JP2010202718A - Alkenylphosphorus compound, alkenylphosphorus compound polymer, and alkenylphosphorus compound copolymer - Google Patents
Alkenylphosphorus compound, alkenylphosphorus compound polymer, and alkenylphosphorus compound copolymer Download PDFInfo
- Publication number
- JP2010202718A JP2010202718A JP2009047433A JP2009047433A JP2010202718A JP 2010202718 A JP2010202718 A JP 2010202718A JP 2009047433 A JP2009047433 A JP 2009047433A JP 2009047433 A JP2009047433 A JP 2009047433A JP 2010202718 A JP2010202718 A JP 2010202718A
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- JP
- Japan
- Prior art keywords
- group
- phosphorus compound
- alkenyl
- polymer
- alkenylphosphorus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000642 polymer Polymers 0.000 title claims abstract description 61
- 229920001577 copolymer Polymers 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 title abstract description 8
- -1 alkene compound Chemical class 0.000 claims abstract description 109
- 229910052698 phosphorus Inorganic materials 0.000 claims description 99
- 239000011574 phosphorus Substances 0.000 claims description 99
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 abstract description 27
- 229920001519 homopolymer Polymers 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 2
- 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 22
- 238000006243 chemical reaction Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 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 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 239000007809 chemical reaction catalyst Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 239000005556 hormone Substances 0.000 description 5
- 229940088597 hormone Drugs 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- UMIPWJGWASORKV-UHFFFAOYSA-N oct-1-yne Chemical compound CCCCCCC#C UMIPWJGWASORKV-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KRMPXSOCACZSED-UHFFFAOYSA-N C=CP1(=O)OC2=CC=CC=C2C2=C1C=CC=C2 Chemical compound C=CP1(=O)OC2=CC=CC=C2C2=C1C=CC=C2 KRMPXSOCACZSED-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VIHUMJGEWQPWOT-UHFFFAOYSA-N 1,2,3-tribromo-4-(3-bromophenoxy)benzene Chemical compound BrC1=CC=CC(OC=2C(=C(Br)C(Br)=CC=2)Br)=C1 VIHUMJGEWQPWOT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- DKFHWNGVMWFBJE-UHFFFAOYSA-N 1-ethynylcyclohexene Chemical group C#CC1=CCCCC1 DKFHWNGVMWFBJE-UHFFFAOYSA-N 0.000 description 1
- ONLFBNDNPYLPCT-UHFFFAOYSA-N 1-phosphorosoethene Chemical compound C=CP=O ONLFBNDNPYLPCT-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LNGIIXGLYTUUHJ-UHFFFAOYSA-N 2-methylbut-2-enoic acid methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.CC=C(C)C(O)=O LNGIIXGLYTUUHJ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-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
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ATVREWZCFIMDOQ-UHFFFAOYSA-N C1=CC=C2P(=O)=CC3=CC=CC=C3C2=C1 Chemical class C1=CC=C2P(=O)=CC3=CC=CC=C3C2=C1 ATVREWZCFIMDOQ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical group 0.000 description 1
- 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 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium 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
- 239000006224 matting agent Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- IQSHMXAZFHORGY-UHFFFAOYSA-N methyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound COC(=O)C=C.CC(=C)C(O)=O IQSHMXAZFHORGY-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QCQALVMFTWRCFI-UHFFFAOYSA-N oct-2-yne Chemical compound CCCCCC#CC QCQALVMFTWRCFI-UHFFFAOYSA-N 0.000 description 1
- UDEISTCPVNLKRJ-UHFFFAOYSA-N oct-3-yne Chemical compound CCCCC#CCC UDEISTCPVNLKRJ-UHFFFAOYSA-N 0.000 description 1
- GZTNBKQTTZSQNS-UHFFFAOYSA-N oct-4-yne Chemical compound CCCC#CCCC GZTNBKQTTZSQNS-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000006187 phenyl benzyl group Chemical group 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- NWIKMSABBNGQRG-UHFFFAOYSA-N tris(3,3-dibromopropyl) phosphate Chemical compound BrC(Br)CCOP(=O)(OCCC(Br)Br)OCCC(Br)Br NWIKMSABBNGQRG-UHFFFAOYSA-N 0.000 description 1
- XHTMGDWCCPGGET-UHFFFAOYSA-N tris(3,3-dichloropropyl) phosphate Chemical compound ClC(Cl)CCOP(=O)(OCCC(Cl)Cl)OCCC(Cl)Cl XHTMGDWCCPGGET-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 150000004794 vinyl magnesium halides Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、アルケニルリン化合物、その単独重合体(ホモポリマー)であるアルケニルリン化合物重合体、及び、アルケニルリン化合物とアルケン化合物との共重合体(コポリマー)であるアルケニルリン化合物共重合体に関するものである。 The present invention relates to an alkenyl phosphorus compound, an alkenyl phosphorus compound polymer which is a homopolymer thereof, and an alkenyl phosphorus compound copolymer which is a copolymer (copolymer) of an alkenyl phosphorus compound and an alkene compound. It is.
周知のように、熱可塑性樹脂(ポリエステル、ポリアミド等)や熱硬化性樹脂(エポキシ樹脂等)等のポリマーは、汎用プラスチックやエンジニアリングプラスチック等として優れた成形加工性、機械的強度、電気特性等を有しているので、電気分野や電子分野を含む各種の分野で広く使用されている。そして、このようなポリマーを成形・加工したポリマー成形品には、火災の発生や延焼を防止するために難燃性が要求されることが多い。 As is well known, polymers such as thermoplastic resins (polyester, polyamide, etc.) and thermosetting resins (epoxy resin, etc.) have excellent moldability, mechanical strength, electrical properties, etc. as general-purpose plastics and engineering plastics. Therefore, it is widely used in various fields including the electric field and the electronic field. In many cases, a polymer molded product obtained by molding and processing such a polymer is required to have flame retardancy in order to prevent the occurrence of fire and the spread of fire.
ポリマーに難燃性を付与するために添加される従来の難燃剤としては、
〔1〕ハロゲン系難燃剤〔テトラブロモジフェニルエーテル、テトラブロモビスフェノールA、トリ(ジクロロプロピル)ホスフェート、トリ(ジブロモプロピル)ホスフェート等〕
の他、
〔2〕有機リン系難燃剤(トリフェニルホスフェート、トリクレジルホスフェート等)、
〔3〕無機難燃剤(金属酸化物、金属水和物、赤リン等)、
〔4〕尿素から誘導されるトリアジン系難燃剤、
〔5〕有機環状リン化合物(9,10−ジヒドロ−9−オキサ−10−フォスファフェナントレン−10−オキシド等)、
等の非ハロゲン系難燃剤も知られている(例えば、特許文献1〜5参照。)。
As conventional flame retardants added to impart flame retardancy to polymers,
[1] Halogen flame retardant [tetrabromodiphenyl ether, tetrabromobisphenol A, tri (dichloropropyl) phosphate, tri (dibromopropyl) phosphate, etc.]
And
[2] Organophosphorous flame retardants (triphenyl phosphate, tricresyl phosphate, etc.),
[3] Inorganic flame retardant (metal oxide, metal hydrate, red phosphorus, etc.)
[4] A triazine flame retardant derived from urea,
[5] Organocyclic phosphorus compounds (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.)
And other non-halogen flame retardants are also known (see, for example, Patent Documents 1 to 5).
前記〔5〕有機環状リン化合物については、環状リン構造を有するエポキシ樹脂の反応原料(反応型難燃剤)として使用可能なもの(例えば、特許文献2参照。)も提案されているが、ポリマー中に練り込むのが一般的である。このような有機環状リン化合物をポリマー中に練り込んだ難燃性ポリマーとしては、有機環状リン化合物からなる難燃剤と、平均粒子径が15μm以下の親水性シリカパウダーと、樹脂とを含有し、前記難燃剤と前記親水性シリカパウダーとの合計含有量が10〜45質量%である樹脂組成物を成形又は塗膜化した難燃性樹脂加工品が提案されている(例えば、特許文献3参照。)。 As for the [5] organic cyclic phosphorus compound, one that can be used as a reaction raw material (reactive flame retardant) of an epoxy resin having a cyclic phosphorus structure has been proposed (for example, see Patent Document 2). It is common to knead into. As a flame retardant polymer in which such an organic cyclic phosphorus compound is kneaded in a polymer, it contains a flame retardant comprising an organic cyclic phosphorus compound, a hydrophilic silica powder having an average particle size of 15 μm or less, and a resin. A flame retardant resin processed product obtained by molding or coating a resin composition having a total content of the flame retardant and the hydrophilic silica powder of 10 to 45% by mass has been proposed (for example, see Patent Document 3). .)
また、反応型難燃剤を化学結合によりポリマー鎖内に導入した難燃性ポリマーとして、
〔6〕ビニルリン化合物重合体(ポリジフェニルビニルホスフィンオキシド等)
等も提案されている(例えば、特許文献5参照。)。
In addition, as a flame retardant polymer in which a reactive flame retardant is introduced into the polymer chain by chemical bonding,
[6] Vinyl phosphorus compound polymer (polydiphenyl vinyl phosphine oxide, etc.)
Etc. have also been proposed (see, for example, Patent Document 5).
前記〔1〕ハロゲン系難燃剤については、熱分解等により生成したハロゲン化ラジカルが燃焼源としての有機ラジカルを捕捉し、燃焼の連鎖反応を停止させることによって、難燃化効果が発揮されると考えられている。しかし、ハロゲン系難燃剤においては、ポリマー組成物の燃焼時に人体に有害なダイオキシンが発生するおそれがあるという問題点がある。 With respect to the above-mentioned [1] halogen flame retardant, when the halogenated radical generated by thermal decomposition or the like captures the organic radical as a combustion source and stops the chain reaction of combustion, the flame retardant effect is exhibited. It is considered. However, the halogen-based flame retardant has a problem that dioxins harmful to the human body may be generated during combustion of the polymer composition.
前記〔2〕有機リン系難燃剤においては、ポリマー組成物中に共存する他の成分の作用により分解され易いので、難燃化効果を十分に発揮できないことがあるという問題点がある。また、ポリマー中に均一に分散されていなければ難燃化効果を十分に発揮できないので、有機リン系難燃剤を添加するポリマーの種類によっては添加量が多くなりがちであるという問題点がある。 [2] The organophosphorus flame retardant has a problem that the flame retarding effect may not be sufficiently exhibited because it is easily decomposed by the action of other components coexisting in the polymer composition. Moreover, since the flame retarding effect cannot be sufficiently exhibited unless it is uniformly dispersed in the polymer, there is a problem that the amount of addition tends to increase depending on the type of polymer to which the organophosphorous flame retardant is added.
前記〔3〕無機難燃剤のうち、金属酸化物(酸化アンチモン、酸化アルミニウム等)や金属水和物(水酸化アルミニウム、水酸化マグネシウム等)においては、難燃化効果が余り高くなく、ポリマー中に多量に配合する必要があるので、ポリマー成形品の成形性が悪いと共に、ポリマー成形品の機械的強度が低下し易いという問題点がある。赤リンにおいては、難燃化効果が高いものの、ポリマーに対する分散不良によりポリマー成形品の成形性や電気特性が低下すると共に、人体に有害なガスが発生し易いという問題点がある。また、赤リンのブリードアウト(外部への放出)が発生するので、ポリマー成形品の難燃性が徐々に低下すると共に、環境ホルモン(内分泌かく乱化学物質)汚染公害を引き起こすおそれがあるという問題点がある。更に、赤リンが空気中の水分と反応してリン酸を生成し、そのリン酸が電子基板を錆びさせるので、電子基板の難燃剤として使いにくいという問題点がある。 Among the above [3] inorganic flame retardants, metal oxides (antimony oxide, aluminum oxide, etc.) and metal hydrates (aluminum hydroxide, magnesium hydroxide, etc.) are not so high in flame retardant effect, Therefore, there are problems that the moldability of the polymer molded product is poor and the mechanical strength of the polymer molded product tends to be lowered. Although red phosphorus has a high flame retardant effect, there are problems that moldability and electrical characteristics of a polymer molded product are lowered due to poor dispersion with respect to the polymer, and gas harmful to the human body is easily generated. In addition, since red phosphorus bleed out (release to the outside) occurs, the flame retardancy of the polymer molded product gradually decreases, and there is a risk of causing pollution of environmental hormones (endocrine disrupting chemicals). There is. In addition, red phosphorus reacts with moisture in the air to produce phosphoric acid, which rusts the electronic substrate, which makes it difficult to use as a flame retardant for the electronic substrate.
前記〔4〕トリアジン系難燃剤においては、ポリマー成形品に光沢が生じ易いので、意匠性が制限されるという問題点がある。ポリマーにタルク、炭酸カルシウム等の艶消し剤を配合した場合には、ポリマー成形品に光沢が生じるのを防止できるものの、ポリマー成形品の靱性が低下するという問題点がある。また、トリアジン系難燃剤のブリードアウトが発生するので、ポリマー成形品の難燃性が徐々に低下すると共に、環境ホルモン汚染公害を引き起こすおそれがあるという問題点がある。 In the above [4] triazine flame retardant, there is a problem that design properties are limited because gloss is easily generated in a polymer molded product. When a matting agent such as talc or calcium carbonate is added to the polymer, the polymer molded product can be prevented from being glossy, but the toughness of the polymer molded product is lowered. Further, since the bleedout of the triazine flame retardant occurs, there is a problem that the flame retardancy of the polymer molded product is gradually lowered and there is a risk of causing environmental hormone pollution pollution.
前記〔5〕有機環状リン化合物においては、それが徐々に加水分解するので、ポリマー成形品の耐水性や電気絶縁性が低いという問題点がある。また、有機環状リン化合物のブリードアウトが発生するので、ポリマー成形品の難燃性が徐々に低下すると共に、環境ホルモン汚染公害を引き起こすおそれがあるという問題点がある。 [5] Since the organic cyclic phosphorus compound is gradually hydrolyzed, there is a problem that the water resistance and electrical insulation of the polymer molded product are low. In addition, since the organic cyclic phosphorus compound bleeds out, there is a problem that the flame retardancy of the polymer molded article is gradually lowered and there is a risk of causing environmental hormone pollution pollution.
前記〔6〕ビニルリン化合物重合体においては、ビニルリン化合物が化学結合によりポリマー鎖内に導入されているが、成形時等における加熱によって着色し易いという問題点がある。 In the above [6] vinyl phosphorus compound polymer, the vinyl phosphorus compound is introduced into the polymer chain by a chemical bond, but there is a problem that it is easily colored by heating at the time of molding or the like.
本発明は、以上のような事情や問題点に鑑みてなされたものであり、前記〔1〕〜〔5〕のような従来の難燃剤の問題点を解決しつつ、加熱しても着色しにくいという特性を兼ね備えたアルケニルリン化合物重合体及びアルケニルリン化合物共重合体、並びにそれらのモノマー(単量体)として好適なアルケニルリン化合物を提供することを目的とする。 The present invention has been made in view of the above circumstances and problems, and is colored even when heated while solving the problems of conventional flame retardants such as [1] to [5]. An object of the present invention is to provide an alkenyl phosphorus compound polymer and an alkenyl phosphorus compound copolymer having the characteristics of being difficult, and an alkenyl phosphorus compound suitable as a monomer thereof.
前記目的を達成するための第1の発明に係るアルケニルリン化合物は、一般式
R1、R2は、それぞれ水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、ヘテロアリール基、アルケニル基、アルコキシ基、アリールオキシ基、又はシリル基を示し、
R3、R4、R5、R6、R7、R8、R9、R10は、それぞれ水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、シアノ基、又はアシル基を示す。)
で表されるものである。
The alkenyl phosphorus compound according to the first invention for achieving the above object has the general formula
R 1 and R 2 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group, an aryloxy group, or a silyl group,
R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyano group, or an acyl group. . )
It is represented by
第2の発明に係るアルケニルリン化合物重合体は、一般式
nは、2以上の整数を示し、
R1、R2は、それぞれ水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、ヘテロアリール基、アルケニル基、アルコキシ基、アリールオキシ基、又はシリル基を示し、
R3、R4、R5、R6、R7、R8、R9、R10は、それぞれ水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、シアノ基、又はアシル基を示す。)
で表されるものである。
The alkenyl phosphorus compound polymer according to the second invention has a general formula
n represents an integer of 2 or more,
R 1 and R 2 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group, an aryloxy group, or a silyl group,
R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyano group, or an acyl group. . )
It is represented by
第3の発明に係るアルケニルリン化合物共重合体は、第1の発明に係るアルケニルリン化合物と、一般式
で表されるアルケン化合物と、を共重合させたものである。
The alkenyl phosphorus compound copolymer according to the third invention comprises an alkenyl phosphorus compound according to the first invention and a general formula
The alkene compound represented by these is copolymerized.
第1の発明によれば、前記アルケニルリン化合物重合体や前記アルケニルリン化合物共重合体のモノマーとして好適に使用することができる。 According to 1st invention, it can use suitably as a monomer of the said alkenyl phosphorus compound polymer or the said alkenyl phosphorus compound copolymer.
第2及び第3の発明によれば、第1の発明に係るアルケニルリン化合物が化学結合によりポリマー鎖内に導入されているので、難燃性を有すると共に、成形時等に加熱しても着色しにくい。また、前記アルケニルリン化合物のブリードアウトが発生しないので、難燃性を長期間(半永久的に)維持できると共に、環境ホルモン汚染公害を引き起こすおそれがない。更に、前記アルケニルリン化合物の部位が加水分解しにくいので、耐水性や電気絶縁性に優れると共に、前記アルケニルリン化合物の部位が加水分解したとしても加水分解物が外部へ放出されることがない。加えて、難燃性を有しないポリマーにブレンド(混合)することによって、そのポリマーに難燃性を付与することができる。 According to the second and third inventions, since the alkenyl phosphorus compound according to the first invention is introduced into the polymer chain by a chemical bond, it has flame retardancy and is colored even when heated during molding or the like. Hard to do. Moreover, since the alkenyl phosphorus compound does not bleed out, flame retardancy can be maintained for a long time (semi-permanently) and there is no possibility of causing environmental hormone pollution pollution. Furthermore, since the site of the alkenyl phosphorus compound is difficult to hydrolyze, it is excellent in water resistance and electrical insulation, and even if the site of the alkenyl phosphorus compound is hydrolyzed, the hydrolyzate is not released to the outside. In addition, flame retardancy can be imparted to the polymer by blending (mixing) with a polymer that does not have flame retardancy.
以下、本発明の実施形態について説明する。
第1実施形態に係るアルケニルリン化合物は、一般式
The alkenyl phosphorus compound according to the first embodiment has a general formula
一般式(1)中のR1、R2は、それぞれ水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、ヘテロアリール基、アルケニル基、アルコキシ基、アリールオキシ基、又はシリル基である。また、一般式(1)中のR3、R4、R5、R6、R7、R8、R9、R10は、それぞれ水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、シアノ基、又はアシル基である。 R 1 and R 2 in the general formula (1) are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group, an aryloxy group, or a silyl group. . In the general formula (1), R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are respectively a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. , A cyano group, or an acyl group.
アルキル基の炭素数としては、1〜18、好ましくは1〜10が適当である。アルキル基としては、メチル基、エチル基、プロピル基、ヘキシル基、デシル基等が挙げられる。 The number of carbon atoms of the alkyl group is 1-18, preferably 1-10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.
シクロアルキル基の炭素数としては、5〜18、好ましくは5〜10が適当である。シクロアルキル基としては、シクロヘキシル基、シクロオクチル基、シクロドデシル基等が挙げられる。 The carbon number of the cycloalkyl group is 5 to 18, preferably 5 to 10. Examples of the cycloalkyl group include a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group.
アリール基の炭素数としては、6〜14、好ましくは6〜10が適当である。アリール基としては、フェニル基、ナフチル基、トリル基、ナフチル基、ベンジルフェニル基等が挙げられる。 The number of carbon atoms in the aryl group is suitably 6 to 14, preferably 6 to 10. Examples of the aryl group include a phenyl group, a naphthyl group, a tolyl group, a naphthyl group, and a benzylphenyl group.
ヘテロアリール基は、ヘテロ原子(酸素、窒素、硫黄等)を含む環式化合物であり、それに含まれる原子数としては、4〜12、好ましくは4〜8が適当である。ヘテロアリール基としては、チエニル基、フリル基、ピリジル基、ピロリル基等が挙げられる。 A heteroaryl group is a cyclic compound containing a heteroatom (oxygen, nitrogen, sulfur, etc.), and the number of atoms contained therein is suitably 4 to 12, preferably 4 to 8. Examples of the heteroaryl group include a thienyl group, a furyl group, a pyridyl group, and a pyrrolyl group.
アラルキル基の炭素数としては、7〜13、好ましくは7〜9が適当である。アラルキル基としては、ベンジル基、フェネチル基、フェニルベンジル基、ナフチルメチル基等が挙げられる。 The number of carbon atoms in the aralkyl group is 7 to 13, preferably 7 to 9. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylbenzyl group, and a naphthylmethyl group.
アルケニル基の炭素数としては、2〜18、好ましくは2〜10が適当である。アルケニル基としては、ビニル基、3−ブテニル基等が挙げられる。 The number of carbon atoms in the alkenyl group is 2-18, preferably 2-10. Examples of the alkenyl group include a vinyl group and a 3-butenyl group.
アルコキシ基の炭素数としては、1〜8、好ましくは1〜4が適当である。アルコキシ基としては、メトキシ基、エトキシ基、ブトキシ基等が挙げられる。 The number of carbon atoms of the alkoxy group is 1-8, preferably 1-4. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group.
アリールオキシ基の炭素数としては、6〜14、好ましくは6〜10が適当である。アリールオキシ基としては、フェノキシ基、ナフチルオキシ基等が挙げられる。 The number of carbon atoms of the aryloxy group is 6 to 14, preferably 6 to 10. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group.
シリル基としては、トリメチルシリル基、トリエチルシリル基、トリフェニルシリル基、フェニルジメチルシリル基、トリメトキシシリル基等が挙げられる。 Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a phenyldimethylsilyl group, and a trimethoxysilyl group.
アシル基の炭素数としては、1〜8、好ましくは1〜4が適当である。アシル基としては、アルデヒド基(ホルミル基)、アセチル基、プロピオニル基、ブチリル基等が挙げられる。 The carbon number of the acyl group is 1-8, preferably 1-4. Examples of the acyl group include an aldehyde group (formyl group), an acetyl group, a propionyl group, and a butyryl group.
一般式(1)で表されるアルケニルリン化合物を製造するには、下記の反応式
金属触媒は、Ni(PMe3)4、Ni[P(n-Bu)3]4等のニッケル(Ni)触媒の他、従来公知のパラジウム(Pd)触媒、ロジウム(Rh)触媒等であってもよい。なお、「n-Bu」は、n−ブチル基を示す。 The metal catalyst includes nickel (Ni) catalysts such as Ni (PMe 3 ) 4 and Ni [P (n-Bu) 3 ] 4 , as well as conventionally known palladium (Pd) catalysts, rhodium (Rh) catalysts, etc. Also good. “N-Bu” represents an n-butyl group.
一般式(5)で表されるアルキン化合物としては、アセチレン、ブチン(1−ブチン、2−ブチン)、オクチン(1−オクチン、2−オクチン、3−オクチン、4−オクチン)、フェニルアセチレン、トリメチルシリルアセチレン、エチニルチオフェン、ヘキシノニトリル、シクロヘキセニルアセチレン等が挙げられる。 Examples of the alkyne compound represented by the general formula (5) include acetylene, butyne (1-butyne, 2-butyne), octyne (1-octyne, 2-octyne, 3-octyne, 4-octyne), phenylacetylene, trimethylsilyl. Examples include acetylene, ethynylthiophene, hexinonitrile, cyclohexenylacetylene, and the like.
得られたアルケニルリン化合物は、分子内にアルケニル基を有しているので、後述するように、第2実施形態のアルケニルリン化合物重合体や第3実施形態のアルケニルリン化合物共重合体のモノマーとして好適に使用することができる。 Since the obtained alkenyl phosphorus compound has an alkenyl group in the molecule, as described later, as a monomer of the alkenyl phosphorus compound polymer of the second embodiment or the alkenyl phosphorus compound copolymer of the third embodiment. It can be preferably used.
第2実施形態に係るアルケニルリン化合物重合体(ホモポリマー)は、一般式
一般式(2)中、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10は、それぞれ一般式(1)中のR1、R2、R3、R4、R5、R6、R7、R8、R9、R10と同じであり、nは2以上の整数である。 In the general formula (2), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are R 1 , R in the general formula (1), respectively. 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are the same, and n is an integer of 2 or more.
一般式(2)で表されるアルケニルリン化合物重合体を製造するには、一般式(1)で表されるアルケニルリン化合物を重合(単独重合)させる。 In order to produce the alkenyl phosphorus compound polymer represented by the general formula (2), the alkenyl phosphorus compound represented by the general formula (1) is polymerized (homopolymerized).
重合反応の温度条件としては、0〜200℃、好ましくは室温〜100℃が適当である。重合反応は、空気雰囲気、又は不活性ガス雰囲気(窒素雰囲気、アルゴン雰囲気等)で行うことができる。重合反応は加熱だけでも進行するが、ラジカル重合開始剤、アニオン重合開始剤等の重合開始剤の存在下で反応させれば、効率良く重合させることができる。重合開始剤の添加割合としては、0.1〜50mol%、好ましくは1〜5mol%が適当である。 The temperature condition for the polymerization reaction is 0 to 200 ° C, preferably room temperature to 100 ° C. The polymerization reaction can be performed in an air atmosphere or an inert gas atmosphere (such as a nitrogen atmosphere or an argon atmosphere). Although the polymerization reaction proceeds only by heating, it can be efficiently polymerized by reacting in the presence of a polymerization initiator such as a radical polymerization initiator or an anionic polymerization initiator. The addition ratio of the polymerization initiator is 0.1 to 50 mol%, preferably 1 to 5 mol%.
ラジカル重合開始剤としては、過酸化物触媒、アゾ系触媒等が挙げられる。過酸化物触媒としては、過硫酸カリウム、過硫酸ナトリウム、過酢酸、過酸化ベンゾイル、クメンヒドロペルオキシド等が挙げられる。アゾ系触媒としては、アゾビスイソブチロニトリル(AIBN)等が挙げられる。 Examples of radical polymerization initiators include peroxide catalysts and azo catalysts. Examples of the peroxide catalyst include potassium persulfate, sodium persulfate, peracetic acid, benzoyl peroxide, cumene hydroperoxide, and the like. Examples of the azo catalyst include azobisisobutyronitrile (AIBN).
アニオン重合開始剤としては、グリニャール化合物、有機リチウム化合物等が挙げられる。グリニャール化合物としては、メチルマグネシウムハライド、n−ブチルマグネシウムハライド、t−ブチルマグネシウムハライド、ビニルマグネシウムハライド、アリルマグネシウムハライド、ベンジルマグネシウムハライド、フェニルマグネシウムハライド等が挙げられる。ここで、ハライドとは、クロリド(塩化物)、ブロミド(臭化物)、及びヨージド(ヨウ化物)を意味する。有機リチウム化合物としては、メチルリチウム、n−ブチルリチウム、t−ブチルリチウム、フェニルリチウム等が挙げられる。 Examples of the anionic polymerization initiator include Grignard compounds and organic lithium compounds. Examples of the Grignard compound include methyl magnesium halide, n-butyl magnesium halide, t-butyl magnesium halide, vinyl magnesium halide, allyl magnesium halide, benzyl magnesium halide, phenyl magnesium halide, and the like. Here, the halide means chloride (chloride), bromide (bromide), and iodide (iodide). Examples of the organic lithium compound include methyl lithium, n-butyl lithium, t-butyl lithium, and phenyl lithium.
また、溶媒中で反応させた場合も、効率良く重合させることができる。溶媒としては、芳香族炭化水素系溶媒、環状エーテル系溶媒等が挙げられる。芳香族炭化水素系溶媒としては、ベンゼン、トルエン、キシレン等が挙げられる。環状エーテル系溶媒としては、THF(テトラヒドロフラン)、テトラヒドロピラン、ジオキサン等が挙げられる。 Moreover, when it reacts in a solvent, it can superpose | polymerize efficiently. Examples of the solvent include aromatic hydrocarbon solvents and cyclic ether solvents. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like. Examples of the cyclic ether solvent include THF (tetrahydrofuran), tetrahydropyran, dioxane and the like.
重合反応は、通常の場合、30分〜24時間程度で終了する。重合反応終了後、必要に応じて反応混合物から溶媒を留去し、水及び希酸水溶液で洗浄してから真空乾燥等により乾燥させれば、一般式(2)で表されるアルケニルリン化合物重合体を得ることができる。 The polymerization reaction is usually completed in about 30 minutes to 24 hours. After completion of the polymerization reaction, if necessary, the solvent is distilled off from the reaction mixture, washed with water and a dilute aqueous acid solution, and then dried by vacuum drying or the like. Coalescence can be obtained.
得られるアルケニルリン化合物重合体の分子量は、特に限定されるものではないが、1000〜100万程度が適当である。 Although the molecular weight of the alkenyl phosphorus compound polymer obtained is not particularly limited, about 1000 to 1,000,000 is appropriate.
得られたアルケニルリン化合物重合体においては、一般式(1)で表されるアルケニルリン化合物が化学結合によりポリマー鎖内に導入されているので、難燃性を有すると共に、成形時等に加熱しても着色しにくいという利点がある。また、前記アルケニルリン化合物のブリードアウトが発生しないので、難燃性を長期間(半永久的に)維持できると共に、環境ホルモン汚染公害を引き起こすおそれがないという利点がある。更に、前記アルケニルリン化合物の部位が加水分解しにくいので、耐水性や電気絶縁性に優れると共に、前記アルケニルリン化合物の部位が加水分解したとしても加水分解物が外部へ放出されることがないという利点がある。 In the obtained alkenyl phosphorus compound polymer, since the alkenyl phosphorus compound represented by the general formula (1) is introduced into the polymer chain by a chemical bond, it has flame retardancy and is heated at the time of molding or the like. There is an advantage that it is difficult to color. In addition, since the alkenyl phosphorus compound does not bleed out, there is an advantage that flame retardancy can be maintained for a long time (semi-permanently) and there is no possibility of causing environmental hormone pollution pollution. Furthermore, since the site of the alkenyl phosphorus compound is difficult to hydrolyze, it is excellent in water resistance and electrical insulation, and even if the site of the alkenyl phosphorus compound is hydrolyzed, the hydrolyzate is not released to the outside. There are advantages.
第3実施形態に係るアルケニルリン化合物共重合体(コポリマー)は、一般式(1)で表されるアルケニルリン化合物と、一般式
一般式(3)中のR11、R12、R13、R14は、それぞれ水素原子、アリール基(フェニル基等)、シアノ基、アルコキシカルボニル基(メトキシカルボニル基等)、アルキル基(メチル基等)、又はカルボキシル基である。このようなアルケン化合物としては、スチレン、アクリロニトリル、アクリル酸メチル(メチルアクリレート)、メタクリル酸メチル(メチルメタクリレート)、アクリル酸、メタクリル酸等が挙げられる。 R 11 , R 12 , R 13 and R 14 in the general formula (3) are each a hydrogen atom, an aryl group (such as a phenyl group), a cyano group, an alkoxycarbonyl group (such as a methoxycarbonyl group), an alkyl group (a methyl group). Etc.) or a carboxyl group. Examples of such alkene compounds include styrene, acrylonitrile, methyl acrylate (methyl acrylate), methyl methacrylate (methyl methacrylate), acrylic acid, and methacrylic acid.
アルケニルリン化合物共重合体を製造するには、第2実施形態と同様の反応条件及び操作で、一般式(1)で表されるアルケニルリン化合物と、一般式(3)で表されるアルケン化合物とを共重合させる。 In order to produce an alkenyl phosphorus compound copolymer, an alkenyl phosphorus compound represented by the general formula (1) and an alkene compound represented by the general formula (3) under the same reaction conditions and operation as in the second embodiment. And are copolymerized.
共重合反応終了後、必要に応じて反応混合物から溶媒を留去し、水及び希酸水溶液で洗浄してから真空乾燥等により乾燥させれば、アルケニルリン化合物共重合体を得ることができる。 After completion of the copolymerization reaction, the alkenyl phosphorus compound copolymer can be obtained by evaporating the solvent from the reaction mixture as necessary, washing with water and dilute aqueous acid solution, and drying by vacuum drying or the like.
前記アルケニルリン化合物に対するコモノマーとしてのアルケン化合物の配合割合は、特に限定されるものではないが、1〜1000程度が適当である。 The blending ratio of the alkene compound as a comonomer with respect to the alkenyl phosphorus compound is not particularly limited, but about 1 to 1000 is appropriate.
得られたアルケニルリン化合物共重合体においては、一般式(1)で表されるアルケニルリン化合物が化学結合によりポリマー鎖内に導入されているので、第2実施形態のアルケニルリン化合物重合体と同様の利点がある。また、第2実施形態のアルケニルリン化合物重合体や第3実施形態のアルケニルリン化合物共重合体においては、難燃性を有しないポリマーにブレンド(混合)することによって、そのポリマーに難燃性を付与できるという利点がある。 In the obtained alkenyl phosphorus compound copolymer, since the alkenyl phosphorus compound represented by the general formula (1) is introduced into the polymer chain by a chemical bond, the same as the alkenyl phosphorus compound polymer of the second embodiment. There are advantages. Further, in the alkenyl phosphorus compound polymer of the second embodiment and the alkenyl phosphorus compound copolymer of the third embodiment, the polymer is made flame retardant by blending (mixing) with a polymer having no flame retardant property. There is an advantage that it can be granted.
以下、実施例を列挙して本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example is enumerated and this invention is demonstrated in detail, this invention is not limited to these Examples.
〔反応触媒の調製〕
下記の反応式
The following reaction formula
具体的には、フラスコ内の空気を窒素ガスで置換した後、フラスコ内に1当量のNi(cod)2を入れ、更に4当量のPMe3を加えた。そして、フラスコを氷浴で冷却しながら溶液を30分間撹拌したところ、固体が得られた。 Specifically, after the air in the flask was replaced with nitrogen gas, 1 equivalent of Ni (cod) 2 was placed in the flask, and 4 equivalents of PMe 3 was further added. The solution was stirred for 30 minutes while cooling the flask in an ice bath to obtain a solid.
〔アルケニルリン化合物の製造〕
下記の反応式
The following reaction formula
具体的には、構造式(4)で表される環状リン化合物12.75gをフラスコに入れ、フラスコ内の空気を窒素ガスで置換した後、フラスコ内にメチルアルコール30mLを入れ、前記環状リン化合物をメチルアルコールに溶解させた。次いで、溶液を脱気した後、溶液に1当量のアセチレンを吹き込み、更に1mol%の前記反応触媒を添加してから70℃で3時間撹拌することにより反応を行った。反応終了後、反応液を濃縮、減圧蒸留(真空度:0.1Pa、沸点:200〜230℃)した。このような操作により、白色の結晶が13.0g(収率:90%)得られた。得られた結晶の融点は、62.6〜62.9℃であった。 Specifically, 12.75 g of the cyclic phosphorus compound represented by the structural formula (4) is put in a flask, the air in the flask is replaced with nitrogen gas, 30 mL of methyl alcohol is put in the flask, and the cyclic phosphorus compound is added. Dissolved in methyl alcohol. Next, after degassing the solution, 1 equivalent of acetylene was blown into the solution, and 1 mol% of the reaction catalyst was further added, followed by stirring at 70 ° C. for 3 hours. After completion of the reaction, the reaction solution was concentrated and distilled under reduced pressure (vacuum degree: 0.1 Pa, boiling point: 200 to 230 ° C.). By this operation, 13.0 g (yield: 90%) of white crystals was obtained. The melting point of the obtained crystal was 62.6 to 62.9 ° C.
また、得られた結晶のNMR(核磁気共鳴)スペクトルデータを測定した。その結果を以下に示す。
1H−NMR(400MHz、CDCl3)δ: 7.87(dt、J=17.1Hz,6.1Hz、2H)、7.70(dt、J=13.4Hz,3.9Hz、1H)、7.61(t、J=7.8Hz、1H)、7.45〜7.39(m、1H)、7.28(q、J=6.4Hz、1H)、7.16(s、1H)、7.13(d、J=9.1Hz、1H)、6.27(ttt、J=32.5Hz,13.2Hz,4.2Hz、3H)
31P−NMR(400MHz、CDCl3): 23.47
Further, NMR (nuclear magnetic resonance) spectrum data of the obtained crystal was measured. The results are shown below.
1 H-NMR (400 MHz, CDCl 3 ) δ: 7.87 (dt, J = 17.1 Hz, 6.1 Hz, 2 H), 7.70 (dt, J = 13.4 Hz, 3.9 Hz, 1 H), 7.61 (t, J = 7.8 Hz 1H), 7.45-7.39 (m, 1H), 7.28 (q, J = 6.4 Hz, 1H), 7.16 (s, 1H), 7.13 (d, J = 9.1 Hz, 1H), 6.27 (ttt, J = (32.5Hz, 13.2Hz, 4.2Hz, 3H)
31 P-NMR (400 MHz, CDCl 3 ): 23.47
更に、得られた結晶の高分解能質量分析スペクトル(HRMS)データを測定した。その結果を以下に示す。
構造式(6)で表されるアルケニルリン化合物の分子式: C14H12O2P
C14H12O2Pの分子量の理論値: 242.0497
得られた結晶の分子量の実測値: 242.0479
Furthermore, high resolution mass spectrometry spectrum (HRMS) data of the obtained crystals were measured. The results are shown below.
Molecular formula of the alkenyl phosphorus compound represented by the structural formula (6): C 14 H 12 O 2 P
Theoretical molecular weight of C 14 H 12 O 2 P: 242.0497
Measured value of molecular weight of the obtained crystal: 242.0479
〔アルケニルリン化合物の製造〕
下記の反応式
The following reaction formula
具体的には、構造式(4)で表される環状リン化合物を1mmolとし、溶媒を2mLのTHFとし、アルキン化合物を1mmolのジフェニルアセチレンとし、反応触媒を5mol%のNi[P(n-Bu)3]4とした以外は、実施例1と同様にして反応を行った。 Specifically, the cyclic phosphorus compound represented by the structural formula (4) is 1 mmol, the solvent is 2 mL of THF, the alkyne compound is 1 mmol of diphenylacetylene, and the reaction catalyst is 5 mol% of Ni [P (n-Bu ) 3 ] The reaction was performed in the same manner as in Example 1 except that 4 .
その結果、白色の結晶が得られた(収率:72%)。得られた結晶の融点は、169.2℃であった。また、得られた結晶のNMRスペクトルデータを測定した。その結果を以下に示す。
1H−NMR(399.78MHz、CDCl3)δ: 6.97〜7.85(m、19H)
As a result, white crystals were obtained (yield: 72%). The melting point of the obtained crystal was 169.2 ° C. Further, NMR spectrum data of the obtained crystal was measured. The results are shown below.
1 H-NMR (399.78 MHz, CDCl 3 ) δ: 6.97-7.85 (m, 19H)
〔アルケニルリン化合物の製造〕
下記の反応式
The following reaction formula
具体的には、構造式(4)で表される環状リン化合物を1mmolとし、溶媒を2mLのTHFとし、アルキン化合物を1mmolの1−オクチンとし、反応触媒を5mol%のNi[P(n-Bu)3]4及び5mol%のジフェニルホスフィン酸とし、25℃で一晩撹拌した以外は、実施例1と同様にして反応を行った。 Specifically, the cyclic phosphorus compound represented by the structural formula (4) is 1 mmol, the solvent is 2 mL of THF, the alkyne compound is 1 mmol of 1-octyne, and the reaction catalyst is 5 mol% of Ni [P (n- Bu) 3 ] The reaction was carried out in the same manner as in Example 1 except that 4 and 5 mol% of diphenylphosphinic acid were used and stirred at 25 ° C. overnight.
その結果、油状物質が得られた(収率:87%)。また、得られた油状物質のNMRスペクトルデータを測定した。その結果を以下に示す。
1H−NMR(399.78MHz、CDCl3)δ: 7.00〜7.99(m、61.6H)、6.10(d、JPH=24.0、5.36H)、5.95(d、JPH=44.0、5.36H)、5.92(d、J=16.0、1H)、5.86(d、J=16.0、1H)、2.17〜2.28(m、3.62H)、1.20〜1.69(m、75.09H)、0.84〜0.90(m、31.67H)
As a result, an oily substance was obtained (yield: 87%). Further, NMR spectrum data of the obtained oily substance was measured. The results are shown below.
1 H-NMR (399.78 MHz, CDCl 3 ) δ: 7.00 to 7.99 (m, 61.6 H), 6.10 (d, J PH = 24.0, 5.36 H), 5.95 (d, J PH = 44.0, 5.36 H), 5.92 (D, J = 16.0, 1H), 5.86 (d, J = 16.0, 1H), 2.17 to 2.28 (m, 3.62H), 1.20 to 1.69 (m, 75.09H), 0.84 to 0.90 (m, 31.67H)
測定したNMRスペクトルデータに基づいて、構造式(8)で表されるアルケニルリン化合物と構造式(9)で表されるアルケニルリン化合物とのモル比率を算出したところ、
76.1:23.9
であった。
Based on the measured NMR spectrum data, the molar ratio between the alkenyl phosphorus compound represented by Structural Formula (8) and the alkenyl phosphorus compound represented by Structural Formula (9) was calculated.
76.1: 23.9
Met.
〔アルケニルリン化合物の製造〕
実施例3の反応式に示すように、構造式(4)で表される環状リン化合物と1−オクチンとを反応させることにより、構造式(8)で表されるアルケニルリン化合物と構造式(9)で表されるアルケニルリン化合物との混合物を製造した。
(Production of alkenyl phosphorus compound)
As shown in the reaction formula of Example 3, by reacting the cyclic phosphorus compound represented by the structural formula (4) with 1-octyne, the alkenyl phosphorus compound represented by the structural formula (8) and the structural formula ( A mixture with the alkenyl phosphorus compound represented by 9) was produced.
具体的には、構造式(4)で表される環状リン化合物を1mmolとし、溶媒を2mLのエチルアルコールとし、アルキン化合物を1mmolの1−オクチンとし、反応触媒を5mol%のNi[P(n-Bu)3]4とした以外は、実施例1と同様にして反応を行った。 Specifically, the cyclic phosphorus compound represented by the structural formula (4) is 1 mmol, the solvent is 2 mL of ethyl alcohol, the alkyne compound is 1 mmol of 1-octyne, and the reaction catalyst is 5 mol% of Ni [P (n -Bu) 3 ] The reaction was performed in the same manner as in Example 1 except that 4 .
その結果、油状物質が得られた(収率:75%)。また、得られた油状物質のNMRスペクトルデータを測定した。その結果を以下に示す。
1H−NMR(399.78MHz、CDCl3)δ: 6.95〜7.98(m、154H)、6.08(d、JPH=24.0、1.03H)、5.94(d、JPH=47.9、1H)、5.92(d、J=16.0、1H)、5.86(d、J=16.0、1.35H)、2.14〜2.28(m、7.5H)、1.68〜1.73(m、8.23H)、1.19〜1.45(m、33.53H)、0.81〜0.87(m、14.3H)
As a result, an oily substance was obtained (yield: 75%). Further, NMR spectrum data of the obtained oily substance was measured. The results are shown below.
1 H-NMR (399.78 MHz, CDCl 3 ) δ: 6.95 to 7.98 (m, 154H), 6.08 (d, J PH = 24.0, 1.03 H), 5.94 (d, J PH = 47.9, 1 H), 5.92 (d , J = 16.0, 1H), 5.86 (d, J = 16.0, 1.35H), 2.14-2.28 (m, 7.5H), 1.68-1.73 (m, 8.23H), 1.19-1.45 (m, 33.53H), 0.81 to 0.87 (m, 14.3H)
測定したNMRスペクトルデータに基づいて、構造式(8)で表されるアルケニルリン化合物と構造式(9)で表されるアルケニルリン化合物とのモル比率を算出したところ、
29.9:70.1
であった。
Based on the measured NMR spectrum data, the molar ratio between the alkenyl phosphorus compound represented by Structural Formula (8) and the alkenyl phosphorus compound represented by Structural Formula (9) was calculated.
29.9: 70.1
Met.
〔アルケニルリン化合物重合体(ホモポリマー)の製造〕
5mol%のアゾビスイソブチロニトリル(AIBN)を重合開始剤として使用し、構造式(6)で表されるアルケニルリン化合物(9,10−ジヒドロ−9−オキサ−10−ビニル−10−フォスファフェナントレン−10−オキシド。以下、「BPVP」という。)をモノマーとして、表1に示す条件(反応温度:80℃、反応時間:16時間)で重合(単独重合)させることにより、一般式
Using 5 mol% of azobisisobutyronitrile (AIBN) as a polymerization initiator, an alkenyl phosphorus compound (9,10-dihydro-9-oxa-10-vinyl-10-phos represented by the structural formula (6)) Faphenanthrene-10-oxide (hereinafter referred to as “BPVP”) as a monomer is polymerized (homopolymerized) under the conditions shown in Table 1 (reaction temperature: 80 ° C., reaction time: 16 hours).
得られた重合体の収率を算出した。また、得られた重合体の重量平均分子量(Mw)及び数平均分子量(Mn)をGPC(ゲル浸透クロマトグラフィー)で測定し、それらから分子量分布(Mw/Mn)を算出した。これらの結果を表1に示す。 The yield of the obtained polymer was calculated. Moreover, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polymer were measured by GPC (gel permeation chromatography), and molecular weight distribution (Mw / Mn) was computed from them. These results are shown in Table 1.
〔アルケニルリン化合物重合体(ホモポリマー)の製造〕
実施例5と同様の操作を、実施例5とは異なる表1に示す条件で行った。得られた重合体の収率、重量平均分子量(Mw)、及び分子量分布(Mw/Mn)を表1に示す。
[Production of alkenyl phosphorus compound polymer (homopolymer)]
The same operation as in Example 5 was performed under the conditions shown in Table 1 different from those in Example 5. Table 1 shows the yield, weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the obtained polymer.
〔アルケニルリン化合物重合体(ホモポリマー)の製造〕
実施例5と同様の操作を、実施例5とは異なる表1に示す条件で行った。得られた重合体の収率、重量平均分子量(Mw)、及び分子量分布(Mw/Mn)を表1に示す。
[Production of alkenyl phosphorus compound polymer (homopolymer)]
The same operation as in Example 5 was performed under the conditions shown in Table 1 different from those in Example 5. Table 1 shows the yield, weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the obtained polymer.
〔アルケニルリン化合物重合体(ホモポリマー)の製造〕
表1に示すように、構造式(6)で表されるアルケニルリン化合物(BPVP)を1mmolとし、溶媒を2mLのTHFとし、0.05mmolのフェニルマグネシウムブロミドを添加し、25℃で3時間撹拌した以外は、実施例5と同様の操作を行った。得られた重合体の収率、重量平均分子量(Mw)、及び分子量分布(Mw/Mn)を表1に示す。
[Production of alkenyl phosphorus compound polymer (homopolymer)]
As shown in Table 1, the alkenyl phosphorus compound (BPVP) represented by the structural formula (6) was 1 mmol, the solvent was 2 mL of THF, 0.05 mmol of phenylmagnesium bromide was added, and the mixture was stirred at 25 ° C. for 3 hours. Except for the above, the same operation as in Example 5 was performed. Table 1 shows the yield, weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the obtained polymer.
〔アルケニルリン化合物共重合体(コポリマー)の製造〕
構造式(6)で表されるアルケニルリン化合物(BPVP)に対して5mol%のアゾビスイソブチロニトリル(AIBN)を重合開始剤として使用し、前記アルケニルリン化合物(BPVP)と、表2に示すコモノマーとを、表2に示す条件で共重合させた。コモノマーとBPVPとのモル比は、
コモノマー:BPVP=5:1
とした。反応温度は80℃、反応時間は16時間とした。なお、表2中の「MeOH」は、メチルアルコールを示す。
[Manufacture of alkenyl phosphorus compound copolymer]
5 mol% of azobisisobutyronitrile (AIBN) is used as a polymerization initiator with respect to the alkenyl phosphorus compound (BPVP) represented by the structural formula (6), and the alkenyl phosphorus compound (BPVP) The comonomer shown was copolymerized under the conditions shown in Table 2. The molar ratio of comonomer to BPVP is
Comonomer: BPVP = 5: 1
It was. The reaction temperature was 80 ° C. and the reaction time was 16 hours. “MeOH” in Table 2 represents methyl alcohol.
得られた共重合体の収率、及び前記アルケニルリン化合物(BPVP)の取込率を算出した。また、得られた共重合体の重量平均分子量(Mw)及び数平均分子量(Mn)をGPCで測定し、それらから分子量分布(Mw/Mn)を算出した。これらの結果を表2に示す。 The yield of the obtained copolymer and the uptake rate of the alkenyl phosphorus compound (BPVP) were calculated. Moreover, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained copolymer were measured by GPC, and molecular weight distribution (Mw / Mn) was computed from them. These results are shown in Table 2.
〔アルケニルリン化合物共重合体(コポリマー)の製造〕
実施例9と同様の操作を、実施例9とは異なる表2に示す条件でそれぞれ行った。得られた共重合体の収率、重量平均分子量(Mw)、及び分子量分布(Mw/Mn)、並びに前記アルケニルリン化合物(BPVP)の取込率を表2に示す。
[Manufacture of alkenyl phosphorus compound copolymer]
The same operations as in Example 9 were performed under the conditions shown in Table 2 different from those in Example 9. Table 2 shows the yield, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and uptake rate of the alkenyl phosphorus compound (BPVP) of the obtained copolymer.
〔アルケニルリン化合物共重合体(コポリマー)の製造〕
実施例9と同様の操作を、実施例9とは異なる表2に示す条件でそれぞれ行った。得られた共重合体の収率、重量平均分子量(Mw)、及び分子量分布(Mw/Mn)、並びに前記アルケニルリン化合物(BPVP)の取込率を表2に示す。
[Manufacture of alkenyl phosphorus compound copolymer]
The same operations as in Example 9 were performed under the conditions shown in Table 2 different from those in Example 9. Table 2 shows the yield, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and uptake rate of the alkenyl phosphorus compound (BPVP) of the obtained copolymer.
〔アルケニルリン化合物共重合体(コポリマー)の製造〕
実施例9と同様の操作を、実施例9とは異なる表2に示す条件でそれぞれ行った。得られた共重合体の収率、重量平均分子量(Mw)、及び分子量分布(Mw/Mn)、並びに前記アルケニルリン化合物(BPVP)の取込率を表2に示す。
[Manufacture of alkenyl phosphorus compound copolymer]
The same operations as in Example 9 were performed under the conditions shown in Table 2 different from those in Example 9. Table 2 shows the yield, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and uptake rate of the alkenyl phosphorus compound (BPVP) of the obtained copolymer.
〔アルケニルリン化合物共重合体(コポリマー)の製造〕
実施例9と同様の操作を、実施例9とは異なる表2に示す条件でそれぞれ行った。得られた共重合体の収率、重量平均分子量(Mw)、及び分子量分布(Mw/Mn)、並びに前記アルケニルリン化合物(BPVP)の取込率を表2に示す。
[Manufacture of alkenyl phosphorus compound copolymer]
The same operations as in Example 9 were performed under the conditions shown in Table 2 different from those in Example 9. Table 2 shows the yield, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and uptake rate of the alkenyl phosphorus compound (BPVP) of the obtained copolymer.
〔アルケニルリン化合物共重合体(コポリマー)の製造〕
実施例9と同様の操作を、実施例9とは異なる表2に示す条件でそれぞれ行った。得られた共重合体の収率、重量平均分子量(Mw)、及び分子量分布(Mw/Mn)、並びに前記アルケニルリン化合物(BPVP)の取込率を表2に示す。
[Manufacture of alkenyl phosphorus compound copolymer]
The same operations as in Example 9 were performed under the conditions shown in Table 2 different from those in Example 9. Table 2 shows the yield, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and uptake rate of the alkenyl phosphorus compound (BPVP) of the obtained copolymer.
以上のように、本発明に係るアルケニルリン化合物重合体及びアルケニルリン化合物共重合体は、従来の難燃剤の問題点を解決しつつ、加熱しても着色しにくいという特性を兼ね備えた難燃性ポリマーとして有用である。また、本発明に係るアルケニルリン化合物は、前記アルケニルリン化合物重合体や前記アルケニルリン化合物共重合体のモノマーとして有用である。
As described above, the alkenyl phosphorus compound polymer and the alkenyl phosphorus compound copolymer according to the present invention solve the problems of the conventional flame retardant, and have the property of being difficult to be colored even when heated. Useful as a polymer. Moreover, the alkenyl phosphorus compound according to the present invention is useful as a monomer of the alkenyl phosphorus compound polymer or the alkenyl phosphorus compound copolymer.
Claims (3)
R1、R2は、それぞれ水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、ヘテロアリール基、アルケニル基、アルコキシ基、アリールオキシ基、又はシリル基を示し、
R3、R4、R5、R6、R7、R8、R9、R10は、それぞれ水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、シアノ基、又はアシル基を示す。)
で表されるアルケニルリン化合物。 General formula
R 1 and R 2 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group, an aryloxy group, or a silyl group,
R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyano group, or an acyl group. . )
The alkenyl phosphorus compound represented by these.
nは、2以上の整数を示し、
R1、R2は、それぞれ水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、ヘテロアリール基、アルケニル基、アルコキシ基、アリールオキシ基、又はシリル基を示し、
R3、R4、R5、R6、R7、R8、R9、R10は、それぞれ水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、シアノ基、又はアシル基を示す。)
で表されるアルケニルリン化合物重合体。 General formula
n represents an integer of 2 or more,
R 1 and R 2 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group, an aryloxy group, or a silyl group,
R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyano group, or an acyl group. . )
The alkenyl phosphorus compound polymer represented by these.
一般式
で表されるアルケン化合物と、
を共重合させたアルケニルリン化合物共重合体。
An alkenyl phosphorus compound according to claim 1;
General formula
An alkene compound represented by:
An alkenyl phosphorus compound copolymer.
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2013023519A (en) * | 2011-07-19 | 2013-02-04 | Panasonic Corp | Modified polyphenylene ether and halogenated organic phosphorus compound, and production method of them |
JP2014087752A (en) * | 2012-10-30 | 2014-05-15 | Toray Eng Co Ltd | Microreactor system, method of producing compound using the same, and method of producing alkenyl phosphorus compound |
US20160060281A1 (en) * | 2013-05-31 | 2016-03-03 | Scott Edward Angell | Butadien2,3-diyl linked di-dopo derivatives as flame retardants |
WO2017043552A1 (en) * | 2015-09-11 | 2017-03-16 | 丸善石油化学株式会社 | Method for producing alkenyl phosphorus compound |
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JP2017222883A (en) * | 2012-05-01 | 2017-12-21 | 株式会社ブリヂストン | Polydienes and diene copolymers having organophosphine functionality |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007091824A (en) * | 2005-09-27 | 2007-04-12 | National Institute Of Advanced Industrial & Technology | High-molecular weight polydiphenylvinylphosphine oxide, its manufacturing method and metal extracting reagent |
JP2007146131A (en) * | 2005-11-04 | 2007-06-14 | National Institute Of Advanced Industrial & Technology | Novel phosphorus-containing alkadiene polymer and method of preparing the same |
JP2009266663A (en) * | 2008-04-25 | 2009-11-12 | Mitsui Chemicals Inc | Nonaqueous electrolyte and lithium secondary battery using the same |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4517235B2 (en) * | 2004-12-06 | 2010-08-04 | ナガセケムテックス株式会社 | Process for producing β, γ-unsaturated phosphinic acid ester |
-
2009
- 2009-02-28 JP JP2009047433A patent/JP5709094B2/en active Active
-
2010
- 2010-02-19 WO PCT/JP2010/001068 patent/WO2010098047A1/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007091824A (en) * | 2005-09-27 | 2007-04-12 | National Institute Of Advanced Industrial & Technology | High-molecular weight polydiphenylvinylphosphine oxide, its manufacturing method and metal extracting reagent |
JP2007146131A (en) * | 2005-11-04 | 2007-06-14 | National Institute Of Advanced Industrial & Technology | Novel phosphorus-containing alkadiene polymer and method of preparing the same |
JP2009266663A (en) * | 2008-04-25 | 2009-11-12 | Mitsui Chemicals Inc | Nonaqueous electrolyte and lithium secondary battery using the same |
Non-Patent Citations (1)
Title |
---|
JPN6014025865; Li-Biao Han et al.: 'Efficient and Selective Nickel-Catalyzed Addition of H-P(O) and H-S Bonds to Alkynes' J.AM.CHE.SOC Vol.126, 2004, p.5080-5081 * |
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JPWO2017043552A1 (en) * | 2015-09-11 | 2018-06-28 | 丸善石油化学株式会社 | Process for producing alkenyl phosphorus compound |
US10479809B2 (en) | 2015-09-11 | 2019-11-19 | Maruzen Petrochemical Co., Ltd. | Method for producing alkenyl phosphorus compound |
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