JPH11158232A - Silicone-containing vinyl polymer and its manufacture - Google Patents
Silicone-containing vinyl polymer and its manufactureInfo
- Publication number
- JPH11158232A JPH11158232A JP9344293A JP34429397A JPH11158232A JP H11158232 A JPH11158232 A JP H11158232A JP 9344293 A JP9344293 A JP 9344293A JP 34429397 A JP34429397 A JP 34429397A JP H11158232 A JPH11158232 A JP H11158232A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silicone
- carbon atoms
- formula
- vinyl polymer
- 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
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 95
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 125000000962 organic group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- -1 siloxane chain Chemical group 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 18
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 238000001879 gelation Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 138
- 239000007787 solid Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 238000010992 reflux Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- CSLWLKZGURFAOD-UHFFFAOYSA-N 2-[(2-carboxy-1-hydroxypropan-2-yl)diazenyl]-3-hydroxy-2-methylpropanoic acid Chemical compound OCC(C)(C(O)=O)N=NC(C)(CO)C(O)=O CSLWLKZGURFAOD-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HYWZOETUAIBWEZ-UHFFFAOYSA-N 3-[hydroxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)O HYWZOETUAIBWEZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RMCCONIRBZIDTH-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 1,3-dioxo-2-benzofuran-5-carboxylate Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 RMCCONIRBZIDTH-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 2
- 229910006294 Si—N Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-UHFFFAOYSA-N 0.000 description 1
- VHJHZYSXJKREEE-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropyl prop-2-enoate Chemical compound FC(F)C(F)(F)COC(=O)C=C VHJHZYSXJKREEE-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- 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 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- OKQXCDUCLYWRHA-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)Cl OKQXCDUCLYWRHA-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-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
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-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
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- WPKWPKDNOPEODE-UHFFFAOYSA-N bis(2,4,4-trimethylpentan-2-yl)diazene Chemical compound CC(C)(C)CC(C)(C)N=NC(C)(C)CC(C)(C)C WPKWPKDNOPEODE-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- MLLIERDVEOBFGZ-UHFFFAOYSA-N chloro-methyl-phenyl-prop-2-enylsilane Chemical compound C=CC[Si](Cl)(C)C1=CC=CC=C1 MLLIERDVEOBFGZ-UHFFFAOYSA-N 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- GKCPCPKXFGQXGS-UHFFFAOYSA-N ditert-butyldiazene Chemical compound CC(C)(C)N=NC(C)(C)C GKCPCPKXFGQXGS-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 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
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、シリコーン含有ビ
ニル系重合体、およびその製造方法に関し、詳しくは、
ケイ素原子結合水素原子をシロキサン鎖の末端のみに有
するシリコーン含有ビニル系重合体、およびこのような
重合体を効率よく製造する方法に関する。TECHNICAL FIELD The present invention relates to a silicone-containing vinyl polymer and a method for producing the same.
The present invention relates to a silicone-containing vinyl polymer having a silicon-bonded hydrogen atom only at the end of a siloxane chain, and a method for efficiently producing such a polymer.
【０００２】[0002]
【従来の技術】分子鎖末端のケイ素原子にアクリル基、
メタクリル基等のラジカル重合性ビニル基を結合したシ
リコーン化合物を単独でラジカル重合、ないしはその他
のラジカル重合性ビニル系単量体とラジカル共重合して
得られる、シリコーン含有ビニル系重合体は公知であ
る。2. Description of the Related Art An acrylic group is added to a silicon atom at a molecular chain terminal.
Silicone-containing vinyl polymers obtained by radical polymerization of a silicone compound having a radical polymerizable vinyl group such as a methacryl group alone or radical copolymerization with another radical polymerizable vinyl monomer are known. .
【０００３】しかし、このような重合体は、それ自体の
反応性が乏しいために、一方の分子鎖末端のケイ素原子
にアクリル基、メタクリル基等のラジカル重合性ビニル
基を結合し、他方の分子鎖末端のケイ素原子にアルケニ
ル基を結合したシリコーン化合物を単独でラジカル重合
するか、またはその他のラジカル重合性ビニル系単量体
とラジカル共重合してなる、ケイ素原子結合アルケニル
基をシロキサン鎖の末端に有するシリコーン含有ビニル
系重合体（特開平１−１４２７２０号公報、および特開
平１−２５２６１６号公報参照）や、一方の分子鎖末端
のケイ素原子にアクリル基、メタクリル基等のラジカル
重合性ビニル基を結合し、他方の分子鎖末端のケイ素原
子に水素原子を結合したシリコーン化合物を単独でラジ
カル重合するか、またはその他のラジカル重合性ビニル
系単量体とラジカル共重合してなる、ケイ素原子結合水
素原子をシロキサン鎖の末端に有するシリコーン含有ビ
ニル系重合体（特開昭６３−２１６０４４号公報、およ
び特開平４−６８００７号公報参照）が提案されてい
る。[0003] However, such a polymer has poor reactivity in itself, so that a radical polymerizable vinyl group such as an acryl group or a methacryl group is bonded to a silicon atom at the terminal of one molecular chain, and the other molecule is bonded. A silicone compound in which an alkenyl group is bonded to a silicon atom at the chain end is subjected to radical polymerization alone or a radical copolymerization with another radically polymerizable vinyl monomer. Or a radically polymerizable vinyl group such as an acryl group or a methacrylic group at the silicon atom at one molecular chain terminal (see JP-A-1-142720 and JP-A-1-252616). Or radically polymerize a silicone compound having a hydrogen atom bonded to a silicon atom at the other end of the molecular chain alone, Or a silicone-containing vinyl polymer having a silicon-bonded hydrogen atom at the end of a siloxane chain, obtained by radical copolymerization with a radical polymerizable vinyl monomer (JP-A-63-216044, and Japanese Laid-Open Patent Publication No. 4-68007) has been proposed.
【０００４】しかし、特開平１−１４２７２０号公報、
および特開平１−２５２６１６号公報により提案されて
いるシリコーン含有ビニル系重合体においては、アルケ
ニル基もラジカル反応に関与してしまい、一部架橋した
ような重合体しか得られず、甚だしい場合には重合体が
ゲル化してしまうという問題があった。また、特開昭６
３−２１６０４４号公報、および特開平４−６８００７
号公報により提案されたシリコーン含有ビニル系重合体
は、分子中に複数のケイ素原子結合水素原子を有するた
めに反応性が非常に高く、これをヒドロシリル化反応に
利用しようとすると、この重合体自体がゲル化してしま
うという問題があった。However, Japanese Patent Application Laid-Open No. 1-142720 discloses
In the silicone-containing vinyl polymer proposed in Japanese Patent Application Laid-Open No. 1-252616, an alkenyl group also participates in a radical reaction, and only a partially crosslinked polymer is obtained. There was a problem that the polymer gelled. In addition, Japanese Unexamined Patent Publication
JP-A-3-216044 and JP-A-4-68007
The silicone-containing vinyl polymer proposed in the above publication has a very high reactivity because it has a plurality of silicon-bonded hydrogen atoms in the molecule. However, there was a problem that the gel was formed.
【０００５】[0005]
【発明が解決しようとする課題】本発明者らは上記の課
題を解決するために鋭意検討した結果、本発明に到達し
た。すなわち、本発明の目的は、ケイ素原子結合水素原
子をシロキサン鎖の末端のみに有するシリコーン含有ビ
ニル系重合体、およびこのような重合体を効率よく製造
する方法を提供することにある。DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, an object of the present invention is to provide a silicone-containing vinyl polymer having a silicon-bonded hydrogen atom only at the end of a siloxane chain, and a method for efficiently producing such a polymer.
【０００６】[0006]
【問題を解決するための手段】本発明のシリコーン含有
ビニル系重合体は、少なくとも一般式：Means for Solving the Problems The silicone-containing vinyl polymer of the present invention has at least a general formula:
【化１３】 （式中、Ｒ1は水素原子またはメチル基であり、Ｒ2は二
価有機基であり、Ｒ3は同じか、または相異なり、置換
または非置換の炭素原子数１〜１０のアルキル基もしく
はアリール基であり、ｍは１〜４００の整数である。）
で示される構造単位からなることを特徴とする。Embedded image (Wherein, R 1 is a hydrogen atom or a methyl group, R 2 is a divalent organic group, and R 3 is the same or different and is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or An aryl group, and m is an integer of 1 to 400.)
Characterized by comprising a structural unit represented by
【０００７】また、本発明のシリコーン含有ビニル系重
合体の製造方法は、少なくとも一般式：The method for producing the silicone-containing vinyl polymer of the present invention comprises at least a compound represented by the following general formula:
【化１４】 （式中、Ｒ1は水素原子またはメチル基であり、Ｒ2は二
価有機基であり、Ｒ3は同じか、または相異なり、置換
または非置換の炭素原子数１〜１０のアルキル基もしく
はアリール基であり、ｍは１〜４００の整数である。）
で示されるシリコーン化合物をラジカル重合することを
特徴とする。Embedded image (Wherein, R 1 is a hydrogen atom or a methyl group, R 2 is a divalent organic group, and R 3 is the same or different and is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or An aryl group, and m is an integer of 1 to 400.)
Is characterized by radical polymerization of the silicone compound represented by
【０００８】[0008]
【発明の実施の形態】はじめに、本発明のシリコーン含
有ビニル系重合体を詳細に説明する。本発明のシリコー
ン含有ビニル系重合体は、少なくとも一般式：DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the silicone-containing vinyl polymer of the present invention will be described in detail. The silicone-containing vinyl polymer of the present invention has at least a general formula:
【化１５】 で示される構造単位からなることを特徴とする。上式中
のＲ1は水素原子またはメチル基である。また、上式中
のＲ2は二価有機基であり、例えば、一般式：Embedded image Characterized by comprising a structural unit represented by R 1 in the above formula is a hydrogen atom or a methyl group. R 2 in the above formula is a divalent organic group.
【化１６】 で示される基が例示される。上式中のＲ9は炭素原子数
１〜１０のアルキレン基であり、メチレン基、エチレン
基、プロピレン基、ブチレン基が例示される。また、上
式中のＲ10は水素原子または炭素原子数１〜１０のアル
キル基であり、Ｒ10のアルキル基としては、メチル基、
エチル基、プロピル基、ブチル基が例示される。また、
上式中のＲ11は単結合または炭素原子数１〜１０のアル
キレン基であり、Ｒ11のアルキレン基としては、前記Ｒ
9と同様のアルキレン基が例示される。また、上式中の
Ｒ3は同じか、または相異なり、置換または非置換の炭
素原子数１〜１０のアルキル基もしくはアリール基であ
り、Ｒ3の置換もしくは非置換のアルキル基としては、
メチル基、エチル基、プロピル基、ブチル基、３−クロ
ロプロピル基、３，３，３−トリフルオロプロピル基が
例示され、また、Ｒ3の置換もしくは非置換のアリール
基としては、フェニル基、トリル基、キシシル基が例示
される。また、上式中のｍは１〜４００の整数であり、
シロキサン鎖の特徴を遺憾なく発揮することができるこ
とから、ｍは２〜４００の範囲内の整数であることが好
ましく、さらに、ｍは５〜４００の範囲内の整数である
ことが好ましく、特に、ｍは１０〜４００の範囲内の整
数であることが好ましく、一方、シリコーン含有ビニル
系重合体中の上記の構造単位の含有率を向上でき、か
つ、高重合度の重合体を得ることができることから、ｍ
は１〜２００の範囲内の整数であることが好ましく、さ
らに、ｍは１〜１００の範囲内の整数であることが好ま
しく、特に、ｍは１〜５０の範囲内の整数であることが
好ましい。Embedded image Are exemplified. R 9 in the above formula is an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group. R 10 in the above formula is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group of R 10 is a methyl group,
Examples include an ethyl group, a propyl group, and a butyl group. Also,
R 11 in the above formula is a single bond or an alkylene group having 1 to 10 carbon atoms, the alkylene group of R 11, wherein R
An alkylene group similar to 9 is exemplified. Further, R 3 in the above formula is the same or different and is a substituted or unsubstituted alkyl group or aryl group having 1 to 10 carbon atoms. As the substituted or unsubstituted alkyl group of R 3 ,
Examples of a methyl group, an ethyl group, a propyl group, a butyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, and a substituted or unsubstituted aryl group for R 3 include a phenyl group, Examples thereof include a tolyl group and a xyl group. Further, m in the above formula is an integer of 1 to 400,
Since the characteristics of the siloxane chain can be exhibited without regret, m is preferably an integer in the range of 2 to 400, and m is preferably an integer in the range of 5 to 400. m is preferably an integer in the range of 10 to 400. On the other hand, the content of the above structural unit in the silicone-containing vinyl polymer can be improved, and a polymer having a high degree of polymerization can be obtained. From m
Is preferably an integer in the range of 1 to 200, more preferably m is an integer in the range of 1 to 100, and particularly preferably, m is an integer in the range of 1 to 50. .
【０００９】さらに、本発明のシリコーン含有ビニル系
重合体は、上記の構造単位式と一般式：Further, the silicone-containing vinyl polymer of the present invention has the above-mentioned structural unit formula and general formula:
【化１７】 で示される構造単位からなることが好ましい。上式中の
Ｒ4は水素原子またはメチル基である。また、上式中の
Ｒ5は、一般式：Embedded image It preferably comprises a structural unit represented by R 4 in the above formula is a hydrogen atom or a methyl group. R 5 in the above formula is a general formula:
【化１８】 で示される基からなる群から選択される少なくとも一種
の基である。上式中のＲ6は置換もしくは非置換の炭素
原子数１〜１０のアルキル基、炭素原子数１〜１０のヒ
ドロキシ基含有アルキル基、または置換もしくは非置換
のアリール基であり、Ｒ6のアルキル基としては、前記
Ｒ3のアルキル基と同様の基が例示され、また、Ｒ6のヒ
ドロキシ基含有アルキル基としては、ヒドロキシメチル
基、２−ヒドロキシエチル基、２−ヒドロキシプロピル
基、３−ヒドロキシプロピル基が例示され、また、Ｒ6
のアリール基としては、前記Ｒ3のアリール基と同様の
基が例示される。また、上式中のＲ7は炭素原子数１〜
１０のアルキル基であり、前記Ｒ10のアルキル基と同様
の基が例示される。また、上式中のＲ8は炭素原子数１
〜１０のアルキル基であり、前記Ｒ10のアルキル基と同
様の基が例示される。また、上式中のＸは水素原子、炭
素原子数１〜１０のアルキル基、アリール基、またはハ
ロゲン原子であり、Ｘのアルキル基としては、前記Ｒ10
のアルキル基と同様の基が例示され、Ｘのアリール基と
しては、前記Ｒ3のアリール基と同様の基が例示され、
また、Ｘのハロゲン原子としては、塩素原子、臭素原子
が例示される。Embedded image And at least one group selected from the group consisting of groups represented by R 6 in the above formula is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, hydroxyalkyl groups containing alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group, an alkyl of R 6 Examples of the group include the same groups as the aforementioned alkyl groups for R 3. Examples of the hydroxy group-containing alkyl group for R 6 include a hydroxymethyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, and a 3-hydroxy group. propyl group and the like, also, R 6
Examples of the aryl group include the same groups as the above-described aryl group for R 3 . R 7 in the above formula has 1 to 1 carbon atoms.
10 is an alkyl group, the same groups as the alkyl groups of said R 10 can be exemplified. Further, R 8 in the above formula has 1 carbon atom.
An 10 alkyl group, the same groups as the alkyl groups of said R 10 can be exemplified. Further, X is a hydrogen atom in the above formulas, an alkyl group having 1 to 10 carbon atoms, an aryl group or a halogen atom, the alkyl group of X, wherein R 10
Examples of the same group as the alkyl group of X include, and examples of the aryl group of X include the same groups as the above-described aryl group of R 3 .
Examples of the halogen atom for X include a chlorine atom and a bromine atom.
【００１０】本発明のシリコーン含有ビニル系重合体
は、前者の構造単位のみからなっていてもよく、また、
後者の構造単位とからなっていてもよく、本発明の重合
体がシロキサン鎖の特徴を遺憾なく発揮することができ
ることから、前者の構造単位が全体の０.１〜１００モ
ル％の範囲内であることが好ましく、特に、１〜１００
モル％の範囲内であることが好ましい。The silicone-containing vinyl polymer of the present invention may be composed of only the former structural unit.
The polymer may be composed of the latter structural unit, and since the polymer of the present invention can exhibit the features of the siloxane chain without regret, the former structural unit may be contained in the range of 0.1 to 100 mol% of the whole. It is preferable that there is
Preferably it is in the range of mol%.
【００１１】続いて、本発明のシリコーン含有ビニル系
重合体の製造方法を詳細に説明する。本発明のシリコー
ン含有ビニル系重合体の製造方法は、少なくとも一般
式：Next, the method for producing the silicone-containing vinyl polymer of the present invention will be described in detail. The method for producing the silicone-containing vinyl polymer of the present invention comprises at least a general formula:
【化１９】 で示されるシリコーン化合物をラジカル重合することを
特徴とする。上式中のＲ 1は水素原子またはメチル基で
ある。また、上式中のＲ2は二価有機基であり、前記と
同様の基が例示される。また、上式中のＲ3は同じか、
または相異なり、置換または非置換の炭素原子数１〜１
０のアルキル基もしくはアリール基であり、前記と同様
の基が例示される。また、上式中のｍは１〜４００の範
囲内の整数であり、好ましい範囲も前記のとおりであ
る。Embedded imageRadical polymerization of the silicone compound represented by
Features. R in the above formula 1Is a hydrogen atom or a methyl group
is there. In addition, R in the above equationTwoIs a divalent organic group, and
Similar groups are exemplified. In addition, R in the above equationThreeAre the same,
Or different, substituted or unsubstituted C 1 -C 1
0 alkyl group or aryl group, similar to the above.
Are exemplified. Also, m in the above equation is in the range of 1 to 400.
Is an integer in the box, and the preferred range is also as described above.
You.
【００１２】さらに、本発明のシリコーン含有ビニル系
重合体の製造方法は、上記のシリコーン化合物とラジカ
ル重合性ビニル系単量体をラジカル共重合することを特
徴とする。このラジカル重合性ビニル系単量体は、ビニ
ル基、ビニレン基、ビニリデン基を有する単量体であれ
ばよく、例えば、一般式：Further, the method for producing a silicone-containing vinyl polymer of the present invention is characterized in that the above-mentioned silicone compound is radically copolymerized with a radically polymerizable vinyl monomer. The radical polymerizable vinyl monomer may be any monomer having a vinyl group, a vinylene group, or a vinylidene group.
【化２０】 で示される化合物であることが好ましい。上式中のＲ4
は水素原子またはメチル基である。また、上式中のＲ5
は、一般式：Embedded image It is preferable that the compound is represented by R 4 in the above formula
Is a hydrogen atom or a methyl group. In addition, R 5 in the above formula
Is the general formula:
【化２１】 で示される基からなる群から選択される少なくとも一種
の基である。上式中のＲ 6は置換もしくは非置換の炭素
原子数１〜１０のアルキル基、炭素原子数１〜１０のヒ
ドロキシ基含有アルキル基、または置換もしくは非置換
のアリール基であり、前記と同様の基が例示される。ま
た、上式中のＲ7は炭素原子数１〜１０のアルキル基で
あり、前記と同様の基が例示される。また、上式中のＲ
8は炭素原子数１〜１０のアルキル基であり、前記と同
様の基が例示される。また、上式中のＸは水素原子、炭
素原子数１〜１０のアルキル基、アリール基、またはハ
ロゲン原子であり、前記と同様である。Embedded imageAt least one selected from the group consisting of groups represented by
It is a group of. R in the above formula 6Is a substituted or unsubstituted carbon
An alkyl group having 1 to 10 atoms, an alkyl group having 1 to 10 carbon atoms
Droxy group-containing alkyl group, or substituted or unsubstituted
And the same groups as described above are exemplified. Ma
R in the above formula7Is an alkyl group having 1 to 10 carbon atoms
And the same groups as described above are exemplified. In addition, R in the above equation
8Is an alkyl group having 1 to 10 carbon atoms,
Similar groups are exemplified. X in the above formula is a hydrogen atom,
An alkyl group having 1 to 10 atoms, an aryl group, or
And is the same as described above.
【００１３】このようなラジカル重合性ビニル系単量体
としては、メチルアクリレート、エチルアクリレート、
ブロピルアクリレート、ｎ−ブチルアクリレート、イソ
ブチルアクリレート、アミルアクリレート、ヘキシルア
クリレート、２−エチルヘキシルアクリレート、シクロ
ヘキシルアクリレート、ｎ−オクチルアクリレート、グ
リシジルアクリレート、２−ヒドロキシエチルアクリレ
ート、２−ヒドロキシプロビルアクリレート、２，２，
３，３−テトラフルオロプロピルアクリレート、オクタ
フルオロペンチルアクリレート、メチルメタクリレー
ト、エチルメタクリレート、ｎ−ブチルメタクリレー
ト、イソプチルメタクリレート、２−エチルヘキシルメ
タクリレート、ラウリルメタクリレート、トリデシルメ
タクリレート、ベンジルメタクリレート、シクロヘキシ
ルメタクリレート、テトラヒドロフルフリルメタクリレ
ート、２−ヒドロキシエチルメククリレート、２−ヒド
ロキシプロピルメタクリレート、グリシジルメタクリレ
ート、２−メトキシエチルメタクリレート、２−エトキ
シエチルメタクリレート、オクタフルオロペンチルメタ
クリレート等の不飽和カルボン酸エステル化合物；メタ
クリル酸、アクリル酸等の不飽和脂肪族カルボン酸化合
物；アクリル酸アミド、メタクリル酸アミド、Ｎ−メチ
ロールアクリル酸アミド等の不飽和脂肪族カルボン酸ア
ミド化合物；アクリロニトリル、メタクリロニトリル等
の不飽和脂肪族ニトリル化合物；酢酸ビニル、プロピオ
ン酸ビニル、バーサティツク酸ビニル等の不飽和脂肪族
化合物；エテン、プロペン、ブテン、ペンテン等のオレ
フィン；塩化ビニル、弗化ビニル等のハロゲン化ビニル
化合物；スチレン、メチルスチレン、ビニルトルエン、
ビニルピリジン等の芳香族ビニル化合物；ブタジエン、
イソプレン等の脂肪族ジエン化合物；その他、無水マレ
イン酸、４−メタクリロキシエチルトリメリット酸無水
物（４−ＭＥＴＡ）等の不飽和カルボン酸無水物が例示
され、これらのラジカル重合性ビニル系単量体を一種も
しくは二種以上用いてもよい。Such radically polymerizable vinyl monomers include methyl acrylate, ethyl acrylate,
Propyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2,2 ,
3,3-tetrafluoropropyl acrylate, octafluoropentyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl Unsaturated carboxylic acid ester compounds such as methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, octafluoropentyl methacrylate; methacrylic acid, acrylic acid, etc. Unsaturated aliphatic carboxylic acid compounds; Acrylamide Unsaturated aliphatic carboxylic acid amide compounds such as methacrylamide and N-methylol acrylamide; unsaturated aliphatic nitrile compounds such as acrylonitrile and methacrylonitrile; unsaturated fats such as vinyl acetate, vinyl propionate and vinyl versatate Olefins such as ethene, propene, butene and pentene; vinyl halide compounds such as vinyl chloride and vinyl fluoride; styrene, methylstyrene, vinyltoluene,
Aromatic vinyl compounds such as vinylpyridine; butadiene,
Aliphatic diene compounds such as isoprene; and unsaturated carboxylic anhydrides such as maleic anhydride and 4-methacryloxyethyl trimellitic anhydride (4-META). One or more bodies may be used.
【００１４】本発明のシリコーン含有ビニル系重合体の
製造方法において、前者のシロキサン化合物を単独でラ
ジカル重合してもよく、また、後者の化合物とラジカル
共重合してもよく、得られる重合体がシロキサン鎖の特
徴を遺憾なく発揮することができることから、前者のシ
ロキサン化合物が全体の０.１〜１００モル％の範囲内
であることが好ましく、特に、１〜１００モル％の範囲
内であることが好ましい。In the method for producing a silicone-containing vinyl polymer of the present invention, the former siloxane compound may be radically polymerized alone or the latter may be radically copolymerized with the latter compound. Since the characteristics of the siloxane chain can be unfailingly exhibited, the former siloxane compound is preferably in the range of 0.1 to 100% by mole, and particularly preferably in the range of 1 to 100% by mole. Is preferred.
【００１５】本発明の製造方法において、上記のシリコ
ーン化合物をラジカル重合する方法、あるいは上記のシ
リコーン化合物と上記の化合物をラジカル共重合する方
法は限定されないが、溶液重合法によることが好まし
い。この溶液重合法において、その反応条件は任意であ
るが、好ましくは、５０〜１５０℃で３〜２０時間反応
させることにより進行する。この際用いることのできる
有機溶媒としては、ヘキサン、オクタン、デカン、シク
ロヘキサン等の脂肪族炭化水素；ベンゼン、トルエン、
キシレン等の芳香族炭化水素；ジエチルエーテル、ジブ
チルエーテル、テトラヒドロフラン、ジオキサン等のエ
ーテル類；アセトン、メチルエチルケトン、メチルイソ
ブチルケトン、ジイソブチルケトン等のケトン類；酢酸
メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル等の
エステル類が例示され、これらの有機溶媒の中でも、ト
ルエン、キシレンが特に好適である。In the production method of the present invention, a method of radically polymerizing the above-mentioned silicone compound or a method of radically copolymerizing the above-mentioned silicone compound with the above-mentioned compound is not limited, but a solution polymerization method is preferable. In this solution polymerization method, the reaction conditions are arbitrary, but preferably, the reaction proceeds at 50 to 150 ° C. for 3 to 20 hours. Organic solvents that can be used at this time include aliphatic hydrocarbons such as hexane, octane, decane, and cyclohexane; benzene, toluene,
Aromatic hydrocarbons such as xylene; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate and the like Esters are exemplified, and among these organic solvents, toluene and xylene are particularly preferred.
【００１６】また、このラジカル重合を行う際に用いら
れるラジカル開始剤としては、通常のラジカル重合法に
用いられる公知の化合物が使用でき、例えば、２，２’
−アゾビス（イソブチロニトリル）、２，２’−アゾビ
ス（２−メチルブチロニトリル）、２，２’−アゾビス
（２，４−ジメチルバレロニトリル）、２，２’−アゾ
ビス（２−ヒドロキシメチルプロピオネート）、２，
２’−アゾビス（２，４，４−トリメチルペンタン）、
２，２’−アゾビス（２−メチルプロパン）等のアゾビ
ス系化合物；過酸化ベンゾイル、過酸化ラウロイル、ｔ
ｅｒｔ−ブチルパーオキシベンゾエート、ｔｅｒｔ−ブ
チルパーオキシ−２−エチルヘキサノエート等の有機過
酸化物、およびこれらの化合物の一種もしくは二種以上
の混合物が挙げられる。これらのラジカル開始剤として
は、得られるシリコーン含有ビニル系重合体を白金系触
媒によりヒドロシリル化する際に、この反応を阻害する
ような物質、例えば、イオウ、リン等を含まない化合物
であることが好ましい。このラジカル開始剤の使用量
は、上記のシリコーン化合物、および上記の化合物の合
計１００重量部に対して０.１〜５重量部の範囲内の量
であることが好ましい。As the radical initiator used in the radical polymerization, a known compound used in a usual radical polymerization method can be used. For example, 2,2 ′
-Azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-hydroxy Methyl propionate), 2,
2'-azobis (2,4,4-trimethylpentane),
Azobis compounds such as 2,2'-azobis (2-methylpropane); benzoyl peroxide, lauroyl peroxide, t
Organic peroxides such as tert-butylperoxybenzoate and tert-butylperoxy-2-ethylhexanoate, and one or a mixture of two or more of these compounds are exemplified. As such a radical initiator, a substance which does not inhibit the reaction when the obtained silicone-containing vinyl-based polymer is hydrosilylated with a platinum-based catalyst, for example, a compound containing no sulfur, phosphorus or the like may be used. preferable. The amount of the radical initiator to be used is preferably in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the total of the above silicone compound and the above compound.
【００１７】また、本発明のシリコーン含有ビニル系重
合体を製造する際には、さらに連鎖移動剤を添加するこ
とが好ましい。この連鎖移動剤としては、例えば、２−
メルカプトエタノール、ブチルメルカプタン、ｎ−ドデ
シルメルカプタン、３−メルカプトプロピルトリメトキ
シシラン等のメルカプト化合物；塩化メチレン、クロロ
ホルム、四塩化炭素、臭化ブチル、３−クロロプロピル
トリメトキシシラン等のハロゲン化物が挙げられる。In producing the silicone-containing vinyl polymer of the present invention, it is preferable to further add a chain transfer agent. As this chain transfer agent, for example, 2-
Mercapto compounds such as mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, and 3-mercaptopropyltrimethoxysilane; and halides such as methylene chloride, chloroform, carbon tetrachloride, butyl bromide, and 3-chloropropyltrimethoxysilane. .
【００１８】[0018]
【実施例】本発明のシリコーン含有ビニル系重合体、お
よびその製造方法を実施例により詳細に説明する。EXAMPLES The silicone-containing vinyl polymer of the present invention and the method for producing the same will be described in detail with reference to examples.
【００１９】［参考例１］窒素気流下、攪拌装置、温度
計、還流冷却管、および滴下ロートを備えた４つ口フラ
スコに、３−メタクリロキシプロピルジメチルヒドロキ
シシラン２０２ｇ(１.０モル)とジエチルアミン１２４
ｇ(１.８モル)を投入した。次に、これらを攪拌しなが
ら、反応温度を３０℃以下に保つように、ジメチルクロ
ロシラン１１３ｇ(１.２モル)を滴下ロートからゆっく
り滴下した。滴下終了後、反応液を３０℃で２時間加熱
した。その後、反応液を室温まで冷却して、反応液をろ
過し、得られたろ液を、減圧蒸留することにより、８１
〜８３℃、３〜５mmHgの留分１８２ｇを得た。この留分
を29Ｓｉ−核磁気共鳴分析(以下、ＮＭＲ)および1Ｈ−
ＮＭＲにより分析した結果、次式で示されるシリコーン
化合物(Ｉ)であることが確認された。Reference Example 1 Under a nitrogen stream, 202 g (1.0 mol) of 3-methacryloxypropyldimethylhydroxysilane was placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. Diethylamine 124
g (1.8 mol). Next, while stirring them, 113 g (1.2 mol) of dimethylchlorosilane was slowly dropped from the dropping funnel so as to keep the reaction temperature at 30 ° C. or lower. After the addition was completed, the reaction solution was heated at 30 ° C. for 2 hours. Thereafter, the reaction solution was cooled to room temperature, the reaction solution was filtered, and the obtained filtrate was distilled under reduced pressure to obtain 81%.
At ８３83 ° C., 182 g of a 3-5 mmHg fraction were obtained. This fraction was subjected to 29 Si-nuclear magnetic resonance analysis (hereinafter, NMR) and 1 H-
As a result of analysis by NMR, it was confirmed that the silicone compound (I) was represented by the following formula.
【化２２】 Embedded image
【００２０】［参考例２］窒素気流下、攪拌装置、温度
計、還流冷却管、および滴下ロートを備えた４つ口フラ
スコに、式：Reference Example 2 A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel under a nitrogen stream was charged with the following formula:
【化２３】 で示されるシリコーン２９８ｇ(１.０モル)とジエチル
アミン１２４ｇ(１.８モル)を投入した。これらを攪拌
しながら、反応温度を３０℃以下に保つように、３−メ
タクリロキシプロピルジメチルクロロシラン２６５ｇ
(１.２モル)を滴下ロートからゆっくり滴下した。滴下
終了後、反応液を３０℃で２時間加熱した。その後、こ
の反応液を室温まで冷却し、反応液をろ過し、得られた
ろ液から低沸点成分を減圧除去することにより、無色透
明液体４８２ｇを得た。この無色透明液体を29Ｓｉ−Ｎ
ＭＲおよび1Ｈ−ＮＭＲにより分析した結果、次式で示
されるシリコーン化合物(II)であることが確認された。Embedded image 298 g (1.0 mol) of silicone represented by the formula (1) and 124 g (1.8 mol) of diethylamine were charged. While stirring these, 265 g of 3-methacryloxypropyldimethylchlorosilane was maintained such that the reaction temperature was maintained at 30 ° C. or lower.
(1.2 mol) was slowly dropped from the dropping funnel. After the addition was completed, the reaction solution was heated at 30 ° C. for 2 hours. Thereafter, the reaction solution was cooled to room temperature, the reaction solution was filtered, and low-boiling components were removed from the obtained filtrate under reduced pressure to obtain 482 g of a colorless transparent liquid. This colorless and transparent liquid is 29 Si-N
As a result of analysis by MR and 1 H-NMR, it was confirmed that the silicone compound (II) was represented by the following formula.
【化２４】 Embedded image
【００２１】［参考例３］窒素気流下、攪拌装置、温度
計、およびＤｅａｎ−Ｓｔａｒｋ還流管を備えた４つ口
フラスコに、ヘキサメチルシクロトリシロキサン２２２
ｇ(１.０モル)、トルエン１６７ｇを投入して、これら
を２時間還流脱水した後、冷却し、３０℃以下に保っ
た。次に、これらに、１５重量％−ｎ−ブチルリチウム
のｎ−ヘキサン溶液０.７４ml(０.００１１７モル)を投
入し、１０分間攪拌した。その後、これに、３−メタク
リロキシプロピルジメチルヒドロキシシラン２３.７ｇ
(０.１１７モル)、ジメチルホルムアミド２７.２ｇ、お
よびアセトニトリル５５.５ｇを投入し、３０℃以下
で、攪拌を継続した。重合の進行をガスクロマトグラフ
ィーにより追跡し、６時間後の転化率が９８.０％とな
ったところで、ジエチルアミン１４.４ｇ(０.２１モ
ル)、ジメチルクロロシラン１３.２ｇ(０.１４モル)を
順に加えて重合を停止させた。反応液をろ過し、得られ
たろ液から低沸点成分を減圧除去することにより、無色
透明液体２１５ｇを得た。この無色透明液体を29Ｓｉ−
ＮＭＲおよび1Ｈ−ＮＭＲにより分析した結果、次式で
示されるシリコーン化合物(III)であることが確認され
た。REFERENCE EXAMPLE 3 Hexamethylcyclotrisiloxane 222 was placed in a four-necked flask equipped with a stirrer, a thermometer, and a Dean-Stark reflux tube under a nitrogen stream.
g (1.0 mol) and 167 g of toluene were added thereto, and they were refluxed and dehydrated for 2 hours, then cooled and kept at 30 ° C. or lower. Next, 0.74 ml (0.00117 mol) of a 15% by weight n-butyllithium n-hexane solution was added thereto, and the mixture was stirred for 10 minutes. Thereafter, 23.7 g of 3-methacryloxypropyldimethylhydroxysilane was added thereto.
(0.1117 mol), 27.2 g of dimethylformamide and 55.5 g of acetonitrile were added, and stirring was continued at 30 ° C. or lower. The progress of the polymerization was monitored by gas chromatography. When the conversion after 6 hours reached 98.0%, 14.4 g (0.21 mol) of diethylamine and 13.2 g (0.14 mol) of dimethylchlorosilane were added. The polymerization was stopped by adding in order. The reaction solution was filtered, and low-boiling components were removed from the obtained filtrate under reduced pressure to obtain 215 g of a colorless transparent liquid. This colorless and transparent liquid is 29 Si-
As a result of analysis by NMR and 1 H-NMR, it was confirmed that it was a silicone compound (III) represented by the following formula.
【化２５】 Embedded image
【００２２】［参考例４］窒素気流下、攪拌装置、温度
計、およびＤｅａｎ−Ｓｔａｒｋ還流管を備えた４つ口
フラスコに、ヘキサメチルシクロトリシロキサン２２２
ｇ(１.０モル)、トルエン１６７ｇを投入し、２時間還
流脱水した後、冷却し、３０℃以下に保った。次に、こ
れに、１５重量％−ｎ−ブチルリチウムのｎ−ヘキサン
溶液０.３６ml(０.０００５８モル)を投入し、１０分間
攪拌した。次に、これに３−メタクリロキシプロピルジ
メチルヒドロキシシラン１１.７ｇ(０.０５８モル)、ジ
メチルホルムアミド２７.２ｇ、およびアセトニトリル
５５.５ｇを投入し、３０℃以下で、攪拌を継続した。
重合の進行をガスクロマトグラフィーにより追跡し、６
時間後に添加率が９８.０％となったところで、ジエチ
ルアミン７.５ｇ(０.１０５モル)、ジメチルクロロシラ
ン６.６ｇ(０.０６９モル)を順に加えて重合を停止させ
た。反応液をろ過し、得られたろ液から低沸点成分を減
圧除去することにより、無色透明液体２１７ｇを得た。
この無色透明液体を29Ｓｉ−ＮＭＲおよび13Ｃ−ＮＭＲ
により分析した結果、次式で示されるシリコーン(IV)で
あることが確認された。REFERENCE EXAMPLE 4 Hexamethylcyclotrisiloxane 222 was placed in a four-necked flask equipped with a stirrer, a thermometer, and a Dean-Stark reflux tube under a nitrogen stream.
g (1.0 mol) and 167 g of toluene, refluxed and dehydrated for 2 hours, cooled, and kept at 30 ° C. or lower. Next, 0.36 ml (0.00588 mol) of a 15 wt% n-butyllithium n-hexane solution was added thereto, and the mixture was stirred for 10 minutes. Next, 11.7 g (0.058 mol) of 3-methacryloxypropyldimethylhydroxysilane, 27.2 g of dimethylformamide and 55.5 g of acetonitrile were added thereto, and stirring was continued at 30 ° C. or lower.
The progress of polymerization was monitored by gas chromatography, and 6
After a lapse of time, when the addition ratio became 98.0%, 7.5 g (0.105 mol) of diethylamine and 6.6 g (0.069 mol) of dimethylchlorosilane were added in that order to terminate the polymerization. The reaction solution was filtered, and low-boiling components were removed from the obtained filtrate under reduced pressure to obtain 217 g of a colorless and transparent liquid.
This colorless and transparent liquid was subjected to 29 Si-NMR and 13 C-NMR.
As a result, the silicone (IV) represented by the following formula was confirmed.
【化２６】 Embedded image
【００２３】［参考例５］窒素気流下、攪拌装置、温度
計、還流冷却管、および滴下ロートを備えた４つ口フラ
スコに、式：Reference Example 5 A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel under a nitrogen stream was prepared by the following formula:
【化２７】 で示されるシリコーン２９８ｇ(１.０モル)、およびジ
エチルアミン１２４ｇ(１.８モル)を投入し、攪拌しな
がら、反応温度を２０℃以下に保つように、式：Embedded image 298 g (1.0 mol) of silicone represented by the formula and 124 g (1.8 mol) of diethylamine are added, and while stirring, the reaction is carried out by the following formula:
【化２８】 で示されるビニルフェニルジメチルクロロシラン２３
５.８ｇ(１.２モル)を滴下ロートからゆっくり滴下し
た。滴下終了後、反応液を３０℃で２４時間攪拌した。
その後、この反応液を室温まで冷却し、反応液をろ過
し、得られたろ液から低沸点成分を減圧除去することに
より、無色透明液体４４５ｇを得た。この無色透明液体
を29Ｓｉ−ＮＭＲおよび13Ｃ−ＮＭＲにより分析した結
果、次式で示されるシリコーン(Ｖ)であることが確認さ
れた。Embedded image Vinylphenyldimethylchlorosilane 23 represented by
5.8 g (1.2 mol) was slowly dropped from the dropping funnel. After the addition was completed, the reaction solution was stirred at 30 ° C. for 24 hours.
Thereafter, the reaction solution was cooled to room temperature, the reaction solution was filtered, and low-boiling components were removed from the obtained filtrate under reduced pressure to obtain 445 g of a colorless transparent liquid. As a result of analyzing this colorless transparent liquid by 29 Si-NMR and 13 C-NMR, it was confirmed that the liquid was silicone (V) represented by the following formula.
【化２９】 Embedded image
【００２４】［実施例１］攪拌装置、温度計、および還
流冷却管を備えた２００mlの４つ口フラスコに、メチル
メタクリレート８８.０ｇ、参考例１で調製したシリコ
ーン化合物(Ｉ)１２.０ｇ、トルエン１５０ｇを仕込
み、窒素雰囲気下、攪拌しながら、７０℃に加熱した。
次に、これらに２，２’−アゾビス（２−ヒドロキシメ
チルプロピオネート）１.０ｇを加え、６時間、加熱攪
拌した。その後、アスピレーターにて減圧下、加熱攪拌
することにより、トルエンの一部を除去した後、残った
トルエン溶液を大過剰のメタノール中に投入、攪拌後、
静置し、沈殿物を分離、減圧乾燥することにより、無色
透明固体９０ｇを得た。この無色透明固体を29Ｓｉ−Ｎ
ＭＲおよび13Ｃ−ＮＭＲにより分析した結果、式：Example 1 In a 200 ml four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 88.0 g of methyl methacrylate, 12.0 g of the silicone compound (I) prepared in Reference Example 1, 150 g of toluene was charged and heated to 70 ° C. while stirring under a nitrogen atmosphere.
Next, 1.0 g of 2,2'-azobis (2-hydroxymethylpropionate) was added to these, and the mixture was heated and stirred for 6 hours. Thereafter, by heating and stirring under reduced pressure with an aspirator, after removing a part of the toluene, the remaining toluene solution was poured into a large excess of methanol, and after stirring,
The mixture was allowed to stand, and the precipitate was separated and dried under reduced pressure to obtain 90 g of a colorless and transparent solid. This colorless and transparent solid was treated with 29 Si-N
As a result of analysis by MR and 13 C-NMR, the formula:
【化３０】 で示される構造単位５モル％と式：Embedded image 5 mol% of a structural unit represented by the formula:
【化３１】 で示される構造単位９５モル％からなるシリコーン含有
ビニル系重合体であることが確認された。Embedded image Was confirmed to be a silicone-containing vinyl polymer composed of 95 mol% of structural units.
【００２５】このシリコーン含有ビニル系重合体１ｇと
トルエン９ｇをガラス瓶に投入し、室温下、１２時間攪
拌した結果、不溶物は観察されず、この重合体はトルエ
ンに完全に溶解することが確認された。1 g of this silicone-containing vinyl polymer and 9 g of toluene were charged into a glass bottle and stirred at room temperature for 12 hours. As a result, no insoluble matter was observed, and it was confirmed that this polymer was completely dissolved in toluene. Was.
【００２６】また、撹拌装置、温度計、環流冷却管を備
えた２００ｍｌの四つ口フラスコに、このシリコーン含
有ビニル系重合体２０ｇ、ビニルトリエトキシシラン
１.７５ｇ、キシレン３０ｇを投入し、窒素雰囲気下、
撹拌しながら１１０℃に加熱した。次に、塩化白金酸の
イソプロピルアルコール溶液を白金量にしてシリコーン
含有ビニル系重合体の重量に対して１００ppmとなる量
を投入し、１１０℃で約３時間撹拌を続けた。その後、
アスピレータにて減圧下、加熱撹拌することにより、ト
ルエンの一部を除去し、残ったトルエン溶液を大過剰の
メタノール中に投入して、得られた沈殿物を濾過後、減
圧乾燥することにより、無色透明固体１９ｇを得た。得
られた無色透明固体１ｇとトルエン９ｇをガラス瓶に投
入し、室温下、１２時間撹拌したが、不溶物は観察され
ず、この固体はトルエンに完全に溶解することが確認さ
れた。In a 200 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 20 g of the silicone-containing vinyl polymer, 1.75 g of vinyltriethoxysilane and 30 g of xylene were charged, and a nitrogen atmosphere was introduced. under,
Heat to 110 ° C. with stirring. Next, the amount of platinum in the isopropyl alcohol solution of chloroplatinic acid was adjusted to 100 ppm based on the weight of the silicone-containing vinyl polymer, and stirring was continued at 110 ° C. for about 3 hours. afterwards,
By heating and stirring under reduced pressure with an aspirator, a part of the toluene was removed, the remaining toluene solution was poured into a large excess of methanol, and the obtained precipitate was filtered and then dried under reduced pressure. 19 g of a colorless transparent solid was obtained. 1 g of the obtained colorless transparent solid and 9 g of toluene were put into a glass bottle and stirred at room temperature for 12 hours, but no insoluble matter was observed, and it was confirmed that this solid was completely dissolved in toluene.
【００２７】［実施例２］攪拌装置、温度計、および還
流冷却管を備えた２００mlの４つ口フラスコに、メチル
メタクリレート６０.６ｇ、参考例１で調製したシリコ
ーン(Ｉ)３９.４ｇ、トルエン１５０ｇを仕込み、窒素
雰囲気下、攪拌しながら、７０℃に加熱した。２，２’
−アゾビス（２−ヒドロキシメチルプロピオネート）
１.０ｇを加え、６時間、加熱攪拌した。アスピレータ
ーにて減圧下、加熱攪拌することにより、トルエンの一
部を除去した後、残ったトルエン溶液を大過剰のメタノ
ール中に投入、攪拌後、静置し、沈殿物を分離、減圧乾
燥することにより、無色透明固体８９ｇを得た。この無
色透明固体を29Ｓｉ−ＮＭＲおよび13Ｃ−ＮＭＲにより
分析した結果、式：Example 2 In a 200 ml four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 60.6 g of methyl methacrylate, 39.4 g of the silicone (I) prepared in Reference Example 1, and toluene 150 g was charged and heated to 70 ° C. while stirring under a nitrogen atmosphere. 2,2 '
-Azobis (2-hydroxymethylpropionate)
1.0 g was added, and the mixture was heated and stirred for 6 hours. After removing part of the toluene by heating and stirring under reduced pressure with an aspirator, the remaining toluene solution is poured into a large excess of methanol, stirred, allowed to stand, the precipitate is separated, and dried under reduced pressure. As a result, 89 g of a colorless transparent solid was obtained. As a result of analyzing this colorless transparent solid by 29 Si-NMR and 13 C-NMR, the following formula was obtained.
【化３２】 で示される構造単位２０モル％と式：Embedded image And a structural unit represented by the formula:
【化３３】 で示される構造単位８０モル％からなるシリコーン含有
ビニル系重合体であることが確認された。Embedded image Was confirmed to be a silicone-containing vinyl polymer composed of 80 mol% of structural units.
【００２８】このシリコーン含有ビニル系重合体１ｇと
トルエン９ｇをガラス瓶に投入し、室温下、１２時間攪
拌した結果、不溶物は観察されず、この重合体はトルエ
ンに完全に溶解することが確認された。1 g of this silicone-containing vinyl polymer and 9 g of toluene were charged into a glass bottle and stirred at room temperature for 12 hours. As a result, no insoluble matter was observed, and it was confirmed that this polymer was completely dissolved in toluene. Was.
【００２９】［実施例３］攪拌装置、温度計、および還
流冷却管を備えた２００mlの４つ口フラスコに、参考例
１で調製したシリコーン(Ｉ)１００ｇ、トルエン１５０
ｇを仕込み、窒素雰囲気下、攪拌しながら、７０℃に加
熱した。２，２’−アゾビス（２−ヒドロキシメチルプ
ロピオネート）１.０ｇを加え、６時間、加熱攪拌し
た。アスピレーターにて減圧下、加熱攪拌することによ
り、トルエンの一部を除去した後、残ったトルエン溶液
を大過剰のメタノール中に投入、攪拌後、静置し、沈殿
物を分離、減圧乾燥することにより、無色透明固体８９
ｇを得た。この無色透明固体を29Ｓｉ−ＮＭＲおよび13
Ｃ−ＮＭＲにより分析した結果、式：Example 3 100 g of the silicone (I) prepared in Reference Example 1 and toluene 150 were placed in a 200 ml four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser.
g, and heated to 70 ° C. while stirring under a nitrogen atmosphere. 1.0 g of 2,2'-azobis (2-hydroxymethylpropionate) was added, and the mixture was heated and stirred for 6 hours. After removing part of the toluene by heating and stirring under reduced pressure with an aspirator, the remaining toluene solution is poured into a large excess of methanol, stirred, allowed to stand, the precipitate is separated, and dried under reduced pressure. To give a colorless transparent solid 89
g was obtained. This colorless transparent solid was subjected to 29 Si-NMR and 13
As a result of analysis by C-NMR, the formula:
【化３４】 で示される構造単位のみからなるシリコーン含有ビニル
系重合体であることが確認された。Embedded image It was confirmed that this was a silicone-containing vinyl polymer consisting of only the structural unit represented by.
【００３０】このシリコーン含有ビニル系重合体１ｇと
トルエン９ｇをガラス瓶に投入し、室温下、１２時間攪
拌した結果、不溶物は観察されず、この重合体はトルエ
ンに完全に溶解することが確認された。1 g of this silicone-containing vinyl polymer and 9 g of toluene were put into a glass bottle and stirred at room temperature for 12 hours. As a result, no insoluble matter was observed, and it was confirmed that this polymer was completely dissolved in toluene. Was.
【００３１】［実施例４］攪拌装置、温度計、および還
流冷却管を備えた２００mlの４つ口フラスコに、ｎ−ブ
チルアクリレート９０.４ｇ、参考例１で調製したシリ
コーン(Ｉ)９.６ｇ、トルエン１５０ｇを仕込み、窒素
雰囲気下、攪拌しながら、７０℃に加熱した。２，２’
−アゾビス（２−ヒドロキシメチルプロピオネート）
１.０ｇを加え、６時間、加熱攪拌した。アスピレータ
ーにて減圧下、加熱攪拌することにより、トルエンの一
部を除去した後、残ったトルエン溶液を減圧乾燥するこ
とにより、無色透明粘ちょう液体９５ｇを得た。この無
色透明粘ちょう液体を29Ｓｉ−ＮＭＲおよび13Ｃ−ＮＭ
Ｒにより分析した結果、式：Example 4 In a 200 ml four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 90.4 g of n-butyl acrylate and 9.6 g of the silicone (I) prepared in Reference Example 1 were placed. And 150 g of toluene, and heated to 70 ° C. while stirring under a nitrogen atmosphere. 2,2 '
-Azobis (2-hydroxymethylpropionate)
1.0 g was added, and the mixture was heated and stirred for 6 hours. A portion of the toluene was removed by heating and stirring under reduced pressure using an aspirator, and the remaining toluene solution was dried under reduced pressure to obtain 95 g of a colorless transparent viscous liquid. This colorless and transparent viscous liquid was subjected to 29 Si-NMR and 13 C-NM
As a result of analysis by R, the formula:
【化３５】 で示される構造単位５モル％と式：Embedded image 5 mol% of a structural unit represented by the formula:
【化３６】 で示される構造単位９５モル％からなるシリコーン含有
ビニル系重合体であることが確認された。Embedded image Was confirmed to be a silicone-containing vinyl polymer composed of 95 mol% of structural units.
【００３２】このシリコーン含有ビニル系重合体１ｇと
トルエン９ｇをガラス瓶に投入し、室温下、１２時間攪
拌した結果、不溶物は観察されず、この重合体はトルエ
ンに完全に溶解することが確認された。1 g of this silicone-containing vinyl polymer and 9 g of toluene were charged into a glass bottle and stirred at room temperature for 12 hours. As a result, no insoluble matter was observed, and it was confirmed that this polymer was completely dissolved in toluene. Was.
【００３３】［実施例５］実施例１において、メチルメ
タクリレートの代わりにスチレンを８８.４ｇ、参考例
１で調製したシリコーン(Ｉ)を１１.６ｇ用いた以外は
実施例１と同様にして無色透明固体状物８５ｇを得た。
この無色透明固体状物を29Ｓｉ−ＮＭＲおよび13Ｃ−Ｎ
ＭＲにより分析した結果、式：Example 5 The same procedure as in Example 1 was repeated except that 88.4 g of styrene was used in place of methyl methacrylate and 11.6 g of the silicone (I) prepared in Reference Example 1 was used. 85 g of a transparent solid were obtained.
This colorless and transparent solid was subjected to 29 Si-NMR and 13 C-N
As a result of analysis by MR, the formula:
【化３７】 で示される構造単位５モル％と式：Embedded image 5 mol% of a structural unit represented by the formula:
【化３８】 で示される構造単位９５モル％からなるシリコーン含有
ビニル系重合体であることが確認された。Embedded image Was confirmed to be a silicone-containing vinyl polymer composed of 95 mol% of structural units.
【００３４】このシリコーン含有ビニル系重合体１ｇと
トルエン９ｇをガラス瓶に投入し、室温下、１２時間攪
拌した結果、不溶物は観察されず、この重合体はトルエ
ンに完全に溶解することが確認された。1 g of this silicone-containing vinyl polymer and 9 g of toluene were charged into a glass bottle and stirred at room temperature for 12 hours. As a result, no insoluble matter was observed, and it was confirmed that this polymer was completely dissolved in toluene. Was.
【００３５】［実施例６］実施例１において、メチルメ
タクリレート７９.８ｇ、参考例１で調製したシリコー
ン(Ｉ)の代わりに参考例２で調製したシリコーン(II)を
２０.２ｇ用いた以外は実施例１と同様にして無色透明
固体状物８７ｇを得た。この無色透明固体状物を29Ｓｉ
−ＮＭＲおよび13Ｃ−ＮＭＲにより分析した結果、式：Example 6 The procedure of Example 1 was repeated except that 79.8 g of methyl methacrylate and 20.2 g of the silicone (II) prepared in Reference Example 2 were used instead of the silicone (I) prepared in Reference Example 1. In the same manner as in Example 1, 87 g of a colorless and transparent solid was obtained. This colorless and transparent solid is 29 Si
As a result of analysis by -NMR and 13 C-NMR, the following formula was obtained.
【化３９】 で示される構造単位５モル％と式：Embedded image 5 mol% of a structural unit represented by the formula:
【化４０】 で示される構造単位９５モル％からなるシリコーン含有
ビニル系重合体であることが確認された。Embedded image Was confirmed to be a silicone-containing vinyl polymer composed of 95 mol% of structural units.
【００３６】このシリコーン含有ビニル系重合体１ｇと
トルエン９ｇをガラス瓶に投入し、室温下、１２時間攪
拌した結果、不溶物は観察されず、この重合体はトルエ
ンに完全に溶解することが確認された。1 g of this silicone-containing vinyl polymer and 9 g of toluene were charged into a glass bottle and stirred at room temperature for 12 hours. As a result, no insoluble matter was observed, and it was confirmed that this polymer was completely dissolved in toluene. Was.
【００３７】［実施例７］実施例１において、メチルメ
タクリレートを６９.８ｇ、参考例１で調製したシリコ
ーン(Ｉ)の代わりに参考例３で調製したシリコーン(II
I)を３０.１ｇ用いた以外は実施例１と同様にして無色
透明固体状物８２ｇを得た。この無色透明固体状物を29
Ｓｉ−ＮＭＲおよび13Ｃ−ＮＭＲにより分析した結果、
式：Example 7 In Example 1, 69.8 g of methyl methacrylate was used. Instead of the silicone (I) prepared in Reference Example 1, the silicone (II) prepared in Reference Example 3 was used.
82 g of a colorless and transparent solid was obtained in the same manner as in Example 1 except that 30.1 g of I) was used. 29 this colorless transparent solid
As a result of analysis by Si-NMR and 13 C-NMR,
formula:
【化４１】 で示される構造単位２モル％と式：Embedded image And 2 mol% of a structural unit represented by the formula:
【化４２】 で示される構造単位９８モル％からなるシリコーン含有
ビニル系重合体であることが確認された。Embedded image Was confirmed to be a silicone-containing vinyl polymer having a structural unit of 98 mol%.
【００３８】このシリコーン含有ビニル系重合体１ｇと
トルエン９ｇをガラス瓶に投入し、室温下、１２時間攪
拌した結果、不溶物は観察されず、この重合体はトルエ
ンに完全に溶解することが確認された。1 g of this silicone-containing vinyl polymer and 9 g of toluene were placed in a glass bottle and stirred at room temperature for 12 hours. As a result, no insoluble matter was observed, and it was confirmed that this polymer was completely dissolved in toluene. Was.
【００３９】［実施例８］実施例１において、メチルメ
タクリレートを５５.３ｇ、参考例１で調製したシリコ
ーン(Ｉ)の代わりに参考例４で調製したシリコーン(IV)
を４４.７ｇ用いた以外は実施例１と同様にして無色透
明固体状物７９ｇを得た。この無色透明固体状物を29Ｓ
ｉ−ＮＭＲおよび13Ｃ−ＮＭＲにより分析した結果、
式：Example 8 In Example 1, 55.3 g of methyl methacrylate was used. Instead of the silicone (I) prepared in Reference Example 1, the silicone (IV) prepared in Reference Example 4 was used.
Was used in the same manner as in Example 1 except that 44.7 g of was used to obtain 79 g of a colorless transparent solid. This colorless and transparent solid is 29 S
As a result of analysis by i-NMR and 13 C-NMR,
formula:
【化４３】 で示される構造単位２モル％と式：Embedded image And 2 mol% of a structural unit represented by the formula:
【化４４】 で示される構造単位９８モル％からなるシリコーン含有
ビニル系重合体であることが確認された。Embedded image Was confirmed to be a silicone-containing vinyl polymer having a structural unit of 98 mol%.
【００４０】このシリコーン含有ビニル系重合体１ｇと
トルエン９ｇをガラス瓶に投入し、室温下、１２時間攪
拌した結果、不溶物は観察されず、この重合体はトルエ
ンに完全に溶解することが確認された。1 g of this silicone-containing vinyl polymer and 9 g of toluene were charged into a glass bottle and stirred at room temperature for 12 hours. As a result, no insoluble matter was observed, and it was confirmed that this polymer was completely dissolved in toluene. Was.
【００４１】［実施例９］実施例１において、メチルメ
タクリレートの代わりにてスチレンを８１.２ｇ、参考
例１で調製したシリコーン(Ｉ)の代わりに参考例５で調
製したシリコーン(Ｖ)を１８.８ｇ用いた以外は実施例
１と同様にして無色透明固体状物７４ｇを得た。この無
色透明固体状物を29Ｓｉ−ＮＭＲおよび13Ｃ−ＮＭＲに
より分析した結果、式：Example 9 In Example 1, 81.2 g of styrene was used instead of methyl methacrylate, and 18 parts of silicone (V) prepared in Reference Example 5 was used instead of silicone (I) prepared in Reference Example 1. Except that 0.8 g was used, 74 g of a colorless transparent solid was obtained in the same manner as in Example 1. The colorless transparent solid was analyzed by 29 Si-NMR and 13 C-NMR.
【化４５】 で示される構造単位５モル％と式：Embedded image 5 mol% of a structural unit represented by the formula:
【化４６】 で示される構造単位９５モル％からなるシリコーン含有
ビニル系重合体であることが確認された。Embedded image Was confirmed to be a silicone-containing vinyl polymer composed of 95 mol% of structural units.
【００４２】このシリコーン含有ビニル系重合体１ｇと
トルエン９ｇをガラス瓶に投入し、室温下、１２時間攪
拌した結果、不溶物は観察されず、この重合体はトルエ
ンに完全に溶解することが確認された。1 g of this silicone-containing vinyl polymer and 9 g of toluene were put into a glass bottle and stirred at room temperature for 12 hours. As a result, no insoluble matter was observed, and it was confirmed that this polymer was completely dissolved in toluene. Was.
【００４３】［比較例１］攪拌装置、温度計、および還
流冷却管を備えた２００ｍｌの４つ口フラスコに、メチ
ルメタクリレート７５.８ｇ、式：Comparative Example 1 A 200 ml four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 75.8 g of methyl methacrylate.
【化４７】 で示されるシリコーン(VI)２４.２ｇ、トルエン１５０
ｇを投入し、窒素雰囲気下、攪拌しながら、７０℃に加
熱した。次に、２，２’−アゾビス（２−ヒドロキシメ
チルプロピオネート）１.０ｇを加え、加熱攪拌した。
加熱開始１時間後、重合溶液全体がゲル状となったた
め、重合を終了した。得られたゲル状物を減圧乾燥し、
得られた固体状物１ｇとトルエン９ｇをガラス瓶に投入
し、室温下、１２時間攪拌したが、固体状物はトルエン
で膨潤するのみで溶解しなかった。Embedded image 24.2 g of silicone (VI), toluene 150
g, and heated to 70 ° C. while stirring under a nitrogen atmosphere. Next, 1.0 g of 2,2'-azobis (2-hydroxymethylpropionate) was added, and the mixture was heated and stirred.
One hour after the start of heating, the polymerization was terminated because the entire polymerization solution became a gel. The obtained gel was dried under reduced pressure,
1 g of the obtained solid substance and 9 g of toluene were put into a glass bottle and stirred at room temperature for 12 hours. However, the solid substance did not dissolve but only swelled with toluene.
【００４４】［比較例２］攪拌装置、温度計、および還
流冷却管を備えた２００mlの４つ口フラスコに、メチル
メタクリレート６７.２ｇ、式：Comparative Example 2 A 200 ml four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 67.2 g of methyl methacrylate.
【化４８】 で示されるシリコーン(VII)３２.８ｇ、トルエン１５０
ｇを投入し、窒素雰囲気下、攪拌しながら、７０℃に加
熱した。次に、２，２’−アゾビス（２−ヒドロキシメ
チルプロピオネート）１.０ｇを加え、６時間、加熱攪
拌した。アスピレーターにて減圧下、加熱攪拌すること
により、トルエンの一部を除去した後、残ったトルエン
溶液を大過剰のメタノール中に投入、攪拌後、静置し、
沈殿物を分離、減圧乾燥することにより、無色透明固体
８５ｇを得た。Embedded image 32.8 g of silicone (VII) represented by
g, and heated to 70 ° C. while stirring under a nitrogen atmosphere. Next, 1.0 g of 2,2′-azobis (2-hydroxymethylpropionate) was added, and the mixture was heated and stirred for 6 hours. By heating and stirring under reduced pressure with an aspirator, after removing part of the toluene, the remaining toluene solution was poured into a large excess of methanol, stirred, and allowed to stand.
The precipitate was separated and dried under reduced pressure to obtain 85 g of a colorless transparent solid.
【００４５】次に、撹拌装置、温度計、環流冷却管を備
えた１００ｍｌの四つ口フラスコに、この無色透明固体
２０ｇ、ビニルトリエトキシシラン２.８４ｇ、トルエ
ン３０ｇを投入し、窒素雰囲気下、撹拌しながら１１０
℃に加熱した。次に、塩化白金酸のイソプロピルアルコ
ール溶液を白金量にしてシリコーン含有ビニル系重合体
の重量に対して１００ppmとなる量を投入し、１１０℃
で撹拌を続けたが、１時間後、重合溶液全体がゲル状と
なった。このゲル状物を減圧乾燥し、得られた固体状物
１ｇとトルエン９ｇをガラス瓶に投入し、室温下、１２
時間攪拌したが、固体状物はトルエンで膨潤するのみで
溶解しなかった。Next, 20 g of the colorless and transparent solid, 2.84 g of vinyltriethoxysilane, and 30 g of toluene were charged into a 100 ml four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, and were charged under a nitrogen atmosphere. 110 with stirring
Heated to ° C. Next, the isopropyl alcohol solution of chloroplatinic acid was put in an amount of 100 ppm with respect to the weight of the silicone-containing vinyl polymer in terms of the amount of platinum.
However, after 1 hour, the entire polymerization solution became a gel. The gel was dried under reduced pressure, and 1 g of the obtained solid and 9 g of toluene were charged into a glass bottle.
After stirring for an hour, the solid matter only swelled with toluene and did not dissolve.
【００４６】[0046]
【発明の効果】本発明のシリコーン含有ビニル系重合体
は、ケイ素原子結合水素原子をシロキサン鎖の末端に有
するシリコーン含有ビニル系重合体であるという特徴が
あり、本発明の製造方法は、このようなシリコーン含有
ビニル系重合体を効率よく製造することができるという
特徴がある。The silicone-containing vinyl polymer of the present invention is characterized in that it is a silicone-containing vinyl polymer having a silicon-bonded hydrogen atom at the end of a siloxane chain. It is characterized in that a silicone-containing vinyl polymer can be efficiently produced.
【図１】 実施例１で調製したシリコーン含有ビニル系
重合体の赤外線分光分析のスペクトルチャートである。FIG. 1 is a spectrum chart of infrared spectroscopic analysis of a silicone-containing vinyl polymer prepared in Example 1.
【図２】 実施例２で調製したシリコーン含有ビニル系
重合体の赤外線分光分析のスペクトルチャートである。FIG. 2 is a spectrum chart of infrared spectroscopic analysis of the silicone-containing vinyl polymer prepared in Example 2.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 三上 隆三 千葉県市原市千種海岸２番２ 東レ・ダウ コーニング・シリコーン株式会社研究開発 本部内 (72)発明者 森田 好次 千葉県市原市千種海岸２番２ 東レ・ダウ コーニング・シリコーン株式会社研究開発 本部内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ryuzou Mikami 2-2 Chikusa Beach, Ichihara-shi, Chiba Prefecture Toray Dow Corning Silicone Co., Ltd. No.2 Toray Dow Corning Silicone Co., Ltd. Research and Development Division
Claims (9)
価有機基であり、Ｒ3は同じか、または相異なり、置換
または非置換の炭素原子数１〜１０のアルキル基もしく
はアリール基であり、ｍは１〜４００の整数である。）
で示される構造単位からなるシリコーン含有ビニル系重
合体。(1) at least a general formula: (Wherein, R 1 is a hydrogen atom or a methyl group, R 2 is a divalent organic group, and R 3 is the same or different and is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or An aryl group, and m is an integer of 1 to 400.)
A silicone-containing vinyl polymer comprising a structural unit represented by the formula:
価有機基であり、Ｒ3は同じか、または相異なり、置換
または非置換の炭素原子数１〜１０のアルキル基もしく
はアリール基であり、ｍは１〜４００の整数である。）
で示される構造単位と一般式： 【化３】 ｛式中、Ｒ4は水素原子またはメチル基であり、Ｒ5は、
一般式： 【化４】 （式中、Ｒ6は置換もしくは非置換の炭素原子数１〜１
０のアルキル基、炭素原子数１〜１０のヒドロキシ基含
有アルキル基、または置換もしくは非置換のアリール基
であり、Ｒ7は炭素原子数１〜１０のアルキル基であ
り、Ｒ8は炭素原子数１〜１０のアルキル基であり、Ｘ
は水素原子、炭素原子数１〜１０のアルキル基、アリー
ル基、またはハロゲン原子である。）で示される基から
なる群から選択される少なくとも一種の基である。｝で
示される構造単位からなるシリコーン含有ビニル系重合
体。2. A compound of the general formula: (Wherein, R 1 is a hydrogen atom or a methyl group, R 2 is a divalent organic group, and R 3 is the same or different and is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or An aryl group, and m is an integer of 1 to 400.)
And a structural unit represented by the general formula: In the formula, R 4 is a hydrogen atom or a methyl group, and R 5 is
General formula: (Wherein, R 6 is a substituted or unsubstituted C 1 -C 1)
0 is an alkyl group, a hydroxy group-containing alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group, R 7 is an alkyl group having 1 to 10 carbon atoms, and R 8 is a carbon atom having 1 to 10 carbon atoms. 1 to 10 alkyl groups, and X
Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or a halogen atom. ) Is at least one group selected from the group consisting of groups represented by A silicone-containing vinyl polymer comprising the structural unit represented by｝.
る。）で示される基であることを特徴とする、請求項１
または２記載のシリコーン含有ビニル系重合体。3. R 2 is a compound represented by the general formula: (Wherein R 9 is an alkylene group having 1 to 10 carbon atoms).
Or the silicone-containing vinyl polymer according to 2.
ルキル基であり、Ｒ11は単結合または炭素原子数１〜１
０のアルキレン基である。）で示される基であることを
特徴とする、請求項１または２記載のシリコーン含有ビ
ニル系重合体。4. R 2 is a compound represented by the general formula: (Wherein, R 10 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 11 is a single bond or 1 to 1 carbon atoms.
It is an alkylene group of 0. The silicone-containing vinyl polymer according to claim 1 or 2, wherein the group is a group represented by the formula:
価有機基であり、Ｒ3は同じか、または相異なり、置換
または非置換の炭素原子数１〜１０のアルキル基もしく
はアリール基であり、ｍは１〜４００の整数である。）
で示されるシリコーン化合物をラジカル重合することを
特徴とする、請求項１記載のシリコーン含有ビニル系重
合体の製造方法。5. At least a general formula: (Wherein, R 1 is a hydrogen atom or a methyl group, R 2 is a divalent organic group, and R 3 is the same or different and is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or An aryl group, and m is an integer of 1 to 400.)
The method for producing a silicone-containing vinyl polymer according to claim 1, wherein the silicone compound represented by the following formula is radically polymerized.
価有機基であり、Ｒ3は同じか、または相異なり、置換
または非置換の炭素原子数１〜１０のアルキル基もしく
はアリール基であり、ｍは１〜４００の整数である。）
で示されるシリコーン化合物とラジカル重合性ビニル系
単量体をラジカル共重合することを特徴とする、請求項
１記載のシリコーン含有ビニル系重合体の製造方法。6. A general formula: (Wherein, R 1 is a hydrogen atom or a methyl group, R 2 is a divalent organic group, and R 3 is the same or different and is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or An aryl group, and m is an integer of 1 to 400.)
The method for producing a silicone-containing vinyl polymer according to claim 1, wherein the silicone compound represented by the formula (1) is radically copolymerized with a radical polymerizable vinyl monomer.
式： 【化９】 ｛式中、Ｒ4は水素原子またはメチル基であり、Ｒ5は、
一般式： 【化１０】 （式中、Ｒ6は置換もしくは非置換の炭素原子数１〜１
０のアルキル基、炭素原子数１〜１０のヒドロキシ基含
有アルキル基、または置換もしくは非置換のアリール基
であり、Ｒ7は炭素原子数１〜１０のアルキル基であ
り、Ｒ8は炭素原子数１〜１０のアルキル基であり、Ｘ
は水素原子、炭素原子数１〜１０のアルキル基、アリー
ル基、またはハロゲン原子である。）で示される基から
なる群から選択される少なくとも一種の基である。｝で
示される化合物であることを特徴とする、請求項６記載
のシリコーン含有ビニル系重合体の製造方法。7. The radical polymerizable vinyl monomer has a general formula: In the formula, R 4 is a hydrogen atom or a methyl group, and R 5 is
General formula: (Wherein, R 6 is a substituted or unsubstituted C 1 -C 1)
0 is an alkyl group, a hydroxy group-containing alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group, R 7 is an alkyl group having 1 to 10 carbon atoms, and R 8 is a carbon atom having 1 to 10 carbon atoms. 1 to 10 alkyl groups, and X
Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or a halogen atom. ) Is at least one group selected from the group consisting of groups represented by The method for producing a silicone-containing vinyl polymer according to claim 6, which is a compound represented by｝.
る。）で示される基であることを特徴とする、請求項５
乃至７のいずれか１項記載のシリコーン含有ビニル系重
合体の製造方法。Is 8. R 2, general formula: 11] (Wherein R 9 is an alkylene group having 1 to 10 carbon atoms).
A method for producing a silicone-containing vinyl polymer according to any one of claims 1 to 7.
ルキル基であり、Ｒ11は単結合または炭素原子数１〜１
０のアルキレン基である。）で示される基であることを
特徴とする、請求項５乃至７のいずれか１項記載のシリ
コーン含有ビニル系重合体の製造方法。9. R 2 is a compound represented by the general formula: (Wherein, R 10 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 11 is a single bond or 1 to 1 carbon atoms.
It is an alkylene group of 0. The method for producing a silicone-containing vinyl polymer according to any one of claims 5 to 7, wherein the group is a group represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9344293A JPH11158232A (en) | 1997-11-28 | 1997-11-28 | Silicone-containing vinyl polymer and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9344293A JPH11158232A (en) | 1997-11-28 | 1997-11-28 | Silicone-containing vinyl polymer and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11158232A true JPH11158232A (en) | 1999-06-15 |
Family
ID=18368127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9344293A Pending JPH11158232A (en) | 1997-11-28 | 1997-11-28 | Silicone-containing vinyl polymer and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11158232A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7058508B2 (en) * | 2001-01-12 | 2006-06-06 | Energy Control Technologies | Automated building service broker |
| JP2010168453A (en) * | 2009-01-22 | 2010-08-05 | Nippon Steel Chem Co Ltd | Method for producing cured product and cured product |
| WO2020142443A1 (en) * | 2018-12-31 | 2020-07-09 | Dow Silicones Corporation | Multifunctional organosilicon compound and related methods, compounds, and compositions |
| CN116096769A (en) * | 2020-06-24 | 2023-05-09 | 陶氏环球技术有限责任公司 | Olefin/siloxane interpolymers and olefin/cyclic silane interpolymers |
| US12227530B2 (en) | 2018-12-31 | 2025-02-18 | Dow Silicones Corporation | Method of preparing functional organosilanol compounds |
| US12312445B2 (en) | 2020-04-30 | 2025-05-27 | Dow Global Technologies Llc | Branched organosilanol compounds and methods for the preparation and use thereof |
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1997
- 1997-11-28 JP JP9344293A patent/JPH11158232A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7058508B2 (en) * | 2001-01-12 | 2006-06-06 | Energy Control Technologies | Automated building service broker |
| JP2010168453A (en) * | 2009-01-22 | 2010-08-05 | Nippon Steel Chem Co Ltd | Method for producing cured product and cured product |
| WO2020142443A1 (en) * | 2018-12-31 | 2020-07-09 | Dow Silicones Corporation | Multifunctional organosilicon compound and related methods, compounds, and compositions |
| US12227530B2 (en) | 2018-12-31 | 2025-02-18 | Dow Silicones Corporation | Method of preparing functional organosilanol compounds |
| US12378264B2 (en) | 2018-12-31 | 2025-08-05 | Dow Silicones Corporation | Multifunctional organosilicon compound and related methods, compounds, and compositions |
| US12312445B2 (en) | 2020-04-30 | 2025-05-27 | Dow Global Technologies Llc | Branched organosilanol compounds and methods for the preparation and use thereof |
| CN116096769A (en) * | 2020-06-24 | 2023-05-09 | 陶氏环球技术有限责任公司 | Olefin/siloxane interpolymers and olefin/cyclic silane interpolymers |
| JP2023532859A (en) * | 2020-06-24 | 2023-08-01 | ダウ グローバル テクノロジーズ エルエルシー | Olefin/Siloxane Interpolymers and Olefin/Cyclic Silane Interpolymers |
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