JPH0413683A - Cyclophosphazene derivative containing p-vinyl-phenoxy group, its production, its polymer and curable composition thereof - Google Patents
Cyclophosphazene derivative containing p-vinyl-phenoxy group, its production, its polymer and curable composition thereofInfo
- Publication number
- JPH0413683A JPH0413683A JP2117041A JP11704190A JPH0413683A JP H0413683 A JPH0413683 A JP H0413683A JP 2117041 A JP2117041 A JP 2117041A JP 11704190 A JP11704190 A JP 11704190A JP H0413683 A JPH0413683 A JP H0413683A
- Authority
- JP
- Japan
- Prior art keywords
- group
- cyclophosphazene
- vinylphenoxy
- alkyl
- derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 p-vinyl-phenoxy group Chemical group 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 229920000642 polymer Polymers 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims abstract description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 23
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011342 resin composition Substances 0.000 claims description 9
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002516 radical scavenger Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 8
- 238000005266 casting Methods 0.000 abstract description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 38
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000002329 infrared spectrum Methods 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 125000001424 substituent group Chemical group 0.000 description 11
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- WJYZUJWXUHDLJI-UHFFFAOYSA-N 1,3,5,7,2,4,6,8-tetrazatetraphosphocine Chemical class N1=PN=PN=PN=P1 WJYZUJWXUHDLJI-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 7
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004342 Benzoyl peroxide Substances 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- LTNCYKRVIPCLLU-UHFFFAOYSA-N 1,2,3,4,5,6-hexahydro-1,3,5,7,2,4,6,8-tetrazatetraphosphocine Chemical compound N1=PNPNPNP1 LTNCYKRVIPCLLU-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- 238000000214 vapour pressure osmometry Methods 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- PEJQKHLWXHKKGS-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octachloro-1,3,5,7-tetraza-2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraphosphacycloocta-1,3,5,7-tetraene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 PEJQKHLWXHKKGS-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VRWJOISQKOAUMR-UHFFFAOYSA-N n,n-dibutylpyridin-4-amine Chemical compound CCCCN(CCCC)C1=CC=NC=C1 VRWJOISQKOAUMR-UHFFFAOYSA-N 0.000 description 2
- ODKLEQPZOCJQMT-UHFFFAOYSA-N n,n-diethylpyridin-4-amine Chemical compound CCN(CC)C1=CC=NC=C1 ODKLEQPZOCJQMT-UHFFFAOYSA-N 0.000 description 2
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- NXDBMYTZSNQBEW-UHFFFAOYSA-N 1,2,3,4-tetrahydro-1,3,5,2,4,6-triazatriphosphinine Chemical class N1=PNPNP1 NXDBMYTZSNQBEW-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OIZOXAITXCKQIN-UHFFFAOYSA-N 3-[4-[[4-(2,5-dioxopyrrol-3-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC(CC=3C=CC(=CC=3)C=3C(NC(=O)C=3)=O)=CC=2)=C1 OIZOXAITXCKQIN-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- WBGPDYJIPNTOIB-UHFFFAOYSA-N n,n-dibenzylethanamine Chemical compound C=1C=CC=CC=1CN(CC)CC1=CC=CC=C1 WBGPDYJIPNTOIB-UHFFFAOYSA-N 0.000 description 1
- KFOQAMWOIJJNFX-UHFFFAOYSA-N n,n-dibutylhexan-1-amine Chemical compound CCCCCCN(CCCC)CCCC KFOQAMWOIJJNFX-UHFFFAOYSA-N 0.000 description 1
- ORSUTASIQKBEFU-UHFFFAOYSA-N n,n-diethylbutan-1-amine Chemical compound CCCCN(CC)CC ORSUTASIQKBEFU-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- XRKQMIFKHDXFNQ-UHFFFAOYSA-N n-cyclohexyl-n-ethylcyclohexanamine Chemical compound C1CCCCC1N(CC)C1CCCCC1 XRKQMIFKHDXFNQ-UHFFFAOYSA-N 0.000 description 1
- CXGFWBPQQXZELI-UHFFFAOYSA-N n-ethylpyridin-2-amine Chemical compound CCNC1=CC=CC=N1 CXGFWBPQQXZELI-UHFFFAOYSA-N 0.000 description 1
- OTIDWUALRXXVIM-UHFFFAOYSA-N n-ethylpyridin-4-amine Chemical compound CCNC1=CC=NC=C1 OTIDWUALRXXVIM-UHFFFAOYSA-N 0.000 description 1
- LSCYTCMNCWMCQE-UHFFFAOYSA-N n-methylpyridin-4-amine Chemical compound CNC1=CC=NC=C1 LSCYTCMNCWMCQE-UHFFFAOYSA-N 0.000 description 1
- MRXDWLZIBLDFKG-UHFFFAOYSA-N n-propylpyridin-4-amine Chemical compound CCCNC1=CC=NC=C1 MRXDWLZIBLDFKG-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はp−ビニルフェノキシ基含有シクロホスファゼ
ン誘導体、その製法、その重合体、および該シクロホス
ファゼン誘導体とビニルモノマーを必須成分として含む
耐熱性および難燃性に優れた熱硬化性樹脂組成物に関す
るものであシ、本発明の重合体および熱硬化性樹脂組成
物は、積層材料、注型材料、成形材料等の原料として用
いられ、構造材料、電気、電子部品材料として有用であ
る。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a p-vinylphenoxy group-containing cyclophosphazene derivative, a method for producing the same, a polymer thereof, and a heat-resistant and The polymer and thermosetting resin composition of the present invention are used as raw materials for laminated materials, casting materials, molding materials, etc., and are used as structural materials. , useful as electrical and electronic component materials.
(従来の技術)
ホスファゼン誘導体は、一般に難燃性で、その燃焼ガス
の毒性が低いことから、その重合体にも同様な性質が期
待されるので、先端複合材料用マトリックス樹脂の原料
の1つとして検討されており、塩化シクロホスファゼン
を出発原料として難燃性、耐熱性の重合体を合成しよう
とする試みは数多くなされてきた。(Prior art) Phosphazene derivatives are generally flame retardant and their combustion gases have low toxicity, so similar properties are expected for their polymers, so they are one of the raw materials for matrix resins for advanced composite materials. Many attempts have been made to synthesize flame-retardant and heat-resistant polymers using cyclophosphazene chloride as a starting material.
たとえば、ヘキサクロロシクロトリホスファゼンとハイ
ドロキノンの反応で耐熱性の優れた架橋構造の樹脂を得
る方法(米国特許2,866,773号、同3,121
,704号)がある。しかし、この方法によると、樹脂
化する際に、塩酸ガスが発生するため、それによる金属
の腐食、ボイドの発生等が問題になり用途が限定される
。また、ヘキサクロロシクロトリホスファゼンのブトキ
シ置換体と、レゾルシン、ハイドロキノン勢、2価フェ
ノール類とのエステル交換反応で、架橋構造の樹脂にす
る試みが、Zhivukhinらによってなされたが、
上記と同様、揮発性のアルコールが発生したり、また、
高分子量のものが得られず、その硬化物の物性も明かで
はない(Vysokomoj、 5oed、、8.72
7(1966))。For example, a method for obtaining a crosslinked resin with excellent heat resistance by the reaction of hexachlorocyclotriphosphazene and hydroquinone (U.S. Pat. Nos. 2,866,773 and 3,121)
, No. 704). However, according to this method, hydrochloric acid gas is generated during resin formation, which causes problems such as corrosion of the metal and generation of voids, which limits its use. In addition, Zhivukhin et al. attempted to create a crosslinked resin through transesterification of a butoxy-substituted hexachlorocyclotriphosphazene with resorcinol, hydroquinone, or dihydric phenols; however,
Similar to the above, volatile alcohol may be generated or
A product with a high molecular weight cannot be obtained, and the physical properties of the cured product are not clear (Vysokomoj, 5oed, 8.72
7 (1966)).
これらの欠点を改良するために、重合性のあるアリル基
含有フェノキシ基(たとえばオキシ安息香酸アリル、オ
キシ安息香酸メタアリル、アリルフェノールから誘導)
、フェノキシ基、アルキルフェ/dl−シ基等を含むシ
クロホスファゼン置換体を硬化させて、架橋構造の樹脂
とする方法が提案された(たとえば、特公昭47−11
226号、同48−8620号、同4g−11099号
、同48−20793号)。In order to improve these drawbacks, polymerizable allyl group-containing phenoxy groups (e.g. derived from allyl oxybenzoate, metaallyl oxybenzoate, allylphenol)
, a method has been proposed in which a cyclophosphazene substituted product containing a phenoxy group, an alkylphene/dl-group, etc. is cured to form a resin with a crosslinked structure (for example, Japanese Patent Publication No. 47-11
No. 226, No. 48-8620, No. 4g-11099, No. 48-20793).
これらの方法では、樹脂化する際、上記の様に揮発成分
が発生しないため成形作業上好都合であるが、了りル基
は反応性が必ずしも良くないため、硬化反応を完結させ
るには、活性の高い触媒を用いたり高温で長時間熱処理
する必要がある。These methods are convenient for molding work because they do not generate volatile components as described above, but the reactivity of the Ryoryl group is not necessarily good, so it is necessary to activate the resin to complete the curing reaction. It is necessary to use a catalyst with a high temperature or heat treatment at high temperature for a long time.
そこで、この欠点を更に改善するために、アリル基より
も反応性に富むビニル基を導入する方法が提案された(
特公昭48−27316号)。しかし、この方法では、
第1段階として当量以下のフェノール類および/または
アルコール類を、アミン存在下で、またはアルカリ金属
塩としてヘキサクロロシクロトリホスファゼンと反応さ
せて、フェノキ7基および/またはアルコキシ基で部分
置換した塩化シクロホスファゼン化合物となし、つぎの
第2段階で、それに当量以下のレゾルシン、カテコール
等、多価フェノールのナトリウム塩を反応させて、部分
置換した塩化シクロホスファゼンオリゴマーとし、最後
の第3段階で残留塩素を0−ビニルフェノールのナトリ
ウム塩で完全置換してプレポリマーとしており、樹脂原
料の合成工程が極めて複雑であるという欠点があった。Therefore, in order to further improve this drawback, a method was proposed to introduce a vinyl group that is more reactive than an allyl group (
Special Publication No. 48-27316). However, with this method,
In the first step, an equivalent amount or less of phenols and/or alcohols is reacted with hexachlorocyclotriphosphazene in the presence of an amine or as an alkali metal salt to partially substitute cyclophosphazene chloride with a phenoxy group and/or an alkoxy group. In the second step, an equivalent amount of sodium salt of a polyhydric phenol such as resorcinol or catechol is reacted with the compound to form a partially substituted chlorinated cyclophosphazene oligomer, and in the third and final step, residual chlorine is removed to zero. - The prepolymer is completely substituted with the sodium salt of vinylphenol, which has the disadvantage that the synthesis process of the resin raw material is extremely complicated.
また、このようKして得られたプレポリマーをさらに架
橋させた硬化物は耐熱性において優れているものの機械
的強度が不十分で用途が限られるという欠点もあった。Further, although the cured product obtained by further crosslinking the prepolymer obtained by K in this way has excellent heat resistance, it also has the disadvantage that its mechanical strength is insufficient and its uses are limited.
また、本発明者らは先に、ビニルフェノキシ基またはイ
ソプロペニルフェノキシ基をJI+1または硬化部位と
して導入した線状ホスファゼン重合体を提供したが(%
開昭62−132935号)、この重合体は、架橋後の
硬化物がエラストマーであり、硬度の高い硬化物が得ら
れないという点で用途が制限される欠点があった。In addition, the present inventors previously provided a linear phosphazene polymer in which a vinylphenoxy group or an isopropenylphenoxy group was introduced as a JI+1 or curing site (%
This polymer had a drawback in that the cured product after crosslinking was an elastomer, and the use of this polymer was limited in that a cured product with high hardness could not be obtained.
従来すされているホスファゼンにビニルフェノール類を
組み合わせた提案は、上記のとおり、シクロホスファゼ
ンのオリゴマーあるいはシクロホスファゼンが開環重合
した線状重合体にビニルフェノキシ基が導入されたもの
であって、ビニルフェノキシ基の導入されたシクロトリ
ホスファゼンあるいはシクロテトラホスファゼンは未だ
提案されていない。As mentioned above, the conventional proposal of combining phosphazene with vinylphenols involves introducing a vinylphenoxy group into a cyclophosphazene oligomer or a linear polymer obtained by ring-opening polymerization of cyclophosphazene. Cyclotriphosphazene or cyclotetraphosphazene into which a phenoxy group has been introduced has not yet been proposed.
(発明が解決しようとする課題)
そこで、本発明者らは、p−ビニルフェノキシ基の導入
されたシクロトリホスファゼンあるいはシクロテトラホ
スファゼンを提供し、また、従来提案されているビニル
フェノキシ基の導入されたシクロホスファゼンのオリゴ
マーあるいはシ・クロホスファゼンが開環重合した線状
重合体の上記の欠点を改善すべく鋭意研究したところ、
塩化シクロホスファゼンに、従来シクロホスファゼンの
オリゴマーあるいはシクロホスファゼンが開環重合した
線状重合体へのビニルフェノキシ基の導入方法として採
用されているようなp−ビニルフェノールのアルカリ金
属塩を作用させる方法を適用しても、p−ビニルフェノ
ールのアルカリ金属塩が重合反応性に富むためK、置換
反応条件下において核フェノラートはモノマーの形で存
在し得す、また、p−ビニルフェノールを第三アミンの
存在下に反応させる方法を適用しても、p−ビニルフェ
ノールが重合反応を引き起こすほどの厳しい条件下でし
か塩化シクロホスファゼンの塩素とp−ビニルフェノキ
シ基の置換反応は進行せず、結局目的とするp−ビニル
フェノキシ基の導入されたシクロホスファゼン誘導体を
好適に得られないことを知見し、さらに研究を進めたと
ころ、一定のピリジン化合物および塩酸捕捉剤の存在下
にシクロホスファゼンとp−ビニルフェノールを反応さ
せると、p−ビニルフェノールの重合反応が抑制されて
容易にほぼ定量的に塩化シクロホスファゼンの塩素とp
−ビニルフェノキシ基の置換反応のみが進行して、目的
とするp−ビニルフェノキシ基を有するシクロホスファ
ゼン誘導体が得られることを見出し、本発明を完成した
。(Problems to be Solved by the Invention) Therefore, the present inventors provided cyclotriphosphazene or cyclotetraphosphazene into which a p-vinylphenoxy group was introduced, and also provided a cyclotriphosphazene or cyclotetraphosphazene into which a p-vinylphenoxy group was introduced. As a result of intensive research to improve the above-mentioned drawbacks of oligomers of cyclophosphazene or linear polymers formed by ring-opening polymerization of cyclophosphazene, we found that
A method in which an alkali metal salt of p-vinylphenol is applied to cyclophosphazene chloride, which has been conventionally adopted as a method for introducing a vinylphenoxy group into a cyclophosphazene oligomer or a linear polymer obtained by ring-opening polymerization of cyclophosphazene, is used. However, since the alkali metal salts of p-vinylphenol have high polymerization reactivity, the nuclear phenolate can exist in the form of a monomer under the substitution reaction conditions. Even if a method of reacting in the presence of p-vinylphenol is applied, the substitution reaction between the chlorine and p-vinylphenoxy groups of cyclophosphazene chloride will only proceed under conditions severe enough to cause the polymerization reaction of p-vinylphenol, and in the end, the desired reaction cannot be achieved. It was discovered that it was not possible to suitably obtain a cyclophosphazene derivative with a p-vinylphenoxy group introduced therein, and further research revealed that cyclophosphazene and p-vinylphenol could be obtained in the presence of a certain pyridine compound and a hydrochloric acid scavenger. When reacting with p-vinylphenol, the polymerization reaction of p-vinylphenol is suppressed, and the chlorine of cyclophosphazene chloride and p-
The present invention was completed based on the discovery that only the substitution reaction of the -vinylphenoxy group proceeds to yield the desired cyclophosphazene derivative having a p-vinylphenoxy group.
したがって、本発明の目的は、新規なp−ビニルフェノ
キシ基を有するシクロホスファゼン誘導体およびその簡
便で収率の高い製法を提供するKあり、さらには耐熱性
、難燃性、機械的性質等の優れた該シクロホスファゼン
誘導体の重合体、および該シクロホスファゼン誘導体と
ビニルモノマーとを必須成分として含む熱硬化性樹脂組
成物を提供することにある。Therefore, an object of the present invention is to provide a novel cyclophosphazene derivative having a p-vinylphenoxy group and a simple and high-yield method for producing the same, as well as to provide excellent heat resistance, flame retardance, mechanical properties, etc. An object of the present invention is to provide a polymer of the cyclophosphazene derivative, and a thermosetting resin composition containing the cyclophosphazene derivative and a vinyl monomer as essential components.
(課題を解決するための手段)
本発明の要旨は、第一には下記の一般式(1)で表わさ
れるp−ビニルフェノキシ基、またはp−ビニルフェノ
キシ基とアルキル置換基を有するまたは有しないフェノ
キシ基を含有するシクロホスファゼン誘導体(以下化合
物(1)と記す);〔1〕
(ただし、n = 3または4、p+q=2、p>O1
q≧0、pnは正の整数であり、qnはOまたは正の整
数であって、R1はベンゼン環のオルソ、メタ、パラの
いづれかに位置するアルキル基または水素である)にあ
り、第二には下記の一般式〔II〕で表わされる4−(
N−アルキルアミノ)ピリジン化合物(以下化合物〔I
I〕と記す);(n)
(ただし、R2は水素または01〜C6のアルキル基、
R3はC1〜C6のアルキル基をそれぞれ表す)および
塩酸捕捉剤存在下における化合物CI)の製法にあり、
第三には化合物(1)のビニル重合体にあり、第四には
化合物〔I〕とビニルモノマーとを必須成分とする熱硬
化性樹脂組成物にある。(Means for Solving the Problems) The gist of the present invention is, firstly, a p-vinylphenoxy group represented by the following general formula (1), or a p-vinylphenoxy group with or without an alkyl substituent. Cyclophosphazene derivative containing a phenoxy group (hereinafter referred to as compound (1)); [1] (However, n = 3 or 4, p + q = 2, p > O1
q≧0, pn is a positive integer, qn is O or a positive integer, R1 is an alkyl group or hydrogen located in the ortho, meta, or para position of the benzene ring), and the second is 4-( represented by the following general formula [II]
N-alkylamino)pyridine compound (hereinafter referred to as compound [I
I]; (n) (wherein R2 is hydrogen or an alkyl group of 01 to C6,
R3 represents a C1 to C6 alkyl group, respectively) and a method for producing compound CI) in the presence of a hydrochloric acid scavenger,
The third problem lies in the vinyl polymer of compound (1), and the fourth problem lies in the thermosetting resin composition containing the compound [I] and a vinyl monomer as essential components.
本発明を詳述すると、化合物CI)の原料の1つは塩化
シクロホスファゼンであ抄、本発明においては、ヘキサ
クロロシクロトリホスファゼン、オクタクロロシクロテ
トラホスファゼン、またはそれらの混合物が使用される
。To elaborate on the present invention, one of the raw materials for compound CI) is cyclophosphazene chloride, and in the present invention, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, or a mixture thereof is used.
もう一方の原料はp−ビニルフェノール、または該p−
ビニルフェノールとアルキル置換基を有するまたは有し
ないフェノール類との混合物(以下フェノール混合物と
記す)であり、アルキルフェノールとしてはアルキル基
の炭素数が1〜5のものが適当であり、好ましくはp−
エチルフェノールまたはp−メチルフェノールが用いら
れる。The other raw material is p-vinylphenol or the p-
It is a mixture of vinylphenol and phenols having or not having an alkyl substituent (hereinafter referred to as a phenol mixture).As the alkylphenol, those having an alkyl group of 1 to 5 carbon atoms are suitable, and preferably p-
Ethylphenol or p-methylphenol is used.
特に好ましいのは、工業的に実施されているp−エチル
フェノールの脱水素により得られるp−ビニルフェノー
ルとp−エチルフェノール並びにその他の不純物をも含
む脱水素反応生成物をそのまま原料として用いることで
ある。It is particularly preferable to use the dehydrogenation reaction product containing p-vinylphenol and p-ethylphenol as well as other impurities obtained by dehydrogenation of p-ethylphenol, which is carried out industrially, as a raw material as it is. be.
また、化合物[11)は相関移動触媒の作用をするもの
で、その代表的なものとして4−メチルアミノピリジン
、4−エチルアミノピリジン、4−プロピルアミノピリ
ジン、4−((N−メチル、N−エチル)アミン)ピリ
ジン、4−1(N−メチル、N−ブチル)アミン)ピリ
ジン、4−((N−エチル、N−ブチル)アミノ)ピリ
ジン、4−((N−ブチル、N−ヘキシル)アミン)ピ
リジン、4−ジメチルアミノピリジン、4−ジエチルア
ミノピリジン、4−ジブチルアミノピリジン、4−ジベ
ンチルアミノピリジン、4−ジエチルアミノピリジン等
があげられるが、これらに限定されない。4−ジメチル
アミノピリジンを用いるのが好ましい。In addition, compound [11] acts as a phase transfer catalyst, and representative examples include 4-methylaminopyridine, 4-ethylaminopyridine, 4-propylaminopyridine, 4-((N-methyl, -ethyl)amine)pyridine, 4-1(N-methyl,N-butyl)amine)pyridine, 4-((N-ethyl,N-butyl)amino)pyridine, 4-((N-butyl,N-hexyl) ) amine) pyridine, 4-dimethylaminopyridine, 4-diethylaminopyridine, 4-dibutylaminopyridine, 4-dibentylaminopyridine, 4-diethylaminopyridine and the like, but are not limited to these. Preference is given to using 4-dimethylaminopyridine.
塩酸捕捉剤としては脂肪族第三アミンが適当で、その代
表的なものとして、たとえばトリメチルアミン、トリエ
チルアミン、トリブチルアミン、トリペンチルアミン、
トリヘキシルアミン、ジメチルエチルアミン、ジメチル
ブチルアミン、ジエチルブチルアミン、ジベンジルエチ
ルアミン、ジブチルヘキシルアミン、ジシクロヘキシル
エチルアミン等があげられるが、これらに限定されない
。Aliphatic tertiary amines are suitable as hydrochloric acid scavengers, and representative examples include trimethylamine, triethylamine, tributylamine, tripentylamine,
Examples include, but are not limited to, trihexylamine, dimethylethylamine, dimethylbutylamine, diethylbutylamine, dibenzylethylamine, dibutylhexylamine, dicyclohexylethylamine, and the like.
このような相間移動触媒および塩酸捕捉剤の存在下、塩
化シクロホスファゼン化合物とp−ビニルフェノールま
たはフェノール混合物を反応させるが、反応は無溶媒で
行うこともできるし、炭化水素類、ハロゲン化炭化水素
類、エーテル類、エステル類、ケトン類等、塩化シクロ
ホスファゼンとの反応性が低く、かつ、これらが溶解す
る適当な溶媒類の存在下でも行うことができる。In the presence of such a phase transfer catalyst and hydrochloric acid scavenger, a cyclophosphazene chloride compound and p-vinylphenol or a phenol mixture are reacted, but the reaction can also be carried out without a solvent, or with hydrocarbons, halogenated hydrocarbons, The reaction can also be carried out in the presence of suitable solvents that have low reactivity with cyclophosphazene chloride and can dissolve them, such as esters, ethers, esters, and ketones.
4−(N−アルキルアミノ)ピリジン化合物の使用量は
、塩化シクロホスファゼンの基本単位(PNCI2)に
対し、0.01〜1.0モル、好ましくは、0.05〜
0.5モルである。塩酸捕捉剤の使用量は、塩化シクロ
ホスファゼン基本単位(PNC12)当り、2.0〜4
.0モル、好ましくは、2.0〜3.0モルである。The amount of the 4-(N-alkylamino)pyridine compound used is 0.01 to 1.0 mol, preferably 0.05 to 1.0 mol, based on the basic unit of cyclophosphazene chloride (PNCI2).
It is 0.5 mole. The amount of hydrochloric acid scavenger used is 2.0 to 4 per basic unit of cyclophosphazene chloride (PNC12).
.. 0 mol, preferably 2.0 to 3.0 mol.
p−ビニルフェノールまたはフェノール混合物の使用量
は、塩化シクロホスファゼン1分子当り少くともp−ビ
ニルフェノキシ基が1個置換されるように、ヘキサクロ
ロシクロホスファゼンの場合は、塩素原子1個当りp−
ビニルフェノール基準で0.17〜6.0モル好ましく
は0.4〜5.0モル、フェノール混合物基準で1.0
〜7.0モル好ましくは1.0〜5.0モルであり、テ
トラクロロシクロホスファゼンの場合は、塩素原子1個
当りp−ビニルフェノール基準で0.13〜4.0モル
好ましくは0.3〜3.0モル、フェノール混合物基準
テ1.0〜7.0モル好ましくは1.0〜5.0モルで
ある。なお、置換反応においては一般にフェノールやア
ルキルフェノールよりp−ビニルフェノールの方力反応
性が大きいことから、原料の塩化シクロホスファゼンに
対して、p−ビニルフェノールまたはフェノール混合物
の使用量を増加させてもp−ビニルフェノキシ基を高濃
度に含む置換体を得ることができる。The amount of p-vinylphenol or phenol mixture to be used is such that at least one p-vinylphenoxy group is substituted per molecule of cyclophosphazene chloride;
0.17 to 6.0 mol based on vinylphenol, preferably 0.4 to 5.0 mol, 1.0 based on phenol mixture
~7.0 mol Preferably 1.0 to 5.0 mol, and in the case of tetrachlorocyclophosphazene, 0.13 to 4.0 mol based on p-vinylphenol per chlorine atom, preferably 0.3 3.0 mol, preferably 1.0 to 7.0 mol, preferably 1.0 to 5.0 mol, based on the phenol mixture. In addition, in the substitution reaction, p-vinylphenol generally has a higher reactivity than phenol or alkylphenol, so even if the amount of p-vinylphenol or phenol mixture used is increased with respect to the raw material cyclophosphazene chloride, p - Substituted products containing a high concentration of vinylphenoxy groups can be obtained.
溶媒の使用量は特に規定されないが、原料の塩化シクロ
ホスファゼン100部に対して、0〜1.000部が適
当である。Although the amount of the solvent to be used is not particularly limited, it is suitably 0 to 1.000 parts per 100 parts of cyclophosphazene chloride as the raw material.
置換反応は一10〜200r、好ましくはθ〜150C
の温度で、1分〜30時間、好ましく10分〜25時間
行われる。The substitution reaction is -10~200r, preferably θ~150C
It is carried out at a temperature of 1 minute to 30 hours, preferably 10 minutes to 25 hours.
このようにして特定構造の相関移動触媒の存在下で、塩
化シクロホスファゼンとフェノール混合物を反応させる
と、p−ビニルフェノールが極めて高い重合反応性を有
しているにも拘らず、反応中、はとんど重合反応を起こ
すことなく優先的に置換反応が進行し、p−ビニルフェ
ノキシ基またはp−ビニルフェノキシ基とアルキル置換
基を有するまたは有しないフェノキシ基で置換されたシ
クロホスファゼン誘導体すなわち化合物〔I〕が生成す
る。かくして得られる化合物(1)にお(・て、p−ビ
ニルフェノキシ基の導入率はテトラホスファゼンでは1
2.5モル係以上、トリホスファゼンでは16.7モル
係以上である。該化合物〔I〕は通常、高粘度の液体な
いし固体であり、極めて高い沸点を有するので蒸留は不
可能であるし、結晶化させることもほとんど不可能であ
る。このものはシクロホスファゼン環を基本骨格として
有している点ではモノマーであるが、
される基本単位が3個または4個環状につながりたオリ
ゴマーとも考えることができる。ビニルフェノキシ基お
よびアルキル置換または未置換フェノキシ基の導入割合
が若干相違するものあるいは導入位置が相違する異性体
の分離は精留、分別晶析、分別抽出、クロマトグラフィ
ー等の分離手段によってはほとんど不可能であるし、ま
た工業的応用においては、これらの分離は本質的に不要
である。In this way, when cyclophosphazene chloride and a phenol mixture are reacted in the presence of a phase transfer catalyst with a specific structure, although p-vinylphenol has extremely high polymerization reactivity, during the reaction, A cyclophosphazene derivative or compound in which the substitution reaction proceeds preferentially without causing a polymerization reaction, and is substituted with a p-vinylphenoxy group or a p-vinylphenoxy group and a phenoxy group with or without an alkyl substituent [ I] is generated. In the thus obtained compound (1), the introduction rate of p-vinylphenoxy group is 1 for tetraphosphazene.
The molar ratio is 2.5 or more, and for triphosphazene it is 16.7 or more. The compound [I] is usually a highly viscous liquid or solid and has an extremely high boiling point, making it impossible to distill and almost impossible to crystallize. Although this product is a monomer in that it has a cyclophosphazene ring as its basic skeleton, it can also be considered an oligomer in which three or four basic units are connected in a ring. Isomers with slightly different introduction ratios or different introduction positions of vinylphenoxy groups and alkyl-substituted or unsubstituted phenoxy groups can hardly be separated by separation methods such as rectification, fractional crystallization, fractional extraction, and chromatography. It is possible, and in industrial applications, these separations are essentially unnecessary.
該化合物〔I〕は単独でまたは適当な1−合間始剤の存
在下で加熱すると重合、硬化し、その硬化物は難燃性、
耐熱性等に優れた積層板、構造材、電気、電子部材とし
て有用である。The compound [I] polymerizes and cures when heated alone or in the presence of a suitable 1-intermediate initiator, and the cured product has flame retardant properties.
It is useful as laminates, structural materials, and electrical and electronic components with excellent heat resistance.
重合、硬化反応は、開始剤を使用しない場合は80C〜
280t11’、好ましくけ100C〜280Cの温度
で、30分〜10時間、好ましくは1時間ないし10時
間加熱すると完結する。また、重合開始剤存在下では、
20C〜280r、好ましくは60C〜250Cの温度
で、10分〜20時間、好ましくは20分〜15時間加
熱処理すると反応は完結する。すなわち、重合開始剤を
用いれは低い温度での重合が可能となる。Polymerization and curing reactions are carried out at 80C or higher when no initiator is used.
The process is completed by heating at a temperature of 280t11', preferably 100C to 280C, for 30 minutes to 10 hours, preferably 1 hour to 10 hours. In addition, in the presence of a polymerization initiator,
The reaction is completed by heating at a temperature of 20C to 280r, preferably 60C to 250C, for 10 minutes to 20 hours, preferably 20 minutes to 15 hours. That is, by using a polymerization initiator, polymerization can be carried out at a low temperature.
重合開始剤としては、各種のアンモニウム化合物、スル
ホニウム化合物、ヨードニウム化合物、スタノニウム化
合物等カチオン開始剤および各種ラジカル開始剤が有効
である。As the polymerization initiator, cationic initiators such as various ammonium compounds, sulfonium compounds, iodonium compounds, and stannonium compounds, and various radical initiators are effective.
アンモニウム化合物としては、たとえばテトラエチルア
ンモニウム塩(((C2H5)4Nl+X )、テトラ
ブチルアンモニウム塩(((C4H0) 4N) +X
−)、スルホニウム塩としては、たとえばジメチル−ベ
ンゾイルメチルスルホニウム!(I C61(5COC
H2S(CH3) 2)”r ’)、ジエチル−p−メ
トキシベンジルスルホニウム塩((p−CH3QC,H
4C)i2S(C2H,)2)”X−)、ヨードニウム
化合物としては、たトエばシフ;ニルヨードニウム塩(
((C6H,) 2I)”X−)、スルホニウム化合物
としては、たとえばトリフェニルスタノニウA[(((
C6H5)。Examples of ammonium compounds include tetraethylammonium salt (((C2H5)4Nl+X), tetrabutylammonium salt (((C4H0)4N)+X
-), the sulfonium salt is, for example, dimethyl-benzoylmethylsulfonium! (IC61(5COC
H2S(CH3) 2)"r'), diethyl-p-methoxybenzylsulfonium salt ((p-CH3QC,H
4C)i2S(C2H,)2)"
((C6H,) 2I)”
C6H5).
Sn )”X”−) 、があげられる。ただし、上記化
学式%式%
PF6などを表す。Sn)"X"-). However, the above chemical formula % formula % PF6 etc. are represented.
またラジカル開始剤としては、クメンハイドロパーオキ
サイド、t−ブチルハイドロパーオキサイド、ジクミル
パーオキサイド、過酸化ベンゾイル、アゾビスインブチ
ロニトリル等が用いられるが、これらに限定されない。Further, as the radical initiator, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, azobisin butyronitrile, etc. can be used, but the invention is not limited thereto.
重合開始剤の使用量はtK規定されないが、−般には化
合物(1)に対して、0.1〜5重量重量間囲で使用す
るのが好ましい。かくして得られた重合体は溶媒に不溶
であり、1HNMHにより分析することはできない。し
かしそれらのIR分析によれば、原料の化合物(1)に
認められたC=C(ビニル結合)伸縮振動に基づく吸収
1650cIn−1が消失し、一方P=N (シクロホ
スファゼン)伸縮振動に基づく吸収1220m−’が実
質的に変らずに認められ、また元素分析値も原料の化合
物CI)のそれと実質的に同一であることから、かくし
て得られた重合体は原料の化合物(1)がビニル重合し
たものであることが明らかである。本発明の重合体のT
BA法により求めたガラス転移温度は120〜160C
の範囲内である。Although the amount of the polymerization initiator to be used is not specified by tK, it is generally preferable to use it in a range of 0.1 to 5% by weight based on compound (1). The polymer thus obtained is insoluble in solvents and cannot be analyzed by 1HNMH. However, according to their IR analysis, the absorption 1650 cIn-1 based on the C=C (vinyl bond) stretching vibration observed in the raw material compound (1) disappeared, while the absorption based on the P=N (cyclophosphazene) stretching vibration disappeared. The absorption of 1220 m-' was observed essentially unchanged, and the elemental analysis value was also substantially the same as that of the raw material compound CI). It is clear that it is a polymerized product. T of the polymer of the present invention
Glass transition temperature determined by BA method is 120-160C
is within the range of
また、該化合物〔I〕は、カチオンまたはラジカル重合
性を示すビニルモノマーと、上記重合体と同様の条件下
で反応させると硬化物が得られ、該硬化物は難燃性、耐
熱性等に優れた積層板、構造材、電気、電子部材として
有用である。なおこの場合、重合開始剤の使用量は特に
規定されないが、一般には化合物〔I〕とビニルモノマ
ーとの混合物に対して、0.1〜5重量重量間囲で使用
するのが好ましい。In addition, when the compound [I] is reacted with a vinyl monomer exhibiting cationic or radical polymerizability under the same conditions as the above polymer, a cured product can be obtained, and the cured product has flame retardancy, heat resistance, etc. It is useful as an excellent laminate, structural material, and electrical and electronic components. In this case, the amount of the polymerization initiator to be used is not particularly limited, but it is generally preferred to use it in an amount of 0.1 to 5% by weight based on the mixture of compound [I] and vinyl monomer.
上記、カチオンまたはラジカル重合性ビニルモノマーと
しては、スチレン、スチレン誘導体、たとえば、a−メ
チルスチレン、p−メチルスチレン、クロルスチレン等
、アクリル酸、アクリル酸エステル、たとえば、アクリ
ル酸メチル、アクリル酸エチル等、メタアクリル酸、メ
タアクリル陵エステル、たとえば、メタアクリル酸メチ
ル、メタアクリル酸エチル、ヒドロキシエチルメタアク
リレート等、カルボン酸ビニルエステル、たとえば、酢
酸ビニル、プロピオン酸ビニル、安息香酸ビニル等、不
飽和ニトリル、たとえば、アクリロニトリル、シアン化
ビニリデン等、マレイミド銹導体、たとえば、フェニル
マレイミド、1.1′(メチレンジー4.1−)ユニし
ン)ビスマレイミド等、などがあけられるが、これらに
限定されない。The above-mentioned cationically or radically polymerizable vinyl monomers include styrene, styrene derivatives such as a-methylstyrene, p-methylstyrene, chlorostyrene, acrylic acid, acrylic esters such as methyl acrylate, ethyl acrylate, etc. , methacrylic acid, methacrylic esters, such as methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, etc., carboxylic acid vinyl esters, such as vinyl acetate, vinyl propionate, vinyl benzoate, etc., unsaturated nitriles Examples include, but are not limited to, acrylonitrile, vinylidene cyanide, maleimide conductors such as phenylmaleimide, 1.1'(methylene di4.1-)unicine) bismaleimide, and the like.
これらビニルモノマーの使用量は特に規定されないが、
一般に該シクロホスファゼン誘導体中のp−ビニルフェ
ノキシ基1モルに対して、0.1モル〜20モルが適当
である。The amount of these vinyl monomers used is not particularly specified, but
Generally, 0.1 mol to 20 mol is suitable for 1 mol of p-vinylphenoxy group in the cyclophosphazene derivative.
本発明のシクロホスファゼン誘導体重合物、および該ホ
スファゼン誘導体とビニルモノマーとから成る熱硬化性
樹脂組成物には、必要に応じて、各種充填材、顔料、カ
ップリング剤、離型剤などを配合することができる。た
とえば、充填剤としては、ガラス繊維、炭素繊維、金属
繊維、リン酸カルシウム、炭酸カルシウム、炭酸マグネ
シウム、水酸化アルミニウム、水酸化マグネシウム、酸
化アンチモン、石膏、シリカ、アルミナ、クレータルク
、石英粉末、鉄粉、カーボンブラックなどがあげられる
が、これらに限定されるものではない。またその使用量
は、用途に応じて規定されるが、一般に該ホスファゼン
誘導体または該熱硬化性樹脂組成物100重量部に対し
て、10〜500重量部である。The cyclophosphazene derivative polymer of the present invention and the thermosetting resin composition comprising the phosphazene derivative and a vinyl monomer may contain various fillers, pigments, coupling agents, mold release agents, etc., as necessary. be able to. For example, fillers include glass fiber, carbon fiber, metal fiber, calcium phosphate, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, antimony oxide, gypsum, silica, alumina, clay talc, quartz powder, iron powder, and carbon. Examples include, but are not limited to, black. The amount used is determined depending on the application, but is generally 10 to 500 parts by weight per 100 parts by weight of the phosphazene derivative or the thermosetting resin composition.
(発明の効果)
本発明は、特定の相間移動触媒の使用によ抄新規なp−
ビニルフェノキシ基含有シクロホスファゼン誇導体を簡
便にしかも高収率で得ることができる。また該ホスファ
ゼン誘導体は、高粘度の液体または融点の低い固体で、
汎用溶媒に可溶性であるため取扱易く、かつ比較的穏和
な条件で硬化反応が完結し、また該ホスファゼン誘導体
と各種ビニルモノマーとから成る熱硬化性樹脂組成物も
同様に反応性に富み、それらの硬化物は耐熱性、難燃性
および機械的強度が優れているため、積層材料、注型材
料、成形材料等の原料樹脂として用いることができる。(Effects of the Invention) The present invention provides novel p-
A vinylphenoxy group-containing cyclophosphazene conductor can be obtained easily and in high yield. Further, the phosphazene derivative is a high viscosity liquid or a low melting point solid,
Because it is soluble in general-purpose solvents, it is easy to handle, and the curing reaction is completed under relatively mild conditions.Also, thermosetting resin compositions composed of the phosphazene derivative and various vinyl monomers are also highly reactive, and their Since the cured product has excellent heat resistance, flame retardancy, and mechanical strength, it can be used as a raw material resin for laminated materials, casting materials, molding materials, etc.
(実施例)
以下、本発明を実施例によ抄さらに詳細に説明するが、
これKよって本発明が限定されるものではない。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited by this K.
実施例1
p−ビニルフェノキシ基およびアルキルフェノキシ基含
有シクロホスファゼン誘導体の合成〜その1−
粗p−ビニルフェノール(p−ビニルフェノール35モ
ル係、p−エチルフェノール58モル係およびp−クレ
ゾール7モル係から成る混合物)17.7グラム、4−
ジメチルアミノピリジン0.53グラム、トリエチルア
ミン19.11/およびジオキサン49m1からなる混
合物に、水冷攪拌下、5.0グラムのへキサクロロシク
ロトリホスファゼン(以下3PNCと略記)および40
m/のジオキサンからなる溶液を10分かかつて滴下し
た。その後、40〜50Cの温度を保ちながら8時間攪
拌を続けた。生成した塩を濾別し、濾液な減圧下で処理
l、て溶媒を除去した。残渣を水酸化ナトリウム水溶液
で処理して未反応のフェノール類を抽出、除去し、分離
した液体を水で充分洗浄した後、真空乾燥したところ1
1.3グラムの高粘度の液体が残った。Example 1 Synthesis of cyclophosphazene derivative containing p-vinylphenoxy group and alkylphenoxy group - Part 1 - Crude p-vinylphenol (p-vinylphenol 35 mol, p-ethylphenol 58 mol and p-cresol 7 mol) ) 17.7 grams, 4-
To a mixture consisting of 0.53 g of dimethylaminopyridine, 19.11 g of triethylamine, and 49 ml of dioxane, 5.0 g of hexachlorocyclotriphosphazene (hereinafter abbreviated as 3PNC) and 40
A solution consisting of m/m dioxane was added dropwise over a period of 10 minutes. Thereafter, stirring was continued for 8 hours while maintaining the temperature at 40 to 50C. The formed salts were filtered off, and the filtrate was treated under reduced pressure to remove the solvent. The residue was treated with an aqueous sodium hydroxide solution to extract and remove unreacted phenols, and the separated liquid was thoroughly washed with water and dried under vacuum.
1.3 grams of highly viscous liquid remained.
NMRおよびIR分析の結果、このものは平均組成トシ
てp−ビニルフェノキシ2$61モル係、p−エチルフ
ェノキシ基34モル係およびp−メチルフェノキシ基5
モル係からなる置換基を含むシクロトリホスファゼン銹
導体、すなわちほとんどテトラ(p−ビニルフェノキシ
)−ジ(p−エチルフェノキシ)シクロトリホスファゼ
ンであることがわかった。As a result of NMR and IR analysis, this product has an average composition of 2 $61 moles of p-vinylphenoxy, 34 moles of p-ethylphenoxy groups, and 5 moles of p-methylphenoxy groups.
It was found to be a cyclotriphosphazene conductor containing substituents consisting of molar ratios, ie, mostly tetra(p-vinylphenoxy)-di(p-ethylphenoxy)cyclotriphosphazene.
NMR結果
D
帰属 ピーク面積
1.2ppm D 5
22.3ppm A
72.6ppm E
355.2〜5.6ppm H63
6,6ppm (
6,7〜7.2ppm B、C,F、G、J、にな
お、2.34ppmK認められるピークは、原料精製時
に用いた残存トルエンのメチル基によるものと思われる
。NMR result D Attribution Peak area 1.2 ppm D 5
22.3ppmA
72.6ppmE
355.2-5.6ppm H63 6.6ppm (6.7-7.2ppm The peak observed at 2.34ppmK in B, C, F, G, J, is the methyl group of the residual toluene used during raw material purification. This seems to be due to
モル分率
CH+O−7/3=2.3 0.05
CHCM +o−35/2=17.5 0.34CH=
cti+o−63/2=31.5 0.61計 51
.3 1.00
IR結果
1220cm−’
P=N(シクロホスファゼン)
伸縮振動
一!
1200.950 on P −0−C伸縮振
動1610、l510cTn 芳香環
〃16506n ’ C=C(ビニル結合
) //まだ、得られた生成物の元素分析値(重f
%)は以下のとおりであった。Molar fraction CH+O-7/3=2.3 0.05 CHCM+o-35/2=17.5 0.34CH=
cti+o-63/2=31.5 0.61 total 51
.. 3 1.00 IR result 1220cm-' P=N (cyclophosphazene) stretching vibration one! 1200.950 on P -0-C stretching vibration 1610, l510cTn aromatic ring
〃16506n' C=C (vinyl bond)
%) were as follows.
CHN P
67.38 5.46 4.94 10.93な
お目的物には活性塩素は殆ど検出されず、またGPC分
析の結果、単一ピークを示した。蒸気圧浸透圧法(VP
O法)VCよ妙分子量を測定1.たところ、その値は8
50 (IJ論値850)であった。CHN P 67.38 5.46 4.94 10.93 Almost no active chlorine was detected in the target product, and the GPC analysis showed a single peak. Vapor pressure osmometry (VP
O method) Measuring the molecular weight of VC 1. The value was 8.
50 (IJ theoretical value 850).
目的物のIRおよびNMRスペクトルをそれぞれ第1図
および第2図に示す。The IR and NMR spectra of the target product are shown in Figures 1 and 2, respectively.
実施例2
p−ビニルフェノキシ基およびアルキルフェノキシ基含
有シクロホスファゼン誘導体の合成−その2−
11p−ビニルフェノール<p−ビニルフェノールl
7−v−# % 、 p −x チルフェノール72モ
ル係およびp−クレゾール11モル係から成る混合物)
200グラム、4−ジブチルアミノピリジン9.2グラ
ムおよびトリブチルアミン3201から成る混合物に、
水冷下、82グラムのオクタクロロシクロテトラホスフ
ァゼン(4PNC)および400dのクロルベンゼンか
らなる溶液を20分かかって滴下した。その後、30r
で16時間、続いて60tl’で15時間加熱攪拌した
。生成した塩を濾別し、濾液を減圧下で処理して溶媒を
除去した。Example 2 Synthesis of cyclophosphazene derivative containing p-vinylphenoxy group and alkylphenoxy group - Part 2- 11 p-vinylphenol < p-vinylphenol l
7-v-#%, a mixture consisting of 72 moles of p-x thylphenol and 11 moles of p-cresol)
200 grams, 9.2 grams of 4-dibutylaminopyridine, and 3201 tributylamine;
Under water cooling, a solution consisting of 82 grams of octachlorocyclotetraphosphazene (4PNC) and 400 d of chlorobenzene was added dropwise over 20 minutes. After that, 30r
The mixture was heated and stirred at 60 tl' for 16 hours, and then heated and stirred at 60 tl' for 15 hours. The formed salts were filtered off and the filtrate was treated under reduced pressure to remove the solvent.
残渣を水酸化す) IJウム水溶液で処理して未反応の
フェノール類を抽出、除去し、分離した液体を水で充分
洗浄した後、真空乾燥したところ205グラムの高粘度
の液体が残った。The residue was treated with an aqueous IJ solution to extract and remove unreacted phenols, and the separated liquid was thoroughly washed with water and vacuum dried, leaving 205 grams of a highly viscous liquid.
NMRおよびIR分析を実施例1におけると同様に行っ
た結果、このものは平均組成としてp−ビニルフェノキ
シ基22モル係、p−エチルフェノキシ基68モル係お
よびp−メチルフェノキシ基10モル係からなる置換基
を含むシクロテトラホスファゼン誘導体、すなわち実質
的にジ(p−ビニルフェノキシ)−ペンタ(p−エチル
フェノキシ)−モノ(p−メチルフェノキシ)シクロテ
トラホスファゼンであることがわかった。NMR and IR analyzes were performed in the same manner as in Example 1, and the average composition was 22 moles of p-vinylphenoxy groups, 68 moles of p-ethylphenoxy groups, and 10 moles of p-methylphenoxy groups. It was found to be a cyclotetraphosphazene derivative containing a substituent, ie essentially di(p-vinylphenoxy)-penta(p-ethylphenoxy)-mono(p-methylphenoxy)cyclotetraphosphazene.
元素分析値(重量%)
CHN P
66.92 5.94 4.94 10.92なお目
的物には活性塩素は殆ど認められず、またGPC分析で
は単一のピークを示し、■PO法による分子量は113
8(理論値1137 )であった。Elemental analysis value (wt%) CHN P 66.92 5.94 4.94 10.92Also, almost no active chlorine was observed in the target product, and GPC analysis showed a single peak, and ■Molecular weight by PO method is 113
8 (theoretical value 1137).
目的物のIRおよびNMRスペクトルをそれぞれ第3図
および第4図に示す。The IR and NMR spectra of the target product are shown in Figures 3 and 4, respectively.
実施例3
p−ビニルフェノキシ基およびアルキルフェノキシ基含
有シクロホスファゼン誘導体の合成−その3−
実m例2で用いた粗p−ビニルフェノール14.5グラ
ム、4−ジメチルアミノビリジン0.4グラム、トリエ
チルアミン14.8−からなる混合物に、水冷下、4.
1グラムの3PNCおよび12.3−のクロルベンゼン
からなる溶液を5分かかって滴下した。その後、室温で
24時間攪拌を続けた。生成した塩を濾別し、濾液を減
圧下で処理して溶媒を除去した。残渣を水酸化ナトリウ
ム水溶液で処理して未反応のフェノール類を抽出、除去
し、分離した液体を水で充分洗浄した後、真空乾燥した
ところ9、θグラムの高粘度の目的物が得られた。Example 3 Synthesis of cyclophosphazene derivative containing p-vinylphenoxy group and alkylphenoxy group - Part 3 - 14.5 g of crude p-vinylphenol used in Example 2, 0.4 g of 4-dimethylaminopyridine, triethylamine 14.To the mixture consisting of 8-, under water cooling, 4.
A solution consisting of 1 gram of 3PNC and 12.3-chlorobenzene was added dropwise over a period of 5 minutes. Thereafter, stirring was continued for 24 hours at room temperature. The formed salts were filtered off and the filtrate was treated under reduced pressure to remove the solvent. The residue was treated with an aqueous sodium hydroxide solution to extract and remove unreacted phenols, and the separated liquid was thoroughly washed with water and dried in vacuum, yielding a highly viscous target product weighing 9.0 grams. .
NMRおよびIR分析を実施例1と同様に行った結果、
このものは平均組成としてp−ビニルフェノキシ基33
モル係、p−エチルフエキシ基60モル係およびp−メ
チルフェノキシ基7モル係からなる置換基を含むシクロ
トリホスファゼン誘導体、すなわち主としてジ(p−ビ
ニルフェノキシ)−テトラ(p−エチルフェノキシ)シ
クロトリホスファゼンであることがわかった。As a result of NMR and IR analysis conducted in the same manner as in Example 1,
This product has an average composition of 33 p-vinylphenoxy groups.
Cyclotriphosphazene derivatives containing substituents consisting of 60 molar groups of p-ethyl phenoxy groups and 7 molar groups of p-methylphenoxy groups, i.e. mainly di(p-vinylphenoxy)-tetra(p-ethylphenoxy)cyclotriphosphazenes It turned out to be.
元素分析値(重量%)
CHN P
67.07 5.82 4.93 10.9】なお
目的物には活性塩素は検出されず、GPC分析では単一
のピークを示し、またそのvPO法による分子量は85
0(31論値852)であった。Elemental analysis value (wt%) CHN P 67.07 5.82 4.93 10.9] Active chlorine was not detected in the target product, and GPC analysis showed a single peak, and its molecular weight by vPO method is 85
It was 0 (31 logical value 852).
そのIRおよびNMRスペクトルをそれぞれ第5図およ
び第6図に示す。Its IR and NMR spectra are shown in FIGS. 5 and 6, respectively.
実施例4
p−ビニルフェノキシ基およびアルキルフェノキシ基含
有シクロホスファゼン誘導体の合成−その4−
粗p−ビニルフェノール(p−ビニルフェノール45モ
ル係、p−エチルフェノール49モル係およびp−クレ
ゾール6モル係から成る混合物)23.0グラム、4−
エチルアミノピリジン0.20グラムおよびトリヘキシ
ルアミン40耐から成る混合物に、水冷攪拌下、5.0
グラムの3PNCおよび40iuのジオキサンから成る
溶液を5分かかって滴下した。その後、40〜50rの
温度で20時間攪拌を続けた。生成した塩を濾別し、濾
液を減圧下で処理して溶媒を除去した。残渣を水酸化ナ
トリウム水溶液で処理して未反応のフェノール類を抽出
、除去し、分離した液体を水で充分洗浄した後、真空乾
燥したところl010グラムの高粘度の液体が得られた
。Example 4 Synthesis of cyclophosphazene derivative containing p-vinylphenoxy group and alkylphenoxy group - Part 4 - Crude p-vinylphenol (p-vinylphenol 45 mols, p-ethylphenol 49 mols and p-cresol 6 mols) 23.0 grams of 4-
To a mixture consisting of 0.20 g of ethylaminopyridine and 40 g of trihexylamine, 5.0 g of
A solution consisting of 3 grams of PNC and 40 iu of dioxane was added dropwise over 5 minutes. Thereafter, stirring was continued for 20 hours at a temperature of 40 to 50 r. The formed salts were filtered off and the filtrate was treated under reduced pressure to remove the solvent. The residue was treated with an aqueous sodium hydroxide solution to extract and remove unreacted phenols, and the separated liquid was thoroughly washed with water and vacuum dried to obtain 1010 grams of a highly viscous liquid.
NMRおよびIR分析を実施例Iと同様に行った結果、
このものは平均組成としてp−ビニルフェノキシ基75
モル係、p−エチルフェノキシ基22モル係およびp−
メチルフェノキシ基3モル係から成る置換基を含むシク
ロトリホスファゼン誘導体、すなわち実質的にペンタ(
p−ビニルフェノキシ)−モノ(p−エチルフェノキシ
)シクロトリホスファゼンとテトラ(p−ビニルフェノ
キシ)−ジ(p−エチルフェノキシ)シクロトリホスフ
ァゼンとの等モル混合物であることがわかった。As a result of NMR and IR analysis conducted in the same manner as in Example I,
This product has an average composition of 75 p-vinylphenoxy groups.
molar ratio, p-ethylphenoxy group 22 molar ratio and p-
Cyclotriphosphazene derivatives containing substituents consisting of 3 molar groups of methylphenoxy groups, i.e., substantially penta(
It was found to be an equimolar mixture of p-vinylphenoxy)-mono(p-ethylphenoxy)cyclotriphosphazene and tetra(p-vinylphenoxy)-di(p-ethylphenoxy)cyclotriphosphazene.
元素分析1[(重量%)
CHN P
67.55 5.29 4.94 10.93な
お目的物には活性塩素は検出されず、そのGPCスペク
トルは単一ピークであり、またそのVPO法による分子
量は850(理論値850)であった。Elemental analysis 1 [(wt%) CHN P 67.55 5.29 4.94 10.93 Active chlorine was not detected in the target product, its GPC spectrum had a single peak, and its molecular weight by VPO method was 850 (theoretical value 850).
目的物のInおよびNMRスペクトルをそれぞれ第7図
および第8図に示す。The In and NMR spectra of the target product are shown in FIGS. 7 and 8, respectively.
実施例5
p−ビニルフェノキシ基およびアルキルフェノキシ基含
有シクロホスファゼン誘導体の合成−その5一
実施例2で用いた粗p−ビニルフェノール18.5グラ
ム、4−ジメチルアミノピリジン0.5グラム、トリエ
チルアミン2011/からなる混合物に、室温下、4.
1グラムの4PNCおよび2Qmlのジオキサンからな
る溶液を5分間で滴下、その後、室温で24時間攪拌を
続けた。生成した塩を濾別、濾液を減圧下で処理して溶
媒を除去した。残渣を水酸化す) IJウム水溶液で処
理して未反応のフェノール類を抽出、除去し、分離した
液体を水で充分洗浄した後、真空乾燥したところ9.1
グラムの高粘度の目的物が得られた。Example 5 Synthesis of cyclophosphazene derivative containing p-vinylphenoxy group and alkylphenoxy group - Part 51 18.5 g of crude p-vinylphenol used in Example 2, 0.5 g of 4-dimethylaminopyridine, 2011 triethylamine / to a mixture consisting of 4. at room temperature.
A solution consisting of 1 gram of 4PNC and 2 Q ml of dioxane was added dropwise over 5 minutes, followed by continued stirring at room temperature for 24 hours. The formed salts were filtered off, and the filtrate was treated under reduced pressure to remove the solvent. The residue was treated with an aqueous IJ solution to extract and remove unreacted phenols, and the separated liquid was thoroughly washed with water and dried under vacuum.9.1
A product with a high viscosity of 1.5 grams was obtained.
NMRおよびIR分析を実施例1と同様に行った結果、
このものは平均組成としてp−ビニルフェノキシ基38
モル係、p−エチルフェノキ7基54モル係およびp−
メチルフェノキシ基8モル%からなる置換基を含むシク
ロテトラホスファゼン銹導体、すなわち主としてトリ(
p−ビニルフェノキシ)−ペンタ(p−エチルフェノキ
シ)シクロトリホスファゼンであることがわかった。As a result of NMR and IR analysis conducted in the same manner as in Example 1,
This product has an average composition of 38 p-vinylphenoxy groups.
molar ratio, p-ethylphenoxy7 groups 54 molar ratio and p-
A cyclotetraphosphazene conductor containing a substituent consisting of 8 mol% of methylphenoxy groups, i.e., mainly tri(
It was found to be p-vinylphenoxy)-penta(p-ethylphenoxy)cyclotriphosphazene.
元素分析値(芦f係)
CHN P
67.10 5.75 4.94 10.93な
お目的物には活性塩素は検出されず、GPC分析では単
一のピークを示12、そのVPO法による分子量は11
35(理論値1134)であった。目的物のIRおよび
NMRスペクトルをそれぞれ第9図および第10図に示
す。Elemental analysis value (Ashif section) CHN P 67.10 5.75 4.94 10.93 Active chlorine was not detected in the target product, and GPC analysis showed a single peak12, and its molecular weight by VPO method is 11
35 (theoretical value 1134). The IR and NMR spectra of the target product are shown in FIGS. 9 and 10, respectively.
実施例6
実施例1で得られたシクロトリホスファゼン誘導体10
グラムをガラス製重合管に仕込み、200でで5時間加
熱したところ、内容物は完全に固化した。Example 6 Cyclotriphosphazene derivative 10 obtained in Example 1
When the sample was placed in a glass polymerization tube and heated at 200℃ for 5 hours, the contents were completely solidified.
ガラス管を割って内容物を取り出1〜粉砕12て、メタ
ノールで洗浄後真空乾燥したところ、9.9グラムのポ
リマーが得られた。このポリマーは融点を示さず、各種
溶媒に不溶であった。IR分析によれば、このポリマー
には原料である実施例】の生成物に認められたC=C(
ビニル結合)の伸縮振動に基づ(1650cm−1の吸
収が認められない点を除けば、そのIR吸収はP=N
(シクロホスファゼン)の伸縮振動に基づ<1220c
rn−1の吸収を含めて実施例1の生成物のそれと本質
的に一致しており、また元素分析の結果も実施例1に示
した値と本質的に一致していた。これらのことから、こ
のものはシクロトリホスファゼン誘導体中のp−ビニル
フェノキシ基がビニル重合したものであることがわかっ
た。またTBA法によりガラス転移温度を測定したとこ
ろ140Cであった。The glass tube was broken and the contents were taken out, crushed 1 to 12, washed with methanol, and vacuum dried to obtain 9.9 grams of polymer. This polymer showed no melting point and was insoluble in various solvents. According to IR analysis, this polymer contains C=C(
The IR absorption is based on the stretching vibration of the vinyl bond (with the exception of no absorption at 1650 cm-1)
Based on the stretching vibration of (cyclophosphazene) <1220c
The absorption including rn-1 was essentially consistent with that of the product of Example 1, and the results of elemental analysis were also essentially consistent with the values shown in Example 1. From these results, it was found that this product was obtained by vinyl polymerization of the p-vinylphenoxy group in the cyclotriphosphazene derivative. Further, the glass transition temperature was measured by TBA method and was found to be 140C.
そのIRスペクトルを第11図に示す。The IR spectrum is shown in FIG.
実施例7
実施例2で得られたシクロテトラホスファゼン誘導体1
0グラムを0.1グラムの過酸化ベンゾイルと共にガラ
ス製重合管に仕込み、200Cで2時間加熱したところ
、内容物は完全に固化した。Example 7 Cyclotetraphosphazene derivative 1 obtained in Example 2
0 grams was charged into a glass polymerization tube together with 0.1 grams of benzoyl peroxide and heated at 200 C for 2 hours, and the contents were completely solidified.
内容物を取り出し粉砕して、メタノールで洗浄後真空乾
燥したところ、9.9グラムのポリマーが得られた。こ
のポリマーは融点を示さず、各種溶媒に不溶であった。The contents were taken out, crushed, washed with methanol, and dried under vacuum to obtain 9.9 grams of polymer. This polymer showed no melting point and was insoluble in various solvents.
分析の結果、実施例6で述べたと同様の理由によ抄、こ
のものは実施例2で得られたシクロテトラホスファゼン
誘導体中のp−ビニルフェノキシ基がビニル重合したも
のであることがわかった。またTBA法によりガラス転
移温度を測定したところ125Cであった。そのIRス
ペクトルを第12図に示す。As a result of the analysis, it was found that the p-vinylphenoxy group in the cyclotetraphosphazene derivative obtained in Example 2 was vinyl-polymerized for the same reason as described in Example 6. Further, the glass transition temperature was measured by the TBA method and was found to be 125C. The IR spectrum is shown in FIG.
実施例8
実施例3で得られたシクロトリホスファゼン誘導体10
グラムを0.1グラムのアゾビスイソブチロニトリルと
共にガラス製重合管に仕込み、180Cで5時間加熱し
たところ、内容物は完全に固化した。内容物を取り出し
粉砕して、メタノールで洗浄後真空乾燥したところ、9
.9グラムのポリマーが得られた。このポリマーは融点
を示さず、各種溶媒に不溶であった。分析の結果、実施
例6に述べたと同様の理由により、このものは実施例3
で得られたシクロトリホスファゼン誘導体中のp−ビニ
ルフェノキシ基がビニル重合したものであると認められ
た。TBA法によるとガラス転移温度は130Cであっ
た。IRスペクトルを第13図に示す。Example 8 Cyclotriphosphazene derivative 10 obtained in Example 3
gram was charged into a glass polymerization tube together with 0.1 gram of azobisisobutyronitrile and heated at 180 C for 5 hours, and the contents were completely solidified. When the contents were taken out, crushed, washed with methanol, and dried under vacuum, the result was 9.
.. Nine grams of polymer was obtained. This polymer showed no melting point and was insoluble in various solvents. As a result of the analysis, for the same reason as stated in Example 6, this product was classified as Example 3.
It was recognized that the p-vinylphenoxy group in the cyclotriphosphazene derivative obtained in the above was vinyl polymerized. According to the TBA method, the glass transition temperature was 130C. The IR spectrum is shown in FIG.
実施例9
実施例4で得られたシクロトリホスファゼン誘導体10
グラムをガラス製重合管に仕込み、260Cで5時間加
熱したところ、内容物は完全に固化した。Example 9 Cyclotriphosphazene derivative 10 obtained in Example 4
When the sample was placed in a glass polymerization tube and heated at 260C for 5 hours, the contents were completely solidified.
内容物を取り出し粉砕した後、メタノールで洗浄後真空
乾燥したところ、9.9グラムのポリマーが得られた。The contents were taken out and crushed, washed with methanol and vacuum dried to obtain 9.9 grams of polymer.
このポリマーは融点を示さず、各種溶媒に不溶であった
。This polymer showed no melting point and was insoluble in various solvents.
TBA法によるガラス転移温度は145Cであった。分
析の結果、実施例6で述べたと同様の理由によね、この
ものは実施例4で得られたシクロトリホスファゼン誘導
体中のp−ビニルフェノキシ基がビニル重合したもので
あることがわかった。The glass transition temperature determined by the TBA method was 145C. As a result of the analysis, for the same reason as stated in Example 6, it was found that this product was obtained by vinyl polymerization of the p-vinylphenoxy group in the cyclotriphosphazene derivative obtained in Example 4.
IRスペクトルを第14図に示す。The IR spectrum is shown in FIG.
実施例10
実施例5で得られたシクロテトラホスファゼン誘導体1
0グラムを0.2グラムのジフヱ二ルヨードニウムへキ
サフルオロアルシネ−)(((C6H5)2工)AsF
6)と共にガラス製重合管に仕込み、220Cで2時間
加熱したところ、内容物は完全に固化した。Example 10 Cyclotetraphosphazene derivative 1 obtained in Example 5
0 grams to 0.2 grams of diphenyl iodonium hexafluoroarsine)(((C6H5)2)AsF
When the mixture was charged into a glass polymerization tube together with 6) and heated at 220C for 2 hours, the contents were completely solidified.
内容物を取り出し粉砕後、メタノールで洗浄後真空乾燥
したところ、9.9グラムのポリマーが得られた。この
ポリマーは融点を示きず、各種溶媒に不溶であった。The contents were taken out, crushed, washed with methanol, and dried under vacuum to obtain 9.9 grams of polymer. This polymer showed no melting point and was insoluble in various solvents.
分析の結果、実施例6で述べたと同様の理由によ抄、こ
のものは実施例5で得られたシクロテトラホスファゼン
誘導体中のp−ビニルフェノキシ基がビニル重合したも
のであることがわかった。As a result of the analysis, it was found that the p-vinylphenoxy group in the cyclotetraphosphazene derivative obtained in Example 5 was vinyl-polymerized for the same reason as described in Example 6.
TBA法によるガラス転移温度は133Cであった。I
Rスペクトルを第15図に示す。The glass transition temperature determined by the TBA method was 133C. I
The R spectrum is shown in FIG.
実施例11
実施例3で得られた平均網成として、p−ビニルフェノ
キシ基33モルチ、p−エチルフェノキシ基60モル係
およびp−メチルフェノキシ基7モル係から成る置換基
を含むシクロトリホスファゼン誘導体60部とリン酸三
カルシウム40部を、該誘導体に対して1重t%の過酸
化ベンゾイルと共に均一に混合し、それを金型に仕込ん
だ。つぎにそれを50kp/儒2の加圧下、200Cで
3時間プレスした。サンプルを金型から取り出し、25
0Cで3時間ポストキュアーした。硬化物の硬さは11
5(ロックウェル硬度、Rスケール)で、また曲げ強度
および曲げ弾性率は、それぞれ6.5 kl/1III
2および475k)7w2であった。Example 11 A cyclotriphosphazene derivative containing substituents consisting of 33 moles of p-vinylphenoxy groups, 60 moles of p-ethylphenoxy groups, and 7 moles of p-methylphenoxy groups as the average network structure obtained in Example 3. 60 parts of tricalcium phosphate and 40 parts of tricalcium phosphate were uniformly mixed together with 1% by weight of benzoyl peroxide based on the derivative, and the mixture was charged into a mold. Next, it was pressed at 200C for 3 hours under a pressure of 50 kp/F2. Remove the sample from the mold and
Post-cure was performed at 0C for 3 hours. The hardness of the cured product is 11
5 (Rockwell hardness, R scale), and the bending strength and bending modulus are respectively 6.5 kl/1III
2 and 475k) 7w2.
実施例12
実施例5で得られた平均組成として、p−ビニルフェノ
キシ基38モル%、p−エチルフェノキシ基54モル係
およびp−メチルフェノキシ基8モル係からなる置換基
を含むシクロテトラホスファゼン誘導体60部とシリカ
40部を、該誘導体に対して2重量係のテトラブチルア
ンモニウムブロマイド(((C4H8)4N)Br)と
共に均一に混合し、それを金型に仕込んだ。つぎにそれ
を50ky / cm 2の加圧下、200Cで3時間
プレスした。Example 12 A cyclotetraphosphazene derivative containing substituents consisting of 38 mol % of p-vinylphenoxy groups, 54 mol % of p-ethylphenoxy groups, and 8 mol % of p-methylphenoxy groups as the average composition obtained in Example 5. 60 parts of silica and 40 parts of silica were uniformly mixed together with 2 parts by weight of tetrabutylammonium bromide (((C4H8)4N)Br), and the mixture was charged into a mold. Next, it was pressed at 200C for 3 hours under a pressure of 50ky/cm2.
サンプルを取り出し、250Cで3時間ボストキエアー
した硬化物の曲げ強度および曲げ弾性率は、それぞれ5
.4ky/w2および500 kg/la2であった。The sample was taken out and air-boosted at 250C for 3 hours.The bending strength and bending modulus of the cured product were 5, respectively.
.. It was 4ky/w2 and 500 kg/la2.
実施例13
実施例3で得られた平均組成として、p−ビニルフェノ
キシ基33モル係、p−エチルフェノキシ基60モル係
およびp−メチルフェノキシ基7モル係から成る置換基
を含むシクロトリホスファゼン誘導体20グラムとメタ
アクリル酸メチルエステル(MMA)20グラムを、0
.1グラムの過酸化ベンゾイルと共にガラス製重合管に
仕込み、100Cで1,0時間加熱したところ、内容物
は完全に固化した。収量は39.8?であった。Example 13 A cyclotriphosphazene derivative containing a substituent consisting of 33 moles of p-vinylphenoxy group, 60 moles of p-ethylphenoxy group, and 7 moles of p-methylphenoxy group as the average composition obtained in Example 3. 20 grams and 20 grams of methacrylic acid methyl ester (MMA), 0
.. When the mixture was charged into a glass polymerization tube together with 1 gram of benzoyl peroxide and heated at 100 C for 1.0 hours, the contents were completely solidified. The yield is 39.8? Met.
内容物を取り出し、ベンゼン抽出したところ不溶部は9
5%、可溶部は5%であった。分析の結果、不溶部はシ
クロトリホスファゼン銹導体9モル係とMMA91モル
係から成る共重合体であり、可溶部はMMAの単独重合
体と該誘導体オリゴマーとの混合物であることがわかっ
た。When the contents were taken out and extracted with benzene, the insoluble portion was 9.
5%, and the soluble portion was 5%. As a result of analysis, it was found that the insoluble portion was a copolymer consisting of 9 moles of cyclotriphosphazene conductor and 91 moles of MMA, and the soluble portion was a mixture of a homopolymer of MMA and an oligomer of the derivative.
共重合体について熱重量分析を行ったところ、300C
での重量減少率は7係であった。ちなみにボIJMMA
については、同一条件でその値は38係であった。When thermogravimetric analysis was performed on the copolymer, it was found that 300C
The weight reduction rate was 7 times. By the way, Bo IJMMA
Under the same conditions, the value was 38.
実施例14
実施例13において使用したシクロトリホスファゼン誘
導体50グラムとMMAIOダラムを、0.15グラム
の過酸化ベンゾイルと共にガラス製重合管に仕込み、1
00Cで10時間加熱したところ、内容物は完全に固化
した。収量は59.854であった。Example 14 50 grams of the cyclotriphosphazene derivative used in Example 13 and MMAIO Dalam were charged into a glass polymerization tube along with 0.15 grams of benzoyl peroxide, and 1
When heated at 00C for 10 hours, the contents were completely solidified. The yield was 59.854.
取り出した内容物について、実施例13と同様な抽出操
作を行ったところ、ベンゼン不溶部(シクロトリホスフ
ァゼン誘導体40モル係とMMA60モル係から成る共
重合体)は90%であった。When the extracted contents were subjected to the same extraction operation as in Example 13, the benzene insoluble portion (copolymer consisting of 40 moles of cyclotriphosphazene derivative and 60 moles of MMA) was 90%.
共重合体について熱重量分析を行ったところ、300C
での重量減少率は3%であった。When thermogravimetric analysis was performed on the copolymer, it was found that 300C
The weight reduction rate was 3%.
実施例15
実施例2で得られた平均組成として、p−ビニルフェノ
キシ基22モル係、p−エチルフェノキシ基68モル係
およびp−メチルフェノキシ基10モル係から成る置換
基を含むシクロテトラホスファゼン誘導体20グラムと
MMA20グラムを、0.15グラムのアゾビスイソブ
チロニトリルと共にガラス製重合管に仕込み、100C
で8時間加熱したところ、内容物は完全に固化した。収
量は39.77であった。Example 15 A cyclotetraphosphazene derivative containing substituents consisting of 22 moles of p-vinylphenoxy groups, 68 moles of p-ethylphenoxy groups, and 10 moles of p-methylphenoxy groups as the average composition obtained in Example 2. 20 grams of MMA and 20 grams of MMA were placed in a glass polymerization tube along with 0.15 grams of azobisisobutyronitrile, and heated at 100C.
When heated for 8 hours, the contents were completely solidified. The yield was 39.77.
取り出した内容物について、実施例13と同様な処理を
施したところ、92%がベンゼン不溶部であった。When the contents taken out were subjected to the same treatment as in Example 13, 92% was found to be benzene-insoluble.
実施例16
実施例5で合成したシクロテトラホスファゼン誘導体5
0グラムとスチレン10グラムを、0,3グラムの過酸
化ベンゾイルと共にガラス製重合管に仕込み、120C
で3時間加熱したところ、内容物は完全に固化した。収
量は59.9Fであった。Example 16 Cyclotetraphosphazene derivative 5 synthesized in Example 5
0 grams and 10 grams of styrene were charged into a glass polymerization tube along with 0.3 grams of benzoyl peroxide, and heated at 120C.
When heated for 3 hours, the contents were completely solidified. The yield was 59.9F.
取抄出した内容物について、実施例13と同様な処理を
施したところ、ベンゼン不溶部(シクロテトラホスファ
ゼン誘導体38モル係とステレフ62モル係から成る共
重合体)は88%であった。When the extracted contents were subjected to the same treatment as in Example 13, the benzene insoluble portion (a copolymer consisting of 38 moles of cyclotetraphosphazene derivative and 62 moles of stereophthalate) was 88%.
共重合体について熱重量分析を行りたところ、400C
および450Cでの重量減少率はそれぞれ12および3
7%であった。ちなみに同一条件で行ったポリスチレン
のこれらの値は、それぞれ32および95%であった。Thermogravimetric analysis of the copolymer revealed that it was 400C.
and the weight loss rate at 450C is 12 and 3, respectively.
It was 7%. Incidentally, these values for polystyrene conducted under the same conditions were 32% and 95%, respectively.
実施例17
実施例13で使用したシクロトリホスファゼン誘導体2
0グラムと酢酸ビニル20グラムを、0.2グラムのア
ゾビスインブチロニトリルと共にガラス製重合管に仕込
み、100Cで12時間加熱したところ、系は完全に固
化した。収量は39.954であった。Example 17 Cyclotriphosphazene derivative 2 used in Example 13
0 grams and 20 grams of vinyl acetate were charged into a glass polymerization tube together with 0.2 grams of azobisin butyronitrile and heated at 100 C for 12 hours, and the system was completely solidified. The yield was 39.954.
取り出した内容物について、実施例13と同様な処理を
施したところ、ベンゼン不溶部(シクロトリホスファゼ
ン誘導体66モル係と酢酸ビニル34モル係から成る共
重合体)は80係であった。When the contents taken out were subjected to the same treatment as in Example 13, the benzene insoluble portion (a copolymer consisting of 66 moles of cyclotriphosphazene derivative and 34 moles of vinyl acetate) was 80 moles.
またベンゼン可溶部は酢酸ビニルの単独重合体と該誘導
体オリゴマーとの混合物であることがわかった。It was also found that the benzene soluble portion was a mixture of vinyl acetate homopolymer and the derivative oligomer.
共重合体について熱重量分析を行ったところ、350C
での重量減少率は8係であった。ちなみに同一条件で行
ったポリ酢酸ビニルのその値は58係であった。When thermogravimetric analysis was performed on the copolymer, it was found that 350C
The weight reduction rate was 8 times. Incidentally, the value for polyvinyl acetate tested under the same conditions was 58.
実施例18
実施例4で得られた平均組成として、p−ビニルフェノ
キシ基75モル係、p−エチルフェノキシ基22モル冬
およびp−メチルフェノキシ基3モル係からなる置換基
を含むシクロトリホスファゼン誘導体30グラムとMM
A 100グラムを均一に混合した後、それを100C
で2時間、続いて200Cで3時間注型成形した。Example 18 A cyclotriphosphazene derivative containing a substituent consisting of 75 moles of p-vinylphenoxy group, 22 moles of p-ethylphenoxy group, and 3 moles of p-methylphenoxy group as the average composition obtained in Example 4. 30 grams and MM
After uniformly mixing 100 grams of A, it was heated to 100C.
for 2 hours, followed by cast molding at 200C for 3 hours.
得られたテストピースの曲げ強度および曲げ弾性率は、
それぞれ11 kl/ws2および400kf/va2
であった。The flexural strength and flexural modulus of the obtained test piece are
11 kl/ws2 and 400kf/va2 respectively
Met.
実施例19
実施例1で得られた平均組成として、p−ビニルフェノ
キシ基61モル係、p−エチルフェノキシ基34モル係
およびp−メチルフェノキシ基5モル係からなる置換基
を含むシクロトリホスファゼン誘導体30グラムと1.
1’−(メチレンジー4.1−フェニレン)ビスマレイ
ミド10グラムを120Cで均一に混合し、それを18
0Cで1時間、200Cで2時間、さらに230Cで5
時間注型成形した。このサンプルの熱変形温度(HDT
)は245Cであった。Example 19 A cyclotriphosphazene derivative containing a substituent consisting of 61 moles of p-vinylphenoxy groups, 34 moles of p-ethylphenoxy groups, and 5 moles of p-methylphenoxy groups as the average composition obtained in Example 1. 30 grams and 1.
Mix 10 grams of 1'-(methylene di-4.1-phenylene) bismaleimide uniformly at 120C, and
1 hour at 0C, 2 hours at 200C, and 5 hours at 230C.
Time cast molded. The heat distortion temperature (HDT) of this sample
) was 245C.
第1図は実施例1の生成物のIRスペクトル、第2図は
その”HNMRスペクトル、第3図は実施例2の生成物
のIRスペクトル、第4図はその”HNMRスペクトル
、第5図は実施例3の生成物のIRスペクトル、第6図
はその HNMRスペクトル、第7図は実施例4の生成
物のIRスペクトル、第8図はその1HNMRスペクト
ル、第9図は実施例5の生成物のIRスペクトル、第1
0図はその”HNMRスペクトル、第11図〜第15図
はそれぞれ実施例6〜100重合体のIRスペクトルで
ある。
特許出願人 丸善石油化学株式会社Figure 1 is the IR spectrum of the product of Example 1, Figure 2 is its ``HNMR spectrum, Figure 3 is the IR spectrum of the product of Example 2, Figure 4 is its ``HNMR spectrum, Figure 5 is its ``HNMR spectrum''. IR spectrum of the product of Example 3, FIG. 6 is its HNMR spectrum, FIG. 7 is its IR spectrum of the product of Example 4, FIG. 8 is its HNMR spectrum, and FIG. 9 is its HNMR spectrum. IR spectrum of, 1st
Figure 0 is its HNMR spectrum, and Figures 11 to 15 are IR spectra of the polymers of Examples 6 to 100, respectively. Patent applicant: Maruzen Petrochemical Co., Ltd.
Claims (6)
ノキシ基、または該p−ビニルフェノキシ基とアルキル
置換基を有するまたは有しないフェノキシ基を含有する
シクロホスファゼン誘導体;▲数式、化学式、表等があ
ります▼ 〔 I 〕 (ただし、n=3または4、p+q=2、p>0、q≧
0、pnは正の整数あり、qnは0または正の整数であ
って、R_1はベンゼン環のオルソ、メタ、パラのいづ
れかに位置するアルキル基または水素である)。(1) A cyclophosphazene derivative containing a p-vinylphenoxy group represented by the following general formula [I], or a p-vinylphenoxy group and a phenoxy group with or without an alkyl substituent; ▲mathematical formula, chemical formula, There are tables, etc.▼ [I] (However, n=3 or 4, p+q=2, p>0, q≧
0 and pn are positive integers, qn is 0 or a positive integer, and R_1 is an alkyl group or hydrogen located in the ortho, meta, or para position of the benzene ring).
ルアミノ)ピリジン化合物; ▲数式、化学式、表等があります▼ 〔II〕 (ただしR_2は、水素またはC_1〜C_6のアルキ
ル基、R_3はC_1〜C_6のアルキル基である)お
よび塩酸捕捉剤存在下、塩化シクロホスファゼンと、p
−ビニルフェノール、またはp−ビニルフェノールとア
ルキル置換基を有するまたは有しないフェノール混合物
を反応させることを特徴とする請求項1記載のシクロホ
スファゼン誘導体の製法。(2) 4-(N-alkylamino)pyridine compound represented by the general formula [II] below; ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [II] (However, R_2 is hydrogen or alkyl of C_1 to C_6 group, R_3 is an alkyl group of C_1 to C_6) and a hydrochloric acid scavenger, cyclophosphazene chloride and p
2. The method for producing a cyclophosphazene derivative according to claim 1, which comprises reacting -vinylphenol or p-vinylphenol with a phenol mixture having or not having an alkyl substituent.
、4−ジメチルアミノピリジンであることを特徴とする
請求項2記載のシクロホスファゼン誘導体の製法。(3) The method for producing a cyclophosphazene derivative according to claim 2, wherein the 4-(N-alkylamino)pyridine compound is 4-dimethylaminopyridine.
ノキシ基、または該p−ビニルフェノキシ基とアルキル
置換基を有するまたは有しないフェノキシ基を含有する
シクロホスファゼン誘導体;▲数式、化学式、表等があ
ります▼ 〔 I 〕 (ただしn=3または4、p>0、q≧0、pnは正の
整数であり、qnは0または正の整数であって、R_1
はベンゼン環のオルソ、メタ、パラのいづれかに位置す
るアルキル基または水素である)をビニル重合させて得
られ、ガラス転移温度(TBA法)が120〜160℃
である重合体。(4) A cyclophosphazene derivative containing a p-vinylphenoxy group represented by the following general formula [I], or a p-vinylphenoxy group and a phenoxy group with or without an alkyl substituent; ▲mathematical formula, chemical formula, There are tables, etc.▼ [I] (However, n=3 or 4, p>0, q≧0, pn is a positive integer, qn is 0 or a positive integer, and R_1
is an alkyl group or hydrogen located in the ortho, meta, or para position of the benzene ring) and has a glass transition temperature (TBA method) of 120 to 160°C.
A polymer that is
ノキシ基、またはp−ビニルフェノキシ基とアルキル置
換基を有するまたは有しないフェノキシ基を含有するシ
クロホスファゼン誘導体; ▲数式、化学式、表等があります▼ 〔 I 〕 (ただしn=3または4、p+q=2、p>0、q≧0
、pnは正の整数であり、qnは0または正の整数であ
って、アルキル基はベンゼン環のオルソ、メタ、パラの
いづれかに位置するアルキル基または水素である)とカ
チオンまたはラジカル重合性ビニルモノマーとを必須成
分として含む熱硬化性樹脂組成物。(5) A cyclophosphazene derivative containing a p-vinylphenoxy group represented by the following general formula [I], or a p-vinylphenoxy group and a phenoxy group with or without an alkyl substituent; ▲Mathematical formula, chemical formula, table etc.▼ [I] (However, n=3 or 4, p+q=2, p>0, q≧0
, pn is a positive integer, qn is 0 or a positive integer, and the alkyl group is an alkyl group or hydrogen located in the ortho, meta, or para position of the benzene ring) and cationically or radically polymerizable vinyl A thermosetting resin composition containing a monomer as an essential component.
アクリル酸、アクリルエステル、メタアクリル酸、メタ
アクリル酸エステル、カルボン酸ビニルエステル、不飽
和ニトリルまたはマレイミド誘導体であることを特徴と
する請求項5記載の熱硬化性樹脂組成物。(6) the vinyl monomer is styrene, a styrene derivative,
6. The thermosetting resin composition according to claim 5, wherein the thermosetting resin composition is acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, carboxylic acid vinyl ester, unsaturated nitrile, or maleimide derivative.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2117041A JPH0413683A (en) | 1990-05-07 | 1990-05-07 | Cyclophosphazene derivative containing p-vinyl-phenoxy group, its production, its polymer and curable composition thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2117041A JPH0413683A (en) | 1990-05-07 | 1990-05-07 | Cyclophosphazene derivative containing p-vinyl-phenoxy group, its production, its polymer and curable composition thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0413683A true JPH0413683A (en) | 1992-01-17 |
Family
ID=14701976
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2117041A Pending JPH0413683A (en) | 1990-05-07 | 1990-05-07 | Cyclophosphazene derivative containing p-vinyl-phenoxy group, its production, its polymer and curable composition thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0413683A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001070904A1 (en) * | 2000-03-21 | 2001-09-27 | Otsuka Kagaku Kabushiki Kaisha | Flame retardant, flame-retardant resin composition, molded object, and electronic part |
JP2011026513A (en) * | 2009-07-28 | 2011-02-10 | Samsung Electro-Mechanics Co Ltd | Curable cyclic phosphazene-based compound and method for producing the same |
JP2013075836A (en) * | 2011-09-29 | 2013-04-25 | Fushimi Pharm Co Ltd | Flame retardant resin composition |
JP2013075942A (en) * | 2011-09-29 | 2013-04-25 | Fushimi Pharm Co Ltd | Flame retardant resin composition |
JP2013075940A (en) * | 2011-09-29 | 2013-04-25 | Fushimi Pharm Co Ltd | Flame retardant resin composition |
WO2015019945A1 (en) * | 2013-08-05 | 2015-02-12 | 株式会社カネカ | Phosphazene-containing rubber graft copolymer and thermoplastic composition thereof |
-
1990
- 1990-05-07 JP JP2117041A patent/JPH0413683A/en active Pending
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001070904A1 (en) * | 2000-03-21 | 2001-09-27 | Otsuka Kagaku Kabushiki Kaisha | Flame retardant, flame-retardant resin composition, molded object, and electronic part |
JP2001335703A (en) * | 2000-03-21 | 2001-12-04 | Otsuka Chem Co Ltd | Flame retardant, flame retardant resin composition, molded article and electronic part |
EP1279720A1 (en) * | 2000-03-21 | 2003-01-29 | Otsuka Kagaku Kabushiki Kaisha | Flame retardant, flame-retardant resin composition, molded object, and electronic part |
EP1279720A4 (en) * | 2000-03-21 | 2004-08-25 | Otsuka Kagaku Kk | Flame retardant, flame-retardant resin composition, molded object, and electronic part |
KR100750972B1 (en) * | 2000-03-21 | 2007-08-22 | 오쯔까 가가꾸 가부시키가이샤 | Flame retardant, flame-retardant resin composition, molded object, and electronic part |
JP2011026513A (en) * | 2009-07-28 | 2011-02-10 | Samsung Electro-Mechanics Co Ltd | Curable cyclic phosphazene-based compound and method for producing the same |
JP2013075836A (en) * | 2011-09-29 | 2013-04-25 | Fushimi Pharm Co Ltd | Flame retardant resin composition |
JP2013075942A (en) * | 2011-09-29 | 2013-04-25 | Fushimi Pharm Co Ltd | Flame retardant resin composition |
JP2013075940A (en) * | 2011-09-29 | 2013-04-25 | Fushimi Pharm Co Ltd | Flame retardant resin composition |
WO2015019945A1 (en) * | 2013-08-05 | 2015-02-12 | 株式会社カネカ | Phosphazene-containing rubber graft copolymer and thermoplastic composition thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU593833B2 (en) | Polyhydroxyethers from hydroxybiphenyls | |
US4116936A (en) | Polyvinylbenzyl ethers of polyphenols, their polymers and copolymers | |
JP2000034339A (en) | Cationic ring-opening polymerization of benzoxazine | |
JPS5912693B2 (en) | Flame retardants | |
US3733349A (en) | Fluorocarbon cyanates | |
JPH0390075A (en) | Epoxy resin, its intermediate and production thereof | |
US5070117A (en) | Aromatic vinyl ether compounds and compositions, and method of making the same | |
US5004842A (en) | Aromatic vinyl ether compounds and compositions, and method of making the same | |
JPH0413683A (en) | Cyclophosphazene derivative containing p-vinyl-phenoxy group, its production, its polymer and curable composition thereof | |
US4709062A (en) | Glycidyl compound | |
US3240722A (en) | alpha-substituted para-xylylene polymers and method for the preparation thereof | |
JPH01132541A (en) | Novel diepoxide and diphenoxy compound | |
JPH07116286B2 (en) | Resin containing triazine ring | |
US4999410A (en) | Acrylate ester ether derivatives | |
US3349142A (en) | Process for the preparation of alkylated di-p-xylylenes | |
JP4389010B2 (en) | NOVOLAC DERIVATIVE HAVING SUBSTITUENT AND PROCESS FOR PRODUCING THE SAME | |
US4142037A (en) | Readily curable fluorocarbon ether bibenzoxazole polymers | |
US4855380A (en) | Cyclopentadiene-containing cyclic polycarbonate oligomer | |
JP2752498B2 (en) | Method for producing hydroxycarboxylic acid derivative | |
JPH0528724B2 (en) | ||
CA1182950A (en) | Mixtures for the preparation of nitrogen-containing polyadducts | |
JPS63312307A (en) | Composition containing reactive polymeric compound and production thereof | |
JP2002012662A (en) | Polycyanoarylether and method for producing the same | |
JPS63305112A (en) | Novel phenolic alternating copolymer and manufacture thereof | |
JPS6344549A (en) | Aryl-bicyclo(2,2,1)hepte-5-ene-2-carboxylic acid ester, manufacture and polymer thereof |