三丁基苯基)膦基]二茂鐵、雙(二苄基膦基)二茂鐵、雙(二萘基膦基)二茂鐵、雙[二(甲氧基苯基)膦基]二茂鐵、雙{二[(二甲基胺基)苯基]膦基}二茂鐵、雙{二[(三氟甲基)苯基]膦基}二茂鐵、雙[二(硝基苯基)膦基]二茂鐵、雙[二(氰基苯基)膦基]二茂鐵、雙[二(乙醯基苯基)膦基]二茂鐵、雙[二(五氟苯基)膦基]二茂鐵、雙[二(二甲氧基苯基)膦基]二茂鐵、雙{二[二(三氟甲基)苯基]膦基}二茂鐵、雙[二(三甲氧基苯基)膦基]二茂鐵、雙{二[三(三氟甲基)苯基]膦基}二茂鐵、雙(二甲基膦基)二茂釩、雙(二乙基膦基)二茂釩、雙(二丙基膦基)二茂釩、雙(二丁基膦基)二茂釩、雙(二戊基膦基)二茂釩、雙(二己基膦基)二茂釩、雙(二環己基膦基)二茂釩、雙(二庚基膦基)二茂釩、雙(二辛基膦基)二茂釩、雙(二環辛基膦基)二茂釩、雙(二苯基膦基)二茂釩、雙[二(甲基苯基)膦基]二茂釩、雙[二(丁基苯基)膦基]二茂釩、雙[二(二甲基苯基)膦基]二茂釩、雙[二(二丁基苯基)膦基]二茂釩、雙[二(三甲基苯基)膦基]二茂釩、雙[二(三丁基苯基)膦基]二茂釩、雙(二苄基膦基)二茂釩、雙(二萘基膦基)
二茂釩、雙(二甲基膦基)二茂鉻、雙(二乙基膦基)二茂鉻、雙(二丙基膦基)二茂鉻、雙(二丁基膦基)二茂鉻、雙(二戊基膦基)二茂鉻、雙(二己基膦基)二茂鉻、雙(二環己基膦基)二茂鉻、雙(二庚基膦基)二茂鉻、雙(二辛基膦基)二茂鉻、雙(二環辛基膦基)二茂鉻、雙(二苯基膦基)二茂鉻、雙[二(甲基苯基)膦基]二茂鉻、雙[二(丁基苯基)膦基]二茂鉻、雙[二(二甲基苯基)膦基]二茂鉻、雙[二(二丁基苯基)膦基]二茂鉻、雙[二(三甲基苯基)膦基]二茂鉻、雙[二(三丁基苯基)膦基]二茂鉻、雙(二苄基膦基)二茂鉻、雙(二萘基膦基)二茂鉻、雙(二甲基膦基)二茂鈷、雙(二乙基膦基)二茂鈷、雙(二丙基膦基)二茂鈷、雙(二丁基膦基)二茂鈷、雙(二戊基膦基)二茂鈷、雙(二己基膦基)二茂鈷、雙(二環己基膦基)二茂鈷、雙(二庚基膦基)二茂鈷、雙(二辛基膦基)二茂鈷、雙(二苯基膦基)二茂鈷、雙[二(甲基苯基)膦基]二茂鈷、雙[二(丁基苯基)膦基]二茂鈷、雙[二(二甲基苯基)膦基]二茂鈷、雙[二(二丁基苯基)膦基]二茂鈷、雙[二(三甲基苯基)膦基]二茂鈷、雙[二(三丁基苯基)膦基]二茂鈷、雙(二苄基膦基)二茂鈷、雙(二萘基膦基)二茂鈷、雙(二甲基膦基)二茂鎳、雙(二乙基膦基)二茂鎳、雙(二丙基膦基)二茂鎳、雙(二丁基膦基)二茂鎳、雙(二戊基膦基)二茂鎳、雙(二己基膦基)二茂鎳、雙(二環己基膦基)二茂鎳、雙(二庚基膦基)二茂鎳、雙(二辛基膦基)二茂鎳、雙(二苯基膦基)二茂鎳、雙[二(甲基苯基)膦基]二茂鎳、雙[二(丁基苯基)膦基]二茂鎳、雙[二(二甲基苯基)膦基]二茂
鎳、雙[二(二丁基苯基)膦基]二茂鎳、雙[二(三甲基苯基)膦基]二茂鎳、雙[二(三丁基苯基)膦基]二茂鎳、雙(二苄基膦基)二茂鎳、雙(二萘基膦基)二茂鎳、雙(二甲基膦基)二茂鋯、雙(二乙基膦基)二茂鋯、雙(二丙基膦基)二茂鋯、雙(二丁基膦基)二茂鋯、雙(二戊基膦基)二茂鋯、雙(二己基膦基)二茂鋯、雙(二環己基膦基)二茂鋯、雙(二庚基膦基)二茂鋯、雙(二辛基膦基)二茂鋯、雙(二苯基膦基)二茂鋯、雙[二(甲基苯基)膦基]二茂鋯、雙[二(丁基苯基)膦基]二茂鋯、雙[二(二甲基苯基)膦基]二茂鋯、雙[二(二丁基苯基)膦基]二茂鋯、雙[二(三甲基苯基)膦基]二茂鋯、雙[二(三丁基苯基)膦基]二茂鋯、雙(二苄基膦基)二茂鋯、雙(二萘基膦基)二茂鋯、雙(二甲基膦基)二茂鈦、雙(二乙基膦基)二茂鈦、雙(二丙基膦基)二茂鈦、雙(二丁基膦基)二茂鈦、雙(二戊基膦基)二茂鈦、雙(二己基膦基)二茂鈦、雙(二環己基膦基)二茂鈦、雙(二庚基膦基)二茂鈦、雙(二辛基膦基)二茂鈦、雙(二苯基膦基)二茂鈦、雙[二(甲基苯基)膦基]二茂鈦、雙[二(丁基苯基)膦基]二茂鈦、雙[二(二甲基苯基)膦基]二茂鈦、雙[二(二丁基苯基)膦基]二茂鈦、雙[二(三甲基苯基)膦基]二茂鈦、雙[二(三丁基苯基)膦基]二茂鈦、雙(二苄基膦基)二茂鈦、雙(二萘基膦基)二茂鈦、雙(二甲基膦基)二茂釕、雙(二乙基膦基)二茂釕、雙(二丙基膦基)二茂釕、雙(二丁基膦基)二茂釕、雙(二戊基膦基)二茂釕、雙(二己基膦基)二茂釕、雙(二環己基膦基)二茂
釕、雙(二庚基膦基)二茂釕、雙(二辛基膦基)二茂釕、雙(二苯基膦基)二茂釕、雙[二(甲基苯基)膦基]二茂釕、雙[二(丁基苯基)膦基]二茂釕、雙[二(二甲基苯基)膦基]二茂釕、雙[二(二丁基苯基)膦基]二茂釕、雙[二(三甲基苯基)膦基]二茂釕、雙[二(三丁基苯基)膦基]二茂釕、雙(二苄基膦基)二茂釕、雙(二萘基膦基)二茂釕、雙(二甲基膦基)二茂鉿、雙(二乙基膦基)二茂鉿、雙(二丙基膦基)二茂鉿、雙(二丁基膦基)二茂鉿、雙(二戊基膦基)二茂鉿、雙(二己基膦基)二茂鉿、雙(二環己基膦基)二茂鉿、雙(二庚基膦基)二茂鉿、雙(二辛基膦基)二茂鉿、雙(二苯基膦基)二茂鉿、雙[二(甲基苯基)膦基]二茂鉿、雙[二(丁基苯基)膦基]二茂鉿、雙[二(二甲基苯基)膦基]二茂鉿、雙[二(二丁基苯基)膦基]二茂鉿、雙[二(三甲基苯基)膦基]二茂鉿、雙[二(三丁基苯基)膦基]二茂鉿、雙(二苄基膦基)二茂鉿、雙(二萘基膦基)二茂鉿、2,2’-雙(二甲基膦基)-1,1’-聯苯、2,2’-雙(二乙基膦基)-1,1’-聯苯、2,2’-雙(二丙基膦基)-1,1’-聯苯、2,2’-雙(二丁基膦基)-1,1’-聯苯、2,2’-雙(二戊基膦基)-1,1’-聯苯、2,2’-雙(二己基膦基)-1,1’-聯苯、2,2’-雙(二環己基膦基)-1,1’-聯苯、2,2’-雙(二庚基膦基)-1,1’-聯苯、2,2’-雙(二辛基膦基)-1,1’-聯苯、2,2’-雙(二苯基膦基)-1,1’-聯苯、2,2’-雙[二(甲基苯基)膦基]-1,1’-聯苯、2,2’-雙[二(丁基苯基)膦基]-1,1’-聯苯、2,2’-雙[二(二甲基苯基)膦基]-1,1’-聯苯、2,2’-雙[二(二丁基苯基)膦
基]-1,1’-聯苯、2,2’-雙[二(三甲基苯基)膦基]-1,1’-聯苯、2,2’-雙[二(三丁基苯基)膦基]-1,1’-聯苯、2,2’-雙(二苄基膦基)-1,1’-聯苯、2,2’-雙(二萘基膦基)-1,1’-聯苯、2,2’-雙[二(甲氧基苯基)膦基]-1,1’-聯苯、2,2’-雙{二[(二甲基胺基)苯基]膦基}-1,1’-聯苯、2,2’-雙{二[(三氟甲基)苯基]膦基}-1,1’-聯苯、2,2’-雙[二(硝基苯基)膦基]-1,1’-聯苯、2,2’-雙[二(氰基苯基)膦基]-1,1’-聯苯、2,2’-雙[二(乙醯基苯基)膦基]-1,1’-聯苯、2,2’-雙[二(五氟苯基)膦基]-1,1’-聯苯、2,2’-雙[二(二甲氧基苯基)膦基]-1,1’-聯苯、2,2’-雙{二[二(三氟甲基)苯基]膦基}-1,1’-聯苯、2,2’-雙[三(二甲氧基苯基)膦基]-1,1’-聯苯、2,2’-雙{三[二(三氟甲基)苯基]膦基}-1,1’-聯苯、2,2’-雙(二甲基膦基)-1,1’-聯萘、2,2’-雙(二乙基膦基)-1,1’-聯萘、2,2’-雙(二丙基膦基)-1,1’-聯萘、2,2’-雙(二丁基膦基)-1,1’-聯萘、2,2’-雙(二戊基膦基)-1,1’-聯萘、2,2’-雙(二己基膦基)-1,1’-聯萘、2,2’-雙(二環己基膦基)-1,1’-聯萘、2,2’-雙(二庚基膦基)-1,1’-聯萘、2,2’-雙(二辛基膦基)-1,1’-聯萘、2,2’-雙(二苯基膦基)-1,1’-聯萘、2,2’-雙[二(甲基苯基)膦基]-1,1’-聯萘、2,2’-雙[二(丁基苯基)膦基]-1,1’-聯萘、2,2’-雙[二(二甲基苯基)膦基]-1,1’-聯萘、2,2’-雙[二(二丁基苯基)膦基]-1,1’-聯萘、2,2’-雙[二(三甲基苯基)膦基]-1,1’-聯萘、2,2’-雙[二(三丁基苯基)膦基]-1,1’-聯萘、2,2’-雙
(二苄基膦基)-1,1’-聯萘、2,2’-雙(二萘基膦基)-1,1’-聯萘、2,2’-雙[二(甲氧基苯基)膦基]-1,1’-聯萘、2,2’-雙{二[(二甲基胺基)苯基]膦基}-1,1’-聯萘、2,2’-雙{二[(三氟甲基)苯基]膦基}-1,1’-聯萘、2,2’-雙[二(硝基苯基)膦基]-1,1’-聯萘、2,2’-雙[二(氰基苯基)膦基]-1,1’-聯萘、2,2’-雙[二(乙醯基苯基)膦基]-1,1’-聯萘、2,2’-雙[二(五氟苯基)膦基]-1,1’-聯萘、2,2’-雙[二(二甲氧基苯基)膦基]-1,1’-聯萘、2,2’-雙{二[二(三氟甲基)苯基]膦基}-1,1’-聯萘、2,2’-雙[三(二甲氧基苯基)膦基]-1,1’-聯萘、2,2’-雙{三[二(三氟甲基)苯基]膦基}-1,1’-聯萘、雙(磷雜環戊烷基)甲烷(bis(phospholano)methane)、雙(磷雜環戊烷基)乙烷、雙(磷雜環戊烷基)丙烷、雙(磷雜環戊烷基)丁烷、雙(磷雜環戊烷基)戊烷、雙(磷雜環戊烷基)己烷、雙(磷雜環戊烷基)環己烷、雙(磷雜環戊烷基)庚烷、雙(磷雜環戊烷基)辛烷、雙(磷雜環戊烷基)苯、雙(磷雜環戊烷基)萘、雙(磷雜環戊烷基)二茂鐵、雙(磷雜環戊烷基)二茂鈦、雙(磷雜環戊烷基)二茂鉻、雙(磷雜環戊烷基)二茂鈷、雙(磷雜環戊烷基)二茂鎳、雙(磷雜環戊烷基)二茂鋯、雙(磷雜環戊烷基)二茂釕、雙(磷雜環戊烷基)二茂鉿、雙(二甲基磷雜環戊烷基)甲烷、雙(二甲基磷雜環戊烷基)乙烷、雙(二甲基磷雜環戊烷基)丙烷、雙(二甲基磷雜環戊烷基)丁烷、雙(二甲基磷雜環戊烷基)戊烷、雙(二甲基磷雜環戊烷基)己烷、雙(二甲基磷雜環戊烷基)環己烷、雙(二
甲基磷雜環戊烷基)庚烷、雙(二甲基磷雜環戊烷基)辛烷、雙(二甲基磷雜環戊烷基)苯、雙(二甲基磷雜環戊烷基)萘、雙(二甲基磷雜環戊烷基)二茂鐵、雙(二甲基磷雜環戊烷基)二茂鈦、雙(二甲基磷雜環戊烷基)二茂鉻、雙(二甲基磷雜環戊烷基)二茂鈷、雙(二甲基磷雜環戊烷基)二茂鎳、雙(二甲基磷雜環戊烷基)二茂鋯、雙(二甲基磷雜環戊烷基)二茂釕、雙(二甲基磷雜環戊烷基)二茂鉿、雙(二乙基磷雜環戊烷基)甲烷、雙(二乙基磷雜環戊烷基)乙烷、雙(二乙基磷雜環戊烷基)丙烷、雙(二乙基磷雜環戊烷基)丁烷、雙(二乙基磷雜環戊烷基)戊烷、雙(二乙基磷雜環戊烷基)己烷、雙(二乙基磷雜環戊烷基)環己烷、雙(二乙基磷雜環戊烷基)庚烷、雙(二乙基磷雜環戊烷基)辛烷、雙(二乙基磷雜環戊烷基)苯、雙(二乙基磷雜環戊烷基)萘、雙(二乙基磷雜環戊烷基)二茂鐵、雙(二乙基磷雜環戊烷基)二茂鈦、雙(二乙基磷雜環戊烷基)二茂鉻、雙(二乙基磷雜環戊烷基)二茂鈷、雙(二乙基磷雜環戊烷基)二茂鎳、雙(二乙基磷雜環戊烷基)二茂鋯、雙(二乙基磷雜環戊烷基)二茂釕、雙(二乙基磷雜環戊烷基)二茂鉿、雙(二丙基磷雜環戊烷基)甲烷、雙(二丙基磷雜環戊烷基)乙烷、雙(二丙基磷雜環戊烷基)丙烷、雙(二丙基磷雜環戊烷基)丁烷、雙(二丙基磷雜環戊烷基)戊烷、雙(二丙基磷雜環戊烷基)己烷、雙(二丙基磷雜環戊烷基)環己烷、雙(二丙基磷雜環戊烷基)庚烷、雙(二丙基磷雜環戊烷基)辛烷、雙(二丙基磷雜環戊烷基)苯、雙(二丙基磷雜環戊烷基)
萘、雙(二丙基磷雜環戊烷基)二茂鐵、雙(二丙基磷雜環戊烷基)二茂鈦、雙(二丙基磷雜環戊烷基)二茂鉻、雙(二丙基磷雜環戊烷基)二茂鈷、雙(二丙基磷雜環戊烷基)二茂鎳、雙(二丙基磷雜環戊烷基)二茂鋯、雙(二丙基磷雜環戊烷基)二茂釕、雙(二丙基磷雜環戊烷基)二茂鉿、雙(二丁基磷雜環戊烷基)甲烷、雙(二丁基磷雜環戊烷基)乙烷、雙(二丁基磷雜環戊烷基)丙烷、雙(二丁基磷雜環戊烷基)丁烷、雙(二丁基磷雜環戊烷基)戊烷、雙(二丁基磷雜環戊烷基)己烷、雙(二丁基磷雜環戊烷基)環己烷、雙(二丁基磷雜環戊烷基)庚烷、雙(二丁基磷雜環戊烷基)辛烷、雙(二丁基磷雜環戊烷基)苯、雙(二丁基磷雜環戊烷基)萘、雙(二丁基磷雜環戊烷基)二茂鐵、雙(二丁基磷雜環戊烷基)二茂鈦、雙(二丁基磷雜環戊烷基)二茂鉻、雙(二丁基磷雜環戊烷基)二茂鈷、雙(二丁基磷雜環戊烷基)二茂鎳、雙(二丁基磷雜環戊烷基)二茂鋯、雙(二丁基磷雜環戊烷基)二茂釕、雙(二丁基磷雜環戊烷基)二茂鉿、雙(二戊基磷雜環戊烷基)甲烷、雙(二戊基磷雜環戊烷基)乙烷、雙(二戊基磷雜環戊烷基)丙烷、雙(二戊基磷雜環戊烷基)丁烷、雙(二戊基磷雜環戊烷基)戊烷、雙(二戊基磷雜環戊烷基)己烷、雙(二戊基磷雜環戊烷基)環己烷、雙(二戊基磷雜環戊烷基)庚烷、雙(二戊基磷雜環戊烷基)辛烷、雙(二戊基磷雜環戊烷基)苯、雙(二戊基磷雜環戊烷基)萘、雙(二戊基磷雜環戊烷基)二茂鐵、雙(二戊基磷雜環戊烷基)二茂鈦、雙(二戊基磷雜環戊烷基)二茂鉻、雙(二戊基磷雜環戊烷基)二茂
鈷、雙(二戊基磷雜環戊烷基)二茂鎳、雙(二戊基磷雜環戊烷基)二茂鋯、雙(二戊基磷雜環戊烷基)二茂釕、雙(二戊基磷雜環戊烷基)二茂鉿、雙(二環戊基磷雜環戊烷基)甲烷、雙(二環戊基磷雜環戊烷基)乙烷、雙(二環戊基磷雜環戊烷基)丙烷、雙(二環戊基磷雜環戊烷基)丁烷、雙(二環戊基磷雜環戊烷基)戊烷、雙(二環戊基磷雜環戊烷基)己烷、雙(二環戊基磷雜環戊烷基)環己烷、雙(二環戊基磷雜環戊烷基)庚烷、雙(二環戊基磷雜環戊烷基)辛烷、雙(二環戊基磷雜環戊烷基)苯、雙(二環戊基磷雜環戊烷基)萘、雙(二環戊基磷雜環戊烷基)二茂鐵、雙(二環戊基磷雜環戊烷基)二茂鈦、雙(二環戊基磷雜環戊烷基)二茂鉻、雙(二環戊基磷雜環戊烷基)二茂鈷、雙(二環戊基磷雜環戊烷基)二茂鎳、雙(二環戊基磷雜環戊烷基)二茂鋯、雙(二環戊基磷雜環戊烷基)二茂釕、雙(二環戊基磷雜環戊烷基)二茂鉿、雙(二己基磷雜環戊烷基)甲烷、雙(二己基磷雜環戊烷基)乙烷、雙(二己基磷雜環戊烷基)丙烷、雙(二己基磷雜環戊烷基)丁烷、雙(二己基磷雜環戊烷基)戊烷、雙(二己基磷雜環戊烷基)己烷、雙(二己基磷雜環戊烷基)環己烷、雙(二己基磷雜環戊烷基)庚烷、雙(二己基磷雜環戊烷基)辛烷、雙(二己基磷雜環戊烷基)苯、雙(二己基磷雜環戊烷基)萘、雙(二己基磷雜環戊烷基)二茂鐵、雙(二己基磷雜環戊烷基)二茂鈦、雙(二己基磷雜環戊烷基)二茂鉻、雙(二己基磷雜環戊烷基)二茂鈷、雙(二己基磷雜環戊烷基)二茂鎳、雙(二己基磷雜環戊烷基)二茂
鋯、雙(二己基磷雜環戊烷基)二茂釕、雙(二己基磷雜環戊烷基)二茂鉿、雙(二環己基磷雜環戊烷基)甲烷、雙(二環己基磷雜環戊烷基)乙烷、雙(二環己基磷雜環戊烷基)丙烷、雙(二環己基磷雜環戊烷基)丁烷、雙(二環己基磷雜環戊烷基)戊烷、雙(二環己基磷雜環戊烷基)環戊烷、雙(二環己基磷雜環戊烷基)己烷、雙(二環己基磷雜環戊烷基)環己烷、雙(二環己基磷雜環戊烷基)庚烷、雙(二環己基磷雜環戊烷基)辛烷、雙(二環己基磷雜環戊烷基)苯、雙(二環己基磷雜環戊烷基)萘、雙(二環己基磷雜環戊烷基)二茂鐵、雙(二環己基磷雜環戊烷基)二茂鈦、雙(二環己基磷雜環戊烷基)二茂鉻、雙(二環己基磷雜環戊烷基)二茂鈷、雙(二環己基磷雜環戊烷基)二茂鎳、雙(二環己基磷雜環戊烷基)二茂鋯、雙(二環己基磷雜環戊烷基)二茂釕、雙(二環己基磷雜環戊烷基)二茂鉿、雙(二苯基磷雜環戊烷基)甲烷、雙(二苯基磷雜環戊烷基)乙烷、雙(二苯基磷雜環戊烷基)丙烷、雙(二苯基磷雜環戊烷基)丁烷、雙(二苯基磷雜環戊烷基)戊烷、雙(二苯基磷雜環戊烷基)己烷、雙(二苯基磷雜環戊烷基)環己烷、雙(二苯基磷雜環戊烷基)庚烷、雙(二苯基磷雜環戊烷基)辛烷、雙(二苯基磷雜環戊烷基)苯、雙(二苯基磷雜環戊烷基)萘、雙(二苯基磷雜環戊烷基)二茂鐵、雙(二苯基磷雜環戊烷基)二茂鈦、雙(二苯基磷雜環戊烷基)二茂鉻、雙(二苯基磷雜環戊烷基)二茂鈷、雙(二苯基磷雜環戊烷基)二茂鎳、雙(二苯基磷雜環戊烷基)二茂鋯、雙(二苯基磷雜環戊
烷基)二茂釕、雙(二苯基磷雜環戊烷基)二茂鉿、雙(二萘基磷雜環戊烷基)甲烷、雙(二萘基磷雜環戊烷基)乙烷、雙(二萘基磷雜環戊烷基)丙烷、雙(二萘基磷雜環戊烷基)丁烷、雙(二萘基磷雜環戊烷基)戊烷、雙(二萘基磷雜環戊烷基)己烷、雙(二萘基磷雜環戊烷基)環己烷、雙(二萘基磷雜環戊烷基)庚烷、雙(二萘基磷雜環戊烷基)辛烷、雙(二萘基磷雜環戊烷基)苯、雙(二萘基磷雜環戊烷基)萘、雙(二萘基磷雜環戊烷基)二茂鐵、雙(二萘基磷雜環戊烷基)二茂鈦、雙(二萘基磷雜環戊烷基)二茂鉻、雙(二萘基磷雜環戊烷基)二茂鈷、雙(二萘基磷雜環戊烷基)二茂鎳、雙(二萘基磷雜環戊烷基)二茂鋯、雙(二萘基磷雜環戊烷基)二茂釕、雙(二萘基磷雜環戊烷基)二茂鉿、1,1’-甲基-2,2’-二磷雜環戊烷(1,1’-methyl-2,2’-diphospholane)、1,1’-乙基-2,2’-二磷雜環戊烷、1,1’-丙基-2,2’-二磷雜環戊烷、1,1’-丁基-2,2’-二磷雜環戊烷、1,1’-戊基-2,2’-二磷雜環戊烷、1,1’-環戊基-2,2’-二磷雜環戊烷、1,1’-己基-2,2’-二磷雜環戊烷、1,1’-環己基-2,2’-二磷雜環戊烷、1,1’-辛基-2,2’-二磷雜環戊烷、1,1’-苯基-2,2’-二磷雜環戊烷、1,1’-甲基苯基-2,2’-二磷雜環戊烷、1,1’-二甲基苯基-2,2’-二磷雜環戊烷、1,1’-三甲基苯基-2,2’-二磷雜環戊烷、1,1’-丁基苯基-2,2’-二磷雜環戊烷、1,1’-二丁基苯基-2,2’-二磷雜環戊烷、1,1’-三丁基苯基-2,2’-二磷雜環戊烷、1,1’-甲氧基苯基-2,2’-二磷雜環戊烷、1,1’-二甲基胺基苯基-2,2’-二磷雜環戊烷、1,1’-三
氟甲基苯基-2,2’-二磷雜環戊烷、1,1’-硝基苯基-2,2’-二磷雜環戊烷、1,1’-氰基苯基-2,2’-二磷雜環戊烷、1,1’-乙醯基苯基-2,2’-二磷雜環戊烷、1,1’-五氟苯基-2,2’-二磷雜環戊烷、1,1’-二甲氧基苯基-2,2’-二磷雜環戊烷、1,1’-二(三氟甲基)苯基-2,2’-二磷雜環戊烷、1,1’-三甲氧基苯基-2,2’-二磷雜環戊烷、1,1’-三(三氟甲基)苯基-2,2’-二磷雜環戊烷。
含有2個三價磷原子之三價磷化合物,較佳是選自以下之群組中至少1種之化合物。
雙(二甲基膦基)甲烷、雙(二乙基膦基)甲烷、雙(二丁基膦基)甲烷、雙(二環己基膦基)甲烷、雙(二苯基膦基)甲烷、雙[二(甲基苯基)膦基]甲烷、雙(二甲基膦基)乙烷、雙(二乙基膦基)乙烷、雙(二丁基膦基)乙烷、雙(二環己基膦基)乙烷、雙(二苯基膦基)乙烷、雙(二甲基膦基)丙烷、雙(二乙基膦基)丙烷、雙(二丁基膦基)丙烷、雙(二環己基膦基)丙烷、雙(二苯基膦基)丙烷、雙(二甲基膦基)丁烷、雙(二乙基膦基)丁烷、雙(二丁基膦基)丁烷、雙(二環己基膦基)丁烷、雙(二苯基膦基)丁烷、雙(二甲基膦基)環己烷、雙(二乙基膦基)環己烷、雙(二丁基膦基)環己烷、雙(二環己基膦基)環己烷、雙(二苯基膦基)環己烷、雙(二甲基膦基)二茂鐵、雙(二乙基膦基)二茂鐵、雙(二丙基膦基)二茂鐵、雙(二丁基膦基)二茂鐵、雙(二環己基膦基)二茂鐵、雙(二苯基膦基)二茂鐵、2,2’-雙(二甲基膦基)-1,1’-聯苯、2,2’-雙(二乙基膦基)-1,1’-聯苯、2,2’-雙(二丁基
膦基)-1,1’-聯苯、2,2’-雙(二環己基膦基)-1,1’-聯苯、2,2’-雙(二苯基膦基)-1,1’-聯苯、2,2’-雙(二甲基膦基)-1,1’-聯萘、2,2’-雙(二乙基膦基)-1,1’-聯萘、2,2’-雙(二丁基膦基)-1,1’-聯萘、2,2’-雙(二環己基膦基)-1,1’-聯萘、2,2’-雙(二苯基膦基)-1,1’-聯萘、2,2’-雙[二(甲基苯基)膦基]-1,1’-聯萘、2,2’-雙[二(二甲基苯基)膦基]-1,1’-聯萘、2,2’-雙[二(三甲基苯基)膦基]-1,1’-聯萘、雙(二甲基磷雜環戊烷基)甲烷、雙(二甲基磷雜環戊烷基)乙烷、雙(二甲基磷雜環戊烷基)丙烷、雙(二甲基磷雜環戊烷基)丁烷、雙(二甲基磷雜環戊烷基)環己烷、雙(二甲基磷雜環戊烷基)苯、雙(二甲基磷雜環戊烷基)二茂鐵、雙(二乙基磷雜環戊烷基)甲烷、雙(二乙基磷雜環戊烷基)乙烷、雙(二乙基磷雜環戊烷基)丙烷、雙(二乙基磷雜環戊烷基)丁烷、雙(二乙基磷雜環戊烷基)環己烷、雙(二乙基磷雜環戊烷基)苯、雙(二乙基磷雜環戊烷基)二茂鐵、雙(二丙基磷雜環戊烷基)甲烷、雙(二丙基磷雜環戊烷基)乙烷、雙(二丙基磷雜環戊烷基)丙烷、雙(二丙基磷雜環戊烷基)丁烷、雙(二丙基磷雜環戊烷基)環己烷、雙(二丙基磷雜環戊烷基)苯、雙(二丙基磷雜環戊烷基)二茂鐵、雙(二丁基磷雜環戊烷基)甲烷、雙(二丁基磷雜環戊烷基)乙烷、雙(二丁基磷雜環戊烷基)丙烷、雙(二丁基磷雜環戊烷基)丁烷、雙(二丁基磷雜環戊烷基)環己烷、雙(二丁基磷雜環戊烷基)苯、雙(二丁基磷雜環戊烷基)二茂鐵、雙(二環己基磷雜環戊烷基)甲烷、雙(二環己基磷雜環戊烷基)乙烷、雙(二環
己基磷雜環戊烷基)丙烷、雙(二環己基磷雜環戊烷基)丁烷、雙(二環己基磷雜環戊烷基)環己烷、雙(二環己基磷雜環戊烷基)苯、雙(二環己基磷雜環戊烷基)二茂鐵、1,1’-甲基-2,2’-二磷雜環戊烷、1,1’-乙基-2,2’-二磷雜環戊烷、1,1’-丁基-2,2’-二磷雜環戊烷、1,1’-環己基-2,2’-二磷雜環戊烷。
含有2個三價磷原子之三價磷化合物,更佳是選自以下之群組中至少1種之化合物。
雙(二環己基膦基)甲烷、雙(二甲基膦基)乙烷、雙(二乙基膦基)乙烷、雙(二環己基膦基)乙烷、雙(二苯基膦基)乙烷、雙(二環己基膦基)丙烷、雙(二苯基膦基)丙烷、雙(二苯基膦基)環己烷、雙(二丙基膦基)二茂鐵、雙(二丁基膦基)二茂鐵、雙(二環己基膦基)二茂鐵、雙(二苯基膦基)二茂鐵、雙(二甲基磷雜環戊烷基)乙烷、雙(二甲基磷雜環戊烷基)二茂鐵、雙(二乙基磷雜環戊烷基)乙烷、雙(二乙基磷雜環戊烷基)苯、雙(二丙基磷雜環戊烷基)乙烷、雙(二丙基磷雜環戊烷基)苯、雙(二丙基磷雜環戊烷基)二茂鐵、1,1’-丁基-2,2’-二磷雜環戊烷。
含有3個以上三價磷原子之三價磷化合物,只要是含有3個以上三價磷原子之化合物即可而無特別限定者,具體而言,可以列舉上述式(1)中,a為3以上所示者。
含有3個以上三價磷原子之三價磷化合物之中,從有變得容易取得,且可以更抑制組成物之成本,且經濟性更
優異之傾向,在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,以選自以下之群組中至少1種之化合物為佳。
雙(二甲基膦基甲基)甲基膦、雙(二乙基膦基甲基)乙基膦、雙(二丙基膦基甲基)丙基膦、雙(二丁基膦基甲基)丁基膦、雙(二己基膦基甲基)己基膦、雙(二環己基膦基甲基)環己基膦、雙(二苯基膦基甲基)苯基膦、雙(二甲基膦基乙基)甲基膦、雙(二乙基膦基乙基)乙基膦、雙(二丙基膦基乙基)丙基膦、雙(二丁基膦基乙基)丁基膦、雙(二己基膦基乙基)己基膦、雙(二環己基膦基乙基)環己基膦、雙(二苯基膦基乙基)苯基膦、雙(二甲基膦基丙基)甲基膦、雙(二乙基膦基丙基)乙基膦、雙(二丙基膦基丙基)丙基膦、雙(二丁基膦基丙基)丁基膦、雙(二己基膦基丙基)己基膦、雙(二環己基膦基丙基)環己基膦、雙(二苯基膦基丙基)苯基膦、雙(二甲基膦基丁基)甲基膦、雙(二乙基膦基丁基)乙基膦、雙(二丙基膦基丁基)丙基膦、雙(二丁基膦基丁基)丁基膦、雙(二己基膦基丁基)己基膦、雙(二環己基膦基丁基)環己基膦、雙(二苯基膦基丁基)苯基膦、雙(二甲基膦基己基)甲基膦、雙(二乙基膦基己基)乙基膦、雙(二丙基膦基己基)丙基膦、雙(二丁基膦基己基)丁基膦、雙(二己基膦基己基)己基膦、雙(二環己基膦基己基)環己基膦、雙(二苯基膦基己基)苯基膦、雙(二甲基膦基環己基)甲基膦、雙(二乙基膦基環己基)乙
基膦、雙(二丙基膦基環己基)丙基膦、雙(二丁基膦基環己基)丁基膦、雙(二己基膦基環己基)己基膦、雙(二環己基膦基環己基)環己基膦、雙(二苯基膦基環己基)苯基膦、參(二甲基膦基)丙烷、參(二乙基膦基)丙烷、參(二丙基膦基)丙烷、參(二丁基膦基)丙烷、參(二己基膦基)丙烷、參(二環己基膦基)丙烷、參(二苯基膦基)丙烷、參[二(甲基苯基)膦基]丙烷、參[二(丁基苯基)膦基]丙烷、參[二(二甲基苯基)膦基]丙烷、參[二(二丁基苯基)膦基]丙烷、參[二(三甲基苯基)膦基]丙烷、參[二(三丁基苯基)膦基]丙烷、參(二甲基膦基)丁烷、參(二乙基膦基)丁烷、參(二丙基膦基)丁烷、參(二丁基膦基)丁烷、參(二己基膦基)丁烷、參(二環己基膦基)丁烷、參(二苯基膦基)丁烷、參[二(甲基苯基)膦基]丁烷、參[二(丁基苯基)膦基]丁烷、參[二(二甲基苯基)膦基]丁烷、參[二(二丁基苯基)膦基]丁烷、參[二(三甲基苯基)膦基]丁烷、參[二(三丁基苯基)膦基]丁烷、參(二甲基膦基)己烷、參(二乙基膦基)己烷、參(二丙基膦基)己烷、參(二丁基膦基)己烷、參(二己基膦基)己烷、參(二環己基膦基)己烷、參(二苯基膦基)己烷、參[二(甲基苯基)膦基]己烷、參[二(丁基苯基)膦基]己烷、參[二(二甲基苯基)膦基]己烷、參[二(二丁基苯基)膦基]己烷、參[二(三甲基苯基)膦基]己烷、參[二(三丁基苯基)膦基]己烷、參(二甲基膦基)環己烷、參(二乙基膦基)環己烷、參(二丙基膦基)環己烷、參(二丁基膦基)環己烷、參(二己基膦基)環己烷、參(二環己基膦基)環己烷、參(二苯基膦基)環己
烷、參[二(甲基苯基)膦基]環己烷、參[二(丁基苯基)膦基]環己烷、參[二(二甲基苯基)膦基]環己烷、參[二(二丁基苯基)膦基]環己烷、參[二(三甲基苯基)膦基]環己烷、參[二(三丁基苯基)膦基]環己烷、參(二甲基膦基甲基)膦、參(二乙基膦基甲基)膦、參(二丙基膦基甲基)膦、參(二丁基膦基甲基)膦、參(二己基膦基甲基)膦、參(二環己基膦基甲基)膦、參(二苯基膦基甲基)膦、參(二甲基膦基乙基)膦、參(二乙基膦基乙基)膦、參(二丙基膦基乙基)膦、參(二丁基膦基乙基)膦、參(二己基膦基乙基)膦、參(二環己基膦基乙基)膦、參(二苯基膦基乙基)膦、參(二甲基膦基丙基)膦、參(二乙基膦基丙基)膦、參(二丙基膦基丙基)膦、參(二丁基膦基丙基)膦、參(二己基膦基丙基)膦、參(二環己基膦基丙基)膦、參(二苯基膦基丙基)膦、參(二甲基膦基丁基)膦、參(二乙基膦基丁基)膦、參(二丙基膦基丁基)膦、參(二丁基膦基丁基)膦、參(二己基膦基丁基)膦、參(二環己基膦基丁基)膦、參(二苯基膦基丁基)膦、參(二甲基膦基己基)膦、參(二乙基膦基己基)膦、參(二丙基膦基己基)膦、參(二丁基膦基己基)膦、參(二己基膦基己基)膦、參(二環己基膦基己基)膦、參(二苯基膦基己基)膦、參(二甲基膦基環己基)膦、參(二乙基膦基環己基)膦、參(二丙基膦基環己基)膦、參(二丁基膦基環己基)膦、參(二己基膦基環己基)膦、參(二環己基膦基環己基)膦、參(二苯基膦基環己基)膦、肆(二甲基膦基)丁烷、肆(二乙基膦基)丁烷、肆(二丙基膦基)丁烷、肆(二丁基膦基)丁烷、肆
(二己基膦基)丁烷、肆(二環己基膦基)丁烷、肆(二苯基膦基)丁烷、肆[二(甲基苯基)膦基]丁烷、肆[二(丁基苯基)膦基]丁烷、肆[二(二甲基苯基)膦基]丁烷、肆[二(二丁基苯基)膦基]丁烷、肆[二(三甲基苯基)膦基]丁烷、肆[二(三丁基苯基)膦基]丁烷、肆(二甲基膦基)己烷、肆(二乙基膦基)己烷、肆(二丙基膦基)己烷、肆(二丁基膦基)己烷、肆(二己基膦基)己烷、肆(二環己基膦基)己烷、肆(二苯基膦基)己烷、肆[二(甲基苯基)膦基]己烷、肆[二(丁基苯基)膦基]己烷、肆[二(二甲基苯基)膦基]己烷、肆[二(二丁基苯基)膦基]己烷、肆[二(三甲基苯基)膦基]己烷、肆[二(三丁基苯基)膦基]己烷、肆(二甲基膦基)環己烷、肆(二乙基膦基)環己烷、肆(二丙基膦基)環己烷、肆(二丁基膦基)環己烷、肆(二己基膦基)環己烷、肆(二環己基膦基)環己烷、肆(二苯基膦基)環己烷、肆[二(甲基苯基)膦基]環己烷、肆[二(丁基苯基)膦基]環己烷、肆[二(二甲基苯基)膦基]環己烷、肆[二(二丁基苯基)膦基]環己烷、肆[二(三甲基苯基)膦基]環己烷、肆[二(三丁基苯基)膦基]環己烷。
含有3個以上三價磷原子之三價磷化合物,較佳是選自以下之群組中至少1種之化合物。
雙(二甲基膦基乙基)甲基膦、雙(二乙基膦基乙基)乙基膦、雙(二丙基膦基乙基)丙基膦、雙(二丁基膦基乙基)丁基膦、雙(二己基膦基乙基)己基膦、雙(二環己基膦基乙基)環己基膦、雙(二苯基膦基乙基)苯基膦、雙(二甲基膦基丙基)甲基膦、雙(二乙基膦基丙基)乙基膦、雙(二丙基
膦基丙基)丙基膦、雙(二丁基膦基丙基)丁基膦、雙(二己基膦基丙基)己基膦、雙(二環己基膦基丙基)環己基膦、雙(二苯基膦基丙基)苯基膦、雙(二甲基膦基丁基)甲基膦、雙(二乙基膦基丁基)乙基膦、雙(二丙基膦基丁基)丙基膦、雙(二丁基膦基丁基)丁基膦、雙(二己基膦基丁基)己基膦、雙(二環己基膦基丁基)環己基膦、雙(二苯基膦基丁基)苯基膦、參(二甲基膦基甲基)膦、參(二乙基膦基甲基)膦、參(二丙基膦基甲基)膦、參(二丁基膦基甲基)膦、參(二己基膦基甲基)膦、參(二環己基膦基甲基)膦、參(二苯基膦基甲基)膦、參(二甲基膦基乙基)膦、參(二乙基膦基乙基)膦、參(二丙基膦基乙基)膦、參(二丁基膦基乙基)膦、參(二己基膦基乙基)膦、參(二環己基膦基乙基)膦、參(二苯基膦基乙基)膦、參(二甲基膦基丙基)膦、參(二乙基膦基丙基)膦、參(二丙基膦基丙基)膦、參(二丁基膦基丙基)膦、參(二己基膦基丙基)膦、參(二環己基膦基丙基)膦、參(二苯基膦基丙基)膦、參(二甲基膦基丁基)膦、參(二乙基膦基丁基)膦、參(二丙基膦基丁基)膦、參(二丁基膦基丁基)膦、參(二己基膦基丁基)膦、參(二環己基膦基丁基)膦、參(二苯基膦基丁基)膦。
含有3個以上三價磷原子之三價磷化合物,更佳是選自以下之群組中至少1種之化合物。
雙(二乙基膦基乙基)乙基膦、雙(二丙基膦基乙基)丙基膦、雙(二丁基膦基乙基)丁基膦、雙(二環己基膦基乙基)
環己基膦、雙(二苯基膦基乙基)苯基膦、參(二乙基膦基乙基)膦、參(二丙基膦基乙基)膦、參(二丁基膦基乙基)膦、參(二環己基膦基乙基)膦、參(二苯基膦基乙基)膦。
本實施形態之成分(A-3)是分子內含有1個以上酮基之酮化合物。作為成分(A-3)者,可以單獨使用1種之酮化合物,也可以組合複數種之酮化合物並使用。
(A-3)酮化合物,從有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,以下述式(2)、(3)、或是(4)所示化合物為佳。
式中,a、c、d及f各自獨立地表示1以上之數,b及e各自獨立地表示2以上之數。
R11及R12各自獨立地表示碳原子數1至20之鏈狀、分枝狀或是環狀之脂肪族烴基,或者是取代或是無取代之芳香族烴基。
R13表示氫,或者是碳原子數1至20之鏈狀、分枝狀、環狀之脂肪族,或者是取代或是無取代之芳香族烴基。
R11、R12、及R13可以互相連結。
R14及R15各自獨立地表示碳原子數1至20之鏈狀、分枝狀或是環狀之脂肪族烴基,或者是取代或是無取代之芳香族烴基。
R15彼此可以相同也可以相異。
R14、R15及R15彼此可以連結。
R16、R17及R18各自獨立地表示碳原子數1至20之鏈狀、分枝狀或是環狀之脂肪族烴基,或者是取代或是無取代之芳香族烴基。
R16及R18彼此可以相同也可以相異。
R16、R17或是R18與R16或是R18可以互相連結。
上述式(3)表示在上述式(2)中,a為2以上,且R12不存在的情形。
式(2)中,在a為1,R11為CH3,R12為CH2,R13為H時,式(2)成為丙酮。又,式(2)中,在a為2,R11為CH3,R12為CH2CH2,R13為H時,式(2)成為2,5-庚二酮。再者,式(2)中,在a為3,R11為CH3,R12為CH2,R13為H時,式(2)成為2,4,6-庚三酮。
式(3)中,在b為2,c為1,R14為CH3,R15為CH3時,式(3)成為2,3-丁二酮。
(A-3)酮化合物之碳原子數,從在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向,及/或是,在室溫下
調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向而言,以3以上為佳。從有蒸氣壓變高,且提高處理性之傾向而言,碳原子數是以4以上為較佳。由同樣之觀點而言,碳原子數是以6以上為更佳。
(A-3)酮化合物之碳原子數,從有取得變容易,且可以更抑制組成物之成本,且經濟性更優良之傾向而言,以31以下為佳。由同樣之觀點而言,碳原子數是以20以下為佳。從在調整組成物之際,有可以更抑制未溶解物之殘留,且可得均勻性更優良之組成物之傾向而言,碳原子數是以14以下為較佳。由同樣之觀點而言,碳原子數是以12以下為特佳。
(A-3)酮化合物之酮基數,從在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向而言,以1以上為佳。由同樣之觀點而言,酮基數是以2以上為更佳。
(A-3)酮化合物之酮基數,從有變得容易取得,且可以更抑制組成物之成本,且經濟性更優良之傾向而言,以8以下為佳。由同樣之觀點而言,酮基數是以6以下為較佳。從在調整組成物之際,有可以抑制未溶解物之殘留,且可得到均勻性優異之組成物之傾向而言,酮基數是以4以下為更佳。由同樣之觀點而言,酮基數是以3以下為特佳。
若具體例示(A)酮化合物,則可以列舉:單官能酮化合物、2官能酮化合物、多官能酮化合物、多酮化合物等。
此等可以單獨使用,也可以組合複數種而使用。
本實施形態相關的單官能酮化合物,只要是含有1個酮基之化合物即可,而無特別限定。
單官能酮化合物之中,從有取得變容易,且可以更抑制組成物之成本,且經濟性更優異之傾向,在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,以選自以下之群組中至少1種之化合物為佳。
丙酮、2-丁酮、甲基丁酮、二甲基丁酮、2-戊酮、3-戊酮、甲基戊酮、二甲基戊酮、2-己酮、3-己酮、甲基己酮、乙基己酮、二甲基己酮、丙基己酮、異丙基己酮、乙基甲基己酮、乙基二甲基己酮、2-庚酮、3-庚酮、4-庚酮、甲基庚酮、乙基庚酮、二甲基庚酮、丙基庚酮、異丙基庚酮、乙基甲基庚酮、2-辛酮、3-辛酮、4-辛酮、甲基辛酮、乙基辛酮、二甲基辛酮、2-壬酮、3-壬酮、4-壬酮、5-壬酮、甲基壬酮、2-癸酮、3-癸酮、4-癸酮、5-癸酮、2-十一烷酮、3-十一烷酮、4-十一烷酮、5-十一烷酮、6-十一烷酮、2-十二烷酮、3-十二烷酮、4-十二烷酮、5-十二烷酮、6-十二烷酮、2-十三烷酮、3-十三烷酮、4-十三烷酮、5-十三烷酮、6-十三烷酮、7-十三烷酮、二乙基十三烷酮、2-十四烷酮、3-十四烷酮、4-十四烷酮、5-十四烷酮、6-十四烷酮、7-十四烷酮、1-[1,1’-聯苯基]-4-基-2-環己烷
乙酮、1-(4’-甲基[1,1’-聯苯基]-4-基)-1-十八烷酮、苯乙酮、甲基苯乙酮、乙基苯乙酮、苯丙酮、甲基苯丙酮、乙基苯丙酮、苯丁酮、甲基苯丁酮、乙基苯丁酮、苯異丁酮、甲基苯異丁酮、乙基苯異丁酮、三級-丁基苯基酮、三級-丁基-甲基苯基酮、三級-丁基-乙基苯基酮、二級-丁基苯基酮、二級-丁基-甲基苯基酮、二級-丁基-乙基苯基酮、苯戊酮、甲基苯戊酮、乙基苯戊酮、異戊基苯基酮、異戊基(甲基苯基)酮、異戊基(乙基苯基)酮、新戊基苯基酮、新戊基(甲基苯基)酮、新戊基(乙基苯基)酮、苯己酮、甲基苯己酮、乙基苯己酮、苯庚酮、甲基苯庚酮、乙基苯庚酮、苯辛酮、甲基苯辛酮、乙基苯辛酮、苯壬酮、甲基苯壬酮、乙基苯壬酮、苯癸酮、甲基苯癸酮、乙基苯癸酮、苯十一烷酮(undecanophenone)、甲基苯十一烷酮、乙基苯十一烷酮、苯十二烷酮(dodecanophenone)、甲基苯十二烷酮、乙基苯十二烷酮萘乙酮、甲基萘乙酮、萘丙酮、甲基萘丙酮、三級-丁基萘基酮、三級-丁基-(甲基萘基)酮、二級-丁基萘基酮、二級-丁基-(甲基萘基)酮、萘異丁酮、甲基萘異丁酮、萘丁酮、甲基萘丁酮、萘戊酮、甲基萘戊酮、異戊基萘基酮、異戊基(甲基萘基)酮、新戊基萘基酮、新戊基(甲基萘基)酮、萘己酮、甲基萘己酮、萘庚酮、甲基萘庚酮、萘辛酮、甲基萘辛酮、萘壬酮、甲基萘壬酮、萘癸酮、甲基萘癸酮、萘十一烷酮(undecanonaphthone)、甲基萘十一烷酮、萘十二烷酮(dodecanonaphthone)、甲基萘十二烷酮、萘基苯基
酮、乙醯基菲、乙醯基蒽、乙醯基芘、苯并[a]茀酮、4H-環戊[def]菲-4-酮、5-乙醯基-1,2-二氫苊烯、3,3,5,5,8,8-五甲基八氫-2(1H)-萘酮、環丙酮、甲基環丙酮、二甲基環丙酮、三甲基環丙酮、四甲基環丙酮、乙基環丙酮、二乙基環丙酮、三乙基環丙酮、四乙基環丙酮、苯基環丙酮、二苯基環丙酮、三苯基環丙酮、四苯基環丙酮、乙基甲基環丙酮、二乙基甲基環丙酮、四乙基環丙酮、二乙基二甲基環丙酮、環丁酮、甲基環丁酮、乙基環丁酮、苯基環丁酮、二甲基環丁酮、三甲基環丁酮、四甲基環丁酮、五甲基環丁酮、六甲基環丁酮、二乙基環丁酮、三乙基環丁酮、三乙基環丁酮、四乙基環丁酮、五乙基環丁酮、六乙基環丁酮、二苯基環丁酮、三苯基環丁酮、四苯基環丁酮、五苯基環丁酮、六苯基環丁酮、環戊酮、甲基環戊酮、乙基環戊酮、苯基環戊酮、二甲基環戊酮、三甲基環戊酮、四甲基環戊酮、五甲基環戊酮、六甲基環戊酮、七甲基環戊酮、二乙基環戊酮、三乙基環戊酮、四乙基環戊酮、五乙基環戊酮、六乙基環戊酮、七乙基環戊酮、八乙基環戊酮、二苯基環戊酮、三苯基環戊酮、四苯基環戊酮、五苯基環戊酮、六苯基環戊酮、七苯基環戊酮、八苯基環戊酮、環己酮、甲基環己酮、二甲基環己酮、三甲基環己酮、四甲基環己酮、五甲基環己酮、六甲基環己酮、七甲基環己酮、八甲基環己酮、九甲基環己酮、十甲基環己酮、乙基環己酮、二乙基環己酮、三乙基環己酮、四乙基環己酮、
五乙基環己酮、六乙基環己酮、七乙基環己酮、八乙基環己酮、九乙基環己酮、十乙基環己酮、苯基環己酮、二苯基環己酮、三苯基環己酮、四苯基環己酮、五苯基環己酮、六苯基環己酮、七苯基環己酮、八苯基環己酮、九苯基環己酮、十苯基環己酮、環庚酮、丙基環己酮、丁基環己酮、戊基環己酮、己基環己酮、甲基環庚酮、二甲基環庚酮、乙基環庚酮、二乙基環庚酮、苯基環庚酮、二苯基環庚酮、環辛酮、甲基環辛酮、二甲基環辛酮、乙基環辛酮、二乙基環辛酮、苯基環辛酮、二苯基環辛酮、環壬酮、甲基環壬酮、二甲基環壬酮、乙基環壬酮、二乙基環壬酮、苯基環壬酮、二苯基環壬酮、環癸酮、甲基環癸酮、二甲基環癸酮、乙基環癸酮、二乙基環癸酮、苯基環癸酮、二苯基環癸酮、環十一烷酮、環十二烷酮、環十三烷酮、環十四烷酮、十氫萘酮(decalone)、金剛烷酮、金剛烷基甲基酮、降冰片烷酮(norbornanone)、聯環[2.2.2]辛烷-1-酮。
單官能酮化合物,較佳係選自以下之群組中至少1種的化合物。
丙酮、2-丁酮、甲基丁酮、二甲基丁酮、2-戊酮、3-戊酮、甲基戊酮、2-己酮、3-己酮、2-庚酮、3-庚酮、4-庚酮、2-辛酮、3-辛酮、4-辛酮、2-壬酮、3-壬酮、4-壬酮、5-壬酮、2-癸酮、3-癸酮、4-癸酮、5-癸酮、2-十一烷酮、3-十一烷酮、4-十一烷酮、5-十一烷酮、6-十一烷酮、2-十二烷酮、3-十二烷酮、4-十二烷酮、5-十二烷酮、6-十二烷酮、2-十三酮、3-十三酮、4-十三酮、5-十三酮、
6-十三酮、7-十三酮、二乙基十三酮、2-十四酮、3-十四酮、4-十四酮、5-十四酮、6-十四酮、7-十四酮、1-[1,1’-聯苯基]-4-基-2-環己烷乙酮、1-(4’-甲基[1,1’-聯苯基]-4-基)-1-十八烷酮、苯乙酮、苯丙酮、苯丁酮、苯異丁酮、三級-丁基苯基酮、苯戊酮、異戊基苯基酮、新戊基苯基酮、苯己酮、苯庚酮、苯辛酮、苯壬酮、苯癸酮、苯十一烷酮、苯十二烷酮、萘乙酮、萘丙酮、三級-丁基萘基酮、二級-丁基萘基酮、萘異丁酮、萘丁酮、萘戊酮、異戊基萘基酮、新戊基萘基酮、萘己酮、萘庚酮、萘辛酮、萘基苯基酮、乙醯基菲、乙醯基蒽、苯并[a]茀酮、4H-環戊[def]菲-4-酮、5-乙醯基-1,2-二氫苊烯、3,3,5,5,8,8-五甲基八氫-2(1H)-萘酮、環丙酮、環丁酮、環戊酮、環己酮、環庚酮、丁基環己酮、環辛酮、環壬酮、環癸酮、環十一烷酮、環十二烷酮、環十三烷酮、環十四烷酮、十氫萘酮、金剛烷酮、金剛烷基甲基酮、降冰片烷酮、聯環[2.2.2.]辛烷-1-酮。
單官能酮化合物,更佳係選自以下之群組中至少1種的化合物。
二甲基丁酮、甲基戊酮、2-己酮、3-己酮、3-庚酮、2-辛酮、3-辛酮、2-壬酮、3-壬酮、5-壬酮、2-癸酮、2-十一烷酮、6-十一烷酮、2-十二烷酮、5-十二烷酮、2-十三烷酮、7-十三烷酮、二乙基十三烷酮、苯乙酮、苯丙酮、苯丁酮、苯異丁酮、三級-丁基苯基酮、苯戊酮、異戊基苯基酮、新戊基苯基酮、苯己酮、苯庚酮、苯辛酮、苯壬酮、
苯癸酮、苯十一烷酮、苯十二烷酮、萘乙酮、萘基苯基酮、乙醯基菲、環己酮、丁基環己酮、環辛酮、環壬酮、環癸酮、環十二烷酮、聯環[2.2.2.]辛烷-1-酮。
本實施形態相關的2官能酮化合物,只要是含有2個酮基,並且,該酮基彼此不隣接之化合物即可,無特別限定者。
2官能酮化合物之中,從有變得容易取得,且可以更抑制組成物之成本,且經濟性更優異之傾向,在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性的傾向,及/或是,當聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,以選自以下之群組中至少1種之化合物為佳。
2,4-戊烷二酮、甲基-2,4-戊烷二酮、二甲基-2,4-戊烷二酮、乙基-2,4-戊烷二酮、二乙基-2,4-戊烷二酮、乙基甲基-2,4-戊烷二酮、2,4-己烷二酮、甲基-2,4-己烷二酮、二甲基-2,4-己烷二酮、乙基-2,4-己烷二酮、二乙基-2,4-己烷二酮、乙基甲基-2,4-己烷二酮、乙基二甲基-2,4-己烷二酮、二乙基甲基-2,4-己烷二酮、二乙基二甲基-2,4-己烷二酮、2,5-己烷二酮、甲基-2,5-己烷二酮、乙基-2,5-己烷二酮、二甲基-2,5-己烷二酮、乙基甲基-2,5-己烷二酮、二乙基-2,5-己烷二酮、三甲基-2,5-己烷二酮、乙基二甲基-2,5-己烷二酮、二乙基甲基-2,5-己烷二酮、三乙基-2,5-己烷二酮、四甲基-2,5-己烷二酮、乙
基三甲基-2,5-己烷二酮、二乙基二甲基-2,5-己烷二酮、三乙基甲基-2,5-己烷二酮、四乙基-2,5-己烷二酮、2,4-庚烷二酮、2,5-庚烷二酮、2,6-庚烷二酮、3,5-庚烷二酮、二甲基-2,4-庚烷二酮、乙基甲基-2,4-庚烷二酮、二乙基-2,4-庚烷二酮、二甲基-2,5-庚烷二酮、乙基甲基-2,5-庚烷二酮、二乙基-2,5-庚烷二酮、甲基-3,5-庚烷二酮、乙基-3,5-庚烷二酮、二甲基-3,5-庚烷二酮、乙基甲基-3,5-庚烷二酮、二乙基-3,5-庚烷二酮、2,4-辛烷二酮、甲基-2,4-辛烷二酮、乙基-2,4-辛烷二酮、二甲基-2,4-辛烷二酮、乙基甲基-2,4-辛烷二酮、二乙基-2,4-辛烷二酮、2,5-辛烷二酮、甲基-2,5-辛烷二酮、二甲基-2,5-辛烷二酮、乙基甲基-2,5-辛烷二酮、二乙基-2,5-辛烷二酮、2,6-辛烷二酮、甲基-2,6-辛烷二酮、乙基-2,6-辛烷二酮、二甲基-2,6-辛烷二酮、乙基甲基-2,6-辛烷二酮、二乙基-2,6-辛烷二酮、2,7-辛烷二酮、甲基-2,7-辛烷二酮、乙基-2,7-辛烷二酮、二甲基-2,7-辛烷二酮、乙基甲基-2,7-辛烷二酮、二乙基-2,7-辛烷二酮、3,5-辛烷二酮、甲基-3,5-辛烷二酮、乙基-3,5-辛烷二酮、二甲基-3,5-辛烷二酮、乙基甲基-3,5-辛烷二酮、二乙基-3,5-辛烷二酮、3,6-辛烷二酮、甲基-3,6-辛烷二酮、乙基-3,6-辛烷二酮、二甲基-3,6-辛烷二酮、乙基甲基-3,6-辛烷二酮、二乙基-3,6-辛烷二酮、2,4-壬烷二酮、2,5-壬烷二酮、2,6-壬烷二酮、2,7-壬烷二酮、2,8-壬烷二酮、3,5-壬烷二酮、3,6-
壬烷二酮、3,7-壬烷二酮、3,8-壬烷二酮、4,6-壬烷二酮、4,7-壬烷二酮、2,4-癸烷二酮、2,5-癸烷二酮、2,6-癸烷二酮、2,7-癸烷二酮、2,8-癸烷二酮、2,9-癸烷二酮、3,5-癸烷二酮、3,6-癸烷二酮、3,7-癸烷二酮、3,8-癸烷二酮、4,6-癸烷二酮、4,7-癸烷二酮、2,4-十一烷二酮、2,5-十一烷二酮、2,6-十一烷二酮、2,7-十一烷二酮、2,8-十一烷二酮、2,9-十一烷二酮、2,10-十一烷二酮、3,5-十一烷二酮、3,6-十一烷二酮、3,7-十一烷二酮、3,8-十一烷二酮、3,9-十一烷二酮、4,6-十一烷二酮、4,7-十一烷二酮、4,8-十一烷二酮、5,7-十一烷二酮、1,3-環丁烷二酮、甲基-1,3-環丁烷二酮、二甲基-1,3-環丁烷二酮、三甲基-1,3-環丁烷二酮、四甲基環丁烷二酮、乙基甲基-1,3-環丁烷二酮、二乙基甲基-1,3-環丁烷二酮、三乙基甲基-1,3-環丁烷二酮、乙基-1,3-環丁烷二酮、二乙基-1,3-環丁烷二酮、三乙基-1,3-環丁烷二酮、四乙基-1,3-環丁烷二酮、1,3-環戊烷二酮、甲基-1,3-環戊烷二酮、乙基-1,3-環戊烷二酮、二甲基-1,3-環戊烷二酮、乙基-2-甲基-1,3-環戊烷二酮、乙基甲基-1,3-環戊烷二酮、二乙基-1,3-環戊烷二酮、三甲基-1,3-環戊烷二酮、四甲基-1,3-環戊烷二酮、五甲基-1,3-環戊烷二酮、六甲基-1,3-環戊烷二酮、三乙基-1,3-環戊烷二酮、四乙基-1,3-環戊烷二酮、五乙基-1,3-環戊烷二酮、六乙基-1,3-環戊烷二酮、1,3-環己烷二酮、甲基-1,3-環己烷二酮、乙基-1,3-環己烷二酮、二甲基-1,3-環己烷二酮、乙基甲基-1,3-環己烷二酮、二乙
基-1,3-環己烷二酮、三甲基-1,3-環己烷二酮、四甲基-1,3-環己烷二酮、五甲基-1,3-環己烷二酮、六甲基-1,3-環己烷二酮、七甲基-1,3-環己烷二酮、八甲基-1,3-環己烷二酮、三乙基-1,3-環己烷二酮、四乙基-1,3-環己烷二酮、五乙基-1,3-環己烷二酮、六乙基-1,3-環己烷二酮、七乙基-1,3-環己烷二酮、八乙基-1,3-環己烷二酮、1,4-環己烷二酮、甲基-1,4-環己烷二酮、乙基-1,4-環己烷二酮、二甲基-1,4-環己烷二酮、乙基甲基-1,4-環己烷二酮、二乙基-1,4-環己烷二酮、三甲基-1,4-環己烷二酮、四甲基-1,4-環己烷二酮、五甲基-1,4-環己烷二酮、六甲基-1,4-環己烷二酮、七甲基-1,4-環己烷二酮、八甲基-1,4-環己烷二酮、三乙基-1,4-環己烷二酮、四乙基-1,4-環己烷二酮、五乙基-1,4-環己烷二酮、六乙基-1,4-環己烷二酮、七乙基-1,4-環己烷二酮、八乙基-1,4-環己烷二酮、1,3-環庚烷二酮、甲基-1,3-環庚烷二酮、乙基-1,3-環庚烷二酮、二甲基-1,3-環庚烷二酮、乙基-2-甲基-1,3-環庚烷二酮、乙基甲基-1,3-環庚烷二酮、二乙基-1,3-環庚烷二酮、1,4-環庚烷二酮、甲基-1,4-環庚烷二酮、乙基-1,4-環庚烷二酮、二甲基-1,4-環庚烷二酮、乙基甲基-1,4-環庚烷二酮、二乙基-1,4-環庚烷二酮、1,3-環辛烷二酮、甲基-1,3-環辛烷二酮、乙基-1,3-環辛烷二酮、二甲基-1,3-環辛烷二酮、乙基甲基-1,3-環辛烷二酮、二乙基-1,3-環辛烷二酮、1,4-環辛烷二酮、甲基-1,4-環辛烷二酮、乙基-1,4-環辛烷二酮、二甲基-1,4-環辛烷二酮、乙基甲基
-1,4-環辛烷二酮、二乙基-1,4-環辛烷二酮、1,5-環辛烷二酮、甲基-1,5-環辛烷二酮、乙基-1,5-環辛烷二酮、二甲基-1,5-環辛烷二酮、乙基甲基-1,5-環辛烷二酮、二乙基-1,5-環辛烷二酮、1,3-環壬烷二酮、甲基-1,3-環壬烷二酮、乙基-1,3-環壬烷二酮、1,4-環壬烷二酮、甲基-1,4-環壬烷二酮、乙基-1,4-環壬烷二酮、1,5-環壬烷二酮、甲基-1,5-環壬烷二酮、乙基-1,5-環壬烷二酮、1,3-環癸烷二酮、甲基-1,3-環癸烷二酮、乙基-1,3-環癸烷二酮、1,4-環癸烷二酮、甲基-1,4-環癸烷二酮、乙基-1,4-環癸烷二酮、1,5-環癸烷二酮、甲基-1,5-環癸烷二酮、1,6-環癸烷二酮、甲基-1,6-環癸烷二酮、乙基-1,6-環癸烷二酮、1,3-環十一烷二酮、1,4-環十一烷二酮、1,5-環十一烷二酮、1,6-環十一烷二酮、1,3-環十二烷二酮、1,4-環十二烷二酮、1,5-環十二烷二酮、1,6-環十二烷二酮、1,7-環十二烷二酮、1,3-環十三烷二酮、1,4-環十三烷二酮、1,5-環十三烷二酮、1,6-環十三烷二酮、1,7-環十三烷二酮、1,3-環十四烷二酮、1,4-環十四烷二酮、1,5-環十四烷二酮、1,6-環十四烷二酮、1,7-環十四烷二酮、1,8-環十四烷二酮、1-[4-(4-丙醯基苄基)苯基-1-丙酮、2-苄醯基環己酮、3-苄醯基環己酮、4-苄醯基環己酮、聯環[2,2,1]庚烷-2,5-二酮、聯環[2,2,1]庚烷-2,6-二酮、聯環[2,2,1]庚烷-2,7-二酮、聯環[2,2,2]辛烷-2,5-二酮、聯環[2,2,2]辛烷-2,6-二酮、八氫-1,3-萘二酮、八氫-1,4-萘二酮、八氫-1,5-萘二酮、八氫-1,6-萘二酮、八氫-1,7-萘二酮、八
氫-1,8-萘二酮、2-乙醯基環丙酮、2-乙醯基-環戊酮、3-乙醯基-環戊酮、2-乙醯基環己酮、3-乙醯基環己酮、4-乙醯基環己酮、二苯基-1,6-己烷二酮。
2官能酮化合物,較佳是選自以下之群組中至少1種之化合物。
2,4-戊烷二酮、甲基-2,4-戊烷二酮、2,4-己烷二酮、2,5-己烷二酮、2,4-庚烷二酮、2,5-庚烷二酮、2,6-庚烷二酮、3,5-庚烷二酮、2,4-辛烷二酮、2,5-辛烷二酮、2,6-辛烷二酮、2,7-辛烷二酮、3,5-辛烷二酮、3,6-辛烷二酮、2,4-壬烷二酮、2,5-壬烷二酮、2,6-壬烷二酮、2,7-壬烷二酮、2,8-壬烷二酮、3,5-壬烷二酮、3,6-壬烷二酮、3,7-壬烷二酮、3,8-壬烷二酮、4,6-壬烷二酮、4,7-壬烷二酮、2,4-癸烷二酮、2,5-癸烷二酮、2,6-癸烷二酮、2,7-癸烷二酮、2,8-癸烷二酮、2,9-癸烷二酮、3,5-癸烷二酮、3,6-癸烷二酮、3,7-癸烷二酮、3,8-癸烷二酮、4,6-癸烷二酮、4,7-癸烷二酮、2,4-十一烷二酮、2,5-十一烷二酮、2,6-十一烷二酮、2,7-十一烷二酮、2,8-十一烷二酮、2,9-十一烷二酮、2,10-十一烷二酮、3,5-十一烷二酮、3,6-十一烷二酮、3,7-十一烷二酮、3,8-十一烷二酮、3,9-十一烷二酮、4,6-十一烷二酮、4,7-十一烷二酮、4,8-十一烷二酮、5,7-十一烷二酮、1,3-環丁烷二酮、四甲基環丁烷二酮、1,3-環戊烷二酮、1,3-環己烷二酮、1,4-環己烷二酮、1,3-環庚烷二酮、1,4-環庚烷二酮、1,3-環辛烷二酮、1,4-環辛烷二酮、1,5-環辛烷二酮、1,3-環壬烷二酮、1,4-環
壬烷二酮、1,5-環壬烷二酮、1,6-環癸烷二酮、1,3-環十一烷二酮、1,4-環十一烷二酮、1,5-環十一烷二酮、1,6-環十一烷二酮、1,3-環十二烷二酮、1,4-環十二烷二酮、1,5-環十二烷二酮、1,6-環十二烷二酮、1,7-環十二烷二酮、1-[4-(4-丙醯基苄基)苯基-1-丙酮、2-苄醯基環己酮、3-苄醯基環己酮、4-苄醯基環己酮、聯環[2,2,1]庚烷-2,5-二酮、聯環[2,2,1]庚烷-2,6-二酮、聯環[2,2,1]庚烷-2,7-二酮、八氫-1,3-萘二酮、八氫-1,4-萘二酮、八氫-1,5-萘二酮、八氫-1,6-萘二酮、八氫-1,7-萘二酮、八氫-1,8-萘二酮、2-乙醯基-環戊酮、2-乙醯基環己酮、二苯基-1,6-己烷二酮。
2官能酮化合物,更佳是選自以下之群組中至少1種之化合物。
2,5-己烷二酮、3,9-十一烷二酮、1,4-環己烷二酮、1,4-環辛烷二酮、聯環[2,2,1]庚烷-2,5-二酮、八氫-1,4-萘二酮、八氫-1,5-萘二酮、二苯基-1,6-己烷二酮。
本實施形態相關的多官能酮化合物,只要是含有3個以上酮基,並且,該酮基彼此不隣接之化合物即可,而無特別限定。
多官能酮化合物之中,從有變得容易取得,且可以更抑制組成物之成本,且經濟性更優異之傾向,在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性的傾向,及/或是,當聚合(C)環硫化合
物之際,有可以更抑制副反應之傾向而言,以選自以下之群組中至少1種之化合物為佳。
2,4,6-庚烷三酮、2,4,6-辛烷三酮、2,5,7-辛烷三酮、1,5-二苯基-1,3,5-戊烷三酮、1,6-二苯基-1,3,5-己烷三酮、1,3,6-己烷三酮、1,6-二苯基-1,3,6-己烷三酮、1,7-二苯基-1,3,5-庚烷三酮、1,7-二苯基-1,3,6-庚烷三酮、1,7-二苯基-1,4,6-庚烷三酮、1,7-二苯基-2,4,6-庚烷三酮、1,7-二苯基-1,3,5,7-庚烷四酮、1,8-二苯基-1,3,5-辛烷三酮、1,3,6-辛烷三酮、1,8-二苯基-1,3,6-辛烷三酮、1,3,7-辛烷三酮、1,8-二苯基-1,3,7-辛烷三酮、1,3,8-辛烷三酮、1,8-二苯基-1,3,8-辛烷三酮、1,8-二苯基-1,4,6-辛烷三酮、1,4,7-辛烷三酮、1,8-二苯基-1,4,7-辛烷三酮、1,4,8-辛烷三酮、1,8-二苯基-1,4,8-辛烷三酮、1,8-二苯基-1,5,7-辛烷三酮、1,5,8-辛烷三酮、1,8-二苯基-1,5,8-辛烷三酮、1,8-二苯基-1,6,8-辛烷三酮、1,8-二苯基-2,4,6-辛烷三酮、2,4,7-辛烷三酮、1,8-二苯基-2,4,7-辛烷三酮、1,8-二苯基-1,3,4,7-辛烷四酮、1,8-二苯基-1,3,4,8-辛烷四酮、1,8-二苯基-1,3,5,7-辛烷四酮、1,8-二苯基-1,3,5,8-辛烷四酮、1,8-二苯基-1,4,6,8-辛烷四酮、1,5-二萘基-1,3,5-戊烷三酮、1,6-二萘基-1,3,5-己烷三酮、1,6-二萘基-1,3,6-己烷三酮、1,7-二萘基-1,3,5-庚烷三酮、1,7-二萘基-1,3,6-庚烷三酮、1,7-二萘基-1,3,7-庚烷三酮、1,7-二萘基-1,4,6-庚烷三酮、1,7-二萘基
-1,4,7-庚烷三酮、1,7-二萘基-1,5,7-庚烷三酮、1,7-二萘基-2,4,6-庚烷三酮、1,7-二萘基-1,3,5,7-庚烷四酮、1,8-二萘基-1,3,5-辛烷三酮、1,8-二萘基-1,3,6-辛烷三酮、1,8-二萘基-1,3,7-辛烷三酮、1,8-二萘基-1,3,8-辛烷三酮、1,8-二萘基-1,4,6-辛烷三酮、1,8-二萘基-1,4,7-辛烷三酮、1,8-二萘基-1,4,8-辛烷三酮、1,8-二萘基-1,5,7-辛烷三酮、1,8-二萘基-1,5,8-辛烷三酮、1,8-二萘基-1,6,8-辛烷三酮、1,8-二萘基-2,4,6-辛烷三酮、1,8-二萘基-2,4,7-辛烷三酮、1,8-二萘基-1,3,5,7-辛烷四酮、1,8-二萘基-1,3,5,8-辛烷四酮、1,8-二萘基-1,4,6,8-辛烷四酮、1,8-二萘基-2,4,5,7-辛烷四酮、1,3,5-環己烷三酮、甲基-1,3,5-環己烷三酮、乙基-1,3,5-環己烷三酮、二甲基-1,3,5-環己烷三酮、乙基甲基-1,3,5-環己烷三酮、二乙基-1,3,5-環己烷三酮、三甲基-1,3,5-環己烷三酮、四甲基-1,3,5-環己烷三酮、五甲基-1,3,5-環己烷三酮、六甲基-1,3,5-環己烷三酮、1,3,5-環庚烷三酮、甲基-1,3,5-環庚烷三酮、乙基-1,3,5-環庚烷三酮、1,3,5-環辛烷三酮、甲基-1,3,5-環辛烷三酮、乙基-1,3,5-環辛烷三酮、1,3,6-環辛烷三酮、甲基-1,3,6-環辛烷三酮、乙基-1,3,6-環辛烷三酮、乙醯基-2,4-戊烷二酮、二乙醯基-2,4-戊烷二酮、乙醯基-2,4-己烷二酮、二乙醯基-2,4-己烷二酮、乙醯基-2,5-己烷二酮、二乙醯基-2,5-己烷二酮、三乙醯基-2,5-己烷二酮、四乙醯基-2,5-己烷二酮、
乙醯基-2,4-庚烷二酮、二乙醯基-2,4-庚烷二酮、乙醯基-2,5-庚烷二酮、二乙醯基-2,5-庚烷二酮、三乙醯基-2,5-庚烷二酮、四乙醯基-2,5-庚烷二酮、乙醯基-2,6-庚烷二酮、二乙醯-2,6-庚烷二酮、三乙醯基-2,6-庚烷二酮、四乙醯基-2,6-庚烷二酮、五乙醯基-2,6-庚烷二酮、六乙醯基-2,6-庚烷二酮、乙醯基-3,5-庚烷二酮、二乙醯基-3,5-庚烷二酮、乙醯基-2,4-辛烷二酮、二乙醯基-2,4-辛烷二酮、乙醯基-2,5-辛烷二酮、二乙醯基-2,5-辛烷二酮、三乙醯基-2,5-辛烷二酮、四乙醯基-2,5-辛烷二酮、乙醯基-2,6-辛烷二酮、二乙醯基-2,6-辛烷二酮、三乙醯基-2,6-辛烷二酮、四乙醯基-2,6-辛烷二酮、五乙醯基-2,6-辛烷二酮、2,6-辛烷二酮、乙醯基-2,7-辛烷二酮、二乙醯基-2,7-辛烷二酮、三乙醯基-2,7-辛烷二酮、四乙醯基-2,7-辛烷二酮、五乙醯基-2,7-辛烷二酮、六乙醯基-2,7-辛烷二酮、七乙醯基-2,7-辛烷二酮、乙醯基-3,5-辛烷二酮、二乙醯基-3,5-辛烷二酮、三乙醯基-3,6-辛烷二酮、四乙醯基-3,6-辛烷二酮、二乙醯基環丙酮、三乙醯基環丙酮、四乙醯基環丙酮、乙醯基-1,3-環丁烷二酮、二乙醯基-1,3-環丁烷二酮、三乙醯基-2,4-環丁烷二酮、四乙醯基-1,3-環丁烷二酮、二乙醯基環戊酮、三乙醯基環戊酮、四乙醯基環戊酮、五乙醯基環戊酮、六乙醯基環戊酮、七乙醯基環戊酮、八乙醯基環戊酮、乙醯基-1,3-環戊烷二酮、二乙醯基-1,3-環戊烷二酮、三乙醯基-1,3-環戊烷二酮、四乙醯基-1,3-環
戊烷二酮、五乙醯基-1,3-環戊烷二酮、六乙醯基-1,3-環戊烷二酮、二乙醯基環己酮、三乙醯基環己酮、四乙醯基環己酮、五乙醯基環己酮、六乙醯基環己酮、七乙醯基環己酮、八乙醯基環己酮、二苄醯基環己酮、乙醯基-1,3-環己烷二酮、二乙醯基-1,3-環己烷二酮、三乙醯基-1,3-環己烷二酮、四乙醯基-1,3-環己烷二酮、五乙醯基-1,3-環己烷二酮、六乙醯基-1,3-環己烷二酮、乙醯基-1,4-環己烷二酮、二乙醯基-1,4-環己烷二酮、三乙醯基-1,4-環己烷二酮、四乙醯基-1,4-環己烷二酮、五乙醯基-1,4-環己烷二酮、六乙醯基-1,4-環己烷二酮、乙醯基-1,3,5-環己烷三酮、二乙醯基-1,3,5-環己烷三酮、三乙醯基-1,3,5-環己烷三酮、四乙醯基-1,3,5-環己烷三酮、五乙醯基-1,3,5-環己烷三酮、六乙醯基-1,3,5-環己烷三酮。
多官能酮化合物,較佳是選自以下之群組中至少1種之化合物。
2,4,6-庚烷三酮、2,4,6-辛烷三酮、1,5-二苯基-1,3,5-戊烷三酮、1,6-二苯基-1,3,5-己烷三酮、1,3,6-己烷三酮、1,6-二苯基-1,3,6-己烷三酮、1,7-二苯基-1,3,5,7-庚烷四酮、1,5-二萘基-1,3,5-戊烷三酮、1,6-二萘基-1,3,5-己烷三酮、1,6-二萘基-1,3,6-己烷三酮、1,7-二萘基-1,3,5,7-庚烷四酮、1,3,5-環己烷三酮、甲基-1,3,5-環己烷三酮、乙基-1,3,5-環己烷三酮、二甲基-1,3,5-環己烷三酮、乙基甲基-1,3,5-環己烷三酮、二乙基-1,3,5-環己烷三酮、三甲基-1,3,5-環己烷三酮、四甲
基-1,3,5-環己烷三酮、五甲基-1,3,5-環己烷三酮、六甲基-1,3,5-環己烷三酮、1,3,5-環庚烷三酮、1,3,5-環辛烷三酮、1,3,6-環辛烷三酮、乙醯基-2,4-戊烷二酮、二乙醯基-2,4-戊烷二酮、乙醯基-2,4-己烷二酮、二乙醯基-2,4-己烷二酮、乙醯基-2,5-己烷二酮、二乙醯基-2,5-己烷二酮、三乙醯基-2,5-己烷二酮、四乙醯基-2,5-己烷二酮、二乙醯基環己酮、三乙醯基環己酮、四乙醯基環己酮、二苄醯基環己酮、乙醯基-1,3-環己烷二酮、二乙醯基-1,3-環己烷二酮、乙醯基-1,4-環己烷二酮、二乙醯基-1,4-環己烷二酮、乙醯基-1,3,5-環己烷三酮、二乙醯基-1,3,5-環己烷三酮。
多官能酮化合物,更佳是選自以下之群組中至少1種之化合物。
2,4,6-庚烷三酮、1,5-二苯基-1,3,5-戊烷三酮、1,7-二苯基-1,3,5,7-庚烷四酮、1,3,5-環己烷三酮、甲基-1,3,5-環己烷三酮、二甲基-1,3,5-環己烷三酮、三甲基-1,3,5-環己烷三酮、四甲基-1,3,5-環己烷三酮、五甲基-1,3,5-環己烷三酮、六甲基-1,3,5-環己烷三酮、乙醯基-2,4-戊烷二酮、二乙醯基-2,4-戊烷二酮、乙醯基-2,5-己烷二酮、二乙醯基-2,5-己烷二酮、二乙醯基環己酮、二苄醯基環己酮、乙醯基-1,3-環己烷二酮、乙醯基-1,4-環己烷二酮、乙醯基-1,3,5-環己烷三酮。
本實施形態相關的多酮化合物,只要是含有2個以上
酮基,並且,具有酮基彼此隣接之結構之化合物即可,無特別限定者。
多酮化合物之中,從有變得容易取得,且可以更抑制組成物之成本,且經濟性更優異之傾向,在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性的傾向,及/或是,當聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,以選自以下之群組中至少1種之化合物為佳。
2,3-丁烷二酮、2,3-戊烷二酮、2,3-己烷二酮、甲基-2,3-己烷二酮、乙基-2,3-己烷二酮、二甲基-2,3-己烷二酮、3,4-己烷二酮、2,3-庚烷二酮、3,4-庚烷二酮、甲基-2,3-庚烷二酮、乙基-2,3-庚烷二酮、二甲基-2,3-庚烷二酮、乙基甲基-2,3-庚烷二酮、二乙基-2,3-庚烷二酮、甲基-3,4-庚烷二酮、二甲基-3,4-庚烷二酮、乙基甲基-3,4-庚烷二酮、乙基-3,4-庚烷二酮、二乙基-3,4-庚烷二酮、2,3-辛烷二酮、甲基-2,3-辛烷二酮、乙基-2,3-辛烷二酮、二甲基-2,3-辛烷二酮、乙基甲基-2,3-辛烷二酮、二乙基-2,3-辛烷二酮、3,4-辛烷二酮、甲基-3,4-辛烷二酮、乙基-3,4-辛烷二酮、二甲基-3,4-辛烷二酮、乙基甲基-3,4-辛烷二酮、二乙基-3,4-辛烷二酮、4,5-辛烷二酮、甲基-4,5-辛烷二酮、乙基-4,5-辛烷二酮、二甲基-4,5-辛烷二酮、乙基甲基-4,5-辛烷二酮、二乙基-4,5-辛烷二酮、2,3-壬烷二酮、3,4-壬烷二酮、4,5-壬烷二酮、2,3-癸烷二酮、3,4-癸烷二酮、4,5-癸烷二酮、5,6-癸烷二酮、
1,2-環丁烷二酮、甲基-1,2-環丁烷二酮、二甲基-1,2-環丁烷二酮、三甲基-1,2-環丁烷二酮、四甲基-1,2-環丁烷二酮、乙基-1,2-環丁烷二酮、二乙基-1,2-環丁烷二酮、三乙基-1,2-環丁烷二酮、四乙基-1,2-環丁烷二酮、乙基甲基-1,2-環丁烷二酮、二乙基甲基-1,2-環丁烷二酮、三乙基甲基-1,2-環丁烷二酮、1,2-環戊烷二酮、甲基-1,2-環戊烷二酮、乙基-1,2-環戊烷二酮、二甲基-1,2-環戊烷二酮、乙基甲基-1,2-環戊烷二酮、二乙基-1,2-環戊烷二酮、三甲基-1,2-環戊烷二酮、二乙基甲基-1,2-環戊烷二酮、三乙基-1,2-環戊烷二酮、四甲基-1,2-環戊烷二酮、五甲基-1,2-環戊烷二酮、六甲基-1,2-環戊烷二酮、四乙基-1,2-環戊烷二酮、五乙基-1,2-環戊烷二酮、六乙基-1,2-環戊烷二酮、1,2-環己烷二酮、甲基-1,2-環己烷二酮、乙基-1,2-環己烷二酮、二甲基-1,2-環己烷二酮、乙基甲基-1,2-環己烷二酮、二乙基-1,2-環己烷二酮、三甲基-1,2-環己烷二酮、四甲基-1,2-環己烷二酮、五甲基-1,2-環己烷二酮、六甲基-1,2-環己烷二酮、七甲基-1,2-環己烷二酮、八甲基-1,2-環己烷二酮、三乙基-1,2-環己烷二酮、四乙基-1,2-環己烷二酮、五乙基-1,2-環己烷二酮、六乙基-1,2-環己烷二酮、七乙基-1,2-環己烷二酮、八乙基-1,2-環己烷二酮、1,2-環庚烷二酮、甲基-1,2-環庚烷二酮、乙基-1,2-環庚烷二酮、二甲基-1,2-環庚烷二酮、乙基甲基-1,2-環庚烷二酮、二乙基-1,2-環庚烷二酮、1,2-環辛烷二酮、甲基
-1,2-環辛烷二酮、乙基-1,2-環辛烷二酮、二甲基-1,2-環辛烷二酮、乙基甲基-1,2-環辛烷二酮、二乙基-1,2-環辛烷二酮、1,2-環壬烷二酮、甲基-1,2-環壬烷二酮、乙基-1,2-環壬烷二酮、1,2-環癸烷二酮、甲基-1,2-環癸烷二酮、乙基-1,2-環癸烷二酮、1,2-環十一烷二酮、1,2-環十二烷二酮、1,2-環十三烷二酮、1,2-環十四烷二酮、聯環[2,2,1]庚烷-2,3-二酮、聯環[2,2,2]辛烷-2,3-二酮、八氫-1,2-萘二酮、2,3,4-戊烷三酮、2,3,4-己烷三酮、2,3,5-己烷三酮、2,3,4,5-己烷四酮、2,3,4-庚烷三酮、2,3,5-庚烷三酮、2,3,6-庚烷三酮、2,4,5-庚烷三酮、2,5,6-庚烷三酮、3,4,5-庚烷三酮、2,3,4,5-庚烷四酮、2,3,4,6-庚烷四酮、2,3,4,5,6-庚烷五酮、2,3,4-辛烷三酮、2,3,5-辛烷三酮、2,3,6-辛烷三酮、2,3,7-辛烷三酮、2,4,5-辛烷三酮、2,4,7-辛烷三酮、2,5,6-辛烷三酮、3,4,5-辛烷三酮、3,4,6-辛烷三酮、3,5,6-辛烷三酮、二苯基-1,2,3-丙烷三酮、二苯基-1,2,3-丁烷三酮、二苯基-1,2,4-丁烷三酮、二苯基-1,2,3,4-丁烷四酮、二苯基-1,2,3-戊烷三酮、二苯基-1,2,4-戊烷三酮、二苯基-1,2,5-戊烷三酮、二苯基-2,3,4-戊烷三酮、二苯基-1,2,3,4-戊烷四酮、二苯基-1,2,3,5-戊烷四酮、二苯基-1,2,3,4,5-戊烷五酮、二苯基-1,2,3-己烷三酮、二苯基-1,2,4-己烷三酮、二苯基-1,2,5-己烷三酮、二苯基-1,2,6-己烷三酮、二苯基-1,3,4-己烷三酮、二苯基-1,4,5-己烷三酮、二苯基-2,3,4-己烷三酮、二苯基-2,3,5-己烷三酮、二苯基
-1,2,3,4-己烷四酮、二苯基-1,2,3,5-己烷四酮、二苯基-1,2,3,6-己烷四酮、二苯基-2,3,4,5-己烷四酮、二苯基-1,2,3,4,5-己烷五酮、二苯基-1,2,3,4,6-己烷五酮、二苯基-1,2,3,4,5,6-己烷六酮、二苯基-1,2,3-庚烷三酮、二苯基-1,2,4-庚烷三酮、二苯基-1,2,5-庚烷三酮、二苯基-1,2,6-庚烷三酮、二苯基-1,3,4-庚烷三酮、二苯基-1,4,5-庚烷三酮、二苯基-1,5,6-庚烷三酮、二苯基-1,2,7-庚烷三酮、二苯基-2,3,4-庚烷三酮、二苯基-2,3,5-庚烷三酮、二苯基-2,3,6-庚烷三酮、二苯基-2,3,7-庚烷三酮、二苯基-2,4,5-庚烷三酮、二苯基-2,5,6-庚烷三酮、二苯基-3,4,5-庚烷三酮、二苯基-1,2,3,4-庚烷四酮、二苯基-1,2,3,5-庚烷四酮、二苯基-1,2,3,6-庚烷四酮、二苯基-1,2,3,7-庚烷四酮、二苯基-2,3,4,5-庚烷四酮、二苯基-2,3,4,6-庚烷四酮、二苯基-1,2,3-辛烷三酮、二苯基-1,2,4-辛烷三酮、二苯基-1,2,5-辛烷三酮、二苯基-1,2,6-辛烷三酮、二苯基-1,2,7-辛烷三酮、二苯基-1,2,8-辛烷三酮、二苯基-1,3,4-辛烷三酮、二苯基-1,4,5-辛烷三酮、二苯基-1,5,6-辛烷三酮、二苯基-1,6,7-辛烷三酮、二苯基-2,3,4-辛烷三酮、二苯基-2,3,5-辛烷三酮、二苯基-2,3,6-辛烷三酮、二苯基-2,3,7-辛烷三酮、二苯基-2,4,5-辛烷三酮、二苯基-2,5,6-辛烷三酮、二苯基-3,4,5-辛烷三酮、二苯基-3,4,6-辛烷三酮、二苯基-1,2,3,4-辛烷四酮、二苯基-1,2,3,5-辛烷四酮、二苯基-1,2,3,6-辛烷四酮、二苯基-1,2,3,7-
辛烷四酮、二苯基-1,2,3,8-辛烷四酮、二苯基-1,3,4,5-辛烷四酮、二苯基-1,3,4,6-辛烷四酮、二苯基-1,3,5,6-辛烷四酮、二苯基-1,4,5,6-辛烷四酮、二苯基-1,4,5,7-辛烷四酮、二苯基-1,4,5,8-辛烷四酮、二苯基-1,4,6,7-辛烷四酮、二苯基-1,5,6,7-辛烷四酮、二苯基-1,5,6,8-辛烷四酮、二苯基-2,3,4,5-辛烷四酮、二苯基-2,3,4,6-辛烷四酮、二苯基-2,3,4,7-辛烷四酮、二苯基-2,4,5,6-辛烷四酮、二苯基-2,4,5,7-辛烷四酮、二苯基-3,4,5,6-辛烷四酮、二萘基-1,2,3-丙烷三酮、二萘基-1,2,3-丁烷三酮、二萘基-1,2,4-丁烷三酮、二萘基-1,2,3,4-丁烷四酮、二萘基-1,2,3-戊烷三酮、二萘基-1,2,4-戊烷三酮、二萘基-1,2,5-戊烷三酮、二萘基-1,3,4-戊烷三酮、二萘基-2,3,4-戊烷三酮、二萘基-1,2,3,4-戊烷四酮、二萘基-1,2,3,5-戊烷四酮、二萘基-1,2,3,4,5-戊烷五酮、二萘基-1,2,3-己烷三酮、二萘基-1,2,4-己烷三酮、二萘基-1,2,5-己烷三酮、二萘基-1,2,6-己烷三酮、二萘基-1,3,4-己烷三酮、二萘基-1,4,5-己烷三酮、二萘基-1,4,5-己烷三酮、二萘基-2,3,4-己烷三酮、二萘基-2,3,5-己烷三酮、二萘基-2,4,5-己烷三酮、二萘基-1,2,3,4-己烷四酮、二萘基-1,2,3,5-己烷四酮、二萘基-1,2,3,6-己烷四酮、二萘基-2,3,4,5-己烷四酮、二萘基-1,2,3,4,5-己烷五酮、二萘基-1,2,3,4,6-己烷五酮、二萘基-1,2,3,4,5,6-己烷六酮、二萘基-1,2,3-庚烷三酮、二萘基-1,2,4-庚烷三酮、二萘
基-1,2,5-庚烷三酮、二萘基-1,2,6-庚烷三酮、二萘基-1,2,7-庚烷三酮、二萘基-1,3,4-庚烷三酮、二萘基-1,4,5-庚烷三酮、二萘基-1,5,6-庚烷三酮、二萘基-2,3,4-庚烷三酮、二萘基-2,3,5-庚烷三酮、二萘基-2,3,6-庚烷三酮、二萘基-2,3,7-庚烷三酮、二萘基-2,4,5-庚烷三酮、二萘基-3,4,5-庚烷三酮、二萘基-1,2,3,4-庚烷四酮、二萘基-1,2,3,5-庚烷四酮、二萘基-1,2,3,6-庚烷四酮、二萘基-1,2,3,7-庚烷四酮、二萘基-1,3,4,5-庚烷四酮、二萘基-1,3,4,6-庚烷四酮、二萘基-1,3,4,7-庚烷四酮、二萘基-1,3,5,6-庚烷四酮、二萘基-1,4,5,6-庚烷四酮、二萘基-2,4,5,6-庚烷四酮、二萘基-2,3,4,5-庚烷四酮、二萘基-2,3,4,6-庚烷四酮、二萘基-1,2,3-辛烷三酮、二萘基-1,2,4-辛烷三酮、二萘基-1,2,5-辛烷三酮、二萘基-1,2,6-辛烷三酮、二萘基-1,2,7-辛烷三酮、二萘基-1,2,8-辛烷三酮、二萘基-1,3,4-辛烷三酮、二萘基-1,4,5-辛烷三酮、二萘基-1,5,6-辛烷三酮、二萘基-1,6,7-辛烷三酮、二萘基-2,3,4-辛烷三酮、二萘基-2,3,5-辛烷三酮、二萘基-2,3,6-辛烷三酮、二萘基-2,3,7-辛烷三酮、二萘基-2,4,5-辛烷三酮、二萘基-2,5,6-辛烷三酮、二萘基-3,4,5-辛烷三酮、二萘基-3,4,6-辛烷三酮、二萘基-1,2,3,4-辛烷四酮、二萘基-1,2,3,5-辛烷四酮、二萘基-1,2,3,6-辛烷四酮、二萘基-1,2,3,7-辛烷四酮、二萘基-1,2,3,8-辛烷四酮、二萘基-1,3,4,5-辛烷四酮、二萘基-1,3,4,6-辛烷四酮、二萘基-1,3,4,7-
辛烷四酮、二萘基-1,3,4,8-辛烷四酮、二萘基-1,3,5,6-辛烷四酮、二萘基-1,4,5,6-辛烷四酮、二萘基-1,4,5,7-辛烷四酮、二萘基-1,4,5,8-辛烷四酮、二萘基-1,4,6,7-辛烷四酮、二萘基-1,5,6,7-辛烷四酮、二萘基-1,5,6,8-辛烷四酮、二萘基-2,3,4,5-辛烷四酮、二萘基-2,3,4,6-辛烷四酮、二萘基-2,3,4,7-辛烷四酮、二萘基-2,4,5,6-辛烷四酮、二萘基-3,4,5,6-辛烷四酮、1,2,3-環丁烷三酮、1,2,3-環戊烷三酮、甲基-1,2,3-環戊烷三酮、乙基-1,2,3-環戊烷三酮、二甲基-1,2,3-環戊烷三酮、乙基甲基-1,2,3-環戊烷三酮、二乙基-1,2,3-環戊烷三酮、三甲基-1,2,3-環戊烷三酮、四甲基-1,2,3-環戊烷三酮、三乙基-1,2,3-環戊烷三酮、四乙基-1,2,3-環戊烷三酮、1,2,4-環戊烷三酮、甲基-1,2,4-環戊烷三酮、乙基-1,2,4-環戊烷三酮、二甲基-1,2,4-環戊烷三酮、乙基甲基-1,2,4-環戊烷三酮、二乙基-1,2,4-環戊烷三酮、三甲基-1,2,4-環戊烷三酮、四甲基-1,2,4-環戊烷三酮、三乙基-1,2,4-環戊烷三酮、四乙基-1,2,4-環戊烷三酮、丁基-1,2,4-環戊烷三酮、1,2,3,4-環戊烷四酮、甲基-1,2,3,4-環戊烷四酮、乙基-1,2,3,4-環戊烷四酮、二甲基-1,2,3,4-環戊烷四酮、乙基甲基-1,2,3,4-環戊烷四酮、二乙基-1,2,3,4-環戊烷四酮、1,2,3-環己烷三酮、甲基-1,2,3-環己烷三酮、乙基-1,2,3-環己烷三酮、二甲基-1,2,3-環己烷三酮、乙基甲基-1,2,3-環己烷三酮、二乙基-1,2,3-環己烷三酮、三甲基-1,2,3-
環己烷三酮、三乙基-1,2,3-環己烷三酮、四甲基-1,2,3-環己烷三酮、五甲基-1,2,3-環己烷三酮、六甲基-1,2,3-環己烷三酮、四乙基-1,2,3-環己烷三酮、五乙基-1,2,3-環己烷三酮、六乙基-1,2,3-環己烷三酮、1,2,4-環己烷三酮、甲基-1,2,4-環己烷三酮、乙基-1,2,4-環己烷三酮、二甲基-1,2,4-環己烷三酮、乙基甲基-1,2,4-環己烷三酮、二乙基-1,2,4-環己烷三酮、三甲基-1,2,4-環己烷三酮、四甲基-1,2,4-環己烷三酮、五甲基-1,2,4-環己烷三酮、六甲基-1,2,4-環己烷三酮、三乙基-1,2,4-環己烷三酮、四乙基-1,2,4-環己烷三酮、五乙基-1,2,4-環己烷三酮、六乙基-1,2,4-環己烷三酮、1,2,3,4-環己烷四酮、1,2,3,5-環己烷四酮、1,2,4,5-環己烷四酮、1,2,3-環庚烷三酮、甲基-1,2,3-環庚烷三酮、乙基-1,2,3-環庚烷三酮、1,2,4-環庚烷三酮、甲基-1,2,4-環庚烷三酮、乙基-1,2,4-環庚烷三酮、1,2,5-環庚烷三酮、甲基-1,2,5-環庚烷三酮、乙基-1,2,5-環庚烷三酮、1,2,3-環辛烷三酮、甲基-1,2,3-環辛烷三酮、乙基-1,2,3-環辛烷三酮、1,2,4-環辛烷三酮、甲基-1,2,4-環辛烷三酮、乙基-1,2,4-環辛烷三酮、1,2,5-環辛烷三酮、甲基-1,2,5-環辛烷三酮、乙基-1,2,5-環辛烷三酮、乙醯基-1,2-環丁烷二酮、二乙醯基-1,2-環丁烷二酮、乙醯基-1,2-環戊烷二酮、二乙醯基-1,2-環戊烷二酮、三乙醯基-1,2-環戊烷二酮、四乙醯基-1,2-環戊烷二酮、五乙醯基-1,2-環戊烷二酮、六乙醯基-1,2-環戊烷二酮、
乙醯基-1,2,3-環戊烷三酮、二乙醯基-1,2,3-環戊烷三酮、三乙醯基-1,2,3-環戊烷三酮、四乙醯基-1,2,3-環戊烷三酮、乙醯基-1,2,4-環戊烷三酮、二乙醯基-1,2,4-環戊烷三酮、三乙醯基-1,2,4-環戊烷三酮、四乙醯基-1,2,4-環戊烷三酮、乙醯基-1,2-環己烷二酮、二乙醯基-1,2-環己烷二酮、三乙醯基-1,2-環己烷二酮、四乙醯基-1,2-環己烷二酮、五乙醯基-1,2-環己烷二酮、六乙醯基-1,2-環己烷二酮、乙醯基-1,2,3-環己烷三酮、二乙醯基-1,2,3-環己烷三酮、三乙醯基-1,2,3-環己烷三酮、四乙醯基-1,2,3-環己烷三酮、五乙醯基-1,2,3-環己烷三酮、六乙醯基-1,2,3-環己烷三酮、乙醯基-1,2,4-環己烷三酮、二乙醯基-1,2,4-環己烷三酮、三乙醯基-1,2,4-環己烷三酮、四乙醯基-1,2,4-環己烷三酮、五乙醯基-1,2,4-環己烷三酮、六乙醯基-1,2,4-環己烷三酮、乙醯基-1,2-環己烷二酮、4,5-芘二酮、5,6-(1,2-苯并菲)二酮(5,6-chrysenedione)。
多酮化合物,較佳是選自以下之群組中至少1種之化合物。
2,3-丁烷二酮、2,3-戊烷二酮、2,3-己烷二酮、3,4-己烷二酮、2,3-庚烷二酮、3,4-庚烷二酮、2,3-辛烷二酮、3,4-辛烷二酮、4,5-辛烷二酮、2,3-壬烷二酮、3,4-壬烷二酮、4,5-壬烷二酮、2,3-癸烷二酮、3,4-癸烷二酮、4,5-癸烷二酮、5,6-癸烷二酮、1,2-環丁烷二酮、1,2-環戊烷二酮、甲基-1,2-環戊烷二酮、二甲基-1,2-環戊烷二酮、
1,2-環己烷二酮、甲基-1,2-環己烷二酮、二甲基-1,2-環己烷二酮、1,2-環庚烷二酮、1,2-環辛烷二酮、1,2-環壬烷二酮、1,2-環癸烷二酮、1,2-環十一烷二酮、1,2-環十二烷二酮、聯環[2,2,1]庚烷-2,3-二酮、聯環[2,2,2]辛烷-2,3-二酮、八氫-1,2-萘二酮、2,3,4-戊烷三酮、2,3,4-己烷三酮、2,3,5-己烷三酮、2,3,4,5-己烷四酮、2,3,4-庚烷三酮、2,3,5-庚烷三酮、2,3,6-庚烷三酮、2,4,5-庚烷三酮、2,5,6-庚烷三酮、3,4,5-庚烷三酮、2,3,4,5-庚烷四酮、2,3,4,6-庚烷四酮、2,3,4,5,6-庚烷五酮、2,3,4-辛烷三酮、2,3,5-辛烷三酮、2,3,6-辛烷三酮、2,3,7-辛烷三酮、2,4,5-辛烷三酮、2,4,7-辛烷三酮、2,5,6-辛烷三酮、3,4,5-辛烷三酮、3,4,6-辛烷三酮、3,5,6-辛烷三酮、二苯基-1,2,3-丙烷三酮、二苯基-1,2,3-丁烷三酮、二苯基-1,2,4-丁烷三酮、二苯基-1,2,3,4-丁烷四酮、二苯基-1,2,3-戊烷三酮、二苯基-1,2,4-戊烷三酮、二苯基-1,2,5-戊烷三酮、二苯基-2,3,4-戊烷三酮、二苯基-1,2,3-己烷三酮、二苯基-1,2,4-己烷三酮、二苯基-1,2,5-己烷三酮、二苯基-1,2,6-己烷三酮、二苯基-1,3,4-己烷三酮、二苯基-1,4,5-己烷三酮、二苯基-2,3,4-己烷三酮、二苯基-2,3,5-己烷三酮、1,2,4-環戊烷三酮、甲基-1,2,4-環戊烷三酮、二甲基-1,2,4-環戊烷三酮、丁基-1,2,4-環戊烷三酮、1,2,3-環己烷三酮、1,2,4-環己烷三酮、1,2,3,4-環己烷四酮、1,2,3,5-環己烷四酮、1,2,4,5-環己烷四酮、
1,2,3-環庚烷三酮、1,2,4-環庚烷三酮、1,2,5-環庚烷三酮、1,2,3-環辛烷三酮、1,2,4-環辛烷三酮、1,2,5-環辛烷三酮、乙醯基-1,2-環丁烷二酮、二乙醯基-1,2-環丁烷二酮、乙醯基-1,2-環戊烷二酮、二乙醯基-1,2-環戊烷二酮、乙醯基-1,2,3-環戊烷三酮、二乙醯基-1,2,3-環戊烷三酮、乙醯基-1,2,4-環戊烷三酮、二乙醯基-1,2,4-環戊烷三酮、乙醯基-1,2-環己烷二酮、二乙醯基-1,2-環己烷二酮、乙醯基-1,2,3-環己烷三酮、二乙醯基-1,2,3-環己烷三酮、乙醯基-1,2,4-環己烷三酮、二乙醯基-1,2,4-環己烷三酮、乙醯基-1,2-環己烷二酮、4,5-芘二酮、5,6-(1,2-苯并菲)二酮。
多酮化合物更佳是選自以下之群組中至少1種之化合物。
2,3-丁烷二酮、2,3-戊烷二酮、2,3-己烷二酮、3,4-己烷二酮、2,3-庚烷二酮、3,4-庚烷二酮、2,3-辛烷二酮、1,2-環丁烷二酮、1,2-環戊烷二酮、甲基-1,2-環戊烷二酮、1,2-環己烷二酮、甲基-1,2-環己烷二酮、1,2-環辛烷二酮、1,2-環癸烷二酮、2,3,4-戊烷三酮、二苯基-1,2,3-丙烷三酮、二苯基-1,2,4-戊烷三酮、1,2,4-環戊烷三酮、甲基-1,2,4-環戊烷三酮、丁基-1,2,4-環戊烷三酮、1,2,3-環己烷三酮、乙醯基-1,2-環戊烷二酮、乙醯基-1,2,4-環戊烷三酮、乙醯基-1,2-環己烷二酮、乙醯基-1,2,3-環己烷三酮、4,5-芘二酮、5,6-(1,2-苯并菲)二酮。
本實施形態之(B)三鹵化硼,是由3個鹵原子與1個硼原子所構成的化合物。
作為(B)三鹵化硼之具體例者,可以列舉:三氟化硼、三氯化硼、三溴化硼及三碘化硼。此等可以單獨使用,也可以組合複數種而使用。
(B)三鹵化硼,從有路易斯酸性降低,處理性提高之傾向而言,以三氟化硼、三氯化硼及三溴化硼為佳。從(A)選自由含有2個以上醚基之醚化合物、三價磷化合物及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼之結合力提高,作為組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向而言,以三氟化硼及三氯化硼為較佳。由同樣之觀點而言,以三氟化硼為更佳。
(A)選自由含有2個以上醚基之醚化合物、三價磷化合物及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼之至少一部份,形成隔著配位鍵之化合物(錯合物),從在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,且更提高組成物安定性之傾向,及/或是,在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,較佳。由同樣之觀點而言,更佳係在組成物中所含有之(B)三鹵化硼全部,與(A)選自由含有2個以上醚基之醚化合物、三價磷化合物及酮化合物所成群組中至少1種之化合物形成隔著配位鍵之化合物(錯合物)。
本實施形態之成分(C)是作為聚合性官能基具有至少1個以上3員環硫醚結構之化合物。作為成分(C)者,可以單獨使用1種環硫化合物,也可以組合複數種環硫化合物來使用。
聚合性官能基表示,在形成由單量體隔著鍵結而連結所成之聚合體之際,可以賦與單量體間的鍵結之取代基。
成分(C),可以只具有3員環硫醚結構作為聚合性官能基,也可以具有3員環硫醚結構並具有一般所使用之聚合性官能基。
作為一般所使用之聚合性官能基者並無特別限定,例如,選自環狀硫醚結構、內酯結構、環狀碳酸酯結構及其含硫之類似結構、環狀縮醛結構及其含硫之類似結構、環狀胺結構、環狀亞胺基醚結構、內醯胺結構、環狀硫脲結構、環狀次膦酸酯(phosphinate)結構、環狀亞膦酸酯(phosphonite)結構、環狀亞磷酸酯(phosphite)結構、乙烯結構、烯丙基結構、(甲基)丙烯酸結構、以及環烷烴結構。
作為聚合性官能基具有3員環硫醚結構及一般所使用之聚合性官能基的環硫化合物者,有具有聚合條件不同的聚合性官能基之情形。因此,該環硫化合物,聚合至少1個聚合性官能基,作成半聚合體,將該半聚合體進行成型等加工後,再一次進行聚合,而作成完全聚合體,對於必需要有得到所期望之物性的步驟之用途,可以使用此作為有效的手段。
作為(C)環硫化合物者,只具有3員環硫醚結構作為聚合性官能基,或是具有3員環硫醚結構作為聚合性官能基,並且以具有選自由內酯結構、環狀碳酸酯結構及其含硫之類似結構、環狀縮醛結構及其含硫之類似結構、環狀胺結構、環狀亞胺基醚結構、內醯胺結構、環狀硫脲結構、環狀次膦酸酯結構、環狀亞膦酸酯結構並且環狀亞磷酸酯結構所成群組中至少1個以上之結構作為聚合性官能基者為佳。
此等之中,從有抑制聚合性官能基的殘留之傾向而言,較佳係只具有3員環硫醚結構作為聚合性官能基,或者是具有3員環硫醚結構作為聚合性官能基,並且具有選自由4員環、6員環、7員環內酯結構;5員環、6員環環狀碳酸酯結構及其含硫之類似結構;5員環環狀縮醛結構及其含硫之類似結構;3員環、4員環環狀胺結構;5員環、6員環環狀亞胺基醚結構;4員環、7員環、8員環內醯胺結構;5員環、6員環環狀硫脲結構;環狀次膦酸酯結構;環狀亞膦酸酯結構;環狀亞磷酸酯結構所成群組中至少1個以上之結構作為聚合性官能基之化合物。再者,從有更容易控制聚合性,可以抑制聚合性官能基殘留之傾向,並且不需多階段之聚合步驟,可以抑制聚合物之成本,優良經濟性之傾向而言,以只具有3員環硫醚結構作為聚合性官能基之化合物為特別佳。
成分(C)之環硫當量(WPT,g/mol),從在環硫化合物之標準狀態中之蒸氣壓高,且有處理變容易之傾向而言,
以65以上為佳。從有可以更抑制聚合時之副反應之傾向而言,環硫當量是以85以上為較佳。由同樣之觀點而言,環硫當量是以100以上為更佳。
成分(C)之環硫當量(WPT,g/mol),從在將組成物聚合之際,有可以抑制環硫基的殘留之傾向而言,以700以下為佳。從由環硫化合物所形成之硬化物的耐熱性有提高之傾向而言,環硫當量是以600以下為較佳。由同樣之觀點而言,環硫當量是以500以下為更佳。
成分(C)只要是具有3員環硫醚結構作為聚合性官能基之化合物即可,而無特別限定,從有取得容易,抑制組成物之成本,經濟性優良之傾向而言,以具有下述式(6)、(7)、(8)或是(9)所示之部分結構為佳。又,從有更提高組成物安定性之傾向而言,以具有下述式(6)或是(7)所示之部分結構為更佳。再者,從在將組成物聚合之際,有可以更抑制副反應之傾向而言,以具有式(6)所示之部分結構為特佳。
式中,R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33及R34各自獨立地表示氫原子或者是碳原子數為1至20之鏈狀、分枝狀或是環狀之脂肪族烴基或者是取代或是無取代之芳香族烴基。
若具體例示成分(C),則可以列舉:單官能環硫化合物、聚酚化合物之硫縮水甘油醚化物的多官能環硫化合物、脂環式環硫化合物、各種酚醛清漆化合物之硫縮水甘油醚化物之多官能環硫化合物、芳香族環硫化合物之核氫
化物、雜環式環硫化合物、硫縮水甘油酯系環硫化合物、硫縮水甘油胺系環硫化合物、及鹵化酚類經硫縮水甘油化之環硫化合物、(含硫)多官能脂肪族環硫化合物、分子內含有環硫基之矽氧化合物、含有異種聚合性官能基之環硫化合物等。此等可以單獨使用,也可以組合複數種而使用。
單官能環硫化合物,只要是具有1個3員環硫醚結構之化合物即可,而無特別限定者,具體而言,可選自下述者:環硫乙烷、環硫丙烷、1-丁烯硫化物、2-丁烯硫化物、丁二烯硫化物、丁二烯二硫環氧化物、環丁烯硫化物、1,3-環丁二烯二硫環氧化物、1-戊烯硫化物、2-戊烯硫化物、1,3-戊二烯二硫環氧化物、1,4-戊二烯二硫環氧化物、2-甲基-2-丁烯硫化物、2-甲基-3-丁烯硫化物、環戊烯硫化物、1,3-環戊二烯二硫環氧化物、1-甲基-環丁烯硫化物、3-甲基-1-環丁烯硫化物、1-己烯硫化物、2-己烯硫化物、3-己烯硫化物、1,3-己二烯二硫環氧化物、1,4-己二烯二硫環氧化物、1,5-己二烯二硫環氧化物、1,3,5-己三烯三硫環氧化物、環己烯硫化物、1,3-環己二烯二硫環氧化物、1,3,5-環己三烯三硫環氧化物、1-甲基-環戊烯硫化物、3-甲基-環戊烯硫化物、1-甲基-1,3-環戊二烯二硫環氧化物、2-甲基-1,3-環戊二烯二硫環氧化物、5-甲基-1,3-環戊二烯二硫環氧化物、3,4-二甲基-環丁烯硫化物、2,3-二甲基-環丁烯硫化物、1,2-二甲基-環丁烯硫化物、1,2-二甲基-1,3-環丁二烯二硫環氧化物、2,3-二甲基-1,3-環
丁二烯二硫環氧化物、3,3-二甲基-1,2-硫環氧基丁烷、1-庚烯硫化物、2-庚烯硫化物、3-庚烯硫化物、1,3-庚二烯二硫環氧化物、1,4-庚二烯二硫環氧化物、1,5-庚二烯二硫環氧化物、1,5-庚二烯二硫環氧化物、1,6-庚二烯二硫環氧化物、1,3,5-庚三烯三硫環氧化物、1,3,6-庚三烯三硫環氧化物、1,4,6-庚三烯三硫環氧化物、環庚烯硫化物、1-甲基-環己烯硫化物、3-甲基-環己烯硫化物、4-甲基-環己烯硫化物、1-甲基-1,3-環己二烯二硫環氧化物、1-甲基-1,4-己二烯二硫環氧化物、1-甲基-1,3,5-己三烯三硫環氧化物、1,2-硫環氧基-5-己烯、1,2-硫環氧基-4-乙烯基環己烯、2-降冰片烯硫化物、7-甲基-2-降冰片烯硫化物、7,7-二甲基-2-降冰片烯硫化物、2-甲基-2-降冰片烯硫化物、2,3-二甲基-2-降冰片烯硫化物、2,7-二甲基-2-降冰片烯硫化物、2,7,7-三甲基-2-降冰片烯硫化物、2,3-硫環氧基-雙環[2,2,2]辛烷、2,3-硫環氧基-2-甲基-雙環[2,2,2]辛烷、2,3-硫環氧基-2,3-二甲基-雙環[2,2,2]辛烷、2,3-硫環氧基-2,5-二甲基-雙環[2,2,2]辛烷、2,3-硫環氧基-2,6-二甲基-雙環[2,2,2]辛烷、2,3-硫環氧基-2,3,5-三甲基-雙環[2,2,2]辛烷、2,3-硫環氧基-2,5,6-三甲基-雙環[2,2,2]辛烷、2,3-硫環氧基-2,3,5,6-四甲基-雙環[2,2,2]辛烷、硫環氧基六氫鄰苯二甲酸二辛酯、硫環氧基六氫鄰苯二甲酸二-2-乙基己酯、二苯乙烯硫化物、苯基硫縮水甘油醚、3-(2,2,3,3-四氟丙氧基)-1,2-硫環氧基丙烷、蒎烯硫化物(pinene sulfide)、異戊二烯單硫化
物、1,2-硫環氧基乙基苯、萘基硫縮水甘油醚、3-(2-聯苯氧基)-1,2-硫環氧基丙烷、烯丙基硫縮水甘油醚、1,1-二苯基-環硫乙烷、(甲基)丙烯酸硫縮水甘油酯、丁酸硫縮水甘油酯、碘甲基環硫乙烷、4-(2,3-硫環氧基丙基)嗎啉、硫縮水甘油基甲基醚、2-苯基-環硫丙烷、2,3-硫環氧基丙基-糠基醚、2,3,4,5,6-五氟苯乙烯硫化物、乙基-3-苯基硫縮水甘油酸酯、檸檬烯硫化物(limonene sulfide)、硫環氧基琥珀酸、3-硫環氧丙氧基丙基三甲氧基矽烷、(3-硫環氧丙氧基丙基)五甲基二矽氧烷、3-硫環氧丙氧基丙基(甲基)二甲氧基矽烷、3-硫環氧丙氧基丙基(甲基)二乙氧基矽烷、3-硫環氧丙氧基丙基(甲基)二丁氧基矽烷、2-(3,4-硫環氧基環己基)乙基(甲基)二甲氧基矽烷、2-(3,4-硫環氧基環己基)乙基(苯基)二乙氧基矽烷、2,3-硫環氧基丙基(甲基)二甲氧基矽烷、2,3-硫環氧基丙基(苯基)二甲氧基矽烷、3-硫環氧丙氧基丙基三甲氧基矽烷、3-硫環氧丙氧基丙基三乙氧基矽烷、3-硫環氧丙氧基丙基三丁氧基矽烷、2-(3,4-硫環氧基環己基)乙基三甲氧基矽烷、2-(3,4-硫環氧基環己基)乙基三乙氧基矽烷、2,3-硫環氧基丙基三甲氧基矽烷及2,3-硫環氧基丙基三乙氧基矽烷。
上述之中,從有在標準狀態中蒸氣壓高,處理容易,作為組成物之安定性更提高之傾向,且有可以更抑制聚合之際的副反應之傾向而言,單官能環硫化合物是以選自以下之群組中至少1種之化合物為佳。
環硫乙烷、環硫丙烷、1-丁烯硫化物、2-丁烯硫化物、丁二烯硫化物、丁二烯二硫環氧化物、環丁烯硫化物、1,3-環丁二烯二硫環氧化物、1-戊烯硫化物、2-戊烯硫化物、1,3-戊二烯二硫環氧化物、1,4-戊二烯二硫環氧化物、2-甲基-2-丁烯硫化物、2-甲基-3-丁烯硫化物、環戊烯硫化物、1,3-環戊二烯二硫環氧化物、1-甲基-環丁烯硫化物、3-甲基-1-環丁烯硫化物、1-己烯硫化物、2-己烯硫化物、3-己烯硫化物、1,3-己二烯二硫環氧化物、1,4-己二烯二硫環氧化物、1,5-己二烯二硫環氧化物、1,3,5-己三烯三硫環氧化物、環己烯硫化物、1,3-環己二烯二硫環氧化物、1,3,5-環己三烯三硫環氧化物、1-甲基-環戊烯硫化物、3-甲基-環戊烯硫化物、1-甲基-1,3-環戊二烯二硫環氧化物、2-甲基-1,3-環戊二烯二硫環氧化物、5-甲基-1,3-環戊二烯二硫環氧化物、3,4-二甲基-環丁烯硫化物、2,3-二甲基-環丁烯硫化物、1,2-二甲基-環丁烯硫化物、1,2-二甲基-1,3-環丁二烯二硫環氧化物、2,3-二甲基-1,3-環丁二烯二硫環氧化物、3,3-二甲基-1,2-硫環氧基丁烷、1-庚烯硫化物、2-庚烯硫化物、3-庚烯硫化物、1,3-庚二烯二硫環氧化物、1,4-庚二烯二硫環氧化物、1,5-庚二烯二硫環氧化物、1,5-庚二烯二硫環氧化物、1,6-庚二烯二硫環氧化物、1,3,5-庚三烯三硫環氧化物、1,3,6-庚三烯三硫環氧化物、1,4,6-庚三烯三硫環氧化物、環庚烯硫化物、1-甲基-環己烯硫化物、3-甲基-環己烯硫化物、4-甲基-環己烯硫化物、1-甲基-1,3-環己二烯二硫環氧化物、1-
甲基-1,4-己二烯二硫環氧化物、1-甲基-1,3,5-己三烯三硫環氧化物、1,2-硫環氧基-5-己烯、1,2-硫環氧基-4-乙烯基環己烯、硫環氧基六氫鄰苯二甲酸二辛酯、硫環氧基六氫鄰苯二甲酸二-2-乙基己酯、二苯乙烯硫化物、苯基硫縮水甘油醚、3-(2,2,3,3-四氟丙氧基)-1,2-硫環氧基丙烷、蒎烯硫化物、異戊二烯單硫化物、1,2-硫環氧基乙基苯、萘基硫縮水甘油醚、3-(2-聯苯氧基)-1,2-硫環氧基丙烷、烯丙基硫縮水甘油醚、1,1-二苯基-環硫乙烷氧化物、(甲基)丙烯酸硫縮水甘油酯、丁酸硫縮水甘油酯、碘甲基環硫乙烷、4-(2,3-硫環氧基丙基)嗎啉、硫縮水甘油基甲基醚、2-苯基-環硫丙烷、2,3-硫環氧基丙基-糠基醚、2,3,4,5,6-五氟苯乙烯硫化物、乙基-3-苯基硫縮水甘油酸酯、檸檬烯硫化物、硫環氧基琥珀酸、3-硫環氧丙氧基丙基三甲氧基矽烷、(3-硫環氧丙氧基丙基)五甲基二矽氧烷、3-硫環氧丙氧基丙基(甲基)二甲氧基矽烷、3-硫環氧丙氧基丙基(甲基)二乙氧基矽烷、3-硫環氧丙氧基丙基(甲基)二丁氧基矽烷、2-(3,4-硫環氧基環己基)乙基(甲基)二甲氧基矽烷、2-(3,4-硫環氧基環己基)乙基(苯基)二乙氧基矽烷、2,3-硫環氧基丙基(甲基)二甲氧基矽烷、2,3-硫環氧基丙基(苯基)二甲氧基矽烷、3-硫環氧丙氧基丙基三甲氧基矽烷、3-硫環氧丙氧基丙基三乙氧基矽烷、3-硫環氧丙氧基丙基三丁氧基矽烷、2-(3,4-硫環氧基環己基)乙基三甲氧基矽烷、2-(3,4-硫環氧基環己基)乙基三乙氧基矽烷、2,3-硫環氧基丙基三甲氧基矽烷及2,3-硫環氧基
丙基三乙氧基矽烷。
單官能環硫化合物,更佳是選自以下之群組中至少1種之化合物。
環硫丙烷、1-丁烯硫化物、2-丁烯硫化物、丁二烯硫化物、丁二烯二硫環氧化物、1-戊烯硫化物、2-戊烯硫化物、1,3-戊二烯二硫環氧化物、1,4-戊二烯二硫環氧化物、2-甲基-2-丁烯硫化物、2-甲基-3-丁烯硫化物、環戊烯硫化物、1-甲基-環丁烯硫化物、3-甲基-1-環丁烯硫化物、1-己烯硫化物、2-己烯硫化物、3-己烯硫化物、1,3-己二烯二硫環氧化物、1,4-己二烯二硫環氧化物、1,5-己二烯二硫環氧化物、1,3,5-己三烯三硫環氧化物、環己烯硫化物、1,3-環己二烯二硫環氧化物、1-甲基-環戊烯硫化物、3-甲基-環戊烯硫化物、2-庚烯硫化物、3-庚烯硫化物、1,3-庚二烯二硫環氧化物、1,4-庚二烯二硫環氧化物、1,5-庚二烯二硫環氧化物、1,5-庚二烯二硫環氧化物、1,6-庚二烯二硫環氧化物、1-甲基-環己烯硫化物、3-甲基-環己烯硫化物、4-甲基-環己烯硫化物、1,2-硫環氧基-5-己烯、1,2-硫環氧基-4-乙烯環己烯、二苯乙烯硫化物、苯基硫縮水甘油醚、3-(2,2,3,3-四氟丙氧基)-1,2-硫環氧基丙烷、蒎烯硫化物、異戊二烯單硫化物、1,2-硫環氧基乙基苯、萘基硫縮水甘油醚、3-(2-聯苯氧基)-1,2-硫環氧基丙烷、烯丙基硫縮水甘油醚、1,1-二苯基-環硫乙烷、(甲基)丙烯酸硫縮水甘油酯、丁酸硫縮水甘油酯、碘甲基環硫乙烷、4-(2,3-硫環氧基丙基)嗎啉、硫縮水甘油基甲基醚、2-苯
基-環硫丙烷、2,3-硫環氧基丙基-糠基醚、2,3,4,5,6-五氟苯乙烯硫化物、乙基-3-苯基硫縮水甘油酸酯、檸檬烯硫化物、硫環氧基琥珀酸、3-硫環氧丙氧基丙基三甲氧基矽烷、(3-硫環氧丙氧基丙基)五甲基二矽氧烷、3-硫環氧丙氧基丙基(甲基)二甲氧基矽烷、3-硫環氧丙氧基丙基(甲基)二乙氧基矽烷、3-硫環氧丙氧基丙基(甲基)二丁氧基矽烷、2-(3,4-硫環氧基環己基)乙基(甲基)二甲氧基矽烷、2-(3,4-硫環氧基環己基)乙基(苯基)二乙氧基矽烷、2,3-硫環氧基丙基(甲基)二甲氧基矽烷、2,3-硫環氧基丙基(苯基)二甲氧基矽烷、3-硫環氧丙氧基丙基三甲氧基矽烷、3-硫環氧丙氧基丙基三乙氧基矽烷、3-硫環氧丙氧基丙基三丁氧基矽烷、2-(3,4-硫環氧基環己基)乙基三甲氧基矽烷、2-(3,4-硫環氧基環己基)乙基三乙氧基矽烷、2,3-硫環氧基丙基三甲氧基矽烷、及2,3-硫環氧基丙基三乙氧基矽烷。
多酚化合物之硫縮水甘油醚化物的多官能環硫化合物並無特別限定者,具體而言,可以選自雙酚A、雙酚F、雙酚S、4,4’-聯酚、四甲基雙酚A、二甲基雙酚A、四甲基雙酚F、二甲基雙酚F、四甲基雙酚S、二甲基雙酚S、四甲基-4,4’-聯酚、二甲基-4,4’-聯酚、1-(4-羥基苯基)-2-[4-(1,1-雙-(4-羥基苯基)乙基)苯基]丙烷、2,2’-亞甲基-雙(4-甲基-6-三級丁基酚)、4,4’-亞丁基-雙(3-甲基-6-三級丁基酚)、參羥基苯基甲烷、間苯二酚(resorcinol)、
氫醌、2,6-二(三級丁基)氫醌、焦棓酚(pyrogallol)、具有二異亞丙基骨架之酚類、1,1-二(4-羥基苯基)茀等具有茀骨架的酚類、及酚化聚丁二烯等多酚化合物的硫縮水甘油醚化物。
上述之中,從製造容易,抑制作為組成物之成本,經濟性優異而言,以具有雙酚A骨架或是雙酚F骨架之酚類的硫縮水甘油醚化物之多官能環硫化合物為佳。
作為具有雙酚骨架之酚類的硫縮水甘油醚化物之多官能環硫化合物代表例者是在下述中表示。
脂環式環硫化合物,只要是具有脂環式環硫結構之環硫化合物即可,而無特別限定者,例如,可選自具有環己烯硫化物基、三環癸烯硫化物基或是環戊烯硫化物基等之環硫化合物。
作為脂環式環硫化合物之具體例者,可以列舉:3,4-硫環氧基環己烯基甲基-3’,4’-硫環氧基環己烯羧酸酯、3,4-硫環氧基環己基甲基-3,4-硫環氧基環己烷羧酸酯、
3,4-硫環氧基環己基辛基-3,4-硫環氧基環己烷羧酸酯、2-(3,4-硫環氧基環己基-5,5-螺-3,4-硫環氧基)環己烷-甲基-二烷、雙(3,4-硫環氧基環己基甲基)己二酸酯、乙烯基環己烯二硫化物、雙(3,4-硫環氧基-6-甲基環己基甲基)己二酸酯、3,4-硫環氧基-6-甲基環己基-3,4-硫環氧基-6-甲基環己烷羧酸酯、亞甲基雙(3,4-硫環氧基環己烷)、二環戊二烯二硫環氧化物、乙二醇二(3,4-硫環氧基環己基甲基)醚、伸乙基雙(3,4-硫環氧基環己烷羧酸酯)、及1,2,8,9-二硫環氧基檸檬烯。作為其他之多官能脂環式環硫化合物者,可以列舉:2,2-雙(羥基甲基)-1-丁醇之1,2-環氧基-4-(2-環硫乙烷基)環己烯或是1,2-硫環氧基-4-(2-環硫乙烷基)環己烯加成物等。
脂環式環硫化合物之代表例在下述表示。
酚醛清漆化合物之硫縮水甘油醚化物的多官能環硫化合物並無特別限定者,例如,可選自將酚、甲酚類、乙基酚類、丁基酚類、辛基酚類、雙酚A、雙酚F、雙酚S、及萘酚類等各種酚當作原料之酚醛清漆化合物,含有伸茬基骨架之酚酚醛清漆化合物、含有二環戊二烯骨架之酚酚醛清漆化合物、含有聯苯基骨架之酚酚醛清漆化合物、以及含有茀骨架之酚酚醛清漆化合物等各種酚醛清漆化合物之硫縮水甘油醚化物。
上述之中,從容易製造,抑制作為組成物之成本,經濟性優異而言,以將酚或是甲酚類等作為原料之酚醛清漆化合物的硫縮水甘油醚化物為佳。
酚醛清漆化合物之硫縮水甘油醚化物的多官能環硫化合物之代表例,表示在下述。
芳香族環硫化合物之核氫化物並無特別限定者,例如,可選自酚化合物(雙酚A、雙酚F、雙酚S、4,4’-聯酚等)之硫縮水甘油醚化物,或是各種酚(酚、甲酚類、乙基酚類、丁基酚類、辛基酚類、雙酚A、雙酚F、雙酚S、萘酚類等)之芳香環經核氫化者,以及,酚醛清漆化合物之硫縮水甘油醚化物之核氫化物。
雜環式環硫化合物並無特別限定者,例如,可選自具有異三聚氰基環、及海因(Hydantoin)環等雜環之雜環式環硫化合物。
硫縮水甘油酯系環硫化合物並無特別限定者,例如,
可選自六氫鄰苯二甲酸二縮水甘油酯及四氫鄰苯二甲酸二縮水甘油酯等,羰酸化合物所衍生之環硫化合物。
硫縮水甘油胺系環硫化合物並無特別限定者,例如,可選自將苯胺,甲苯胺,對-苯二胺,間-苯二胺,二胺基二苯基甲烷衍生物及二胺基甲基苯衍生物等將胺經硫縮水甘油化之環硫化合物。
將鹵化酚類經硫縮水甘油化之環硫化合物並無特別限定者,例如,可選自溴化雙酚A、溴化雙酚F、溴化雙酚S、溴化酚酚醛清漆、溴化甲酚酚醛清漆、氯化雙酚S、及氯化雙酚A等鹵化酚類經硫縮水甘油醚化之環硫化合物。
作為(含硫)多官能脂肪族環硫化合物者,無特別限定者,具體而言,可選自:1,1-雙(環硫乙基)甲烷、1-(環硫乙基)-1-(β-環硫丙基)甲烷、1,1-雙(β-環硫丙基)甲烷、1-(環硫乙基)-1-(β-環硫丙基)乙烷、1,2-雙(β-環硫丙基)乙烷、1-(環硫乙基)-3-(β-環硫丙基)丁烷、1,3-雙(β-環硫丙基)丙烷、1-(環硫乙基)-4-(β-環硫丙基)戊烷、1,4-雙(β-環硫丙基)丁烷、1-(環硫乙基)-5-(β-環硫丙基)己烷、1-(環硫乙基)-2-(γ-環硫丁基硫基)乙烷、1-(環硫乙基)-2-[2-(γ-環硫丁基硫基)乙基硫基]乙烷、肆(β-環硫丙基)甲烷、1,1,1-參(β-環硫丙基)丙烷、1,3-雙(β-環硫丙基)-1-(β-環硫丙基)-2-硫雜丙烷、
1,5-雙(β-環硫丙基)-2,4-雙(β-環硫丙基)-3-硫雜戊烷、1,3或1,4-雙(環硫乙基)環己烷、1,3或1,4-雙(β-環硫丙基)環己烷、2,5-雙(環硫乙基)-1,4-二硫雜環己烷、2,5-雙(β-環硫丙基)-1,4-二硫雜環己烷、4-環硫乙基-1,2-環己烯硫化物、2,2-雙[4-(環硫乙基)環己基]丙烷、2,2-雙[4-(β-環硫丙基)環己基]丙烷、雙[4-(環硫乙基)環己基]甲烷、雙[4-(β-環硫丙基)環己基]甲烷、雙[4-(β-環硫丙基)環己基]硫化物、雙[4-(環硫乙基)環己基]硫化物、雙(β-環硫丙基)醚、雙(β-環硫丙氧基)甲烷、1,2-雙(β-環硫丙氧基)乙烷、1,3-雙(β-環硫丙氧基)丙烷、1,2-雙(β-環硫丙氧基)丙烷、1-(β-環硫丙氧基)-2-(β-環硫丙氧基甲基)丙烷、1,4-雙(β-環硫丙氧基)丁烷、1,3-雙(β-環硫丙氧基)丁烷、1-(β-環硫丙氧基)-3-(β-環硫丙氧基甲基)丁烷、1,5-雙(β-環硫丙氧基)戊烷、1-(β-環硫丙氧基)-4-(β-環硫丙氧基甲基)戊烷、1,6-雙(β-環硫丙氧基)己烷、1-(β-環硫丙氧基)-5-(β-環硫丙氧基甲基)己烷、1-(β-環硫丙氧基)-2-[(2-β-環硫丙氧基乙基)氧基]乙烷、1-(β-環硫丙氧基)-2-[[2-(2-β-環硫丙氧基乙基)氧基乙基]氧基]乙烷、肆(β-環硫丙氧基甲基)甲烷、1,1,1-參(β-環硫丙氧基甲基)丙烷、1,5-雙(β-環硫丙氧基)-2-(β-環硫丙氧基甲基)-3-硫雜戊烷、1,5-雙(β-環硫丙氧基)-2,4-雙(β-環硫丙氧基甲基)-3-硫雜戊烷;1-(β-環硫丙氧基)-2,2-雙(β-環硫丙氧基甲基)-4-
硫雜己烷、1,5,6-參(β-環硫丙氧基)-4-(β-環硫丙氧基甲基)-3-硫雜己烷、1,8-雙(β-環硫丙氧基)-4-(β-環硫丙氧基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙氧基)-4,5-雙(β-環硫丙氧基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙氧基)-4,4-雙(β-環硫丙氧基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙氧基)-2,4,5-參(β-環硫丙氧基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙氧基)-2,5-雙(β-環硫丙氧基甲基)-3,6-二硫雜辛烷、1,9-雙(β-環硫丙氧基)-5-(β-環硫丙氧基甲基)-5-[(2-β-環硫丙氧基乙基)氧基甲基]-3,7-二硫雜壬烷、1,10-雙(β-環硫丙氧基)-5,6-雙[(2-β-環硫丙氧基乙基)氧基]-3,6,9-三硫雜癸烷、1,11-雙(β-環硫丙氧基)-4,8-雙(β-環硫丙氧基甲基)-3,6,9-三硫雜十一烷、1,11-雙(β-環硫丙氧基)-5,7-雙(β-環硫丙氧基甲基)-3,6,9-三硫雜十一烷、1,11-雙(β-環硫丙氧基)-5,7-[(2-β-環硫丙氧基乙基)氧基甲基]-3,6,9-三硫雜十一烷、1,11-雙(β-環硫丙氧基)-4,7-雙(β-環硫丙氧基甲基)-3,6,9-三硫雜十一烷、1,3或1,4-雙(β-環硫丙氧基)環己烷、1,3或1,4-雙(β-環硫丙氧基甲基)環己烷、雙[4-(β-環硫丙氧基)環己基]甲烷、2,2-雙[4-(β-環硫丙氧基)環己基]丙烷、雙[4-(β-環硫丙氧基)環己基]硫化物、2,5-雙(β-環硫丙氧基甲基)-1,4-二硫雜環己烷、2,5-雙(β-環硫丙氧基乙氧基甲基)-1,4-二硫雜環己烷、雙(β-環硫丙基)硫化物、雙(β-環硫丙基)二硫化物、雙(β-環硫丙基)三硫化物、雙(β-
環硫丙基硫基)甲烷、雙(β-環硫丙基二硫基)甲烷、雙(β-環硫丙基二硫基)乙烷、雙(β-環硫丙基二硫基乙基)硫化物、雙(β-環硫丙基二硫基乙基)二硫化物、1,2-雙(β-環硫丙基硫基)乙烷、1,3-雙(β-環硫丙基硫基)丙烷、1,2-雙(β-環硫丙基硫基)丙烷、1-(β-環硫丙基硫基)-2-(β-環硫丙基硫基甲基)丙烷、1,4-雙(β-環硫丙基硫基)丁烷、1,3-雙(β-環硫丙基硫基)丁烷、1-(β-環硫丙基硫基)-3-(β-環硫丙基硫基甲基)丁烷、1,5-雙(β-環硫丙基硫基)戊烷、1-(β-環硫丙基硫基)-4-(β-環硫丙基硫基甲基)戊烷、1,6-雙(β-環硫丙基硫基)己烷、1-(β-環硫丙基硫基)-5-(β-環硫丙基硫基甲基)己烷、1-(β-環硫丙基硫基)-2-[(2-β-環硫丙基硫基乙基)硫基]乙烷、1-(β-環硫丙基硫基)-2-[[2-(2-β-環硫丙基硫基乙基)硫基乙基]硫基]乙烷、肆(β-環硫丙基硫基甲基)甲烷、肆(β-環硫丙基二硫基甲基)甲烷、1,1,1-參(β-環硫丙基硫基甲基)丙烷、1,2,3-參(β-環硫丙基二硫基)丙烷、1,5-雙(β-環硫丙基硫基)-2-(β-環硫丙基硫基甲基)-3-硫雜戊烷、1,5-雙(β-環硫丙基硫基)-2,4-雙(β-環硫丙基硫基甲基)-3-硫雜戊烷、1,6-雙(β-環硫丙基二硫基甲基)-2-(β-環硫丙基二硫基乙基硫基)-4-硫雜己烷、1-(β-環硫丙基硫基)-2,2-雙(β-環硫丙基硫基甲基)-4-硫雜己烷、1,5,6-參(β-環硫丙基硫基)-4-(β-環硫丙基硫基甲基)-3-硫雜己烷、1,8-雙(β-環硫丙基硫基)-4-(β-環硫丙基硫基甲基)-3,6-二硫雜
辛烷、1,8-雙(β-環硫丙基硫基)-4,5-雙(β-環硫丙基硫基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙基硫基)-4,4-雙(β-環硫丙基硫基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙基硫基)-2,4,5-參(β-環硫丙基硫基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙基硫基)-2,5-雙(β-環硫丙基硫基甲基)-3,6-二硫雜辛烷、1,9-雙(β-環硫丙基硫基)-5-(β-環硫丙基硫基甲基)-5-[(2-β-環硫丙基硫基乙基)硫基甲基]-3,7-二硫雜壬烷、1,10-雙(β-環硫丙基硫基)-5,6-雙[(2-β-環硫丙基硫基乙基)硫基]-3,6,9-三硫雜癸烷、1,11-雙(β-環硫丙基硫基)-4,8-雙(β-環硫丙基硫基甲基)-3,6,9-三硫雜十一烷、1,11-雙(β-環硫丙基硫基)-5,7-雙(β-環硫丙基硫基甲基)-3,6,9-三硫雜十一烷、1,11-雙(β-環硫丙基硫基)-5,7-[(2-β-環硫丙基硫基乙基)硫基甲基]-3,6,9-三硫雜十一烷、1,11-雙(β-環硫丙基硫基)-4,7-雙(β-環硫丙基硫基甲基)-3,6,9-三硫雜十一烷、四[2-(β-環硫丙基硫基)乙醯基甲基]甲烷、1,1,1-三[2-(β-環硫丙基硫基)乙醯基甲基]丙烷、四[2-(β-環硫丙基硫基甲基)乙醯基甲基]甲烷、1,1,1-三[2-(β-環硫丙基硫基甲基)乙醯基甲基]丙烷、1,3或1,4-雙(β-環硫丙基硫基)環己烷、1,3或1,4-雙(β-環硫丙基硫基甲基)環己烷、2,5-雙(β-環硫丙基硫基甲基)-1,4-二硫雜環己烷、2,5-雙(β-環硫丙基二硫基甲基)-1,4-二硫雜環己烷、2,5-雙(β-環硫丙基硫基乙基硫基甲基)-1,4-二硫雜環己烷、雙[4-(β-環硫丙基硫基)
環己基]甲烷、2,2-雙[4-(β-環硫丙基硫基)環己基]丙烷、雙[4-(β-環硫丙基硫基)環己基]硫化物、2,2-雙[4-(β-環硫丙基硫基)環己基]丙烷、雙[4-(β-環硫丙基硫基)環己基]硫化物。
上述之中,從由於製造容易,可以抑制作為組成物之成本,經濟性優異而言,作為(含硫)多官能脂肪族環硫化合物者,是以選自以下之群組中至少1種之化合物為佳。
雙(β-環硫丙氧基)甲烷、1,2-雙(β-環硫丙氧基)乙烷、1,3-雙(β-環硫丙氧基)丙烷、1,2-雙(β-環硫丙氧基)丙烷、1-(β-環硫丙氧基)-2-(β-環硫丙氧基甲基)丙烷、1,4-雙(β-環硫丙氧基)丁烷、1,3-雙(β-環硫丙氧基)丁烷、1-(β-環硫丙氧基)-3-(β-環硫丙氧基甲基)丁烷、1,6-雙(β-環硫丙氧基)己烷、1-(β-環硫丙氧基)-5-(β-環硫丙氧基甲基)己烷、1-(β-環硫丙氧基)-2-[(2-β-環硫丙氧基乙基)氧基]乙烷、1-(β-環硫丙氧基)-2-[[2-(2-β-環硫丙氧基乙基)氧基乙基]氧基]乙烷、肆(β-環硫丙氧基甲基)甲烷、1,1,1-參(β-環硫丙氧基甲基)丙烷、1-(β-環硫丙氧基)-2,2-雙(β-環硫丙氧基甲基)-4-硫雜己烷、1,5,6-參(β-環硫丙氧基)-4-(β-環硫丙氧基甲基)-3-硫雜己烷、1,8-雙(β-環硫丙氧基)-4-(β-環硫丙氧基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙氧基)-4,5-雙(β-環硫丙氧基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙氧基)-4,4-雙(β-環硫丙氧基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環
硫丙氧基)-2,4,5-參(β-環硫丙氧基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙氧基)-2,5-雙(β-環硫丙氧基甲基)-3,6-二硫雜辛烷、1,3或1,4-雙(β-環硫丙氧基)環己烷、1,3或1,4-雙(β-環硫丙氧基甲基)環己烷、雙[4-(β-環硫丙氧基)環己基]甲烷、2,2-雙[4-(β-環硫丙氧基)環己基]丙烷、雙[4-(β-環硫丙氧基)環己基]硫化物、2,5-雙(β-環硫丙氧基甲基)-1,4-二硫雜環己烷、2,5-雙(β-環硫丙氧基乙氧基甲基)-1,4-二硫雜環己烷、雙(β-環硫丙基)硫化物、雙(β-環硫丙基)二硫化物、雙(β-環硫丙基硫基)甲烷、雙(β-環硫丙基二硫基)甲烷、雙(β-環硫丙基二硫基)乙烷、雙(β-環硫丙基二硫基乙基)硫化物、雙(β-環硫丙基二硫基乙基)二硫化物、1,2-雙(β-環硫丙基硫基)乙烷、1,3-雙(β-環硫丙基硫基)丙烷、1,2-雙(β-環硫丙基硫基)丙烷、1-(β-環硫丙基硫基)-2-(β-環硫丙基硫基甲基)丙烷、1,4-雙(β-環硫丙基硫基)丁烷、1,3-雙(β-環硫丙基硫基)丁烷、1-(β-環硫丙基硫基)-3-(β-環硫丙基硫基甲基)丁烷、1,6-雙(β-環硫丙基硫基)己烷、1-(β-環硫丙基硫基)-5-(β-環硫丙基硫基甲基)己烷、1-(β-環硫丙基硫基)-2-[(2-β-環硫丙基硫基乙基)硫基]乙烷、1-(β-環硫丙基硫基)-2-[[2-(2-β-環硫丙基硫基乙基)硫基乙基]硫基]乙烷、肆(β-環硫丙基硫基甲基)甲烷、肆(β-環硫丙基二硫基甲基)甲烷、1,1,1-參(β-環硫丙基硫基甲基)丙烷、1,2,3-參(β-環硫丙基二硫基)丙烷、1,6-雙(β-環硫
丙基二硫基甲基)-2-(β-環硫丙基二硫基乙基硫基)-4-硫雜己烷、1-(β-環硫丙基硫基)-2,2-雙(β-環硫丙基硫基甲基)-4-硫雜己烷、1,5,6-參(β-環硫丙基硫基)-4-(β-環硫丙基硫基甲基)-3-硫雜己烷、1,8-雙(β-環硫丙基硫基)-4-(β-環硫丙基硫基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙基硫基)-4,5-雙(β-環硫丙基硫基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙基硫基)-4,4-雙(β-環硫丙基硫基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙基硫基)-2,4,5-參(β-環硫丙基硫基甲基)-3,6-二硫雜辛烷、1,8-雙(β-環硫丙基硫基)-2,5-雙(β-環硫丙基硫基甲基)-3,6-二硫雜辛烷、四[2-(β-環硫丙基硫基)乙醯基甲基]甲烷、1,1,1-三[2-(β-環硫丙基硫基)乙醯基甲基]丙烷、四[2-(β-環硫丙基硫基甲基)乙醯基甲基]甲烷、1,1,1-三[2-(β-環硫丙基硫基甲基)乙醯基甲基]丙烷、1,3或1,4-雙(β-環硫丙基硫基)環己烷、1,3或1,4-雙(β-環硫丙基硫基甲基)環己烷、2,5-雙(β-環硫丙基硫基甲基)-1,4-二硫雜環己烷、2,5-雙(β-環硫丙基二硫基甲基)-1,4-二硫雜環己烷、2,5-雙(β-環硫丙基硫基乙基硫基甲基)-1,4-二硫雜環己烷、雙[4-(β-環硫丙基硫基)環己基]甲烷、2,2-雙[4-(β-環硫丙基硫基)環己基]丙烷、雙[4-(β-環硫丙基硫基)環己基]硫化物、2,2-雙[4-(β-環硫丙基硫基)環己基]丙烷、雙[4-(β-環硫丙基硫基)環己基]硫化物。
在分子內有環硫基之矽氧化合物並無特別限定者,例如,可選自下述式(13)所示化合物。
(R70R71R72SiO1/2)a(R73R74SiO2/2)b(R75SiO3/2)c(SiO4/2)d (13)
式(13)中,a、b、c及d是分別滿足a+b+c+d=1.0之數值,0≦a/(a+b+c+d)≦1,0≦b/(a+b+c+d)≦1,0≦c/(a+b+c+d)≦1,並且0≦d/(a+b+c+d)<1。R70至R75之中至少1個表示含有環硫基之基,其他之R70至R75,表示直鏈狀或是分枝狀之碳原子數1至8之烴基或是該烴基經氟化之基。此等是互相可以相同也可以相異。
含有異種聚合性官能基之環硫化合物並無特別限定者,例如可選自下述式(14)所示化合物。
上述式(14)中,R80至R82表示可以經硫化之取代或是未取代之鏈狀、分枝狀、環狀之脂肪族或是芳香族烴基。m、n、o及p表示個別獨立,1以上之數。X表示環硫基。Y表示單種之聚合性官能基時,表示選自環狀硫醚結構、內酯結構、環狀碳酸酯結構及其含硫類相似結構、環狀縮醛結構及其含硫類相似結構、環狀胺結構、環狀亞胺基醚結構、內醯胺結構、環狀硫脲結構、環狀次磷酸酯(phosphinate)結構、環狀亞膦酸酯(phosphonite)結構、環狀亞磷酸酯(phosphite)結構、乙烯結構、烯丙基結構、(甲基)丙烯酸結構、環烷結構中之結構。表示複數種之聚合性官能基時,
表示選自上述之群組中至少2種之結構。
(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與前述(B)三鹵化硼之混合比率,是可以用以下之式(5)算出之指標α來表示。
指標α=(α e+α p+α k)/α b (5)
α e:(A-1)醚化合物之醚基的物質量(mol)
α p:(A-2)三價磷化合物中所含有之三價磷原子的物質量(mol)
α k:(A-3)酮化合物之酮基的物質量(mol)
α b:(B)三鹵化硼的物質量(mol)
指標α是,在組成物中所含有之(B)三鹵化硼全部,與(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,形成隔著配位鍵之化合物(錯合物),於室溫下調整組成物之際,從有可以更抑制(C)環硫化合物之聚合,更提高組成物安定性的傾向而言,是以1以上為佳。由同樣之觀點而言,指標α是以1.5以上為更佳。
(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼,隔著配位鍵之化合物有改質可能性的情形,為了提高該化合物之安定性,指標α是以2以上為佳。
在聚合組成物之際,從有可以更抑制在(C)環硫化合物中所含有之環硫基之殘留的傾向而言,指標α是以在1000
以下為佳。聚合組成物,當需要將得到之聚合物中所含有的(A)選自由含有2個以上醚基的醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物除去的步驟之情形,從有可以更抑制該步驟所需要之成本,經濟性更優異之傾向而言,指標α是以在500以下為較佳。由同樣之觀點而言,指標α是以在100以下為更佳。
(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,為只有(A-1)醚化合物的情形,上述式(5)是以式(15)之指標α 2表示。
指標α 2=α e/α b (15)
α e:(A-1)醚化合物之醚基的物質量(mol)
α b:(B)三鹵化硼之物質量(mol)
在組成物中所含有之(B)三鹵化硼全部,與(A-1)含有2個以上醚基之醚化合物,形成隔著配位鍵之化合物,從在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,更提高組成物安定性的傾向而言,指標α 2是以1以上為佳。由同樣之觀點而言,指標α 2是以1.5以上為更佳。
(A-1)含有2個以上醚基的醚化合物,與(B)三鹵化硼隔著配位鍵之化合物有可能改質的情形,為了提高該化合物之安定性,指標α 2是以2以上為佳。
從在聚合組成物之際,有可以更抑制在(C)環硫化合物中所含有之環硫基之殘留的傾向而言,指標α 2是以在1000以下為佳。需要有聚合組成物,並將得到之聚合物中
所含有之(A-1)含有2個以上醚基之醚化合物除去之步驟的情形,從有可以更抑制該步驟所需要的成本,經濟性更優異之傾向而言,指標α 2是以500以下為較佳。由同樣之觀點而言,指標α 2是以100以下為更佳。
(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物為只有(A-2)三價磷化合物的情形,上述式(5)是以式(16)之指標α 3表示。
指標α 3=α p/α b (16)
α p:(A-2)三價磷化合物中所含有之三價磷原子的物質量(mol)
α b:(B)三鹵化硼的物質量(mol)
在組成物中所含有之(B)三鹵化硼全部,與(A-2)三價磷化合物形成隔著配位鍵之化合物,從在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,更提高組成物安定性之傾向而言,指標α 3是以1以上為佳。
在(A-2)三價磷化合物與(B)三鹵化硼隔著配位鍵之化合物有可能改質的情形,為了提高該化合物之安定性,指標α 3是以1.2以上為佳。由同樣之觀點而言,指標α 3是以1.5以上為更佳。
從在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,指標α 3是以10以下為佳。需要有聚合組成物,並將得到之聚合物中含有之(A-2)三價磷化合物除去的步驟的情形,從有可以更抑制在該步驟所需要之成本,經濟
性更優異的傾向而言,指標α 3是以5以下為更佳。由同樣之觀點而言,指標α 3是以2以下為更佳。
(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,為只有(A-3)酮化合物的情形,上述式(5)是以式(17)之指標α 4表示。
指標α 4=α k/α b (17)
α k:(A-3)酮化合物的酮基之物質量(mol)
α b:(B)三鹵化硼之物質量(mol)
在組成物中所含有之(B)三鹵化硼全部,與(A-2)酮化合物形成隔著配位鍵之化合物,從在室溫下調整組成物之際,有可以更抑制聚合(C)環硫化合物,更提高組成物之安定性的傾向而言,指標α 4是以1以上為佳。由同樣之觀點而言,指標α 4是以1.5以上為更佳。
(A-3)酮化合物與(B)三鹵化硼隔著配位鍵之化合物有可能改質的情形,為了提高該化合物之安定性,指標α 4是以2以上為佳。
在聚合組成物之際,有可以更抑制在(C)環硫化合物中所含有之環硫基殘留之傾向而言,指標α 4是以1000以下為佳。需要有聚合組成物,並將得到之聚合物中所含有之(A-3)酮化合物除去之步驟的情形,有可以更抑制在該步驟中所需要之成本,經濟性更優異之傾向而言,指標α 4是以500以下為較佳。由同樣之觀點而言,指標α 4是以100以下為更佳。
有關(B)三鹵化硼與(C)環硫化合物之混合比率,前述
(B)之物質量(mol),與前述(C)中所含之環硫基之物質量(mol)的比是以1:10至1:100000為佳。
將(B)之物質量(mol)當作1的情形,在(C)中所含有之環硫基的物質量(mol)為10以上時,從在室溫下調整組成物之際,有可以更抑制(C)環硫化合物之聚合,更提高組成物安定性之傾向而言較佳。將(B)之物質量(mol)當作1的情形,在(C)中所含有之環硫基的物質量(mol)為20以上時,從在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言較佳。由同樣之觀點而言,將(B)之物質量(mol)當作1的情形,在(C)中所含有的環硫基之物質量(mol)以在50以上為更佳。
將(B)之物質量(mol)當作1的情形,在(C)中所含有的環硫基之物質量(mol)為在50以上時,藉由(A)選自由含有2個以上醚基的醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼,與(C)環硫化合物之組合,由於得到之透明聚合物之透明性可以長期間維持,故為理想的情形。由同樣之觀點而言,將(B)之物質量(mol)當作1的情形,在(C)中所含有的環硫基之物質量(mol)為100以上時為較佳,更佳的是200以上。
將(B)之物質量(mol)當作1的情形,在(C)中所含有的環硫基之物質量(mol)為100000以下時,從當聚合組成物之際,有可以更抑制在(C)環硫化合物中所含有之環硫基之殘留的傾向而言較佳。將(B)之物質量(mol)當作1的情形,在(C)中所含有的環硫基之物質量(mol)為20000以下
時,從當聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言更佳。由同樣之觀點而言,將(B)之物質量(mol)當作1的情形,在(C)中所含有的環硫基之物質量(mol)為10000以下時,為更佳。
(B)三鹵化硼與(C)環硫化合物之混合比率,也可以是以下述式(18)表示。
指標β=α b/α t×100 (18)
α b:(B)三鹵化硼之物質量(mol)
α t:在(C)環硫化合物中所含有的環硫基之物質量(mol)
(B)三鹵化硼之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比,為1:10時,成為指標β=10。
(B)三鹵化硼之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:20時,成為指標β=5。
(B)三鹵化硼之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:50時,成為指標β=2。
(B)三鹵化硼之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:100時,成為指標β=1。
(B)三鹵化硼之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:200時,成為指標β=0.5。
(B)三鹵化硼之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:100000時,成為指標β=0.001。
(B)三鹵化硼之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:20000時,成為指標β=0.005。
(B)三鹵化硼之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:10000時,成為指標β=0.01。
作為調製組成物之方法者,只要一般使用之方法即可,無特別限定,可以列舉:將(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,(B)三鹵化硼,及(C)環硫化合物同時添加之方法;(A)、(B)及(C)之中,任意混合所選擇之2種成分後,添加到殘留之成分中;或是添加殘留之成分之方法。此等之中,從有可以安定地調製組成物,作為組成物之安定性也優異的傾向而言,係以調製含有(A)與(B)之混合物後,添加到(C)中,或是添加(C)之方法為佳。
作為調製含有(A)與(B)之混合物的方法者,只要一般所使用的方法即可,無特別限定,可以列舉:使(A)與(B)直接反應之方法、與使(A)與含有(B)之化合物反應的方法等。此等之中,使(A)與含有(B)之化合物反應的方法,從有含有(B)之化合物的處理性提高,組成物的調製變容易之傾向而言較佳。
調製含有(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼之混合物的溫度並無特別限定,只要一般可能利用之溫度即可,以-80至100℃為佳。調製混合物之溫度,並不是必需要固定,也可以在途中變化。
從有可以更縮短在(A)與(B)間之配位鍵形成所需要的時間傾向而言,作為調製混合物之溫度者,以-80℃以上為佳。由同樣之觀點而言,調製混合物之溫度是以-60℃以上為更佳。
依原料之選擇,原料會凝固,在可能妨礙形成由(A)與(B)所成之隔著配位鍵之化合物的情形中,為了抑制凝固,以將調製混合物之溫度設定在原料之凝固點以上為佳。
在由(A)與(B)所成之隔著配位鍵之化合物不安定的情形中,以將調製混合物之溫度設定在100℃以下為佳。由同樣之觀點而言,調製混合物之溫度是以80℃以下為更佳。
依原料之選擇,原料會揮發,在(A)與(B)之混合比率有可能脫離所期望之比率的情形中,為了抑制揮發,以將調製混合物之溫度,設定在原料之沸點以下為佳。將調製混合物之壓力,設定在大氣壓以上之所期望的壓力,也是抑制原料揮發的有效手段。
作為調製含有(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼之混合物的環境者,只要一般的可以使用的環境即可,而無特別限定,通常是在大氣環境、氮
氣環境、及氬氣環境等中使用。此等之中,從有可以安定地處理(B)之傾向而言,係以氮氣環境,及氬氣環境為佳。又,從有優良經濟性之傾向,係以氮氣環境為更佳。
調製含有(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼之混合物的壓力並無特別限定,通常是在大氣壓下進行反應。但是,(A)之標準狀態的蒸氣壓低,在反應中(A)有可能揮發的情形中,進行大氣壓以上之加壓,係有效的手段。
調製含有(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼的混合物之際,在(A)為固體之情形,從藉由使用可溶解(A)之化合物,可容易得到均勻之混合物而言,有成為有效的手段之情形。
可溶解(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物的化合物,只要是使用一般之溶劑即可而無特別限定,作為具體例者,可以列舉:正-戊烷、正-己烷、異己烷、正-庚烷、正-辛烷、異辛烷、正-壬烷、正-癸烷、環戊烷、環己烷、環庚烷及環辛烷等飽和烴化合物;苯、甲苯、二甲苯、乙基苯、二乙基苯、異丙基苯、萘、四氫萘及聯苯等芳香族烴化合物;二氯甲烷、氯仿、四氯化碳、二氯乙烷、三氯乙烷、四氯乙烷、五氯乙烷、六氯乙烷、二氯乙烯、三氯乙烯、四氯乙烯、二氯丙烷、三氯丙烷、氯化異丙烷、氯
化丁烷、氯化己烷、氯苯、二氯苯、三氯苯、氯甲苯及氯萘等鹵化烴化合物;甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇、十一烷醇、十二烷醇、環己醇及苄醇等醇類;丙酮、甲基丙酮、乙基甲基酮、甲基丙基酮、甲基丁基酮、甲基異丁基酮、甲基己基酮、二乙基酮、乙基丁基酮、二丙基酮、二異丁基酮及環己酮等酮類;以及乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸異丁酯、乙酸戊酯、乙酸己酯、乙酸辛酯、乙酸環己酯、丙酸甲酯、丙酸乙酯、丙酸丁酯、苄酸甲酯、苄酸乙酯、苄酸丙酯、苄酸丁酯及苄酸苄酯等酯類。此等之化合物可以單獨使用,也可以組合複數種而使用。
此等之中,從有對(B)三鹵化硼之安定性高,可以安定地調製混合物之傾向而言,係以:正-戊烷、正-己烷、異己烷、正-庚烷、正-辛烷、異辛烷、正-壬烷、正-癸烷、環戊烷、環己烷、環庚烷及環辛烷等飽和烴化合物;二氯甲烷、氯仿、四氯化碳、二氯乙烷、三氯乙烷、四氯乙烷、五氯乙烷、六氯乙烷、二氯乙烯、三氯乙烯、四氯乙烯、二氯丙烷、三氯丙烷、氯化異丙烷、氯化丁烷、氯化己烷、氯苯、二氯苯、三氯苯、氯甲苯及氯萘等鹵化烴化合物為佳。
在調製含有(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼的混合物之際,使用可溶解(A)之化合物,或含有(B)之化合物,有在混合物中含有所期望之化
合物以外者的情形。如此之情形中,藉由進行蒸餾,而可得到將所期望之化合物作為蒸餾物,或是作為蒸餾殘渣者。蒸餾溫度、蒸餾壓力,是由蒸餾所分離之化合物的沸點而適當設定。
蒸餾溫度是以100℃以下為佳,以80℃以下為較佳,以60℃以下為更佳。蒸餾溫度設定在100℃以下,有可以抑制由(A)與(B)所成之隔著配位鍵之化合物的分解之情形。由同樣之觀點而言,係以80℃以下為更佳,再更佳的是60℃以下。蒸餾溫度並不是必需要固定,也可以在途中變化。
蒸餾壓力是藉由蒸餾溫度而適當設定,當蒸餾溫度超過100℃的情形,以設定成比大氣壓更低的壓力為佳。蒸餾壓力並不是必需要固定,也可以在途中變化。
作為調製含有(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼,與(C)環硫化合物之組成物的溫度者,無特別限定,在一般可能利用之溫度中進行,而以-80至100℃為佳。調製組成物之溫度,並不是必需要固定,也可以在途中變化。
調製含有(A)與(B)與(C)的組成物之際,在原料有可能凝固之情形,從藉由抑制原料之凝固,或是使原料之黏度下降,而有更容易得到均勻之組成物的傾向而言,調製組成物之溫度是以-80℃以上為佳。由同樣之觀點而言,調製組成物之溫度是以在-40℃以上為更佳。從使用大型之冷卻
設備之必要性降低,而有可以抑制製造組成物用之成本的傾向而言,調製組成物之溫度是以-20℃以上為更佳。由同樣之觀點而言,以0℃以上為特佳。
在調製含有(A)與(B)與(C)之組成物之際,從有可以更抑制(C)環硫化合物之聚合,更容易得到均勻的組成物之傾向而言,調製組成物之溫度是以在100℃以下為佳。由同樣之觀點而言,調製組成物之溫度是以80℃以下為較佳。從有可以更抑制(C)環硫化合物之聚合,更提高組成物之安定性的傾向而言,調製組成物之溫度是以60℃以下為更佳。由同樣之觀點而言,以40℃以下為特佳。
作為調製含有(A)與(B)與(C)之組成物的環境者,只要一般可使用的環境即可,而無特別限定,通常是使用大氣環境、氮氣環境、及氬氣環境等。此等之中,從有提高在組成物中所含有之(B)三鹵化硼的安定性之傾向而言,是以氮氣環境及氬氣環境為佳。又,從有經濟性優良之傾向而言,是以氮氣環境為更佳。
作為調製含有(A)與(B)與(C)之組成物之壓力者,並無特別限定,通常是在大氣壓下進行調製。但是,在組成物中所含有之化合物之標準狀態的蒸氣壓低,有可能揮發的情形,進行大氣壓以上之加壓為有效之手段。
調製含有(A)與(B)與(C)之組成物之際,在所含有之化合物有固體的情形,或是在含有(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼之混合物為固體的情形,
藉由使用可溶之化合物,容易得到均勻的組成物,故有成為有效手段的情形。
在此所謂可溶化合物是指,在組成物中所含有之化合物中,是固體者,以及在含有(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物與(B)三鹵化硼之混合物為固體的情形,可能將此溶解之化合物的意思。
可溶化合物,只要是使用一般者即可而無特別限定,作為具體例者,可以列舉:正-戊烷、正-己烷、異己烷、正-庚烷、正-辛烷、異辛烷、正-壬烷、正-癸烷、環戊烷、環己烷、環庚烷及環辛烷等飽和烴化合物;苯、甲苯、二甲苯、乙基苯、二乙基苯、異丙基苯、萘、四氫萘及聯苯等芳香族烴化合物;二氯甲烷、氯仿、四氯化碳、二氯乙烷、三氯乙烷、四氯乙烷、五氯乙烷、六氯乙烷、二氯乙烯、三氯乙烯、四氯乙烯、二氯丙烷、三氯丙烷、氯化異丙烷、氯化丁烷、氯化己烷、氯苯、二氯苯、三氯苯、氯甲苯及氯萘等鹵化烴化合物;甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇、十一烷醇、十二烷醇、環己醇及苄基醇等醇類;丙酮、甲基丙酮、乙基甲基酮、甲基丙基酮、甲基丁基酮、甲基異丁基酮、甲基己基酮、二乙基酮、乙基丁基酮、二丙基酮及二異丁基酮、環己酮等酮類;以及乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸異丁酯、乙酸戊酯、乙酸己酯、乙酸辛酯、乙酸環己酯、丙酸甲酯、丙酸乙酯、丙酸丁酯、苄酸甲酯、
苄酸乙酯、苄酸丙酯、苄酸丁酯及苄酸苄酯等酯類。前述化合物可以單獨使用,也可以組合複數種而使用。
此等之中,從有提高對(B)三鹵化硼之安定性,可以安定地調製含有(A)與(B)與(C)之組成物的傾向而言,係以:正-戊烷、正-己烷、異己烷、正-庚烷、正-辛烷、異辛烷、正-壬烷、正-癸烷、環戊烷、環己烷、環庚烷及環辛烷等飽和烴化合物;二氯甲烷、氯仿、四氯化碳、二氯乙烷、三氯乙烷、四氯乙烷、五氯乙烷、六氯乙烷、二氯乙烯、三氯乙烯、四氯乙烯、二氯丙烷、三氯丙烷、氯化異丙烷、氯化丁烷、氯化己烷、氯苯、二氯苯、三氯苯、氯甲苯及氯萘等鹵化烴化合物為佳。
在調製含有(A)與(B)與(C)之組成物之際,使用可溶化合物,而有組成物中含有所期望之化合物以外者的情形。在此情形,藉由減壓蒸餾去除可溶化合物的方法,係有成為有效手段的情形。
減壓餾去的溫度,從有可以更抑制(C)環硫化合物之聚合,更提高含有(A)與(B)與(C)之組成物之安定性之傾向而言,係以40℃以下為佳。由同樣之觀點而言,較佳是在35℃以下,更佳是25℃以下。減壓餾去壓力是依照減壓餾去溫度而適當設定。前述減壓餾去溫度、減壓餾去壓力並不是必需要固定,也可以在途中變化。
作為由含有(A)與(B)與(C)之組成物得到聚合物的方法者,只要是一般的方法即可而無特別限定,適合使用藉由加熱組成物進行聚合的方法,及/或是藉由照射能源線
進行聚合的方法。此等之中,藉由加熱進行聚合的方法,從有在各種場合中容易利用,泛用性優良的傾向而言,為更佳的方法。又,組成物中所含有之環硫化合物具有2個以上聚合性官能基的情形,藉由同樣之方法,可以得到硬化物。
作為藉由加熱進行聚合,且得到聚合物之際的聚合溫度者,並無特別限定,係以-80至160℃為佳。聚合溫度是沒有必需要固定,也可以在途中變化。
從在聚合(C)環硫化合物之際,有藉由產生之聚合熱,可以減低得到之聚合物著色的可能性之傾向而言,作為聚合溫度者,是以160℃以下為佳。從在聚合(C)環硫化合物之際,有可以更抑制副反應之傾向而言,是以140℃以下為較佳。由同樣之觀點而言,聚合溫度是以120℃以下為更佳,在100℃以下時為特佳。
(C)環硫化合物之聚合,在有藉由組成物中存在之成分(A)、(B)、(C),由成分(A)與(B)所成之隔著配位鍵之化合物等的凝固而妨礙之可能性的情形中,聚合溫度是設為-80℃以上為佳。從有使用大型之冷卻設備的必要性減少,可以抑制製造聚合物用之成本的傾向而言,聚合溫度是以在-40℃以上為更佳。由同樣之觀點而言,是在0℃以上為再更佳。從有聚合物之聚合末端的運動性更高,而可使(C)環硫化合物之聚合時間更短的傾向而言,聚合溫度是以40℃以上為佳。由同樣之觀點而言,聚合溫度是以50℃以上為較佳,更佳是70℃以上。
作為藉由加熱進行聚合,且得到聚合物之際的聚合環境者,只要一般使用的環境即可而無特別限定,通常是使用大氣環境、氮氣環境、及氬氣環境等。此等之中,從聚合之際有可以形成所期望之結合的傾向而言,以氮氣環境氣、及氬氣環境為佳。又,從有優良經濟性之傾向而言,以氮氣環境為更佳。
作為藉由加熱進行聚合,且得到聚合物之際的聚合壓力者,並無特別限定,通常是在大氣壓下進行反應。但是,作為組成物所含有之成分,使用標準狀態之蒸氣壓低,有揮發之可能性之化合物的情形,以進行大氣壓以上的加壓為有效之手段。
在含有(A)與(B)與(C)之組成物為高黏度,或是固體的情形,藉由非反應性化合物,使組成物低黏度化,得到實施有所期望之成形之聚合物,為有效的手段。
作為非反應性化合物者,只要使用一般者即可而無特別限定,作為具體例者,可以列舉:正-戊烷、正-己烷、異己烷、正-庚烷、正-辛烷、異辛烷、正-壬烷、正-癸烷、環戊烷、環己烷、環庚烷及環辛烷等飽和烴化合物;苯、甲苯、二甲苯、乙基苯、二乙基苯、異丙基苯、萘、四氫萘及聯苯等芳香族烴化合物;二氯甲烷、氯仿、四氯化碳、二氯乙烷、三氯乙烷、四氯乙烷、五氯乙烷、六氯乙烷、二氯乙烯、三氯乙烯、四氯乙烯、二氯丙烷、三氯丙烷、氯化異丙烷、氯化丁烷、氯化己烷、氯苯、二氯苯、三氯苯、氯甲苯及氯萘等鹵化烴化合物;丙酮、甲基丙酮、乙
基甲基酮、甲基丙基酮、甲基丁基酮、甲基異丁基酮、甲基己基酮、二乙基酮、乙基丁基酮、二丙基酮及二異丁基酮、環己酮等酮類;以及乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸異丁酯、乙酸戊酯、乙酸己酯、乙酸辛酯、乙酸環己酯、丙酸甲酯、丙酸乙酯、丙酸丁酯、苄酸甲酯、苄酸乙酯、苄酸丙酯、苄酸丁酯及苄酸苄酯等酯類。前述化合物可以單獨使用,也可以組合複數種而使用。
此等之中,從有提高對(B)三鹵化硼之安定性,可以調製安定的組成物之傾向而言,係以正-戊烷、正-己烷、異己烷、正-庚烷、正-辛烷、異辛烷、正-壬烷、正-癸烷、環戊烷、環己烷、環庚烷及環辛烷等飽和烴化合物;二氯甲烷、氯仿、四氯化碳、二氯乙烷、三氯乙烷、四氯乙烷、五氯乙烷、六氯乙烷、二氯乙烯、三氯乙烯、四氯乙烯、二氯丙烷、三氯丙烷、氯化異丙烷、氯化丁烷、氯化己烷、氯苯、二氯苯、三氯苯、氯甲苯及氯萘等鹵化烴化合物為佳。
以在藉由加熱進行聚合得到聚合物之際,加速聚合反應之目的,或是,以作為在組成物中所含有之(C)環硫化合物者,使用具有3員環硫醚結構,並具有3員環硫醚結構以外之其他聚合性官能基的化合物之情形,容易進行其他之聚合性官能基的聚合之目的,而添加下述之(1)至(11)之化合物作為熱聚合促進劑,有成為有效的手段之情形。
(1)乙基胺、正-丙基胺、二級-丙基胺、正-丁基胺、二級-丁基胺、異-丁基胺、三級-丁基胺、戊基胺、己基胺、
庚基胺、辛基胺、癸基胺、十二烷基胺、肉豆蔻基胺、1,2-二甲基己基胺、3-戊基胺、2-乙基己基胺、烯丙基胺、胺乙醇、1-胺丙醇、2-胺丙醇、胺丁醇、胺戊醇、胺己醇、3-乙氧基丙基胺、3-丙氧基丙基胺、3-異丙氧基丙基胺、3-丁氧基丙基胺、3-異丁氧基丙基胺、3-(2-乙基已氧基)丙基胺、胺基環戊烷、胺基環己烷、胺基降冰片烯、胺基甲基環己烷、胺基苯、苄基胺、苯乙胺、α-苯基乙基胺、萘基胺及糠基胺等1級胺;伸乙基二胺、1,2-二胺丙烷、1,3-二胺丙烷、1,2-二胺丁烷、1,3-二胺丁烷、1,4-二胺丁烷、1,5-二胺戊烷、1,6-二胺己烷、1,7-二胺庚烷、1,8-二胺辛烷、二甲基胺丙基胺、二乙基胺丙基胺、雙-(3-胺丙基)醚、1,2-雙-(3-胺丙氧基)乙烷、1,3-雙-(3-胺丙氧基)-2,2’-二甲基丙烷、胺乙基乙醇胺、1,2-雙胺環己烷、1,3-雙胺環己烷、1,4-雙胺環己烷、1,3-雙胺甲基環己烷、1,4-雙胺甲基環己烷、1,3-雙胺乙基環己烷、1,4-雙胺乙基環己烷、1,3-雙胺丙基環己烷、1,4-雙胺丙基環己烷、氫化4,4’-二胺二苯基甲烷、2-胺哌啶、4-胺哌啶、2-胺甲基哌啶、4-胺甲基哌啶、2-胺乙基哌啶、4-胺乙基哌啶、N-胺乙基哌啶、N-胺丙基哌啶、N-胺乙基嗎啉、N-胺丙基嗎啉、異佛酮二胺、薄荷烷二胺、1,4-雙胺丙基哌、鄰-苯二胺、間-苯二胺、對-苯二胺、2,4-甲苯二胺(2,4-tolylenediamine)、2,6-甲苯二胺、2,4-甲苯二胺(2,4-toluenediamine)、間-胺苄基胺、4-氯-鄰-苯二胺、四氯-對-苯二甲胺、4-甲氧
基-6-甲基-間-苯二胺、間-苯二甲胺、對-苯二甲胺、1,5-萘二胺、2,6-萘二胺、聯苯胺、4,4’-雙(鄰-甲苯胺)、聯茴香胺(dianisidine)、4,4’-二胺二苯基甲烷、2,2-(4,4’-二胺二苯基)丙烷、4,4’-二胺二苯基醚、4,4’-硫基二苯胺(4,4’-thiodianiline)、4,4’-二胺二苯基碸、4,4’-二胺二甲苯基碸、亞甲基雙(鄰-氯苯胺)、3,9-雙(3-胺丙基)、2,4,8,10-四螺[5,5]十一烷、二伸乙基三胺、亞胺基雙丙基胺、甲基亞胺基雙丙基胺、雙(六亞甲基)三胺、三伸乙基四胺、四伸乙基五胺、五伸乙基六胺、N-胺乙基哌、N-胺丙基哌、1,4-雙(胺乙基哌)、1,4-雙(胺丙基哌)及2,6-二胺吡啶、雙(3,4-二胺苯基)碸等1級多胺;二乙基胺、二丙基胺、二-正-丁基胺、二-二級-丁基胺、二異丁基胺、二-正-戊基胺、二-3-戊基胺、二己基胺、二辛基胺、二(2-乙基己基)胺、甲基己基胺、二烯丙基胺、吡咯啶、哌啶、2-甲基吡啶(2-picoline)、3-甲基吡啶、4-甲基吡啶、2,4-二甲基哌啶(2,4-lupetidine)、2,6-二甲基哌啶、3,5-二甲基哌啶、二苯基胺、N-甲基苯胺、N-乙基苯胺、二苄基胺、甲基苄基胺、二萘基胺、吡咯、吲哚啉、吲哚及嗎啉等2級胺;N,N’-二甲基伸乙基二胺、N,N’-二甲基-1,2-二胺丙烷、N,N’-二甲基-1,3-二胺丙烷、N,N’-二甲基-1,2-二胺丁烷、N,N’-二甲基-1,3-二胺丁烷、N,N’-二甲基-1,4-二胺丁烷、N,N’-二甲基-1,5-二胺戊烷、N,N’-二甲基-1,6-二胺己烷、N,N’-二甲基-1,7-二胺庚烷、N,N’-二乙基伸乙
基二胺、N,N’-二乙基-1,2-二胺丙烷、N,N’-二乙基-1,3-二胺丙烷、N,N’-二乙基-1,2-二胺丁烷、N,N’-二乙基-1,3-二胺丁烷、N,N’-二乙基-1,4-二胺丁烷、N,N’-二乙基-1,6-二胺己烷、哌、2-甲基哌、2,5-二甲基哌、2,6-二甲基哌、高哌(homopiperazine)、1,1-二-(4-哌啶基)甲烷、1,2-二-(4-哌啶基)乙烷、1,3-二-(4-哌啶基)丙烷、1,4-二-(4-哌啶基)丁烷及四甲基胍等2級多胺;三甲基胺、三乙基胺、三-正-丙基胺、三-異-丙基胺、三-1,2-二甲基丙基胺、三-3-甲氧基丙基胺、三-正-丁基胺、三-異-丁基胺、三-二級-丁基胺、三-戊基胺、三-3-戊基胺、三-正-己基胺、三-正-辛基胺、三-2-乙基己基胺、三-十二烷基胺、三-月桂基胺、二環己基乙基胺、環己基二乙基胺、三-環己基胺、N,N-二甲基己基胺、N-甲基二己基胺、N,N-二甲基環己基胺、N-甲基二環己基胺、N,N-二乙基乙醇胺、N,N-二甲基乙醇胺、N-乙基二乙醇胺、三乙醇胺、三苄基胺、N,N-二甲基苄基胺、二乙基苄基胺、三苯基胺、N,N-二甲基胺基-對-甲酚、N,N-二甲基胺甲基酚、2-(N,N-二甲基胺甲基)酚、N,N-二甲基苯胺、N,N-二乙基苯胺、吡啶、喹啉、N-甲基嗎啉、N-甲基哌啶及2-(2-二甲基胺乙氧基)-4-甲基-1,3,2-二莰烷等3級胺;四甲基伸乙基二胺、吡、N,N’-二甲基哌、N,N’-雙((2-羥基)丙基)哌、六亞甲基四胺、N,N,N’,N’-四甲基-1,3-丁烷胺、2-二甲基胺-2-羥基丙烷、二乙基胺乙醇、N,N,N-參(3-二甲基胺丙基)胺、2,4,6-參(N,N-二甲基胺甲
基)酚及七甲基異雙胍等3級多胺;咪唑、N-甲基咪唑、2-甲基咪唑、4-甲基咪唑、N-乙基咪唑、2-乙基咪唑、4-乙基咪唑、N-丁基咪唑、2-丁基咪唑、N-十一烷基咪唑、2-十一烷基咪唑、N-苯基咪唑、2-苯基咪唑、N-苄基咪唑、2-苄基咪唑、1-苄基-2-甲基咪唑、N-(2’-氰基乙基)-2-甲基咪唑、N-(2’-氰基乙基)-2-十一烷基咪唑、N-(2’-氰基乙基)-2-苯基咪唑、3,3-雙-(2-乙基-4-甲基咪唑基)甲烷、烷基咪唑與異氰酸之加成物及烷基咪唑與甲醛之縮合物等各種咪唑類;1,8-二氮雜雙環(5,4,0)十一烯-7、1,5-二氮雜雙環(4,3,0)壬烯-5、6-二丁基胺基-1,8-二氮雜雙環(5,4,0)十一烯-7等脒類。
(2)(1)之胺類與硼烷及三氟化硼之複合物。
(3)三甲基膦、三乙基膦、三-異-丙基膦、三-正-丁基膦、三-正-己基膦、三-正-辛基膦、三環己基膦、三苯基膦、三苄基膦、參(2-甲基苯基)膦、參(3-甲基苯基)膦、參(4-甲基苯基)膦、參(二乙基胺)膦、參(4-甲基苯基)膦、二甲基苯基膦、二乙基苯基膦、二環己基苯基膦、乙基二苯基膦、二苯基環己基膦及氯二苯基膦等膦類。
(4)四甲基銨氯化物、四甲基銨溴化物、四甲基銨乙酸酯、四乙基銨氯化物、四乙基銨溴化物、四乙基銨乙酸酯、四-正-丁基銨氟化物、四-正-丁基銨氯化物、四-正-丁基銨溴化物、四-正-丁基銨碘化物、四-正-丁基銨乙酸酯、四-正-丁基銨硼氫化物、四-正-丁基銨六氟亞磷酸酯、四-
正-丁基銨亞硫酸氫酯、四-正-丁基銨四氟硼酸酯、四-正-丁基銨四苯基硼酸酯、四-正-丁基銨對甲苯磺酸酯、四-正-己基銨氯化物、四-正-己基銨溴化物、四-正-己基銨乙酸酯、四-正-辛基銨氯化物、四-正-辛基銨溴化物、四-正-辛基銨乙酸酯、三甲基-正-辛基銨氯化物、三甲基苄基銨氯化物、三甲基苄基銨溴化物、三乙基-正-辛基銨氯化物、三乙基苄基銨氯化物、三乙基苄基銨溴化物、三-正-丁基-正-辛基銨氯化物、三-正-丁基苄基銨氟化物、三-正-丁基苄基銨氯化物、三-正-丁基苄基銨溴化物、三-正-丁基苄基銨碘化物、甲基三苯基銨氯化物、甲基三苯基銨溴化物、乙基三苯基銨氯化物、乙基三苯基銨溴化物、正-丁基三苯基銨氯化物、正-丁基三苯基銨溴化物、1-甲基吡啶鎓溴化物、1-乙基吡啶鎓溴化物、1-正-丁基吡啶鎓溴化物、1-正-己基吡啶鎓溴化物、1-正-辛基吡啶鎓溴化物、1-正-十二烷基吡啶鎓溴化物、1-正-苯基吡啶鎓溴化物、1-甲基甲基吡啶鎓溴化物、1-乙基甲基吡啶鎓溴化物、1-正-丁基甲基吡啶鎓溴化物、1-正-己基甲基吡啶鎓溴化物、1-正-辛基甲基吡啶鎓溴化物、1-正-十二烷基甲基吡啶鎓溴化物及1-正-苯基甲基吡啶鎓溴化物等4級銨鹽。
(5)四甲基鏻氯化物、四甲基鏻溴化物、四乙基鏻氯化物、四乙基鏻溴化物、四-正-丁基鏻氯化物、四-正-丁基鏻溴化物、四-正-丁基鏻碘化物、四-正-己基鏻溴化物、四-正-辛基鏻溴化物、甲基三苯基鏻溴化物、甲基三苯基鏻碘化物、乙基三苯基鏻溴化物、乙基三苯基鏻碘化物、
正-丁基三苯基鏻溴化物、正-丁基三苯基鏻碘化物、正-己基三苯基鏻溴化物、正-辛基三苯基鏻溴化物、四苯基鏻溴化物、肆羥基甲基鏻氯化物、肆羥基甲基鏻溴化物、肆羥基乙基鏻氯化物及肆羥基丁基鏻氯化物等鏻鹽。
(6)三甲基鋶溴化物、三乙基鋶溴化物、三-正-丁基鋶氯化物、三-正-丁基鋶溴化物、三-正-丁基鋶碘化物、三-正-丁基鋶四氟硼酸酯、三-正-己基鋶溴化物、三-正-辛基鋶溴化物、三苯基鋶氯化物、三苯基鋶溴化物及三苯基鋶碘化物等鋶鹽。
(7)二苯基錪氯化物、二苯基錪溴化物及二苯基錪碘化物等錪鹽。
(8)鹽酸、硫酸、硝酸、磷酸、碳酸等礦酸及此等之半酯。
(9)三氟化硼及三氟化硼之醚合物(etherate)等所代表之路易斯酸。
(10)有機酸及此等之半酯。
(11)矽酸及四氟化硼酸。
此等化合物可以單獨使用,也可以組合複數種而使用。
藉由照射能源線之聚合是指藉由照射能源線(紫外線、近紫外線、可見光、近紅外線及紅外線等光線,以及電子束等)而生成聚合物的方法。能源線之種類並無特別限定者,理想的是光線,更佳的是紫外線。
能源線之產生源並無特別限定者,例如,可以列舉:低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、
UV燈、氙燈、碳弧燈、金屬鹵素燈、螢光燈、鎢絲燈、氬離子雷射、氦鎘雷射、氦氖雷射、氪離子雷射、各種半導體雷射、YAG雷射、準分子(Excimer)雷射、發光二極管、CRT光源、電漿(Plasma)光源及電子束照射器等各種光源。
藉由能源線照射進行聚合之際,為了加速聚合,添加作為光聚合促進劑之以下的化合物,係有成為有效手段的情形。
苯偶姻(benzoin)類及苯偶姻烷基醚類(苯偶姻、二苯甲醯(benzil)、苯偶姻甲基醚及苯偶姻異丙基醚)、苯乙酮類(苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、1-羥基環己基苯基酮、2-甲基-1-(4-(甲基硫基)苯基)-2-(N-嗎啉基)-丙烷-1-酮及N,N-二甲基胺苯乙酮等)、蒽醌類(2-甲基蒽醌、2-乙基蒽醌、2-三級-丁基蒽醌、1-氯蒽醌、2-戊基蒽醌及2-胺蒽醌等)、噻噸酮(thioxanthone)類(2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2-氯噻噸酮及2,4-二異丙基噻噸酮等)、縮酮類(苯乙酮二甲基縮酮及二苯甲醯二甲基縮酮等)、二苯甲酮類(二苯甲酮、甲基二苯甲酮、4,4’-二氯二苯甲酮及4,4’-雙二乙基胺二苯甲酮等)、呫噸酮(xanthone)類、苄酸酯類(4-二甲基胺苄酸乙酯及苄酸2-(二甲基胺)乙酯等)、胺類(三乙基胺及三乙醇胺等)、錪鹽化合物、鋶鹽化合物、銨鹽化合物、鏻鹽化合物、鉮鹽化合物、四氫銻(stibonium)鹽化合物、氧鎓(oxonium)鹽化合物、硒鎓(selenonium)鹽化合物、以及錫鎓鹽化合物。此等可以單
獨使用,也可以組合複數種使用。
含有(A)與(B)與(C)之組成物中,也可以更含有(D)鏈轉移劑。藉由使用(D)鏈轉移劑,得到之聚合物及硬化物,有在高溫下長期保持之際的揮發分更為降低,可以更抑制藉由熔融加工而成形之際的空洞(void)產生,或者是更抑制在聚合物或是硬化物附近的金屬構件之污染或是腐蝕的傾向。
作為(D)鏈轉移劑者,只要一般使用者即可,無特別限定,係以選自由環狀酯化合物、環狀碳酸酯化合物、環狀矽氧烷化合物、含有羥基之化合物所成群組中至少1種之化合物為佳。此等可以單獨使用,也可以組合複數種來使用。由於依(C)環硫化合物之選擇,得到之聚合物的透明性有下降之情形,故作為(D)鏈轉移劑者,係以選自由環狀酯化合物、環狀碳酸酯化合物、含有羥基之化合物所成群組中至少1種之化合物為更佳。從有可以更縮短(C)環硫化合物的聚合時間之傾向而言,作為(D)鏈轉移劑者,以含有羥基之化合物者為更佳。
環狀酯化合物,只要是在環狀結構內有酯基之化合物即可,而無特別限定者,具體而言,可以選自乙-2-內酯、丙-2-內酯、丙-3-內酯、丁-2-內酯、丁-3-內酯、丁-4-內酯、3-甲基-丁-4-內酯、戊-2-內酯、戊-3-內酯、戊-4-內酯、戊-5-內酯、4-甲基-戊-4-內酯、己-2-內酯、己-3-內酯、己-4-內酯、己-5-內酯、己-6-內酯、庚-2-內酯、
庚-3-內酯、庚-4-內酯、庚-5-內酯、庚-6-內酯、庚-7-內酯、辛-2-內酯、辛-3-內酯、辛-4-內酯、辛-5-內酯、辛-6-內酯、辛-7-內酯、辛-8-內酯、壬-2-內酯、壬-3-內酯、壬-4-內酯、壬-5-內酯、壬-6-內酯、壬-7-內酯、壬-8-內酯、壬基-9-內酯、癸-2-內酯、癸-3-內酯、癸-4-內酯、癸-5-內酯、癸-6-內酯、癸-7-內酯、癸-8-內酯、癸-9-內酯、癸-10-內酯、十一烷-2-內酯、十一烷-3-內酯、十一烷-4-內酯、十一烷-5-內酯、十一烷-6-內酯、十一烷-7-內酯、十一烷-8-內酯、十一烷-9-內酯、十一烷-10-內酯、十一烷-11-內酯、十二烷-2-內酯、十二烷-3-內酯、十二烷-4-內酯、十二烷-5-內酯、十二烷-6-內酯、十二烷-7-內酯、十二烷-8-內酯、十二烷-9-內酯、十二烷-10-內酯、十二烷-11-內酯、十二烷-12-內酯、十三烷-2-內酯、十三烷-3-內酯、十三烷-4-內酯、十三烷-5-內酯、十三烷-6-內酯、十三烷-7-內酯、十三烷-8-內酯、十三烷-9-內酯、十三烷-10-內酯、十三烷-11-內酯、十三烷-12-內酯、十三烷-13-內酯、十四烷-2-內酯、十四烷-3-內酯、十四烷-4-內酯、十四烷-5-內酯、十四烷-6-內酯、十四烷-7-內酯、十四烷-8-內酯、十四烷-9-內酯、十四烷-10-內酯、十四烷-11-內酯、十四烷-12-內酯、十四烷-13-內酯、十四烷-14-內酯、十五烷-2-內酯、十五烷-3-內酯、十五烷-4-內酯、十五烷-5-內酯、十五烷-6-內酯、十五烷-7-內酯、十五烷-8-內酯、十五烷-9-內酯、十五烷-10-內酯、十五烷-11-內酯、
十五烷-12-內酯、十五烷-13-內酯、十五烷-14-內酯、十五烷-15-內酯、十六烷-2-內酯、十六烷-3-內酯、十六烷-4-內酯、十六烷-5-內酯、十六烷-6-內酯、十六烷-7-內酯、十六烷-8-內酯、十六烷-9-內酯、十六烷-10-內酯、十六烷-11-內酯、十六烷-12-內酯、十六烷-13-內酯、十六烷-14-內酯、十六烷-15-內酯、十六烷-16-內酯。
上述之中,從抑制對(D)鏈轉移劑之聚合物或是硬化物中之殘留,及/或是有抑制(C)環硫化合物之聚合時間増長的傾向而言,環狀酯化合物是以選自以下之群組中至少1種之化合物為佳。
丁-4-內酯、戊-4-內酯、戊-5-內酯、己-4-內酯、己-6-內酯、庚-4-內酯、庚-7-內酯、辛-4-內酯、辛-8-內酯、癸-10-內酯、十二烷-12-內酯、十四烷-14-內酯、十六烷-16-內酯。
更佳的是選自以下之群組中至少1種之化合物。丁-4-內酯、戊-4-內酯、己-4-內酯。
環狀碳酸酯化合物只要是在環狀結構內有碳酸酯基的化合物即可,而無特別限定者,具體而言,可以選自:碳酸伸乙酯、碳酸伸丙酯、碳酸伸丁酯、碳酸伸戊酯、碳酸伸己酯、碳酸伸庚酯、碳酸伸辛酯、碳酸伸壬酯、碳酸伸癸酯、碳酸伸十一烷酯、碳酸伸十二烷酯、碳酸伸十三烷酯、碳酸伸十四烷酯、基碳酸伸十五烷酯、碳酸伸十六烷酯、丙基-1,3-二氧戊環-2-酮、丁基-1,3-二氧戊環-2-酮、
戊基-1,3-二氧戊環-2-酮、己基-1,3-二氧戊環-2-酮、環己基-1,3-二氧戊環-2-酮、1,3-二烷-2-酮、甲基-1,3-二烷-2-酮、二甲基-1,3-二烷-2-酮、乙基-1,3-二烷-2-酮、丙基-1,3-二烷-2-酮、丁基-1,3-二烷-2-酮、戊基-1,3-二烷-2-酮、己基-1,3-二烷-2-酮、環己基-1,3-二烷-2-酮。
上述之中,從抑制對(D)鏈轉移劑之聚合物或是硬化物中之殘留,及/或是有抑制(C)環硫化合物之聚合時間増長的傾向而言,環狀碳酸酯化合物是以選自以下之群組中至少1種之化合物為佳。
碳酸伸乙酯、碳酸伸丙酯、碳酸伸丁酯、碳酸伸戊酯、碳酸伸己酯、丙基-1,3-二氧戊環-2-酮、丁基-1,3-二氧戊環-2-酮、1,3-二烷-2-酮、二甲基-1,3-二烷-2-酮、乙基-1,3-二烷-2-酮、丙基-1,3-二烷-2-酮、丁基-1,3-二烷-2-酮。
較佳的是選自以下之群組中至少1種之化合物。碳酸伸乙酯、碳酸伸丙酯、碳酸伸丁酯、1,3-二烷-2-酮、二甲基-1,3-二烷-2-酮。
環狀矽氧烷化合物,只要係環狀結構為藉由矽氧烷鍵而形成之化合物即可而無特別限定者,具體而言可以選自:三甲基環三矽氧烷、三乙基環三矽氧烷、三丙基環三矽氧烷、三丁基環三矽氧烷、三戊基環三矽氧烷、三己基環三矽氧烷、三庚基環三矽氧烷、三辛基環三矽氧烷、三
壬基環三矽氧烷、三癸基環三矽氧烷、三苯基環三矽氧烷、六甲基環三矽氧烷、六乙基環三矽氧烷、六丙基環三矽氧烷、六丁基環三矽氧烷、六戊基環三矽氧烷、六己基環三矽氧烷、六庚基環三矽氧烷、六辛基環三矽氧烷、六壬基環三矽氧烷、六癸基環三矽氧烷、六苯基環三矽氧烷、三甲基三苯基環三矽氧烷、四甲基環四矽氧烷、四乙基環四矽氧烷、四丙基環四矽氧烷、四丁基環四矽氧烷、四戊基環四矽氧烷、四己基環四矽氧烷、四庚基環四矽氧烷、四辛基環四矽氧烷、四壬基環四矽氧烷、四癸基環四矽氧烷、四苯基環四矽氧烷、八甲基環四矽氧烷、八乙基環四矽氧烷、八丙基環四矽氧烷、八丁基環四矽氧烷、八戊基環四矽氧烷、八己基環四矽氧烷、八庚基環四矽氧烷、八辛基環四矽氧烷、八壬基環四矽氧烷、八癸基環四矽氧烷、八苯基環四矽氧烷、四甲基四苯基環四矽氧烷、五甲基環五矽氧烷、五乙基環五矽氧烷、五丙基環五矽氧烷、五丁基環五矽氧烷、五戊基環五矽氧烷、五己基環五矽氧烷、五庚基環五矽氧烷、五辛基環五矽氧烷、五壬基環五矽氧烷、五癸基環五矽氧烷、五苯基環五矽氧烷、十甲基環五矽氧烷、十乙基環五矽氧烷、十丙基環五矽氧烷、十丁基環五矽氧烷、十戊基環五矽氧烷、十己基環五矽氧烷、十庚基環五矽氧烷、十辛基環五矽氧烷、十壬基環五矽氧烷、十癸基環五矽氧烷、十苯基環五矽氧烷、五甲基五苯基環五矽氧烷。
上述之中,從抑制對(D)鏈轉移劑之聚合物或是硬化物中之殘留,及/或是有抑制(C)環硫化合物之聚合時間増長的傾向而言,環狀矽氧烷化合物是以選自以下之群組中至少1種之化合物為佳。
六甲基環三矽氧烷、六乙基環三矽氧烷、六丙基環三矽氧烷、六丁基環三矽氧烷、六戊基環三矽氧烷、六己基環三矽氧烷、三甲基三苯基環三矽氧烷、八甲基環四矽氧烷、八乙基環四矽氧烷、八丙基環四矽氧烷、八丁基環四矽氧烷、八戊基環四矽氧烷、八己基環四矽氧烷、四甲基四苯基環四矽氧烷、十甲基環五矽氧烷、十乙基環五矽氧烷、十丙基環五矽氧烷、十丁基環五矽氧烷、十戊基環五矽氧烷、十己基環五矽氧烷、五甲基五苯基環五矽氧烷。
更佳的是選自以下之群組中至少1種之化合物。六甲基環三矽氧烷、八甲基環四矽氧烷、十甲基環五矽氧烷。
含有羥基之化合物,只要係在結構內有羥基之化合物即可,而無特別限定者,具體而言,可以選自:甲醇、乙醇、1-丙醇、2-丙醇、環丙醇、甲基環丙醇、二甲基環丙醇、乙基環丙醇、丙基環丙醇、丁基環丙醇、1-丁醇、2-丁醇、三級-丁醇、環丁醇、甲基環丁醇、二甲基環丁醇、乙基環丁醇、丙基環丁醇、丁基環丁醇、1-戊醇、2-戊醇、3-戊醇、環戊醇、甲基環戊醇、二甲基環戊醇、乙基環戊醇、丙基環戊醇、丁基環戊醇、甲基-1-丁醇、甲基-2-丁醇、二甲基-1-丁醇、二甲基-2-丁醇、乙基-1-丁醇、乙基
-2-丁醇、1-己醇、2-己醇、3-己醇、環己醇、甲基環己醇、二甲基環己醇、乙基環己醇、丙基環己醇、丁基環己醇、甲基-1-戊醇、甲基-2-戊醇、甲基-3-戊醇、二甲基-1-戊醇、二甲基-2-戊醇、二甲基-3-戊醇、乙基-1-戊醇、乙基-2-戊醇、乙基-3-戊醇、1-庚醇、2-庚醇、3-庚醇、環庚醇、甲基環庚醇、二甲基環庚醇、乙基環庚醇、甲基-1-己醇、甲基-2-己醇、甲基-3-己醇、二甲基-1-己醇、二甲基-2-己醇、乙基-1-己醇、乙基-2-己醇、乙基-3-己醇、1-辛醇、2-辛醇、3-辛醇、4-辛醇、環辛醇、甲基環辛醇、二甲基環辛醇、乙基環辛醇、壬醇、環壬醇、癸醇、環癸醇、十一烷醇、十二烷醇、十三烷醇、十四烷醇、十五烷醇、十六烷醇、乙二醇、1,2-丙烷二醇、1,3-丙烷二醇、甲基丙烷二醇、二甲基丙烷二醇、環丙烷二醇、1,2-丁烷二醇、1,3-丁烷二醇、1,4-丁烷二醇、2,3-丁烷二醇、甲基丁烷二醇、二甲基丁烷二醇、環丁烷二醇、甲基環丁烷二醇、二甲基環丁烷二醇、乙基環丁烷二醇、丙基環丁烷二醇、丁基環丁烷二醇、1,2-戊烷二醇、1,3-戊烷二醇、1,4-戊烷二醇、1,5-戊烷二醇、甲基戊烷二醇、二甲基戊烷二醇、環戊烷二醇、甲基環戊烷二醇、二甲基環戊烷二醇、乙基環戊烷二醇、丙基環戊烷二醇、丁基環戊烷二醇、1,2-己烷二醇、1,3-己烷二醇、1,4-己烷二醇、1,5-己烷二醇、1,6-己烷二醇、甲基己烷二醇、二甲基己烷二醇、環己烷二醇、甲基環己烷二醇、二甲基環己烷二醇、乙基環己烷二醇、丙
基環己烷二醇、丁基環己烷二醇、1,2-庚烷二醇、1,3-庚烷二醇、1,4-庚烷二醇、1,5-庚烷二醇、1,6-庚烷二醇、1,7-庚烷二醇、環庚烷二醇、甲基環庚烷二醇、二甲基環庚烷二醇、1,2-辛烷二醇、1,3-辛烷二醇、1,4-辛烷二醇、1,5-辛烷二醇、1,6-辛烷二醇、1,7-辛烷二醇、1,8-辛烷二醇、環辛烷二醇、甲基環辛烷二醇、二甲基環辛烷二醇、壬烷二醇、環壬烷二醇、癸烷二醇、環癸烷二醇、十一烷二醇、十二烷二醇、十三烷二醇、十四烷二醇、十五烷二醇、十六烷二醇、丙三醇、丁四醇、戊五醇、甘露糖醇、庚七醇(volemitol)、葡萄糖、蔗糖、二乙二醇、三乙二醇、四乙二醇、五乙二醇、六乙二醇、八乙二醇、十二乙二醇、甲醛縮二甲醇、PEG200、PEG300、PEG400、PEG600、PEG1000、PEG1500、PEG1540、PEG4000、PEG6000、聚碳酸酯二醇、聚酯-8-羥基-1-乙炔雙-MPA dendron generation 3(製品名,Aldrich公司製)、聚酯-16-羥基-1-乙炔雙-MPAdendron generation 4(製品名,Aldrich公司製)、聚酯-32-羥基-1-乙炔雙-MPA dendron generation 5(製品名,Aldrich公司製)、聚酯-8-羥基-1-羧基雙-MPAdendron generation 3(製品名,Aldrich公司製)、聚酯-16-羥基-1-羧基雙-MPA dendron generation 4(製品名,Aldrich公司製)、聚酯-32-羥基-1-羧基雙-MPAdendron generation 5(製品名,Aldrich公司製)、超分枝(Hyperbranched)雙-MPA聚酯-16-羥基,generation
2(製品名,Aldrich公司製)、超分枝雙-MPA聚酯-32-羥基,generation 3(製品名,Aldrich公司製)。
上述之中,從抑制對(D)鏈轉移劑之聚合物或是硬化物中之殘留,及/或是有抑制(C)環硫化合物之聚合時間増長的傾向而言,含有羥基之化合物是以選自以下之群組中至少1種之化合物為佳。
甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、環戊醇、1-己醇、2-己醇、3-己醇、環己醇、乙二醇、1,2-丙烷二醇、1,3-丙烷二醇、1,2-丁烷二醇、1,3-丁烷二醇、1,4-丁烷二醇、2,3-丁烷二醇、1,2-戊烷二醇、1,3-戊烷二醇、1,4-戊烷二醇、1,5-戊烷二醇、環戊烷二醇、1,2-己烷二醇、1,3-己烷二醇、1,4-己烷二醇、1,5-己烷二醇、1,6-己烷二醇、環己烷二醇、丙三醇、甲醛縮二甲醇。
更佳的是選自以下之群組中至少1種之化合物。2-丙醇、2-丁醇、2-戊醇、3-戊醇、環戊醇、2-己醇、3-己醇、環己醇、乙二醇、1,2-丙烷二醇、1,3-丙烷二醇、1,2-丁烷二醇、1,3-丁烷二醇、1,4-丁烷二醇、2,3-丁烷二醇、甲醛縮二甲醇。
(D)鏈轉移劑與(C)環硫化合物之混合比率,前述(D)之物質量(mol),與前述(C)中所含有的環硫基之物質量(mol)的比是以1:10至1:10000為佳。
將(D)鏈轉移劑之物質量(mol)當作1的情形,當(C)中所含有的環硫基之物質量(mol)為10以上時,從抑制對
(D)鏈轉移劑之聚合物或是硬化物中之殘留,將聚合(C)環硫化合物所得到之聚合物及硬化物,在高溫下長期保持之際的揮發分有更降低之傾向而言較佳。將(D)鏈轉移劑之物質量(mol)當作1的情形,當(C)中所含有的環硫基之物質量(mol)為20以上時,從由(C)環硫化合物所形成之硬化物的機械強度有提高之傾向而言較佳。由同樣之觀點而言,將(D)鏈轉移劑之物質量(mol)當作1的情形,在(C)中所含有的環硫基之物質量(mol)為50以上為更佳。
將(D)鏈轉移劑之物質量(mol)當作1的情形,在(C)中所含有的環硫基之物質量(mol)為10000以下時,由於將聚合(C)環硫化合物所得到的聚合物及硬化物,在高溫下長期保持之際揮發分有更減低之傾向,故佳。由同樣之觀點而言,將(D)鏈轉移劑之物質量(mol)當作1的情形,在(C)中所含有的環硫基之物質量(mol)是以2000以下為較佳,更佳是1000以下。含有(A)與(B)與(C)之組成物中,更含有(D)鏈轉移劑,將得到的聚合物及硬化物,在高溫下長期保持之際的揮發分有減低之傾向的理由尚未確定,但認為藉由(D)鏈轉移劑,有抑制聚合物及硬化物之解聚合的可能性。
(D)鏈轉移劑與(C)環硫化合物之混合比率可以用以下述式(19)表示。
指標γ=α d/α t×100 (19)
α d:鏈轉移劑之物質量(mol)
α t:(C)環硫化合物中所含有的環硫基之物質量(mol)
(D)鏈轉移劑之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:10時,指標變成γ=10。
(D)鏈轉移劑之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:20時,指標變成γ=5。
(D)鏈轉移劑之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:50時,指標變成γ=2。
(D)鏈轉移劑之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:10000時,指標變成γ=0.01。
(D)鏈轉移劑之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:2000時,指標變成γ=0.05。
(D)鏈轉移劑之物質量(mol),與在(C)環硫化合物中所含有的環硫基之物質量(mol)的比為1:1000時,指標變成γ=0.1。
作為調製含有(A)與(B)與(C)與(D)之組成物的方法者,只要使用一般的方法即可而無特別限定,可以列舉:同時添加(A)、(B)、(C)、(D)的方法;(A)、(B)、(C)、(D)之中,混合任意選擇之至少2種成分後,添加到殘留之成分中,及/或是,添加殘留成分的方法。此等之中,從有可以安定地調製組成物,作為組成物的安定性亦優良之傾
向而言,係以將含有(A)與(B)之混合物經調製後,添加到殘留成分之(C)、(D)中,及/或是,添加前述殘留成分的方法為佳。
聚合組成物所得到的聚合物及硬化物可因應目的,適當地含有各種有機樹脂、無機填充劑、著色劑、調平劑、潤滑劑、界面活性劑、矽氧系化合物、反應性稀釋劑、非反應性稀釋劑、抗氧化劑及光安定劑等。其他,作為一般樹脂用之添加劑(可塑劑、難燃劑、安定劑、抗靜電劑、耐衝撃強化劑、發泡劑、抗菌/防黴劑、導電性填充劑、防霧劑、交聯劑等)所供應之物質,也不妨摻配到聚合物或是硬化物中。
作為有機樹脂者,並無特別限定,例如,可以列舉:丙烯酸樹脂、聚酯樹脂及聚醯亞胺樹脂等。
作為無機填充材者,例如,可以列舉:二氧化矽類(熔融破碎二氧化矽、結晶破碎二氧化矽、球狀二氧化矽、氣相二氧化矽(fumed silica)、膠態的二氧化矽及沉澱性二氧化矽等)、碳化矽、氮化矽、氮化硼、碳酸鈣、碳酸鎂、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氧化鎂、氧化鋯、氧化鈦、氫氧化鋁、氫氧化鎂、矽酸鈣、矽酸鋁、矽酸鋰鋁、矽酸鋯、鈦酸鋇、玻璃纖維、碳纖維、及二硫化鉬。此等之中,以二氧化矽類、碳酸鈣、氧化鋁、氧化鋯、氧化鈦、氫氧化鋁、矽酸鈣及鈦酸鋇為佳,再考慮到硬化物之物性時,以二氧化矽類為更佳。此等之無機填充材可以單獨,也可以組合複數種而使用。
著色劑只要是以著色為目的所使用的物質即可而無特別限定,例如可選自酞菁、偶氮、雙偶氮、喹吖酮、蒽醌、黃士酮(flavanthrone)、紫環酮(perinone)、苝(peryleue)、二(dioxazine)、縮合偶氮及甲亞胺(azomethine)系之各種有機系色素,以及氧化鈦、硫酸鉛、鉻黃、鋅黃、鉻朱砂(chrome vermilion)、氧化鐵、鈷紫、普魯士藍、群青、碳黑、鉻綠、氧化鉻及鈷綠等無機顏料。此等之著色劑可以單獨,也可以組合複數種而使用。
調平劑並無特別限定,例如可選自丙烯酸乙酯、丙烯酸丁酯、及丙烯酸2-乙基己酯等由丙烯酸酯形成的分子量4000至12000之寡聚物,環氧化大豆脂肪酸、環氧化松香醇、氫化蓖麻油(Castor oil)、以及鈦系偶合劑。此等之調平劑可以單獨,也可以組合複數種而使用。
潤滑劑並無特別限定,可選自石臘、微晶蠟及聚乙烯蠟等烴系潤滑劑;月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、花生酸及蘿酸等高級脂肪酸系潤滑劑;硬脂醯胺、棕櫚醯胺、油基醯胺、亞甲基雙硬脂醯胺及伸乙基雙硬脂醯胺等高級脂肪酸醯胺系潤滑劑;硬化蓖麻油、硬脂酸丁酯、乙二醇單硬脂酸酯及新戊四醇(單-、二-、三-、或是四-)硬脂酸酯等高級脂肪酸酯系潤滑劑;十六烷醇、硬脂醇、聚乙二醇及聚丙三醇等醇系潤滑劑;月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、花生酸、蘿酸、蓖麻油酸及環烷酸等之鎂、鈣、鎘、鋇、鋅及鉛等之金屬鹽的金屬皂;以及巴西棕櫚蠟、小燭樹蠟、蜂蠟及褐煤蠟等天然蠟。此等之滑劑可以
單獨,也可以組合複數種而使用。
界面活性劑是指在分子中具有對溶劑沒有親和性的疏水基,與對溶劑持有親和性的親媒基(通常是親水基)之兩親媒性物質。界面活性劑之種類並無特別限定者,例如,可以列舉:矽系界面活性劑及氟系界面活性劑等。界面活性劑可以單獨,也可以組合複數種而使用。
矽氧系化合物並無特別限定,例如,可以列舉:矽氧樹脂、矽氧縮合物、矽氧部分縮合物、矽氧油、矽烷偶合劑、矽氧油、及聚矽氧烷。也可以在矽氧化合物之兩末端、單邊末端、或是側鏈導入有機基並改質。矽氧系化合物之改質方法也無特別限定,例如,可以列舉:胺改質、環氧基改質、脂環式環氧基改質、甲醇改質、甲基丙烯酸改質、聚醚改質、氫硫基改質、羧基改質、酚改質、矽醇改質、聚醚改質、聚醚-甲氧基改質、及二醇改質。
反應性稀釋劑並無特別限定,例如可選自,烷基縮水甘油醚、烷基酚之單縮水甘油醚、新戊基二醇二縮水甘油醚、1,6-己烷二醇二縮水甘油醚、烷酸縮水甘油酯、乙二醇二縮水甘油醚、及丙二醇二縮水甘油醚。
非反應性稀釋劑並無特別限定,例如可選自,苄基醇、丁基二醇及丙二醇單甲基醚等高沸點溶劑。
抗氧化劑並無特別限定者,例如可選自,酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑及胺系抗氧化劑。此等可以單獨使用,也可以組合複數種而使用。作為抗氧化劑之具體例者,可以列舉:以下之(1)至(4)者。
(1)酚系抗氧化劑:例如,以下之烷基酚類、氫醌類、硫烷基或是硫芳基類、雙酚類、苄基化合物類、三類、β-(3,5-二-三級-丁基-4-羥基苯基)丙酸與一元或是多元醇之酯、β-(5-三級-丁基-4-羥基-3-甲基苯基)丙酸與一元或是多元醇之酯、β-(3,5-二環己基-4-羥基苯基)丙酸與一元或是多元醇之酯、3,5-二-三級-丁基-4-羥基苯基乙酸與一元或是多元醇之酯、β-(3,5-二-三級-丁基-4-羥基苯基)丙酸之醯胺、及維他命類。
(1-1)烷基酚類:2,6-二-三級-丁基-4-甲基酚、2-三級-丁基-4,6-二甲基酚、2,6-二-三級-丁基-4-乙基酚、2,6-二-三級-丁基-4-正-丁基酚、2,6-二-三級-丁基-4-異丁基酚、2,6-二環戊基-4-甲基酚、2-(α-甲基環己基)-4,6-二甲基酚、2,6-二-十八烷基-4-甲基酚、2,4,6-三環己基酚、2,6-二-三級-丁基-4-甲氧基甲基酚、有直鏈狀或是分枝鏈狀之側鏈之壬基酚類(例如2,6-二-壬基-4-甲基酚)、2,4-二甲基-6-(1’-甲基十一烷-1’-基)酚、2,4-二甲基-6-(1’-甲基十七烷-1’-基)酚、2,4-二甲基-6-(1’-甲基十三烷-1’-基)酚及此等之混合物、4-羥基月桂醯苯胺、4-羥基硬脂醯苯胺、以及N-(3,5-二-三級-丁基-4-羥基苯基)胺基甲酸辛酯。
(1-2)氫醌類:2,6-二-三級-丁基-4-甲氧基酚、2,5-二-三級-丁基氫醌、2,5-二-三級-戊基氫醌、2,6-二苯基-4-十八烷氧基酚、2,6-二-三級-丁基氫醌、2,5-二-三級-丁基-4-羥基茴香醚、3,5-二-三級-丁基-4-羥基茴香醚、
3,5-二-三級-丁基-4-羥基苯基硬脂酸酯及雙(3,5-二-三級-丁基-4-羥基苯基)己二酸酯。
(1-3)硫烷基或是硫芳基類:2,4-二辛基硫甲基-6-三級-丁基酚、2,4-二辛基硫甲基-6-甲基酚、2,4-二辛基硫甲基-6-乙基酚、2,6-二-十二烷基硫甲基-4-壬基酚、2,2’-硫雙(6-三級-丁基-4-甲基酚)、2,2’-硫雙(4-辛基酚)、4,4’-硫雙(6-三級-丁基-3-甲基酚)、4,4’-硫雙(6-三級-丁基-2-甲基酚)、4,4’-硫雙(3,6-二-二級-戊基酚)及4,4’-雙(2,6-二甲基-4-羥基苯基)二硫化物。
(1-4)雙酚類:2,2’-亞甲基雙(6-三級-丁基-4-甲基酚)、2,2’-亞甲基雙(6-三級-丁基-4-乙基酚)、2,2’-亞甲基雙[4-甲基-6-(α-甲基環己基)酚]、2,2’-亞甲基雙(4-甲基-6-環己基酚)、2,2’-亞甲基雙(6-壬基-4-甲基酚)、2,2’-亞甲基雙(4,6-二-三級-丁基酚)、2,2’-亞乙基雙(4,6-二-三級-丁基酚)、2,2’-亞乙基雙(6-三級-丁基-4-異丁基酚)、2,2’-亞甲基雙[6-(α-甲基苄基)-4-壬基酚]、2,2’-亞甲基雙[6-(α,α-二甲基苄基)-4-壬基酚]、4,4’-亞甲基雙(2,6-二-三級-丁基酚)、4,4’-亞甲基雙(6-三級-丁基-2-甲基酚)、1,1-雙(5-三級-丁基-4-羥基-2-甲基苯基)丁烷、2,6-雙(3-三級-丁基-5-甲基-2-羥基苄基)-4-甲基酚、1,1,3-參(5-三級-丁基-4-羥基-2-甲基苯基)丁烷、1,1-雙(5-三級-丁基-4-羥基-2-甲基苯基)-3-正-十二烷基氫硫基丁烷、乙二醇雙[3,3-雙(3’-三級-丁基-4’-羥基苯基)丁酸酯]、雙(3-三級-丁基-4-羥基-5-甲基-
苯基)二環戊二烯、雙[2-(3’-三級-丁基-2’-羥基-5’-甲基苄基)-6-三級-丁基-4-甲基苯基]對苯二甲酸酯、1,1-雙(3,5-二甲基-2-羥基苯基)丁烷、2,2-雙(3,5-二-三級-丁基-4-羥基苯基)丙烷、2,2-雙(5-三級-丁基-4-羥基-2-甲基苯基)-4-正-十二烷基氫硫基丁烷及1,1,5,5-四(5-三級-丁基-4-羥基-2-甲基苯基)戊烷。
(1-5)苄基化合物類:3,5,3’,5’-四-三級-丁基-4,4’-二羥基二苄基醚、十八烷基-4-羥基-3,5-二甲基苄基氫硫基乙酸酯、十三烷基-4-羥基-3,5-二-三級-丁基苄基氫硫基乙酸酯、參(3,5-二-三級-丁基-4-羥基苄基)胺、雙(4-三級-丁基-3-羥基-2,6-二甲基苄基)二硫代對苯二甲酸酯、雙(3,5-二-三級-丁基-4-羥基苄基)硫化物、異辛基-3,5-二-三級-丁基-4-羥基苄基氫硫基乙酸酯、二-十八烷基-2,2-雙(3,5-二-三級-丁基-2-羥基苄基)丙二酸酯、二-十八烷基-2-(3-三級-丁基-4-羥基-5-甲基苄基)丙二酸酯、二-十二烷基氫硫基乙基-2,2-雙(3,5-二-三級-丁基-4-羥基苄基)丙二酸酯、雙[4-(1,1,3,3-四甲基丁基)苯基]-2,2-雙(3,5-二-三級-丁基-4-羥基苄基)丙二酸酯、1,3,5-參(3,5-二-三級-丁基-4-羥基苄基)-2,4,6-三甲基苯、1,4-雙(3,5-二-三級-丁基-4-羥基苄基)-2,3,5,6-四甲基苯及2,4,6-參(3,5-二-三級-丁基-4-羥基苄基)酚。
(1-6)三類:2,4-雙(辛基氫硫基)-6-(3,5-二-三級-丁基-4-羥基苯胺基)-1,3,5-三、2-辛基氫硫基-4,6-雙(3,5-二-三級-丁基-4-羥基苯胺基)-1,3,5-三、2-辛基
氫硫基-4,6-雙(3,5-二-三級-丁基-4-羥基苯氧基)-1,3,5-三、2,4,6-參(3,5-二-三級-丁基-4-羥基苯氧基)-1,2,3-三、1,3,5-參(3,5-二-三級-丁基-4-羥基苄基)三聚異氰酸酯、1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苄基)三聚異氰酸酯、2,4,6-參(3,5-二-三級-丁基-4-羥基苯基乙基)-1,3,5-三、1,3,5-參(3,5-二-三級-丁基-4-羥基苯基丙醯基)-六氫-1,3,5-三及1,3,5-參(3,5-二環己基-4-羥基苄基)三聚異氰酸酯。
(1-7)β-(3,5-二-三級-丁基-4-羥基苯基)丙酸與一元或是多元醇之酯:β-(3,5-二-三級-丁基-4-羥基苯基)丙酸,與選自甲醇、乙醇、正-辛醇、異-辛醇、十八烷醇、1,6-己烷二醇、1,9-壬烷二醇、乙二醇、1,2-丙烷二醇、新戊基二醇、硫代二乙二醇、二乙二醇、三乙二醇、新戊四醇、參(羥基乙基)三聚異氰酸酯、N,N’-雙(羥基乙基)乙二醯二胺、3-硫雜十一烷醇、3-硫雜十五烷醇、三甲基己烷二醇、三羥甲基丙烷、及4-羥基甲基-1-磷雜-2,6,7-三雙環[2.2.2]辛烷等一元或是多元醇之酯。
(1-8)β-(5-三級-丁基-4-羥基-3-甲基苯基)丙酸與一元或是多元醇之酯:β-(5-三級-丁基-4-羥基-3-甲基苯基)丙酸,與選自甲醇、乙醇、正-辛醇、異-辛醇、十八烷醇、1,6-己烷二醇、1,9-壬烷二醇、乙二醇、1,2-丙烷二醇、新戊基二醇、硫代二乙二醇、二乙二醇、三乙二醇、新戊四醇、參(羥基乙基)三聚異氰酸酯、N,N’-雙(羥基乙基)乙二醯二胺、3-硫雜十一烷醇、3-硫雜十五烷醇、三甲
基己烷二醇、三羥甲基丙烷、4-羥基甲基-1-磷雜-2,6,7-三雙環[2.2.2]辛烷、及3,9-雙[2-{3-(3-三級-丁基-4-羥基-5-甲基苯基)丙醯基氧基}-1,1-二甲基乙基]-2,4,8,10-四螺[5.5]十一烷等一元或是多元醇之酯。
(1-9)β-(3,5-二環己基-4-羥基苯基)丙酸與一元或是多元醇之酯:β-(3,5-二環己基-4-羥基苯基)丙酸,與選自甲醇、乙醇、辛醇、十八烷醇、1,6-己烷二醇、1,9-壬烷二醇、乙二醇、1,2-丙烷二醇、新戊基二醇、硫代二乙二醇、二乙二醇、三乙二醇、新戊四醇、參(羥基乙基)三聚異氰酸酯、N,N’-雙(羥基乙基)乙二醯二胺、3-硫雜十一烷醇、3-硫雜十五烷醇、三甲基己烷二醇、三羥甲基丙烷、及4-羥基甲基-1-磷雜-2,6,7-三雙環[2.2.2]辛烷等一元或是多元醇之酯。
(1-10)3,5-二-三級-丁基-4-羥基苯基乙酸與一元或是多元醇之酯:3,5-二-三級-丁基-4-羥基苯基乙酸,與選自甲醇、乙醇、辛醇、十八烷醇、1,6-己烷二醇、1,9-壬烷二醇、乙二醇、1,2-丙烷二醇、新戊基二醇、硫代二乙二醇、二乙二醇、三乙二醇、新戊四醇、參(羥基乙基)三聚異氰酸酯、N,N’-雙(羥基乙基)乙二醯二胺、3-硫雜十一烷醇、3-硫雜十五烷醇、三甲基己烷二醇、三羥甲基丙烷、及4-羥基甲基-1-磷雜-2,6,7-三雙環[2.2.2]辛烷之一元或是多元醇之酯。
(1-11)β-(3,5-二-三級-丁基-4-羥基苯基)丙酸之醯胺:N,N’-雙(3,5-二-三級-丁基-4-羥基苯基丙醯基)六亞
甲基二醯胺、N,N’-雙(3,5-二-三級-丁基-4-羥基苯基丙醯基)三亞甲基二醯胺、N,N’-雙(3,5-二-三級-丁基-4-羥基苯基丙醯基)醯肼及N,N’-雙[2-(3-[3,5-二-三級-丁基-4-羥基苯基]丙醯基氧基)乙基]乙二醯二胺。
(1-12)維生素類:α-生育酚、β-生育酚、γ-生育酚、δ-生育酚及此等之混合物、生育三烯醇(tocotrienol)、以及抗壞血酸。
(2)磷系抗氧化劑:以下之膦酸酯類、亞磷酸酯類及氧雜磷雜菲(oxaphosphaphenanthrene)類。
(2-1)膦酸酯類:二甲基-2,5-二-三級-丁基-4-羥基苄基膦酸酯、二乙基-3,5-二-三級-丁基-4-羥基苄基膦酸酯、二-十八烷基-3,5-二-三級-丁基-4-羥基苄基膦酸酯、二-十八烷基-5-三級-丁基-4-羥基-3-甲基苄基膦酸酯、肆(2,4-二-三級-丁基苯基)-4,4’-伸聯苯二膦酸酯及3,5-二-三級-丁基-4-羥基苄基膦酸之單乙基酯的鈣鹽。
(2-2)亞磷酸酯類:亞磷酸三辛基酯、亞磷酸三月桂基酯、亞磷酸三癸基酯、亞磷酸辛基二苯基酯、參(2,4-二-三級-丁基苯基)亞磷酸酯、亞磷酸三苯基酯、參(丁氧基乙基)亞磷酸酯、參(壬基苯基)亞磷酸酯、二硬脂基新戊四醇二亞磷酸酯、四(十三烷基)-1,1,3-參(2-甲基-5-三級-丁基-4-羥基苯基)丁烷二亞磷酸酯、四(C12至C15混合烷基)-4,4’-亞異丙基二苯基二亞磷酸酯、四(十三烷基)-4,4’-亞丁基雙(3-甲基-6-三級-丁基酚)二亞磷酸酯、參(3,5-二-三級-丁基-4-羥基苯基)亞磷酸酯、參(單、二混
合壬基苯基)亞磷酸酯、氫化-4,4’-亞異丙基二酚聚亞磷酸酯、雙(辛基苯基)-雙[4,4’-亞丁基雙(3-甲基-6-三級-丁基酚)]-1,6-己烷二醇二亞磷酸酯、苯基-4,4’-亞異丙基二酚-新戊四醇二亞磷酸酯、雙(2,4-二-三級-丁基苯基)新戊四醇二亞磷酸酯、雙(2,6-二-三級-丁基-4-甲基苯基)新戊四醇二亞磷酸酯、參[4,4’-亞異丙基雙(2-三級-丁基酚)]亞磷酸酯、苯基二異癸基亞磷酸酯、二(壬基苯基)新戊四醇二亞磷酸酯)、參(1,3-二-硬脂醯氧基異丙基)亞磷酸酯、及4,4’-亞異丙基雙(2-三級-丁基酚)-二(壬基苯基)亞磷酸酯。
(2-3)氧雜磷雜菲類:9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、8-氯-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物及8-三級-丁基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物。
(3)硫系抗氧化劑:以下之硫代丙酸二烷基酯類、辛基硫代丙酸與多元醇之酯、月桂基硫代丙酸與多元醇之酯、及硬脂基硫代丙酸與多元醇之酯。
(3-1)硫代丙酸二烷基酯類:硫代二丙酸二月桂基酯、硫代二丙酸二肉豆蔻基酯、及硫代二丙酸二硬脂基酯。
(3-2)辛基硫代丙酸與多元醇之酯:辛基硫代丙酸,與選自甘油、三羥甲基乙烷、三羥甲基丙烷、新戊四醇及參羥基乙基三聚異氰酸酯等多元醇之酯。
(3-3)月桂基硫代丙酸與多元醇之酯:月桂基硫代丙酸,與甘油、三羥甲基乙烷、三羥甲基丙烷、新戊四醇、
及參羥基乙基三聚異氰酸酯之酯。
(3-4)硬脂基硫代丙酸與多元醇之酯:硬脂基硫代丙酸,與選自甘油、三羥甲基乙烷、三羥甲基丙烷、新戊四醇、及參羥基乙基三聚異氰酸酯等多元醇之酯。
(4)胺系抗氧化劑:N,N’-二-異丙基-對-苯二胺、N,N’-二-二級-丁基-對-苯二胺、N,N’-雙(1,4-二甲基戊基)-對-苯二胺、N,N’-雙(1-乙基-3-甲基戊基)-對-苯二胺、N,N’-雙(1-甲基庚基)-對-苯二胺、N,N’-二環己基-對-苯二胺、N,N’-二苯基-對-苯二胺、N,N’-雙(2-萘基)-對-苯二胺、N-異丙基-N’-苯基-對-苯二胺、N-(1,3-二甲基丁基)-N’-苯基-對-苯二胺、N-(1-甲基庚基)-N’-苯基-對-苯二胺、N-環己基-N’-苯基-對-苯二胺、4-(對-甲苯胺磺醯基)二苯基胺、N,N’-二甲基-N,N’-二-二級-丁基-對-苯二胺、二苯基胺、N-烯丙基二苯基胺、4-異丙氧基二苯基胺、N-苯基-1-萘基胺、N-(4-三級-辛基苯基)-1-萘基胺、N-苯基-2-萘基胺、辛基化二苯基胺(例如p,p’-二-三級-辛基二苯基胺)、4-正-丁基胺酚、4-丁醯基胺酚、4-壬醯基胺酚、4-十二烷醯基胺酚、4-十八烷醯基胺酚、雙(4-甲氧基苯基)-胺、2,6-二-三級-丁基-4-二甲基胺甲基酚、2,4’-二胺二苯基甲烷、4,4’-二胺二苯基甲烷、N,N,N’,N’-四甲基-4,4’-二胺二苯基甲烷、1,2-雙[(2-甲基苯基)胺基]乙烷、1,2-雙(苯基胺基)丙烷、(鄰-甲苯基)雙胍、雙[4-(1’,3’-二甲基丁基)苯基]胺、三級-辛基化N-苯基-1-萘基胺、單-及二-烷基化三級-丁基-/三級-辛基二苯基胺
之混合物、單-及二-烷基化壬基二苯基胺之混合物、單-及二-烷基化十二烷基二苯基胺之混合物、單-及二-烷基化異丙基/異己基二苯基胺之混合物、單-及二-烷基化三級-丁基二苯基胺之混合物、2,3-二氫-3,3-二甲基-4H-1,4-苯并噻、啡噻(phenothiazine)、單-及二-烷基化三級-丁基/三級-辛基啡噻類之混合物、單-及二-烷基化三級-辛基啡噻類之混合物、N-烯丙基啡噻、N,N,N’,N’-四苯基-1,4-二胺丁-2-烯、N、N-雙(2,2,6,6-四甲基哌啶-4-基)六亞甲基二胺、雙(2,2,6,6-四甲基哌啶-4-基)癸二酸酯、2,2,6,6-四甲基哌啶-4-酮、以及2,2,6,6-四甲基哌啶-4-醇。
光安定劑並無特別限定者,可選自三唑系、二苯甲酮系、酯系、丙烯酸酯系、鎳系、三系及乙二醯二胺系等紫外線吸收劑,以及受阻胺系光安定劑。此等可以單獨使用,也可以組合複數種而使用。作為光安定劑之具體例者,可以列舉以下之(1)至(8)者。
(1)三唑類:2-(2’-羥基-5’-(1,1,3,3-四甲基丁基)苯基)苯并三唑、2-(2’-羥基-4’-辛氧基苯基)苯并三唑、2-(3’-三級-丁基-2’-羥基-5’-(2-辛氧基羰基乙基)苯基)-5-氯苯并三唑、2-(3’-三級-丁基-5’-[2-(2-乙基己氧基)羰基乙基]-2’-羥基苯基)-5-氯苯并三唑、2-(3’-三級-丁基-2’-羥基-5’-(2-甲氧基羰基乙基)苯基)-5-氯苯并三唑、2-(3’-三級-丁基-2’-羥基-5’-(2-甲氧基羰基乙基)苯基)苯并三唑、2-(3’-三級-丁基-2’-羥基-5’-(2-辛氧基
羰基乙基)苯基)苯并三唑、2-(3’-三級-丁基-5’-[2-(2-乙基己氧基)羰基乙基]-2’-羥基苯基)苯并三唑、2-(3’-十二烷基-2’-羥基-5’-甲基苯基)苯并三唑、2-(3’-三級-丁基-2’-羥基-5’-(2-異辛氧基羰基乙基)苯基)苯并三唑、2,2’-亞甲基雙[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基酚]、2-[3’-三級-丁基-5’-(2-甲氧基羰基乙基)-2’-羥基苯基]-2H-苯并三唑與聚乙二醇300之酯交換生成物、下述式(18)所示之三唑化合物、以及2-[2’-羥基-3’-(α,α-二甲基苄基)-5’-(1,1,3,3-四甲基丁基)苯基]苯并三唑;2-[2’-羥基-3’-(1,1,3,3-四甲基丁基)-5’-(α,α-二甲基苄基)苯基]苯并三唑。
上述式(20)中,R是3’-三級-丁基-4’-羥基-5’-2H-苯并三唑-2-基苯基。
(2)二苯甲酮系:4-癸氧基、4-苄氧基、4,2’,4’-三羥基及2’-羥基-4,4’-二甲氧基衍生物類。
(3)酯系:水楊酸4-三級-丁基苯酯、水楊酸苯酯、水楊酸辛基苯酯、二苄醯基間苯二酚、雙(4-三級-丁基苄醯基)間苯二酚、苄醯基間苯二酚、3,5-二-三級-丁基-4-羥基苄酸2,4-二-三級丁基苯酯、3,5-二-三級-丁基-4-羥基苄酸十六烷基酯、3,5-二-三級-丁基-4-羥基苄酸十八烷基酯及3,5-二-三級-丁基-4-羥基苄酸2-甲基-4,6-二-三級-丁基苯酯。
(4)丙烯酸酯系:α-氰基-β,β-二苯基丙烯酸乙酯、α-氰基-β,β-二苯基丙烯酸異辛酯、α-甲氧羰基桂皮酸甲酯、α-氰基-β-甲基-對-甲氧基桂皮酸甲酯、α-氰基-β-甲基-對-甲氧基桂皮酸丁酯、α-甲氧羰基-對-甲氧基桂皮酸甲酯及N-(β-甲氧羰基-β-氰基乙烯基)-2-甲基吲哚啉。
(5)鎳系:具有或未具有如正-丁基胺、三乙醇胺及N-環己基二乙醇胺之追加之配合基(ligand)的1:1或是1:2錯合物(例如、2,2’-硫雙[4-(1,1,3,3-四甲基丁基)酚]之鎳錯合物),二丁基二硫代胺基甲酸鎳、4-羥基-3,5-二-三級-丁基苄基磷酸之單烷基酯(例如,甲基或是乙基酯)之鎳鹽、酮肟類之鎳錯合物(例如,2-羥基-4-甲基苯基十一烷基酮肟之鎳錯合物)、以及具有或未具有追加配位基之1-苯基-4-月桂醯基-5-羥基吡唑之鎳錯合物。
(6)三系:2,4,6-參(2-羥基-4-辛氧基苯基)-1,3,5-三、2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三、2,4-雙(2-羥基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三、2-(2-羥基-4-辛氧基苯基)-4,6-雙(4-甲基苯基)-1,3,5-三、2-(2-羥基-4-十二烷氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三、2-(2-羥基-4-十三烷氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三、2-[2-羥基-4-(2-羥基-3-丁氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)-1,3,5-三、2-[2-羥基-4-(2-羥基-3-辛氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)
-1,3,5-三、2-[2-羥基-4-(2-羥基-3-十二烷氧基丙氧基)苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三、2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三、2,4,6-參[2-羥基-4-(3-丁氧基-2-羥基丙氧基)苯基]-1,3,5-三、2-(2-羥基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三及2-{2-羥基-4-[3-(2-乙基己基-1-氧基)-2-羥基丙氧基]苯基}-4,6-雙(2,4-二甲基苯基)-1,3,5-三。
(7)乙二醯二胺系:4,4’-二辛氧基草醯苯胺、2,2’-二乙氧基草醯苯胺、2,2’-二辛氧基-5,5’-二-三級-丁醯苯胺、2,2’-二-十二烷氧基-5,5’-二-三級-丁醯苯胺、2-乙氧基-2’-乙基草醯苯胺、N,N’-雙(3-二甲基胺丙基)乙二醯二胺、2-乙氧基-5-三級-丁基-2’-乙醯苯胺及其與2-乙氧基-2’-乙基-5,4’-二-三級-丁醯苯胺之混合物、鄰-及對-甲氧基-二取代草醯苯胺之混合物、以及鄰-及對-乙氧基-二取代草醯苯胺之混合物。
(8)受阻胺系:雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)正-丁基-3,5-二-三級-丁基-4-羥基苄基丙二酸酯、1-(2-羥基乙基)-2,2,6,6-四甲基-4-羥基哌啶與琥珀酸之縮合物、N,N’-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺與4-三級-辛基胺基-2,6-二氯-1,3,5-三之直鏈或是環式縮合物、參(2,2,6,6-四甲基-4-哌啶基)氮基三乙酸
酯、肆(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、1,1’-(1,2-乙烷二基)-雙(3,3,5,5-四甲基哌酮)、4-苄醯-2,2,6,6-四甲基哌啶、4-硬脂基氧基-2,2,6,6-四甲基哌啶、雙(1,2,2,6,6-五甲基哌啶基)-2-正-丁基-2-(2-羥基-3,5-二-三級-丁基苄基)丙二酸酯、3-正-辛基-7,7,9,9-四甲基-1,3,8-三氮雜螺[4.5]癸烷-2,4-二酮、雙(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯、N,N’-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺與4-(N-嗎啉基)-2,6-二氯-1,3,5-三之直鏈或是環式縮合物;2-氯-4,6-雙(4-正-丁基胺基-2,2,6,6-四甲基哌啶基)-1,3,5-三與1,2-雙(3-胺丙基胺基)乙烷之縮合物、2-氯-4,6-二-(4-正-丁基胺基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三與1,2-雙(3-胺丙基胺基)乙烷之縮合物、8-乙醯基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮雜螺[4.5]癸烷-2,4-二酮、3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯啶-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯啶-2,5-二酮、5-(2-乙基己醯基)-氧基甲基-3,3,5-三甲基-2-嗎啉酮、1-(2-羥基-2-甲基丙基)-4-十八烷醯基氧基-2,2,6,6-四甲基哌啶、1,3,5-參(N-環己基-N-(2,2,6,6-四甲基哌-3-酮-4-基)胺基)-s-三、1,3,5-參(N-環己基-N-(1,2,2,6,6-五甲基哌-3-酮-4-基)胺基)-s-三、2,4-雙[(1-環己氧基-2,2,6,6-哌啶-4-基)丁基胺基]-6-氯-s-三與N,N’-雙(3-胺丙基)
伸乙基二胺)之反應生成物、4-十六烷基氧基-及4-硬脂基氧基-2,2,6,6-四甲基哌啶之混合物;N,N’-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺與4-環己基胺-2,6-二氯-1,3,5-三之縮合物,1,2-雙(3-胺基丙胺基)乙烷與2,4,6-三氯-1,3,5-三、還有與4-丁基胺基-2,2,6,6-四甲基哌啶之縮合物,1,6-己烷二胺與2,4,6-三氯-1,3,5-三、還有N,N-二丁基胺與4-丁基胺基-2,2,6,6-四甲基哌啶之縮合物,N-(2,2,6,6-四甲基-4-哌啶基)-正-十二烷基琥珀醯亞胺、N-(1,2,2,6,6-五甲基-4-哌啶基)-正-十二烷基琥珀醯亞胺、2-十一烷基-7,7,9,9-四甲基-1-氧雜-3,8-二氮雜-4-側氧基-螺[4.5]癸烷;5-(2-乙基己醯基)氧基甲基-3,3,5-三甲基-2-嗎啉酮、7,7,9,9-四甲基-2-環十一烷基-1-氧雜-3,8-二氮雜-4-側氧基螺-[4.5]癸烷與表氯醇之反應生成物、1,1-雙(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯、N,N’-雙-甲醯基-N,N’-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺、4-甲氧基亞甲基丙二酸與1,2,2,6,6-五甲基-4-羥基哌啶之二酯、聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]矽氧烷、以及馬來酸酐α-烯烴共聚物與2,2,6,6-四甲基-4-胺基哌啶或是1,2,2,6,6-五甲基-4-胺基哌啶之反應生成物。
將組成物中之環硫化合物聚合後形成的聚合物或是硬化物中所含有之乙烯鍵量,從有抑制在高溫下長期保持之際的變色之傾向而言,將聚合物或是硬化物之全體質量當
作基準乙烯鍵是以2質量%以下為佳。由同樣之觀點而言,乙烯鍵含量是以1質量%以下為較佳,更佳的是0.5質量%以下。
在聚合環硫化合物而形成之聚合物或是硬化物中所含有的乙烯鍵量,從有可以縮短聚合所需要的時間,可以抑制聚合物或是硬化物之生產成本的傾向而言,將聚合物或是硬化物之全體質量當作基準乙烯鍵是以0.01質量%以上為佳。由同樣之觀點而言,乙烯鍵含量是以0.05質量%以上為較佳,更佳的是0.07質量%以上。
將組成物中之環硫化合物聚合後形成的聚合物或是硬化物中所含有之硼原子含量,從有減低在高溫下長期保持之際的揮發分,可以抑制藉由熔融加工而成形之際之空洞的產生,或是抑制聚合物或是硬化物附近的金屬構件之污染或是腐蝕之傾向而言,將聚合物或是硬化物之全體質量當作基準硼原子含量是以6500ppm以下為佳。由同樣之觀點而言,硼原子之含量是以3500ppm以下為較佳,更佳的是1500ppm以下。在聚合環硫化合物而形成的聚合物或是硬化物中所含有之硼原子的含量為6500ppm以下,雖然在高溫下長期保持之際的揮發分減低的理由尚未確定,但認為有可能是含有硼原子之化合物揮發,或是由含有硼原子之化合物促進聚合物或是硬化物之分解反應。
在聚合組成物中之環硫化合物而形成的聚合物或是硬化物中所含有之硼原子之含量,從有減低在高溫下長期保持之際的揮發分,可以抑制藉由熔融加工成形之際之空洞
產生,或抑制在聚合物或是硬化物附近的金屬構件之污染或腐蝕之傾向而言,將聚合物或是硬化物之全體質量當作基準硼原子含量是以1ppm以上為佳。由同樣之觀點而言,硼原子含量是5ppm以上為較佳,更佳的是10ppm以上。在聚合環硫化合物所形成的聚合物或是硬化物中所含有之硼原子之含量為1ppm以上,在高溫下長期保持之際之揮發分減低的理由雖未確定,但認為可能是含有硼原子之化合物與環硫基之聚合末端反應,構築交聯結構,而抑制聚合物或是硬化物之分解反應。
在聚合組成物中之環硫化合物而形成的聚合物或是硬化物中所含有之磷原子之含量,從有抑制在類似太陽光之光線中長期間曝露之際的變色之傾向而言,將聚合物或是硬化物之全體質量當作基準磷原子含量是以14000ppm以下為佳。由同樣之觀點而言,硼原子之含量是以8500ppm以下為較佳,更佳的是3500ppm以下,特佳的是2000ppm以下。聚合環硫化合物所成之聚合物或是硬化物中所含有之磷原子之含量是14000ppm以下,有抑制在類似太陽光之光線中長期間曝露時的變色之傾向的理由雖未確定,但認為有可能是因光線而產生的磷自由基彼此結合,形成不安定的化合物,使聚合物或是硬化物變質。
在聚合環硫化合物所成之聚合物或是硬化物中所含有之磷原子含量,從有抑制在類似太陽光之光線中長期間曝露之際之變色的傾向而言,將聚合物或是硬化物之全體質量當作基準磷原子含量是以1ppm以上為佳。由同樣之觀點
而言,磷原子之含量是以5ppm以上為較佳,更佳是10ppm以上。聚合環硫化合物所成之聚合物或是硬化物中所含有之磷原子之含量為1ppm以上,有抑制在類似太陽光之光線中長期間曝露時的變色傾向的理由雖未確定,但認為可能是因光線而在聚合物或是硬化物中所產生的磷自由基由含有磷原子之化合物而補足。
組成物及聚合該組成物所形成的聚合物或是硬化物之用途並無特別限定者,例如,可以使用作為:電子材料(絕緣體類、交流變壓器、開關裝置等之注模及電路單元,各種零組件之包裝,IC/LED/半導體之周邊材料[密封材、透鏡材、基板材、晶粒黏著(Die Bonding)材、晶片塗布(chip coat)材、積層板、光纖維、光波導、濾光器、電子零組件用之接著劑、塗布材、密封材、絕緣材、光阻、包膠(encapsulation)材、裝填(potting)材、光碟之光透過層或層間絕緣層、導光板、抗反射膜等],發電機、馬達等之旋轉機線圈(rotator coil)、繞組浸漬(winding impregnation)、印刷配線基板、積層板、絕緣板、中型絕緣體類、線圈類、連接器、端子、各種盒子(case)類、電氣零組件類等)、塗料(防蝕塗料、維修、船舶塗裝、耐蝕襯裡、汽車/家電製品用底塗層(primer)、飲料/啤酒罐、外面漆(outside lacquer)、擠壓管塗裝、一般防蝕塗裝、維修塗裝、木工製品用漆、汽車用電沉積底塗層、其他工業用電沉積塗裝、飲料/啤酒罐內面漆、線圈塗膜、圓桶/罐內面塗裝、耐酸襯裡、線瓷漆(wire enamel)、絕緣塗料、
汽車用底塗層、各種金屬製品之美裝兼防蝕塗裝、管(pipe)內外面塗裝、電氣零組件絕緣塗裝等)、複合材料(化學工廠用管/桶(tank)類、飛機材、汽車構件、各種運動用品、碳纖維複合材料、聚芳醯胺纖維複合材料等)、土木建築材料(地板材、鋪裝材、薄膜(membrane)、止滑兼薄層鋪裝、混凝土連接/加高、錨(anchor)填入接著、預鑄混凝土接合、瓷磚接著、混凝土結構物之龜裂修補、台座之灌漿/調平、自來水及下水道設施之防蝕/防水塗裝、桶類之耐蝕積層襯裡、鐵結構物之防蝕塗裝、建築物外壁之膠黏(mastic)塗裝等)、接著劑(金屬、玻璃、陶磁器、水泥混凝土、木材、塑膠等之同種或是異種材質之接著劑,汽車、鐵路車輛、飛機等之組合用接著劑,預製用複合平板(panel)製造用接著劑等:包含一液型、二液型、片狀型(sheet type))、飛機/汽車/塑膠成形之模具(jig)及工具(沖壓模(press die)、拉伸模(stretched die)、配對模(matched die)等樹脂模型,真空成形/吹塑成型用塑模、基準模型(master model)、鑄物用圖案、積層模具及工具、各種檢査用模具及工具等)、改質劑/安定劑(纖維之樹脂加工、聚氯乙烯用安定劑、合成橡膠之添加劑等)、橡膠之改質劑(硫化劑、硫化促進劑等)等。
作為透鏡材之例者,可以列舉:光學儀器用透鏡、汽車燈用透鏡、眼鏡透鏡、CD/DVD等之攝影(pickup)用透鏡及投射器(projector)用透鏡。
作為LED密封材之用途者,並無特別之限定,顯示器、
電光顯示板、信號機、顯示器之背光(有機EL顯示器、行動電話、可攜帶PC等)、汽車之內外裝照明、發光(illumination)、照明器具、手電筒等,可以廣範圍地展開用途。
以下例示具體說明本實施形態的實施例。在沒有超過主旨的情況下本發明是不侷限於以下實施例者。
11B-NMR測定是用以下的順序進行。又,以下是列舉在三鹵化硼-醚化合物中所含有的錯合物之檢測作為例子,在三鹵化硼-三價磷化合物、三鹵化硼-酮化合物、三鹵化硼-醚化合物、三價磷化合物、酮化合物中,也同樣實施11B-NMR測定。
(1)在試樣瓶中,秤取10mg三甲氧基硼烷(和光純藥工業股份有限公司製),並添加氯仿-d(和光純藥工業股份有限公司製),將全體量調整成1g。
(2)在試樣瓶中,秤取在調製三鹵化硼-醚化合物之際使用的三鹵化硼化合物10mg,並添加氯仿-d(和光純藥工業股份有限公司製),將全體量調整成1g。
(3)在試樣瓶中,秤取調製之三鹵化硼-醚化合物10mg,並添加氯仿-d(和光純藥工業股份有限公司製),將全體量調整成1g。
(4)將上述(2)之溶液,移到可挿入至直徑5mm 之NMR管內的特殊NMR管(例如,日本精密化學股份有限公司製「N-502B」等)中。
(5)將上述(1)之溶液移到直徑5mm 之NMR管中,並將上述(4)之特殊NMR管挿入,以下述條件,測定11B-NMR。
傅立葉(Fourier)變換核磁共振裝置:日本電子股份有限公司製「α-400型」
核種:11B
累計次數:1000次
(6)將上述(3)之溶液,移到可挿入至直徑5mm 之NMR管內的特殊NMR管(例如,日本精密化學股份有限公司製「N-502B」等)中。
(7)將上述(1)之溶液移到直徑5mm 之NMR管中,將上述(6)之特殊NMR管挿入,以與上述(5)同樣之方法,測定11B-NMR。
(8)上述(5)及(7)所得到之測定結果中,將三甲氧基硼烷之波峰當作18ppm,在(7)所得到之波峰中,當有檢測到與(5)所得到之波峰不同之波峰的情形,則判定所調製之三鹵化硼-醚化合物是形成錯合物。
1H-NMR測定是用以下之順序進行。
(1)在試樣瓶中,秤取10mg之試樣與20mg之內部標準物質,再添加氯仿-d(和光純藥工業股份有限公司製),將全體量調整成1g。
‧內部標準物質:1,1,2,2-四溴乙烷(東京化成工業股份有限公司製,以下稱為「TBE」)
(2)將上述(1)之溶液,移到直徑5mm φ之NMR管中,用下述條件,測定1H-NMR。
傅立葉變換核磁共振裝置:日本電子股份有限公司製「α-400型」
核種:1H
累積次數:200次
由上述測定結果,用以下之順序,算出環硫化物之當量。
(3)由1H-NMR圖表,算出源自環硫基之波峰面積值。
在此,源自環硫基之波峰是指源自構成環硫基之烴上的1個氫的波峰。適當選擇與源自於除了源自構成環硫化合物之環硫基之氫以外的氫之波峰不重複的波峰。
(4)由1H-NMR圖表,算出源自內部標準物質之波峰的面積值。
(5)將上述(3)及(4)所算出之面積值,代入下述式,求取環硫當量(g/mol)。
環硫當量(g/mol)=(SAMG/EPIA)×(TBEM/TBEG)×(TBEA/2)
EPIA:源自環硫基之波峰之面積值
TBEA:源自TBE之2個氫之波峰之面積值
TBEG:調製進行1H-NMR測定的溶液之際使用的TBE之重量(g)(本實施例中是20mg)
TBEM:TBE之分子量
SAMG:調製進行1H-NMR測定的溶液之際使用之試樣的重量(g)(本實施例中是10mg)
觀測到構成試樣中所含有之環硫化合物中的環硫基之烴上之氫在1H-NMR測定上為同一波峰的情形,將(5)之順序變更為如以下方式而可以算出。
(5-2)將上述(3)及(4)所算出之面積值,代入到下述式中,求出環硫當量(g/mol)。
環硫當量(g/mol)=SAMG×(構成源自環硫基的波峰之氫的個數/EPIA)×(TBEM/TBEG)×(TBEA/2)
混合指標α是藉由以下之式(5)算出。
指標α=(α e+α p+α k)/α b (5)
在此,分別表示如下:α e:(A-1)醚化合物之醚基的物質量(mol)
α p:在(A-2)三價磷化合物中所含有之三價磷原子的物質量(mol)
α k:(A-3)酮化合物之酮基的物質量(mol)
α b:(B)三鹵化硼的物質量(mol)。
混合指標β是藉由以下之式(18)算出。
指標β=α b/α t×100 (18)
在此,分別表示α b:(B)三鹵化硼之物質量(mol)
α t:在(C)環硫化合物中所含之環硫基之物質量(mol)。
1H-NMR測定是用以下之順序進行。
(1)在試樣瓶中,秤取10mg之試樣,與20mg之內部標準物質,更添加氯仿-d(和光純藥工業股份有限公司製),將全體量調整成1g。
‧內部標準物質:1,1,2,2-四溴乙烷(東京化成工業股份有限公司製,以下稱為「TBE」)
(2)將上述(1)之溶液,移到直徑5mm 之NMR管中,以下述條件,測定1H-NMR。
傅立葉變換核磁共振裝置:日本電子股份有限公司製「α-400型」
核種:1H
累積次數:200次
由上述測定結果,用以下之順序,算出環硫基反應率。
(3)由1H-NMR圖表,算出源自環硫基之波峰之面積值。
在此,源自環硫基之波峰是指,源自構成環硫基之烴上的1個氫之波峰。適宜選擇與源自於除了源自構成環硫化合物之環硫基之氫以外的氫之波峰不重複的波峰。
(4)由1H-NMR圖表,算出源自內部標準物質之波峰之面積值。
(5)將上述(3)及(4)所算出之面積值,代入到下述式中,求得環硫基的反應率(%)。
環硫基反應率(%)=100-EPIA×(TBEG/TBEM)×(2/TBEA)×(REAG/SAMG)×(WPT/EPIG)×100
EPIA:源自環硫基之波峰之面積值
TBEA:源自TBE的2個氫之波峰之面積值
EPIG:調製聚合性組成物之際使用的環硫化合物之重量(g)
WPT:調製聚合性組成物之際使用之環硫化合物的環硫當量(g/mol)
REAG:聚合性組成物之重量(g)
TBEG:在調製進行1H-NMR測定的溶液之際使用之TBE之重量(g)(本實施例中是20mg)
TBEM:TBE之分子量
SAMG:調製進行1H-NMR測定的溶液之際使用的試樣之重量(g)(本實施例中是10mg)
觀測到構成試樣中所含有之環硫化合物之環硫基之烴上的氫在1H-NMR測定上為同一波峰之情形,將(5)之順序變更為如以下方式而可以算出。
(5-2)將上述(3)及(4)所算出之面積值,代入下述式,求取環硫基反應率(%)。
環硫基反應率(%)=100-{EPIA/(構成源自環硫基之波峰之氫的個數)}×(TBEG/TBEM)×(2/TBEA)×(REAG/SAMG)×(WPT/EPIG)×100
EA法中,在試樣不溶解於氯仿-d中的情形,藉由EB
法算出環硫基反應率。
FT-IR測定是以下述之順序進行。
(1)瑪瑙製缽中,秤取2mg之試樣,與100mg之臭化鉀(Aldrich公司製,IR級),使用瑪瑙製杵均勻地粉碎。
(2)將上述(1)之試料50mg使用錠劑成型器成型為圓盤狀。
(3)將上述(2)之成型體設置在錠劑試樣持有台(holder)上,以下述條件,進行FT-IR測定。
傅立葉變換紅外線分光裝置:Thermo Fisher Scientific公司製「Nicolet 6700型」
分解能:4cm-1
測定法:透過法
累積次數:128次
由上述測定結果,用以下之順序算出環硫基反應率。
(4)由FT-IR圖表,算出源自環硫基之波峰之面積值。
在此,源自環硫基之波峰是指,源自構成環硫基之原子間的振動之波峰。在試樣所含有的化合物中,適當選擇與源自除了源自環硫基之波峰以外之原子間的振動之波峰不重複的波峰。
(5)將(4)所算出之面積值,代入下述式,求得環硫基反應率(%)。
環硫基反應率(%)=100-RIRA/SIRA×100
RIRA:測定試樣之結果而得到的FT-IR圖表中,源自環硫基之波峰的面積
SIRA:測定製作試樣之際使用之聚合前的環硫化合物的結果而得到之FT-IR圖表中,源自環硫基之波峰的面積
1H-NMR測定是用以下之順序進行。
(1)在試樣瓶中,秤取10mg之試樣,與20mg之內部標準物質,再添加氯仿-d(和光純藥工業股份有限公司製),將全體量調整成1g。
‧內部標準物質:1,1,2,2-四溴乙烷(東京化成工業股份有限公司製,以下稱為「TBE」)
(2)將上述(1)之溶液,移到直徑5mm 之NMR管中,以下述條件,測定1H-NMR。
傅立葉變換核磁共振裝置:日本電子股份有限公司製「α-400型」
核種:1H
累積次數:200次
由上述測定結果,用以下之順序,算出乙烯基生成率。
(3)由1H-NMR圖表,算出源自乙烯基之波峰之面積值。
在此,源自乙烯基之波峰是指,源自構成乙烯基之烴上的1個氫的波峰。適宜選擇與源自構成試樣中所含有之化合物之氫且除了源自乙烯基之氫以外的氫之波峰不重複之波峰。
(4)由1H-NMR圖表,算出源自內部標準物質之波峰之面積值。
(5)將上述(3)及(4)所算出之面積值,代入下述式,求
得環硫當量(g/mol)。
乙烯基生成率(%)=VINA×(TBEG/TBEM)×(2/TBEA)×(REAG/SAMG)×(WPT/EPIG)×100
VINA:源自乙烯基之波峰之面積值
TBEA:源自TEB之2個氫之波峰之面積值
EPIG:在調製聚合性組成物之際使用的環硫化合物之重量(g)
WPT:在調製聚合性組成物之際使用的環硫化合物之環硫當量(g/mol)
REAG:聚合性組成物之重量(g)
TBEG:在調製進行1H-NMR測定的溶液之際使用的TBE之重量(g)(本實施例中是20mg)
TBEM:TBE之分子量
SAMG:在調製進行1H-NMR測定的溶液之際使用的試樣之重量(g)(本實施例中是10mg)
觀測到在構成乙烯基之烴上的氫在1H-NMR測定上為同一波峰的情形,將(5)之順序變更為如以下之方式而可能算出。
(5-2)將上述(3)及(4)所算出之面積值,代入下述式,求取乙烯基生成率(%)。
乙烯基生成率(%)={VINA/(構成源自乙烯基之波峰之氫的個數)}×(TBEG/TBEM)×(2/TBEA)×(REAG/SAMG)×(WPT/EPIG)×100
將所調製之聚合性組成物之一部分,放入設定在20℃之恆溫器內,保持1小時後,以EA法算出環硫基之反應率。
安定性,當環硫基反應率為10%以下的情形,判定為良好(「A」),5%以下的情形判定為特別良好(「AA」),此等以外之情形判定為不良(「C」)。
安定性評估A中,當聚合組成物並未完全溶解到氯仿-d中的情形,用EB法算出環硫基反應率。
安定性,當環硫基反應率為10%以下的情形判定為良好(「A」),5%以下之情形判定為特別良好(「AA」),在此等以外之情形判定為不良(「C」)。
以EA法,算出得到的聚合物之環硫基反應率。
聚合性,當環硫基反應率為90%以上之情形判定為良好(「A」),95%以上之情形判定為特別良好(「AA」),在此等以外之情形判定為不良(「C」)。
聚合性評估A中,當聚合物並未完全溶解到氯仿-d中的情形,以EB法算出環硫基反應率。
聚合性,當環硫基反應率為90%以上之情形判定為良好(「A」),95%以上之情形判定為特別良好(「AA」),在此等以外之情形判定為不良(「C」)。
算出調製之聚合物的乙烯基生成率。
副反應性,當乙烯基生成率為5%以下之情形判定為良好(「A」),2%以下之情形判定為特別良好(「AA」),在此等以外之情形判定為不良(「C」)。
副反應性評估A中,當聚合物並未完全溶解到氯仿-d中的情形,用以下之方法實施評估。
(1)將評估用試樣使用凍結粉碎機,作成粉體狀試樣。
(2)將上述(1)之粉體狀試樣,移到直徑4mm 的NMR管中,以下述條件,測定固體13C-NMR。
傅立葉變換核磁共振裝置:日本電子股份有限公司製「ECA700型」
核種:13C
累積次數:16,000次
測定方法:CP/MAS法
MAS:10,000Hz
(3)由上述測定結果,在沒有觀測到源自乙烯基之波峰的情形,判定為特別良好(「AA」),觀測到的情形判定為不良(「C」)。
安定性評估、聚合性評估、副反應性評估之所有評估中,在判定為特別良好的情形,及至少有1個評估中判定為良好,此以外之評估中判定為特別良好或是良好的情形中,綜合判定為合格(「AA」或是「A」)。此以外之情形是當作全部不合格(「C」)。
在製造例、實施例、比較例中使用的原材料,在以下之(1)至(214)中表示。
(1)環氧化合物B:環氧乙烷(Aldrich公司製,以下,稱為「EO」)
‧環氧當量(WPE):44g/eq.
(2)環氧化合物C:環氧丙烷(和光純藥工業股份有限公司製,以下,稱為「PO」)
‧環氧當量(WPE):58g/eq.
(3)環氧化合物D:1,2-環氧丁烷(東京化成工業股份有限公司製,以下,稱為「12EB」)
‧環氧當量(WPE):72 g/eq.
(4)環氧化合物E:1,2-環氧戊烷(東京化成工業股份有限公司製,以下,稱為「12EP」)
‧環氧當量(WPE):86g/eq.
(5)環氧化合物F:1,2-環氧己烷(東京化成工業股份有限公司製,以下,稱為「12EH」)
‧環氧當量(WPE):100g/eq.
(6)環氧化合物G:1,2-環氧庚烷(東京化成工業股份有限公司製,以下,稱為「12EHP」)
‧環氧當量(WPE):114g/eq.
(7)環氧化合物H:1,2-環氧辛烷(和光純藥工業股份有限公司製,以下,稱為「12EO」)
‧環氧當量(WPE):128g/eq.
(8)環氧化合物I:1,2-環氧癸烷(和光純藥工業股份有限公司製,以下,稱為「12ED」)
‧環氧當量(WPE):156g/eq.
(9)環氧化合物J:1,2-環氧十二烷(和光純藥工業股份有限公司製,以下,稱為「12EDD」)
‧環氧當量(WPE):184g/eq.
(10)環氧化合物K:1,2-環氧十四烷(和光純藥工業股份有限公司製,以下,稱為「12ETD」)
‧環氧當量(WPE):212g/eq.
(11)環氧化合物L:1,2-環氧十六烷(東京化成工業股份有限公司製,以下,稱為「12EHD」)
‧環氧當量(WPE):240g/eq.
(12)環氧化合物M:1,2-環氧十八烷(東京化成工業股份有限公司製,以下,稱為「12EOD」)
‧環氧當量(WPE):268g/eq.
(13)環氧化合物N:1,2-環氧二十烷(東京化成工業股份有限公司製,以下,稱為「12EEC」)
‧環氧當量(WPE):297g/eq.
(14)環氧化合物A:苯基縮水甘油醚(和光純藥工業股份有限公司製,以下,稱為「PGE」)
‧環氧當量(WPE):150g/eq.
(15)環氧化合物O:雙酚A型環氧化合物(以下,稱為「Bis-A-1」)
‧商品名:旭化成環氧(Asahi Kasei Epoxy)股份有限公司
製,「AER」
‧環氧當量(WPE):189g/eq.
(16)環氧化合物P:氫化雙酚A型環氧化合物(以下,稱為「氫化Bis-A」)
‧商品名:Japan Epoxy Resins公司製,「YX8000」
‧環氧當量(WPE):205 g/eq.
(17)環氧化合物Q:雙酚A型環氧化合物(以下,稱為「Bis-A-2」)
‧商品名:旭化成環氧股份有限公司製,「AER」
‧環氧當量(WPE):480g/eq.
(18)環氧化合物R:雙酚A型環氧化合物(以下,稱為「Bis-A-3」)
‧商品名:旭化成環氧股份有限公司製,「AER」
‧環氧當量(WPE):560g/eq.
(19)環氧化合物S:雙酚A型環氧化合物(以下,稱為「Bis-A-4」)
‧商品名:旭化成環氧股份有限公司製,「AER」
‧環氧當量(WPE):650g/eq.
(20)環氧化合物T:環氧環戊烷(Aldrich公司製,以下,稱為「C5O」)
‧環氧當量(WPE):84 g/eq.
(21)環氧化合物U:環氧環己烷(Aldrich公司製,以下,稱為「C6O」)
‧環氧當量(WPE):98g/eq.
(22)環氧化合物V:環氧環庚烷(Aldrich公司製,以下,稱為「C7O」)
‧環氧當量(WPE):112g/eq.
(23)環氧化合物W:環氧環辛烷(Aldrich公司製,以下,稱為「C8O」)
‧環氧當量(WPE):126g/eq.
(24)環氧化合物X:脂環式環氧化合物(以下,稱為「CEL」)
‧商品名:Daicel化學工業股份有限公司,「CELLOXIDE 2021P」
‧環氧當量(WPE):131g/eq.
(25)環氧化合物Y:雙(2,3-環氧丙基)二硫化物(以下,稱為「BEDS」)
依日本特開2002-194083中記載之方法合成BEDS。
‧環氧當量(WPE):91g/eq.
(26)環氧化合物Z:1,3-雙(3-環氧丙氧基丙基)-1,1,3,3-四甲基二矽氧烷(以下,稱為「BGTD」)
‧商品名:信越化學工業股份有限公司,「LS-7970」
‧環氧當量(WPE):182g/eq.
(27)環氧化合物AA:雙[2-(3,4-環氧環己基)乙基]四甲基二矽氧烷(以下,稱為「BCTD」)
‧商品名:Gelest,Inc.,「SIB 1092.0」
‧環氧當量(WPE):192g/eq.
(28)環氧化合物AB:1,3,5,7-四-(3-環氧丙氧基丙基)
四甲基環四矽氧烷(以下,稱為「TGCS」)
依Euro.Polym.J.2010,46,1545.記載的方法,合成TGCS。
‧環氧當量(WPE):174g/eq.
(29)環氧化合物AC:1,3,5,7-四-[2-(3,4-環氧環己基乙基)]四甲基環四矽氧烷(以下,稱為「TCCS」)
依日本特開2000-103859記載之方法,合成TCCS。
‧環氧當量(WPE):184g/eq.
(30)環氧化合物AD:丁二烯單氧化物(和光純藥工業股份有限公司製,以下,稱為「BDMO」)
‧環氧當量(WPE):70g/eq.
(31)環氧化合物AE:1,2-環氧-5-己烯(和光純藥股份有限公司製,以下,稱為「EPHE」)
‧環氧當量(WPE):98g/eq.
(32)環氧化合物AF:烯丙基縮水甘油醚(和光純藥股份有限公司製,以下,稱為「AGE」)
‧環氧當量(WPE):114g/eq.
(33)環氧化合物AG:1,2-環氧-4-乙烯基環己烷(Aldrich公司製,以下,稱為「EVCH」)
‧環氧當量(WPE):124g/eq.
(34)環氧化合物AH:甲基丙烯酸縮水甘油酯(和光純藥股份有限公司製,以下,稱為「GLMT」)
‧環氧當量:142g/eq
(35)硫雜化劑:硫脲(和光純藥工業股份有限公司製,以下,稱為「TU」)
(36)羥基化合物A:1,2-丙二醇(和光純藥工業股份有限公司製,以下,稱為「12PG」)
(37)羥基化合物B:1,3-丙二醇(和光純藥工業股份有限公司製,以下,稱為「13PG」)
(38)多元羥基化合物C:1,2-丁烷二醇(和光純藥工業股份有限公司製,以下,稱為「12BD」)
(39)多元羥基化合物D:1,3-丁烷二醇(和光純藥工業股份有限公司製,以下,稱為「13BD」)
(40)醚化合物A:二甲醇縮甲醛(formaldehyde dimethyl acetal)(Aldrich公司製,以下,稱為「MECA」)
(41)醚化合物B:1,3-二烷(Aldrich公司製,以下,稱為「MECB」)
(42)醚化合物C:1,4-二烷(Aldrich公司製,以下,稱為「MECC」)
(43)醚化合物D:1,2-二甲氧基乙烷(Aldrich公司製,以下,稱為「MECD」)
(44)醚化合物E:1,2-二乙氧基乙烷(Aldrich公司製,以下,稱為「MECE」)
(45)醚化合物F:二乙二醇二甲基醚(Aldrich公司製,以下,稱為「MECF」)
(46)醚化合物G:二乙二醇二乙基醚(Aldrich公司製,以下,稱為「MECG」)
(47)醚化合物H:1,2-雙(2-甲氧基乙氧基)乙烷(和光純藥工業股份有限公司製,以下,稱為「MECH」)
(48)醚化合物I:2,2-二乙基-1,4-二烷(Aldrich公司製,以下,稱為「MECI」)
(49)醚化合物J:12-冠-4(Aldrich公司製,以下,稱為「MEC J」)
(50)醚化合物K:乙二醇二丁基醚(和光純藥工業股份有限公司製,以下,稱為「MECK」)
(51)醚化合物L:雙[2-(2-甲氧基乙氧基)乙基]醚(和光純藥工業股份有限公司製,以下,稱為「MECL」)
(52)醚化合物M:2-(四氫糠氧基)四氫吡喃(和光純藥股份有限公司製,以下,稱為「MECM」)
(53)醚化合物N:15-冠-5(Aldrich公司製,以下,稱為「MECN」)
(54)醚化合物O:雙(2-丁氧基乙基)醚(和光純藥股份有限公司製,以下,稱為「MECO」)
(55)醚化合物P:苯并-12-冠-4(和光純藥股份有限公司製,以下,稱為「MECP」)
(56)醚化合物Q:18-冠-6(Aldrich公司製,以下,稱為「MECQ」)
(57)醚化合物R:苯并-15-冠-5(和光純藥股份有限公司製,以下,稱為「MECR」)
(58)醚化合物S:苯并-18-冠-6(Aldrich公司製,以下,稱為「MECS」)
(59)醚化合物T:2,3-萘并-15-冠-5(和光純藥工業股份有限公司製,以下,稱為「MECT」)
(60)醚化合物U:二環己烷并-18-冠-6(和光純藥工業股份有限公司製,以下,稱為「MECU」)
(61)醚化合物V:二苯并-24-冠-8(Aldrich公司製,以下,稱為「MECV」)
(62)醚化合物W:二環己烷并-24-冠-8(和光純藥工業股份有限公司製,以下,稱為「MECW」)
(63)醚化合物X:二苯并-30-冠-10(Aldrich公司製,以下,稱為「MECX」)
(64)醚化合物Y:1,14-雙(2-萘氧基)-3,6,9,12-四氧雜十四烷(Aldrich公司製,以下,稱為「MECY」)
(65)醚化合物Z:2,2’-聯萘基-14-冠-4(和光純藥股份有限公司製,以下,稱為「MECZ」)
(66)三價磷化合物A:三甲基膦(Aldrich公司製,以下,稱為「3PCA」)
(67)三價磷化合物B:乙基二甲基膦(以下,稱為「3PCB」)
依Inorganica Chemica Acta 1980,41,161-164記載之方法,合成3PCB。
(68)三價磷化合物C:二乙基甲基膦(以下,稱為
「3PCC」)
依Inorganica Chemica Acta 1980,41,161-164記載之方法,合成3PCC。
(69)三價磷化合物D:三乙基膦(Aldrich公司製,以下,稱為「3PCD」)
(70)三價磷化合物E:三-正-丙基膦(Aldrich公司製,以下,稱為「3PCE」)
(71)三價磷化合物F:三異丙基膦(Aldrich公司製,以下,稱為「3PCF」)
(72)三價磷化合物G:二-三級-丁基甲基膦(Aldrich公司製,以下,稱為「3PCG」)
(73)三價磷化合物H:三級-丁基-二-異丙基膦(Aldrich公司製,以下,稱為「3PCH」)
(74)三價磷化合物I:三-正-丁基膦(Aldrich公司製,以下,稱為「3PCI」)
(75)三價磷化合物J:三異丁基膦(Aldrich公司製,以下,稱為「3PC J」)
(76)三價磷化合物K:三-三級-丁基膦(Aldrich公司製,以下,稱為「3PCK」)
(77)三價磷化合物L:二-三級-丁基新戊基膦(Aldrich公司製,以下,稱為「3PCL」)
(78)三價磷化合物M:二-三級-丁基-環己基膦(Aldrich公司製,以下,稱為「3PCM」)
(79)三價磷化合物N:二環己基乙基膦(Aldrich公司
製,以下,稱為「3PCN」)
(80)三價磷化合物O:三環戊基膦(Aldrich公司製,以下,稱為「3PCO」)
(81)三價磷化合物P:三級-丁基-二環己基膦(Aldrich公司製,以下,稱為「3PCP」)
(82)三價磷化合物Q:三環己基膦(和光純藥工業股份有限公司製,以下,稱為「3PCQ」)
(83)三價磷化合物R:三-正-辛基膦(Aldrich公司製,以下,稱為「3PCR」)
(84)三價磷化合物S:二(1-金剛烷基)丁基膦(Aldrich公司製,以下,稱為「3PCS」)
(85)三價磷化合物T:三苯基膦(Aldrich公司製,以下,稱為「3PCT」)
(86)三價磷化合物U:二苯基(對-甲苯基)膦(和光純藥股份有限公司製,以下,稱為「3PCU」)
(87)三價磷化合物V:二苯基(鄰-甲氧基苯基)膦(和光純藥股份有限公司製,以下,稱為「3PCV」)
(88)三價磷化合物W:4-(二甲基胺基苯基)二苯基膦(Aldrich公司製,以下,稱為「3PCW」)
(89)三價磷化合物X:五氟苯基二苯基膦(和光純藥股份有限公司製,以下,稱為「3PCX」)
(90)三價磷化合物Y:雙(鄰-甲氧基苯基)苯基膦(和光純藥股份有限公司製,以下,稱為「3PCY」)
(91)三價磷化合物Z:雙(五氟苯基)苯基膦(和光純藥
股份有限公司製,以下,稱為「3PCZ」)
(92)三價磷化合物AA:三-鄰-甲苯基膦(和光純藥股份有限公司製,以下,稱為「3PCAA」)
(93)三價磷化合物AB:三-間-甲苯基膦(和光純藥股份有限公司製,以下,稱為「3PCAB」)
(94)三價磷化合物AC:三-對-甲苯基膦(和光純藥股份有限公司製,以下,稱為「3PCAC」)
(95)三價磷化合物AD:參(鄰-甲氧基苯基)膦(和光純藥股份有限公司製,以下,稱為「3PCAD」)
(96)三價磷化合物AE:參(對-甲氧基苯基)膦(和光純藥股份有限公司製,以下,稱為「3PCAE」)
(97)三價磷化合物AF:參(2,4-二甲基苯基)膦Aldrich公司製,以下,稱為「3PCAF」)
(98)三價磷化合物AG:三(2,5-二甲苯基)膦(和光純藥股份有限公司製,以下,稱為「3PCAG」)
(99)三價磷化合物AH:三(3,5-二甲苯基)膦(和光純藥股份有限公司製,以下,稱為「3PCAH」)
(100)三價磷化合物AI:參(2,6-二甲氧基苯基)膦(Aldrich公司製,以下,稱為「3PCAI」)
(101)三價磷化合物A J:參(2,4,6-三甲基苯基)膦(Aldrich公司製,以下,稱為「3PCA J」)
(102)三價磷化合物AK:參(2,4,6-三甲氧基苯基)膦(Aldrich公司製,以下,稱為「3PCAK」)
(103)三價磷化合物AL:參(3-氟苯基)膦(和光純藥股
份有限公司製,以下,稱為「3PCAL」)
(104)三價磷化合物AM:參(對-氟苯基)膦(和光純藥股份有限公司製,以下,稱為「3PCAM」)
(105)三價磷化合物AN:參(五氟苯基)膦(和光純藥股份有限公司製,以下,稱為「3PCAN」)
(106)三價磷化合物AO:參(4-三氟甲基苯基)膦(Aldrich公司製,以下,稱為「3PCAO」)
(107)三價磷化合物AP:參[3,5-雙(三氟甲基)苯基]膦(Aldrich公司製,以下,稱為「3PCAP」)
(108)三價磷化合物AQ:環己基二苯基膦(Aldrich公司製,以下,稱為「3PCAQ」)
(109)三價磷化合物AR:二環己基苯基膦(Aldrich公司製,以下,稱為「3PCAR」)
(110)三價磷化合物AS:2-[二(三級-丁基)膦基]-1,1’-聯苯(Aldrich公司製,以下,稱為「3PCAS」)
(111)三價磷化合物AT:2-(二環己基膦基)-1,1’-聯苯(Aldrich公司製,以下,稱為「3PCAT」)
(112)三價磷化合物AU:1,2-雙(二甲基膦基)乙烷(Aldrich公司製,以下,稱為「3PCAU」)
(113)三價磷化合物AV:1,2-雙(二乙基膦基)乙烷(Aldrich公司製,以下稱為「3PCAV」)
(114)三價磷化合物AW:二環己基[(二環己基膦基)甲基]膦(Aldrich公司製,以下,稱為「3PCAW」)
(115)三價磷化合物AX:1,2-雙(二環己基膦基)乙烷
(Aldrich公司製,以下,稱為「3PCAX」)
(116)三價磷化合物AY:1,3-雙(二環己基膦基)丙烷(Aldrich公司製,以下,稱為「3PCAY」)
(117)三價磷化合物AZ:1,4-雙(二環己基膦基)丁烷(Aldrich公司製,以下,稱為「3PCAZ」)
(118)三價磷化合物BA:1,2-雙(2,5-二甲基磷雜環戊烷基)乙烷(Aldrich公司製,以下,稱為「3PCBA」)
(119)三價磷化合物BB:1,1’-三級-丁基-2,2’-二磷雜環戊烷(Aldrich公司製,以下,稱為「3PCBB」)
(120)三價磷化合物BC:1-{2-[2,5-二乙基-1-磷雜環戊烷基]乙基}-2,5-二乙基磷雜環戊烷(Aldrich公司製,以下,稱為「3PCBC」)
(121)三價磷化合物BD:1-{2-[2,5-二異丙基-1-磷雜環戊烷基]乙基}-2,5-二異丙基磷雜環戊烷(Aldrich公司製,以下,稱為「3PCBD」)
(122)三價磷化合物BE:1,2-雙(二苯基膦基)乙烷(Aldrich公司製,以下,稱為「3PCBE」)
(123)三價磷化合物BF:1,3-雙(二苯基膦基)丙烷(Aldrich公司製,以下,稱為「3PCBF」)
(124)三價磷化合物BG:1,4-雙(二苯基膦基)丁烷(Aldrich公司製,以下,稱為「3PCBG」)
(125)三價磷化合物BH:2,2’-雙(二苯基膦基)-1,1’-聯萘(Aldrich公司製,以下,稱為「3PCBH」)
(126)三價磷化合物BI:2,2’-雙[二(3,5-二甲苯基)
膦基]-1,1’-聯萘(2,2’-雙[二(3,5-二甲基苯基)膦基]-1,1’-聯萘),(Aldrich公司製,以下,稱為「3PCBI」)
(127)三價磷化合物B J:1,1’-雙(二異丙基膦基)二茂鐵(東京化成工業股份有限公司製,以下,稱為「3PCB J」)
(128)三價磷化合物BK:1,1’-雙(二-三級-丁基膦基)二茂鐵(東京化成工業股份有限公司製,以下,稱為「3PCBK」)
(129)三價磷化合物BL:1,1’-雙(二苯基膦基)二茂鐵(Aldrich公司製,以下,稱為「3PCBL」)
(130)三價磷化合物BM:1,1’-雙[2,5-二甲基磷雜環戊烷基]二茂鐵(Aldrich公司製,以下,稱為「3PCBM」)
(131)三價磷化合物BN:雙(2-二苯基膦基乙基)苯基膦(Aldrich公司製,以下,稱為「3PCBN」)
(132)三價磷化合物BO:參[2-(二苯基膦基)乙基]膦(Aldrich公司製’以下’稱為「3PCBO」)
(133)酮化合物A:丙酮(Aldrich公司製,以下,稱為「MKCA」)
(134)酮化合物B:2-丁酮(Aldrich公司製,以下,稱為「MKCB」)
(135)酮化合物C:環丁酮(Aldrich公司製,以下,稱為「MKCC」)
(136)酮化合物D:3-戊酮(Aldrich公司製,以下,稱
為「MKCD」)
(137)酮化合物E:3-甲基-2-丁酮(Aldrich公司製,以下,稱為「MKCE」)
(138)酮化合物F:環戊酮(Aldrich公司製,以下,稱為「MKCF」)
(139)酮化合物G:3-己酮(Aldrich公司製,以下,稱為「MKCG」)
(140)酮化合物H:3,3-二甲基-2-丁酮(Aldrich公司製,以下,稱為「MKCH」)
(141)酮化合物I:3-甲基-2-戊酮(Aldrich公司製,以下,稱為「MKCI」)
(142)酮化合物J:環己酮(Aldrich公司製,以下,稱為「MKCJ」)
(143)酮化合物K:3-庚酮(Aldrich公司製,以下,稱為「MKCK」)
(144)酮化合物L:3-辛酮(Aldrich公司製,以下,稱為「MKCL」)
(145)酮化合物M:環辛酮(Aldrich公司製,以下,稱為「MKCM」)
(146)酮化合物N:5-壬酮(Aldrich公司製,以下,稱為「MKCN」)
(147)酮化合物O:環壬酮(Aldrich公司製,以下,稱為「MKCO」)
(148)酮化合物P:2-癸酮(Aldrich公司製,以下,稱
為「MKCP」)
(149)酮化合物Q:環癸酮(Aldrich公司製,以下,稱為「MKCQ」)
(150)酮化合物R:2-十一烷酮(Aldrich公司製,以下,稱為「MKCR」)
(151)酮化合物S:3-十二烷酮(Aldrich公司製,以下,稱為「MKCS」)
(152)酮化合物T:環十二烷酮(Aldrich公司製,以下,稱為「MKCT」)
(153)酮化合物U:7-十三烷酮(Aldrich公司製,以下,稱為「MKCU」)
(154)酮化合物V:3-十四烷酮(Aldrich公司製,以下,稱為「MKCV」)
(155)酮化合物W:1-[1,1’-聯苯]-4-基-2-環己烷乙酮(Aldrich公司製,以下,稱為「MKCW」)
(156)酮化合物X:1-(4’-甲基[1,1’-聯苯]-4-基)-1-十八烷酮(Aldrich公司製,以下,稱為「MKCX」)
(157)酮化合物Y:2,3-丁烷二酮(Aldrich公司製,以下,稱為「MKCY」)
(158)酮化合物Z:2,3-戊烷二酮(Aldrich公司製,以下,稱為「MKCZ」)
(159)酮化合物AA:2,4-戊烷二酮(Aldrich公司製,以下稱為「MKCAA」)
(160)酮化合物AB:2,3-己烷二酮(Aldrich公司製,
以下,稱為「MKCAB」)
(161)酮化合物AC:2,5-己烷二酮(Aldrich公司製,以下,稱為「MKCAC」)
(162)酮化合物AD:1,2-環己烷二酮(Aldrich公司製,以下,稱為「MKCAD」)
(163)酮化合物AE:1,3-環己烷二酮(Aldrich公司製,以下,稱為「MKCAE」)
(164)酮化合物AF:1,4-環己烷二酮(Aldrich公司製,以下,稱為「MKCAF」)
(165)酮化合物AG:3-甲基-1,2-環戊烷二酮(Aldrich公司製,以下,稱為「MKCAG」)
(166)酮化合物AH:2,3-庚烷二酮(Aldrich公司製,以下,稱為「MKCAH」)
(167)酮化合物AI:雙環[2,2,1]庚烷-2,5-二酮(Aldrich公司製,以下,稱為「MKCAI」)
(168)酮化合物A J:1,4-環辛烷二酮(Aldrich公司製,以下,稱為「MKCAJ」)
(169)酮化合物AK:八氫-1,5-萘二酮(Aldrich公司製,以下,稱為「MKCAK」)
(170)酮化合物AL:1,2-環癸烷二酮(Aldrich公司製,以下,稱為「MKCAL」)
(171)酮化合物AM:3,9-十一烷二酮(Aldrich公司製,以下,稱為「MKCAM」)
(172)酮化合物AN:1,2-環十二烷二酮(Aldrich公司
製,以下,稱為「MKCAN」)
(173)酮化合物AO:1,6-二苯基-1,6-己烷二酮(Aldrich公司製,以下,稱為「MKCAO」)
(174)酮化合物AP:2-乙醯基-1,3-環戊烷二酮(Aldrich公司製,以下,稱為「MKCAP」)
(175)酮化合物AQ:1,3-二苯基-1,2,3-丙烷三酮(Aldrich公司製,以下,稱為「MKCAQ」)
(176)酮化合物AR:2,6-二苄醯基環己酮(Aldrich公司製,以下,稱為「MKCAR」)
(177)酮化合物AS:3,4-二乙醯基-2,5-己烷二酮(Aldrich公司製,以下,稱為「MKCAS」)
(178)三鹵化硼化合物A:三氟化硼二甲基醚錯合物(和光純藥工業股份有限公司製,以下,稱為「BF3DME」)
(179)三鹵化硼化合物B:三氟化硼二乙基醚錯合物(和光純藥工業股份有限公司製,以下,稱為「BF3DEE」)
(180)三鹵化硼化合物C:三氟化硼二丁基醚錯合物(Aldrich公司製,以下,稱為「BF3DBE」)
(181)三鹵化硼化合物D:三氟化硼三級-丁基甲基醚錯合物(Aldrich公司製,以下,稱為「BF3TBME」)
(182)三鹵化硼化合物E:三氟化硼四氫呋喃錯合物(Aldrich公司製,以下,稱為「BF3THF」)
(183)三鹵化硼化合物F:三氟化硼甲基硫化物錯合物(Aldrich公司製,以下,稱為「BF3DMS」)
(184)三鹵化硼化合物G:三氟化硼甲醇錯合物(東京化成工業股份有限公司製,以下,稱為「BF3MNOL」)
(185)三鹵化硼化合物H:三氟化硼丙醇錯合物(Aldrich公司製,以下,稱為「BF3PNOL」)
(186)三鹵化硼化合物I:三氟化硼乙酸錯合物(Aldrich公司製,以下,稱為「BF3ACOH」)
(187)三鹵化硼化合物J:三氟化硼酚錯合物(Aldrich公司製,以下,稱為「BF3PHNOL」)
(188)三鹵化硼化合物K:三氟化硼乙基胺錯合物(Aldrich公司製,以下,稱為「BF3MEA」)
(189)三鹵化硼化合物L:三氟化硼哌啶錯合物(東京化成工業股份有限公司製,以下,稱為「BF3PPD」)
(190)三鹵化硼化合物M:三氯化硼(1.0mol/L二氯甲烷溶液)(Aldrich公司製,以下,稱為「BC13DCM」)
(191)三鹵化硼化合物N:三溴化硼(1.0mol/L二氯甲烷溶液)(Aldrich公司製’以下’稱為「BBr3DCM」)
(192)鏻鹽化合物:四-正-丁基鏻溴化物(和光純藥工業股份有限公司製,以下,稱為「TBPB」)
(193)胺化合物A:三丁基胺(和光純藥工業股份有限公司製,以下,稱為「TBA」)
(194)胺化合物B:N,N-二甲基環己基胺(和光純藥工業股份有限公司製,以下,稱為「DMCHA」)
(195)胺化合物C:N,N-二乙基乙醇胺(和光純藥工業
股份有限公司製,以下,稱為「DEENA」)
(196)鋶鹽化合物A:商品名「SI-25」(三新化學工業股份有限公司製,以下,稱為「S25」)
(197)鋶鹽化合物B:商品名「SI-60」(三新化學工業股份有限公司製,以下,稱為「S60」)
(198)鋶鹽化合物C:商品名「SI-100」(三新化學工業股份有限公司製,以下,稱為「S100」)
(199)鋶鹽化合物D:商品名「SI-150」(三新化學工業股份有限公司製,以下,稱為「S150」)
(200)鋶鹽化合物E:商品名「SI-180」(三新化學工業股份有限公司製,以下,稱為「S180」)
(201)添加化合物A:二氯甲烷(和光純藥工業股份有限公司製,以下,稱為「DCM」)
(202)添加化合物B:二乙基醚(和光純藥工業股份有限公司製,以下,稱為「DEE」)
(203)鏈轉移劑A:1-丁醇(和光純藥工業股份有限公司製,以下,稱為「CTRA」)
(204)鏈轉移劑B:2-丁醇(和光純藥工業股份有限公司製,以下,稱為「CTRB」)
(205)鏈轉移劑C:乙二醇(和光純藥工業股份有限公司製,以下,稱為「CTRC」)
(206)鏈轉移劑D:1,2-丙烷二醇(和光純藥工業股份
有限公司製,以下,稱為「CTRD」)
(207)鏈轉移劑E:2,3-丁烷二醇(和光純藥工業股份有限公司製,以下,稱為「CTRE」)
(208)鏈轉移劑F:丁-4-內酯(和光純藥工業股份有限公司製,以下,稱為「CTRF」)
(209)鏈轉移劑G:戊-4-內酯(Aldrich公司製,以下,「稱為CTRG」)
(210)鏈轉移劑H:碳酸伸乙酯(和光純藥工業股份有限公司製,以下,稱為「CTRH」)
(211)鏈轉移劑I:碳酸伸丙酯(Aldrich公司製,以下,稱為「CTRI」)
(212)鏈轉移劑J:1,3-二烷-2-酮(Aldrich公司製,以下,稱為「CTRJ」)
(213)鏈轉移劑K:六甲基環三矽氧烷(信越化學公司製,以下,稱為「CTRK」)
(214)鏈轉移劑L:八甲基環四矽氧烷(信越化學公司製,以下,稱為「CTRL」)
依以下之順序,製造環硫化合物。
(1)準備:在磁攪拌器上載有:配置有加入水及攪拌子之投入式冷卻加熱單元之水浴,或是加入油及攪拌子之油浴,設定為預定之溫度。
(2)將各原料,依表1之組成比率,放入至投入了攪拌
子的燒杯中並混合攪拌,作成硫雜化劑經溶解均勻的反應液。
(3)依表2之反應溫度、反應時間,進行反應。
(4)將反應液,靜置至溫度成為室溫為止。
(5)在反應液中加入二乙基醚(和光純藥工業股份有限公司製)及超純水(和光純藥工業股份有限公司製),混合攪拌後,停止攪拌,靜置到分離成二乙基醚層與超純水層為止,取出二乙基醚層。
(6)在上述(5)所得到之二乙基醚層中,加入飽和食鹽水,混合攪拌。之後,停止攪拌,靜置到分離成二乙基醚層與飽和食鹽水層為止,只取出二乙基醚層。
(7)在上述(6)所得到之二乙基醚層中加入無水硫酸鎂(和光純藥股份有限公司製),混合攪拌,藉由過濾以除去無水硫酸鎂,得到二乙基醚層。
(8)將上述(7)所得到之二乙基醚層中所含有之低沸點化合物(包含二乙基醚),使用旋轉蒸發器餾去,得到含有環硫化合物之反應生成物。
(9)將上述(8)所得到之反應生成物,藉由以下之(A)或是(B)之方法精製。
(A)參考在新實驗科學講座(丸善股份有限公司)及化學實驗手冊(技報堂出版股份有限公司)所例示之方法,以蒸餾精製環硫化合物。
(B)參考在新實驗科學講座(丸善股份有限公司)及化學實驗手冊(技報堂出版股份有限公司)例示之方法,藉由
管柱層析分析法分離,將所使用之展開溶劑餾去,而精製環硫化合物。
又,作為管柱層析分析方法之條件者,使用二氧化矽凝膠60N(球狀,中性)(關東化學股份有限公司製)作為填充劑,作為展開溶劑者是使用由正-己烷,緩慢的增加乙酸乙酯含量的混合溶劑。
在本製造例是藉由(A)的方法精製。
(10)算出上述(9)所得到之環硫化合物之WPT。
除了使用表1之組成比率,及表2之反應溫度、反應時間、精製方法以外,其餘藉由與製造例1同樣的方法,製造環硫化物化合物。
(1)準備:在磁攪拌器上,載有配置有投入式冷卻加熱單元之水浴,在此之中加入水及攪拌子。起動投入式冷卻加熱單元,設定水之溫度為20℃。
(2)在上述(1)之水浴中設置作成氮氣環境之反應容器,依表3之組成比率將各原料添加到反應容器中,攪拌1小時。
(3)反應容器中配置減壓餾去裝置,緩慢地進行減壓,最終減壓到2kPa為止,維持4小時。
(4)使用上述(3)所得到之反應液,藉由進行11B-NMR解析,確認形成了錯合物。
進行上述(1)至(4)之順序,準備三鹵化硼-醚化合物(以下,稱為「BF3-MECA」)。
(5)與上述(1)同樣之順序進行準備。
(6)在上述(5)之水浴中設置作成氮氣環境之反應容器,依表3之組成比率,將各原料添加到反應容器中,攪拌調製聚合性組成物。
(7)將上述(6)中調製之聚合性組成物,依表4之聚合條件聚合,得到聚合物。
除了使用表3至32之組成比率,及聚合條件以外,其餘藉由與實施例1同樣之方法,調製聚合性組成物,得到聚合物。
又,在實施例29至35、47至50、57至61、148至154、166至169、176至180、245至251、263至266、273至277、311至317、329至332、339至343,進行評估,於封管之耐壓瓶內準備聚合性評估及副反應性評估用之試樣。
將實施例1至360所調製之聚合性組成物之評估結果在表7、8、15、16、17、24、25、31、32中表示。
依表33、34之組成,藉由與上述實施例1同樣之方法,調製比較例1至56之聚合性組成物,依表35、36之聚合條件,得到聚合物。比較例23至29、41至44、51至55,
當進行評估時,於封管之耐壓瓶內準備聚合性評估及副反應性評估用之試樣。將比較例1至56所調製的聚合性組成物之評估結果在表35、36中表示。
如表1至36所示,本實施形態相關的,含有:(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼,與(C)環硫化合物之組成物,確認有安定性及聚合性優良,聚合聚合性組成物之際的副反應少,聚合該聚合性組成物可得到聚合物。相對於此,含有:選自由含有1個醚基之醚化合物、硫化合物、醇化合物、酸性化合物、含氮化合物1種之化合物,與三鹵化硼,與環硫化合物之聚合性組成物;或依照使用聚合環硫化合物之際所使用的公知之熱聚合促進劑的比較例,沒有確認到在安定性、聚合性、副反應性之評估中完全滿足者。
(1)將實施例71得到之聚合物,溶解到同重量之二氯甲烷(和光純藥股份有限公司製)中,得到聚合物溶液。
又,為了溶解聚合物而使用的化合物是無特別限定,只要可以溶解聚合物,並且在之後的步驟中可以除去者即可。
(2)在兩面經光學研磨之四方型石英玻璃板(GL Sciences Inc.股份有限公司製,尺寸10mm×10mm,厚度1mm)上,滴下上述(1)之聚合物溶液,用棒塗布機(第一理化股份有限公司,號碼線之號碼No.18)塗布成約41μm。
(3)在真空乾燥器(東京理化器械股份有限公司製,VOS-451D,又,使用的真空泵是ULVAC機工股份有限公司
製,小型油旋轉真空泵GCD-201X)中放入上述(2)得到之石英玻璃板,室溫,13Pa下,乾燥24小時。
又,乾燥之際的溫度、壓力是無特別限定,只要在聚合物溶液中所含有之揮發物不急劇揮發的條件下適當選擇即可。本實施例中是緩慢地進行減壓,最終成為13kPa。
(4)在乾燥後之石英玻璃板上之聚合物塗布部之全光線透過率,使用霧值計(Haze meter)(日本電色工業股份有限公司製,NDH-5000W)測定(將在此得到之全光線透過率,稱為「TLT0」)。本實施例的全光線透過率是86%。
(5)將乾燥後之石英玻璃板放入設定溫度為25℃,濕度60% RH之恆溫恆濕器(Espec股份有限公司製,PSL-4 J)中300天並保持之。
(6)在上述(5)得到之石英玻璃板上之聚合物塗布部之全光線透過率,與上述(4)同樣方式測定(將在此得到的全光線透過率,稱為「TLT300」)。
(7)TLT300在80%以上的情形判定為良好(「A」),85%以上的情形判定為特別良好(「AA」),此之外的情形判定為不良(「C」)。本實施例由於TLT300為80%,故判定為良好。
(8)將透明性之維持比率(以下,稱為「dTLT」),使用下述式算出。
dTLT(%)=TLT300/TLT0×100
(9)透明性之維持比率為90%以上的情形判定為良好
(「A」),95%以上的情形判定為特別良好(「AA」),此以外的情形判定為不良(「C」)。本實施例,由於透明性之維持比率為93%,故判定為良好。
(10)上述(7)及(9)之評估中,同時判定為特別良好的情形,及至少1個之評估中判定為良好,此以外之評估中判定為特別良好或是良好的情形,綜合判定當作合格(「AA」或是「A」)。此以外的情形是作為完全不合格(「C」)。
又,本實施例,由於TLT300是80%故為良好(「A」),dTLT是93%故為良好(「A」),由於兩評估中同為良好,故綜合判定為判定良好(「A」)。
除了使用表37中記載之實施例所得到之聚合物以外,其餘是藉由與實施例361同樣之方法,評估塗布有聚合物之玻璃基板。
如表37所示,本實施形態相關的,將含有(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼,與(C)環硫化合物的組成物加以聚合而得到之聚合物,確認到即使長期保管透明性之變化仍少。
用以下之順序,算出聚合物中之乙烯鍵含量。
(1)在試樣瓶中,秤取10mg之聚合物,與20mg之內部標準物質,再加入氯仿-d(和光純藥工業股份有限公司製),調整全體量為1g。
‧內部標準物質:1,1,2,2-四溴乙烷(東京化成工業股份有限公司製,以下,稱為「TBE」)
(2)將上述(1)之溶液,移到直徑4mm φ之NMR管中,以下述條件,測定1H-NMR。
傅立葉變換核磁共振裝置:日本電子股份有限公司製「ECA700型」
核種:1H
累積次數:30000次
由上述測定結果,用以下之順序,算出聚合物中之乙烯鍵含量。
(3)由1H-NMR圖表,算出源自乙烯基之波峰之面積值。
在此,源自乙烯基之波峰是指源自構成乙烯基之烴上1個氫的波峰,適當選擇與源自除了源自構成聚合物之乙
烯基的氫以外之氫所得之波峰不重複的波峰。
(4)由1H-NMR圖表,算出源自內部標準物質之波峰之面積值。
(5)將上述(3)及(4)所算出之面積值,代入下述式,求出乙烯鍵含量(%)。
乙烯鍵含量(%)=VINA×(TBEG/TBEM)×(2/TBEA)/×VINM/POLG×100
VINA:源自乙烯基之波峰之面積值
VINM:乙烯基之物質量(本實施例中是相當於C=C鍵的24)
TBEA:源自TBE之2個氫的波峰之面積值
TBEG:在調製進行1H-NMR測定之溶液之際使用的TBE之重量(g)(本實施例中是20mg)
TBEM:TBE之分子量
POLG:在調製進行1H-NMR測定之溶液之際使用之聚合物的重量(g)(本實施例中是10mg)
聚合物在不溶解於氯仿-d中的情形,藉由以下之順序,算出聚合物中之乙烯鍵含量。
(1)將聚合物1g,與內部標準物質0.1g之混合物,使用凍結粉碎機,作成粉體。
‧內部標準物質:1,1,1,2,2,2-六氯乙烷(Aldrich公司製,以下,稱為「HCE」)
(2)將上述(1)之試料,移到直徑4mm φ之NMR管中,
以下述條件,測定13C-NMR。
傅立葉變換核磁共振裝置:日本電子股份有限公司製「ECA700型」
核種:13C
測定方法:DD/MAS法
脈沖寛:45°
累積次數:100000次
MAS:10000Hz
由上述測定結果,用以下之順序,算出聚合物中之乙烯鍵含量。
(3)由13C-NMR圖表,算出源自乙烯基之波峰之面積值。
在此,源自乙烯基之波峰是指,源自構成乙烯基之碳的波峰,適當選擇與源自除了來自構成聚合物之乙烯基的碳以外之碳之波峰不重複的波峰。
(4)由13C-NMR圖表,算出源自內部標準物質之波峰之面積值。
(5)將上述(3)及(4)所算出之面積值,代入下述式,求得乙烯鍵含量(%)。
乙烯鍵含量(%)=VICA×(HCEG/HCEM)×(2/HCEA)/×VICM/POCG×100
VICA:源自乙烯基之波峰之面積值
VICM:乙烯基之物質量(本實施例中是相當於C=C鍵之24)
HCEA:源自TBE之2個氫之波峰的面積值
HCEG:在調製進行13C-NMR測定之溶液之際使用的HCE之重
量(g)(本實施例中是0.1g)
HCEM:HCE之分子量
POCG:在調製進行13C-NMR測定之溶液之際使用的聚合物之重量(g)(本實施例中是1g)
ICP測定是用以下之順序進行。
(1)在鐵氟龍(Teflon)(註冊商標)製容器中,放入聚合物及硝酸,加熱、攪拌使其溶解。
又,在聚合物只用硝酸則無法溶解的情形,使用硝酸與氟酸之混合液。
又,在聚合物只用加熱則無法溶解的情形,照射微波。
如上述,作為在聚合物之溶解有困難時可以使用的手法者,係參考「ICP發光分析/ICP質量分析之基礎與實際-熟練地使用裝置用(Ohm公司製)」或「Practical Guide to ICP-MS:A Tutorial for Beginners,Second Edition (Practical Spectroscopy)(CRC Press公司製)」,而實施。
(2)將上述(1)得到之溶解液,取出到鐵氟龍(註冊商標)燒杯中,在加熱板上乾燥凝固。
(3)在上述(2)之乾燥凝固物中,添加硝酸與鹽酸之混合液,在加熱板上加熱溶解。
(4)在上述(3)之溶解液中加入純水,作成一定溶量。
(5)將上述(4)之溶液,使用ICP質量分析裝置(Agilent公司製,「7500cs」)或是ICP發光分光分析裝置(Agilent公司製,「730-ES」),測定聚合物中之硼、及磷
原子含量。
(1)準備:在磁攪拌器上,載有配置有投入式冷卻加熱單元之水浴,在此之中放入水及攪拌子。起動投入式冷卻加熱單元,設定水之溫度成為20℃。
(2)在上述(1)之水浴中設置作成氮氣環境之反應容器,將1,4-二烷24質量%、三氟化硼二乙基醚錯合物76質量%,添加到反應容器中,攪拌1小時。
(3)在反應容器中配置減壓餾去裝置,緩緩的進行減壓,最終減壓到2 kPa為止,維持4小時。
(4)使用在上述(3)得到者,藉由進行11B-NMR解析,確認形成錯合物。
(5)與上述(1)同樣之順序進行準備。
(6)將作成氮氣環境的反應容器設置在上述(5)之水浴中,依表18之組成比率,添加到反應容器內,攪拌調製組成物。
(7)將上述(6)中經調製之組成物,依表19之聚合條件聚合,得到聚合物。
(8)將上述(7)所得到之聚合物的環硫基反應率,藉由表19之方法測定,確認來源之環硫化合物中之環硫基聚合。
(9)在真空乾燥器(東京理化器械股份有限公司製,
VOS-451D,同時,真空泵是使用ULVAC機工股份有限公司製,小型油旋轉真空泵GCD-201X)中放入上述(8)得到之聚合物,100℃、13Pa下乾燥24小時。
又,乾燥之際之溫度、壓力是無特別限定,只要適當選擇在聚合物內所含有之揮發物為不會急劇地揮發之條件即可。本實施例中是緩慢地進行減壓,最終成為13kPa。
(10)將上述(9)所得到之聚合物中的乙烯基含量,藉由表19之方法測定。
(11)將上述(9)得到之聚合物,溶解到同重量之二氯甲烷(和光純藥股份有限公司製)中,得到聚合物溶液。
又,為了溶解聚合物而使用之化合物是無特別限定,只要將聚合物溶解,並且可以在後面之步驟中除去者即可。
(12)在兩面經光學研磨之四方型石英玻璃板(GL Sciences Inc.股份有限公司製,尺寸10mm×10mm,厚度1mm)上,將上述(11)之聚合物溶液滴下,用棒塗布機(第一理化股份有限公司,號碼線之號碼No.18)塗布成約41μm。
(13)在真空乾燥器(東京理化器械股份有限公司製,VOS-451D,又,使用的真空泵是ULVAC機工股份有限公司製,小型油旋轉真空泵GCD-201X)內放入上述(12)得到之石英玻璃板,室溫、13Pa下,乾燥24小時。
又,乾燥之際之溫度、壓力是無特別限定,只要適當選擇在聚合物溶液中所含有之揮發物不會急劇揮發的條件
即可。本實施例中是緩慢地進行減壓,最終成為13kPa。
(14)將乾燥後之石英玻璃板,在設定溫度為130℃之恆溫器(Espec股份有限公司製,PVHC-332)中,放置1000小時並保持之。
(15)上述(14)所得到之石英玻璃板上之聚合物塗布部分之黃色指數(Yellow index)(以下,稱為「YI」),使用分光測色計(Konica minolta公司製,CM-3600d)測定。
又,本實施例中YI是1。
(16)YI為10以下的情形判定為良好(「A」),在5以下的情形判定為特別良好(「AA」),此以外的情形判定為不良(「C」)。本實施例,由於YI是1,判定為特別良好。
(17)在兩面經光學研磨之四方型石英玻璃板(GL Sciences Inc.股份有限公司製,尺寸10mm×10mm,厚度1mm)上,將上述(6)調製之組成物滴下,用棒塗布機(第一理化股份有限公司,號碼線之號碼No.18)塗布成約41μm。
(18)將上述(17)得到之石英玻璃板,依表格所示之聚合條件聚合,在石英玻璃板上得到聚合物。
(19)在真空乾燥器(東京理化器械股份有限公司製,VOS-451D,又,使用的真空泵是ULVAC機工股份有限公司製,小型油旋轉真空泵GCD-201X)中放入上述(18)得到之石英玻璃板,100℃、13Pa下,乾燥24小時。
又,乾燥之際之溫度、壓力是無特別限定,只要適當
選擇在聚合物內所含有之揮發物不會急劇揮發的條件即可。本實施例中是緩慢地進行減壓,最終成為13kPa。
(20)將在上述(19)得到之石英玻璃板,在設定溫度為130℃之恆溫器(Espec股份有限公司製,PVHC-332)中,放置1000小時並保持之。
(21)上述(20)所得到之石英玻璃板上之聚合物塗布部分之黃色指數(以下,稱為「YI」),使用分光測色計(Konica minolta公司製,CM-3600d)測定。
(22)YI為10以下的情形判定為良好(「A」),在5以下的情形判定為特別良好(「AA」),此以外的情形判定為不良(「C」)。
除了使用表38、39之組成比率,及表40、41之聚合條件之外,其餘藉由與實施例376同樣的方法,得到聚合物。將實施例377至419得到之聚合物評估結果在表40,41中表示。
又,實施例382至388、395至403,係在已封管的耐壓瓶內準備聚合物。
三鹵化硼-三價磷化合物(BF3-3PCR-1)之準備中,除了使用三-正-辛基膦72質量%、三氟化硼二乙基醚錯合物28質量%,使用表42之組成比率,表44之聚合條件之外,其餘是藉由與實施例376同樣之方法來進行。
除了使用表42、43之組成比率,及表44、45之聚合條件之外,其餘是藉由與實施例420同樣之方法,得到聚合物。將實施例421至463得到之聚合物評估結果在表44、45中表示。
又,實施例426至432、439至447,是在已封管之耐壓瓶內準備聚合物。
三鹵化硼-酮化合物(BF3-MKCJ-1)之準備中,除了使用環己酮41質量%、三氟化硼二乙基醚錯合物59質量%,使用表46之組成比率,表48之聚合條件之外,其餘藉由與實施例376同樣之方法進行。
除了使用表46、47之組成比率,及表48、49之聚合條件之外,其餘藉由與實施例464同樣之方法,得到聚合物。將實施例465至507得到之聚合物評估結果在表48、49中表示。
又,實施例470至476、483至491,係在己封管之耐壓瓶內準備聚合物。
依表50之組成,藉由與上述實施例376同樣之方法,調製比較例57至90之組成物,依表51之聚合條件,得到聚合物。將比較例57至79得到之聚合物評估結果在表51中表示。比較例80至90,由於在調製組成物之際,變成聚合物,故不能評估。
又,比較例57至63、71至79,係在已封管之耐壓瓶內準備聚合物。
如表38至51所示,確認本實施形態相關的,乙烯基含量為2質量%以下,環硫化合物之聚合物,即使在高溫下長期保持也變色少,高溫下之安定性高。
(1)準備:在磁攪拌器上,載有配置有投入式冷卻加熱
單元之水浴,在此之中放入水及攪拌子。起動投入式冷卻加熱單元,水之溫度設定成為20℃。
(2)將作成氮氣環境之反應容器設置在上述(1)之水浴中,將1,4-二烷24質量%、三氟化硼二乙基醚錯合物76質量%,添加到反應容器中,攪拌1小時。
(3)在反應容器中安裝減壓餾去裝置,緩慢地進行減壓,最終減壓到2kPa為止,維持4小時。
(4)使用上述(3)所得到者,藉由進行11B-NMR解析,確認形成錯合物。
(5)與上述(1)同樣之順序進行準備。
(6)將作成氮氣環境之反應容器設置在上述(5)之水浴中,依表52之組成比率,添加到反應容器中,攪拌調製組成物。
(7)將上述(6)中調製之組成物,依表54之聚合條件聚合,得到聚合物。
(8)將上述(7)得到之聚合物的環硫基反應率,藉由表54之方法測定,確認來源之環硫化合物中之環硫基聚合。
(9)使用上述(7)得到之聚合物,進行ICP測定,求得聚合物中之硼原子含量。
(10)在真空乾燥器(東京理化器械股份有限公司製,VOS-451D,又,使用的真空泵是ULVAC機工股份有限公司
製,小型油旋轉真空泵GCD-201X)中放入上述(7)得到之聚合物,50℃、13Pa下,乾燥24小時。
(11)將上述(10)得到之聚合物,移到己乾燥之玻璃製容器中,測定聚合物之重量(以下,稱為「JGWS」)。
(12)放到恆溫器(Espec公司製,IPHH-202)中,作成氮氣環境後,器內溫度作成150℃,保持1000小時。
(13)測定上述(12)得到之聚合物的重量(以下,稱為「JGWF」)。
(14)聚合物之重量變化(以下,稱為「JGW」),藉由以下之式算出。
JGW(%)=100-JGWF/JGWS×100
(15)JGW為5%以下之情形判定為良好(「A」),在2%以下之情形判定為特別良好(「AA」),此以外之情形判定為不良(「C」)。本實施例,由於JGW為5%,故判定為良好。
除了恆溫器之器內溫度設成200℃之外,其餘與TA法同樣方式進行。
除了使用表52、53之組成比率,及表54、55之聚合條件之外,其餘藉由與實施例508同樣之方法,得到聚合物。將實施例509至557得到之聚合物評估結果在表54、55中表示。
又,實施例517至523、530至538,係在經封管之耐壓瓶內準備聚合物。
三鹵化硼-三價磷化合物(BF3-3PCR-1)之準備中,除了使用三-正-辛基膦72質量%、三氟化硼二乙基醚錯合物體28質量%,使用表56之組成比率,表58之聚合條件之外,藉由與實施例508同樣之方法來進行。
除了使用表56、57之組成比率,及表58、59之聚合條件之外,其餘是藉由與實施例558同樣之方法,得到聚合物。將實施例559至607得到的聚合物評估結果在表58、59中表示。
又,實施例567至573、580至588,係在經封管之耐壓瓶內準備聚合物。
三鹵化硼-酮化合物(BF3-MKCJ-1)之準備中,除了使用環己酮41質量%、三氟化硼二乙基醚錯合物59質量%,使用表60之組成比率,表62之聚合條件之外,其餘藉由與實施例508同樣之方法進行。
除了使用表60、61之組成比率,及表62、63之聚合條件之外,其餘藉由與實施例608同樣之方法,得到聚合物。將實施例609至657得到之聚合物評估結果在表62、63中表示。
又,實施例617至623、630至638,係在經封管之耐壓瓶內準備聚合物。
依表64之組成,藉由與上述實施例508同樣之方法,調製比較例91至127之聚合性組成物,依表65之聚合條件,得到聚合物。
將比較例91至127得到之聚合物評估結果在表65中表示。
又,比較例91至97、105至113,係在經封管之耐壓瓶內準備聚合物。
如表52至65所示,確認本實施形態相關的,硼原子含量為1至6500 ppm,環硫化合物之聚合物,即使高溫下長期保持也揮發分少,高溫下之安定性高。
(1)準備:在磁攪拌器上,載有安裝有投入式冷卻加熱單元之水浴,在此之中放入水及攪拌子。起動投入式冷卻加熱單元,水之溫度設定為20℃。
(2)將作成氮氣環境的反應容器設置在上述(1)之水浴中,將三-正-辛基膦72質量%、三氟化硼二乙基醚錯合物28質量%,添加到反應容器中,攪拌1小時。
(3)在反應容器中安裝減壓餾去裝置,緩慢地進行減壓,最終減壓到2kPa為止,維持4小時。
(4)使用上述(3)得到者,進行藉由11B-NMR解析,確認形成錯合物。
(5)與上述(1)同樣之順序進行準備。
(6)將作成氮氣環境的反應容器設置在上述(5)之水浴中,依表34之組成比率,添加到反應容器中,攪拌調製組成物。
(7)將上述(6)中調製之組成物,依表35之聚合條件聚合,得到聚合物。
(8)上述(7)得到之聚合物的環硫基反應率,藉由表35之方法測定,確認來源之環硫化合物中之環硫基有聚合。
(9)使用上述(7)得到之聚合物,進行ICP測定,求得聚合物中之磷原子含量。
(10)將上述(7)得到之聚合物,溶解到同重量之二氯甲烷(和光純藥股份有限公司製)中,得到聚合物溶液。
又,為了溶解聚合物而使用的化合物是無特別限定,只要可以溶解聚合物,並且在之後的步驟中可以除去者即可。
(11)在兩面經光學研磨之四方型石英玻璃板(GL Sciences Inc.股份有限公司製,尺寸10mm×10mm,厚度1mm)上,滴下上述(1)之聚合物溶液,以棒塗布機(第一理化股份有限公司,號碼線之號碼No.18)塗布成約41μm。
(12)在真空乾燥器(東京理化器械股份有限公司製,VOS-451D,又,使用的真空泵是ULVAC機工股份有限公司製,小型油旋轉真空泵GCD-201X)中,放入上述(11)得到之石英玻璃板,室溫、13Pa下,乾燥24小時。
又,乾燥之際之溫度、壓力是無特別限定,只要適當選擇在聚合物溶液內所含有之揮發物不會急劇揮發的條件即可。本實施例中是緩慢地進行減壓,最終成為13kPa。
(13)將乾燥後之石英玻璃板,在以下之條件,進行耐候性試驗。
耐候性試驗機:Suga試驗機股份有限公司製「SX120」
試驗時間:5000小時
放射照度:60 W/m2
黑盤(Black panel)溫度:63℃
濕度:50%
(14)將上述(13)得到之石英玻璃板上之聚合物塗布部分之黃色指數(以下,稱為「YI」),使用分光測色計(Konicaminolta公司製,CM-3600d)測定。本實施例中YI是9。
(15)YI為10以下的情形判定為良好(「A」),在5以下的情形判定為特別良好(「AA」),此以外的情形判定為不良(「C」)。本實施例中,由於YI為9,故判定為良好。
(16)在兩面經光學研磨之四方型石英玻璃板(GL Sciences Inc.股份有限公司製,尺寸10mm×10mm,厚度1mm)上,滴下上述(6)調製之組成物,用棒塗布機(第一理化股份有限公司,號碼線之號碼No.18)塗布成約41μm。
(17)將上述(16)得到之石英玻璃板,依表格所示之聚合條件聚合,在石英玻璃上得到聚合物。
(18)將上述(17)得到之石英玻璃板,用以下之條件,進行耐候性試驗。
耐候性試驗機:Suga試驗機股份有限公司製「SX120」
試驗時間:5000小時
放射照度:60W/m2
黑盤溫度:63℃
濕度:50%
(19)將上述(18)得到之石英玻璃板上之聚合物塗布部分之黃色指數(以下,稱為「YI」),使用分光測色計(Konicaminolta公司製,CM-3600d)測定。
(20)YI為10以下的情形判定為良好(「A」),在5以下的情形判定為特別良好(「AA」),此以外的情形判定為不良(「C」)。
除了使用表66、67之組成比率,及表68、69之聚合條件之外,其餘是藉由與實施例658同樣之方法,得到聚合物。將實施例659至707所得到之聚合物評估結果在表68、69中表示。
又,實施例667至673、680至688,是在己封管的耐壓瓶內準備聚合物。
依表70之組成,藉由與上述實施例658同樣之方法,調製比較例125至158之組成物,依表71之聚合條件,得到聚合物。將比較例125至147所得到之聚合物評價結果在表71中表示。比較例148至158,由於在調製組成物之際,變成聚合物,故不能評估。
又,比較例125至131、139至147,係在己封管之耐壓瓶內準備聚合物。
如表66至71所示,確認本實施形態相關的,磷原子含量有1至14000ppm,環硫化合物之聚合物,即使以類似太陽光之光線長期間曝曬也是變色少,對光之安定性高。
(1)準備:在磁攪拌器上,載有安裝有投入式冷卻加熱
單元之水浴,在此之中放入水及攪拌子。起動投入式冷卻加熱單元,水之溫度設定為20℃。
(2)將作成氮氣環境之反應容器設置在上述(1)之水浴中,將1,4-二烷24質量%、三氟化硼二乙基醚錯合物76質量%,添加到反應容器中,攪拌1小時。
(3)反應容器中安裝減壓餾去裝置,緩慢地進行減壓,最終減壓到2kPa為止,維持4小時。
(4)使用上述(3)得到者,進行藉由11B-NMR解析,確認有形成錯合物。
(5)以與上述(1)同樣之順序進行準備。
(6)將作成氮氣環境之反應容器設置在上述(5)之水浴中,依表72之組成比率,添加到反應容器中,攪拌調製組成物。
(7)將上述(6)中調製之組成物,依表77之聚合條件聚合,得到聚合物。
又,混合指標γ是藉由以下之式(19)算出。
指標γ=α d/α t×100 (19)
在此,分別表示:α d:鏈轉移劑之物質量(mol)
α t:(C)環硫化合物中所含有的環硫基之物質量(mol)。
(8)上述(7)所得到之聚合物之環硫基反應率,藉由表77之方法測定,確認來源之環硫化合物中之環硫基是有聚合。
(9)在真空乾燥器(東京理化器械股份有限公司製,VOS-451D,又,使用的真空泵是ULVAC機工股份有限公司製,小型油旋轉真空泵GCD-201X)中,放入上述(7)得到之聚合物,於50℃、13Pa下,乾燥24小時。
(10)將上述(9)得到之聚合物,移到已乾燥之玻璃製容器中,測定聚合物之重量(以下,稱為「RGWS」)。
(11)放到恆溫器(Espac公司製,IPHH-202)中,作成氮氣環境後,器內溫度設定成180℃,保持1000小時。
(12)測定上述(11)得到之聚合物之重量(以下,稱為「RGWF」)。
(13)聚合物之重量變化(以下,稱為「RGW」),藉由以下之式算出。
RGW(%)=100-RGWF/RGWS×100
(14)RGW為5%以下之情形判定為良好(「A」),2%以下之情形判定為特別良好(「AA」),此以外之情形判定為不良(「C」)。本實施例由於RGW為1%,故判定為特別良好。
除了將恆溫器之器內溫度設定成250℃之外,與TA法同樣方式進行。
除了使用表72至76之組成比率,及表77至81之聚
合條件之外,藉由與實施例708同樣之方法,得到聚合物。將實施例709至860所得到之聚合物評估結果在表77至81中表示。
又,實施例738至744、751至765、772至786、793至800,係在已封管之耐壓瓶內準備聚合物。
三鹵化硼-三價磷化合物(BF3-3PCR-1)之準備中,除了使用三-正-辛基膦72質量%、三氟化硼二乙基醚錯合物28質量%,使用表82之組成比率,表87之聚合條件之外,藉由與實施例708同樣之方法進行。
使用表82至86之組成比率,及表87至91之聚合條件以外,其餘是藉由與實施例708同樣之方法,得到聚合物。將在實施例862至1013所得到之聚合物評估結果在表87至91中表示。
又,實施例891至897、904至918、925至939、946至953,係在已封管之耐壓瓶內準備聚合物。
三鹵化硼-酮化合物(BF3-MKCJ-1)之準備中,除了使用環己酮41質量%、三氟化硼二乙基醚錯合體59質量%,使用表92之組成比率,表97之聚合條件之外,藉由與實施例708同樣之方法進行。
除了使用表92至96之組成比率,及表97至101之聚
合條件之外,藉由與實施例708同樣之方法,得到聚合物。將實施例1015至1166所得到之聚合物評估結果在表97至101中表示。
又,實施例1044至1050、1057至1071、1078至1092、1099至1106,係在已封管之耐壓瓶內準備聚合物。
如表77至81、87至91、97至101所示,確認將本實施形態相關的,含有:(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與(B)三鹵化硼,與(C)環硫化合物,與(D)鏈轉移劑之組成物加以聚合所得到之聚合物及硬化物,即使長期保持在高溫下也揮發分少,在高溫下之安定性高。
本實施形態之組成物及聚合該組成物所成之聚合物或是硬化物,是作為下述者而具有產業上之可利用性:電子材料(絕緣體類、交流變壓器、開關裝置等之注模及電路單元,各種零組件之包裝,IC/LED/半導體之周邊材料[密封材、透鏡材、基板材、晶粒黏著(Die Bonding)材、晶片塗布材、積層板、光纖維、光波導、濾光器、電子零組件用之接著劑、塗布材、密封材、絕緣材、光阻、包膠
(encapsulation)材、裝填(potting)材、光碟之光透過層或層間絕緣層、導光板、抗反射膜等],發電器、馬達等之旋轉機線圈(coil)、繞組浸漬(winding impregnation)、印刷配線基板、積層板、絕緣板、中型絕緣體類、線圈類、連接器、端子、各種盒子類、電氣構件類等)、塗料(防蝕塗料、維修、船舶塗裝、耐蝕襯裡、汽車/家電製品用底塗層、飲料/啤酒罐、外面漆、擠壓管塗裝、一般防蝕塗裝、維修塗裝、木工製品用漆、汽車用電沉積底塗層、其他工業用電沉積塗裝、飲料/啤酒罐內面漆、線圈塗膜、圓桶/罐內面塗裝、耐酸襯裡、線瓷漆、絕緣塗料、汽車用底塗層、各種金屬製品之美裝兼防蝕塗裝、管內外面塗裝、電氣零組件絕緣塗裝等)、複合材料(化學工廠用管/桶類、飛機材、汽車構件、各種運動用品、碳纖維複合材料、聚芳醯胺纖維複合材料等)、土木建築材料(地板材、鋪裝材、薄膜、止滑兼薄層鋪裝、混凝土連接/加高、錨填入接著、預鑄混凝土接合、瓷磚接著、混凝土結構物之龜裂修補、台座之灌漿/調平、自來水及下水道設施之防蝕/防水塗裝、桶類之耐蝕積層襯裡、鐵結構物之防蝕塗裝、建築物外壁之膠黏塗裝等)、接著劑(金屬、玻璃、陶磁器、水泥混凝土、木材、塑膠等之同種或是異種材質之接著劑,汽車、鐵路車輛、飛機等之組合用接著劑,預製用複合平板製造用接著劑等:包含一液型、二液型、片狀型)、飛機/汽車/塑膠成形之模具(jig)及工具(沖壓模、拉伸模、配對模等樹脂模型,真空成形/吹塑成型用塑模、基準模型、鑄
物用圖案、積層模具及工具、各種檢査用模具及工具等)、改質劑/安定劑(纖維之樹脂加工、聚氯乙烯用安定劑、合成橡膠之添加劑等)、橡膠之改質劑(硫化劑、硫化促進劑等)。
Claims (24)
- 一種組成物,含有:(A)選自由含有2個以上醚基之醚化合物、三價磷化合物、及酮化合物所成群組中至少1種的化合物,(B)三鹵化硼,與(C)環硫化合物。
- 如申請專利範圍第1項所述之組成物,其中,前述醚化合物的醚基數是2至8。
- 如申請專利範圍第1項所述之組成物,其中,前述醚化合物之碳原子數為3至50。
- 如申請專利範圍第1項所述之組成物,其中,前述三價磷化合物為以下述式(1)所示之化合物,
[式中,a表示1以上之數,R1表示碳原子數1至33之鏈狀、分枝狀或是環狀的脂肪族烴基、取代或是無取代的芳香族烴基,或者是取代或是無取代之金屬茂基(metallocenyl),R2及R3各自獨立地表示碳原子數1至33之鏈狀、分枝狀或是環狀的脂肪族烴基、或者是取代或是無取代之芳香族烴基,R1與R2、R1與R3、或者是R2與R3可經連結,a為2以上時,存在複數個之R2及R3是可以相同也可以相異,R2彼此或者是R3彼此可經連結]。 - 如申請專利範圍第4項所述之組成物,其中,式(1)中,a為1,R1、R2、及R3全部為芳香族烴基,R1、R2、及R3之中至少1個為經取代之芳香族烴基。
- 如申請專利範圍第4項所述之組成物,其中,前述三價磷化合物之碳原子數為4至52。
- 如申請專利範圍第4項所述之組成物,其中,式(1)中,a為1至4。
- 如申請專利範圍第1項所述之組成物,其中,前述酮化合物為下述式(2)、(3)或是(4)所示之化合物,
[式中,a、c、d及f各自獨立地表示1以上的數,b及e各自獨立地表示2以上之數,R11及R12各自獨立地表示碳原子數1至20之鏈狀、分枝狀或是環狀的脂肪族烴基,或者是取代或是無取代之芳香族烴基,R13表示氫原子或是碳原子數1至20之鏈狀、分枝狀或是環狀之脂肪族,或者是取代或是無取代 之芳香族烴基,R11、R12、及R13可以互相連結,R14及R15各自獨立地表示碳原子數1至20之鏈狀、分枝狀或是環狀的脂肪族烴基,或者是取代或是無取代之芳香族烴基,R15彼此可以相同也可以相異,R14、R15及R15彼此可以互相連結,R16、R17及R18各自獨立地表示碳原子數1至20之鏈狀、分枝狀或是環狀的脂肪族烴基,或者是取代或是無取代之芳香族烴基,R16及R18彼此可以相同也可以相異,R16、R17或者是R18與R16或者是R18可以互相連結]。 - 如申請專利範圍第8項所述之組成物,其中,式(2)中,a為2時,2個酮基間之碳原子數為2至20。
- 如申請專利範圍第8項所述之組成物,其中,前述酮化合物之碳原子數為3至31。
- 如申請專利範圍第8項所述之組成物,其中,前述酮化合物之酮基數為1至8。
- 如申請專利範圍第1項所述之組成物,其中,前述(A)選自由含有2個以上醚基的醚化合物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與前述(B)三鹵化硼之至少一部份形成錯合物。
- 如申請專利範圍第1所述之組成物,其中,下述式(5)所示之表示前述(A)選自由含有2個以上醚基之醚化合 物、三價磷化合物、及酮化合物所成群組中至少1種之化合物,與前述(B)三鹵化硼之比率的指標α為1至1000,指標α=(α e+α p+α k)/α b (5)α e:前述醚化合物之醚基的物質量(mol)α p:前述三價磷化合物中所含有的三價磷原子之物質量(mol)α k:前述酮化合物之酮基的物質量(mol)α b:前述三鹵化硼之物質量(mol)。
- 如申請專利範圍第13項所述之組成物,其中,α p/α b為10以下。
- 如申請專利範圍第1項所述之組成物,其中,前述三鹵化硼為選自由三氟化硼、三氯化硼、及三溴化硼所成群組中至少1種的化合物。
- 如申請專利範圍第1項所述之組成物,其中,前述環硫化合物為只具有3員環硫醚結構作為聚合性官能基的化合物。
- 如申請專利範圍第1項所述之組成物,其中,前述三鹵化硼之物質量(mol),與前述環硫化合物中所含有之環硫基之物質量(mol)的比為1:10至1:100000。
- 如申請專利範圍第1項所述之組成物,其中,前述環硫化合物之環硫當量為65至700g/mol。
- 如申請專利範圍第1項所述之組成物,其中,前述環硫化合物具有下述式(6)、(7)、(8)或是(9)所示之部分結 構,
[式中,R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33及R34各自獨立地表示氫原子或者是碳原子數1至20之鏈狀、分枝狀或是環狀的脂肪族烴基,或者是取代或是無取代之芳香族烴基]。 - 一種聚合物,係將申請專利範圍第1項所述之組成物中的前述環硫化合物聚合而形成者。
- 一種製造聚合物之方法,將申請專利範圍第1項所述之 組成物中之前述環硫化合物,藉由加熱及/或是照射能量線而聚合。
- 一種聚合物,係將含有環硫化合物之組成物中的前述環硫化合物聚合而形成的聚合物,將該聚合物之全體質量當作基準,乙烯鍵之含量為2質量%以下。
- 一種聚合物,係將含有環硫化合物之組成物中的前述環硫化合物聚合而形成的聚合物,將該聚合物之全體質量當作基準,硼原子之含量為1至6500ppm。
- 一種聚合物,係將含有環硫化合物之組成物中的前述環硫化合物聚合而形成的聚合物,將該聚合物之全體質量當作基準,磷原子之含量為1至14000ppm。
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| JP7201344B2 (ja) * | 2017-06-22 | 2023-01-10 | 株式会社ダイセル | 脂環を有するエピスルフィド化合物、硬化性エピスルフィド樹脂組成物及びその硬化物 |
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| JP2015110799A (ja) | 2015-06-18 |
| KR20130135992A (ko) | 2013-12-11 |
| US9334371B2 (en) | 2016-05-10 |
| CN103502315B (zh) | 2016-08-17 |
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| EP2735581A1 (en) | 2014-05-28 |
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| KR101538876B1 (ko) | 2015-07-22 |
| JP5718466B2 (ja) | 2015-05-13 |
| US9738757B2 (en) | 2017-08-22 |
| CN103502315A (zh) | 2014-01-08 |
| TWI461417B (zh) | 2014-11-21 |
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