JP6677731B2 - アルコキシアミンの低温ラジカル重合 - Google Patents
アルコキシアミンの低温ラジカル重合 Download PDFInfo
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- JP6677731B2 JP6677731B2 JP2017532745A JP2017532745A JP6677731B2 JP 6677731 B2 JP6677731 B2 JP 6677731B2 JP 2017532745 A JP2017532745 A JP 2017532745A JP 2017532745 A JP2017532745 A JP 2017532745A JP 6677731 B2 JP6677731 B2 JP 6677731B2
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- Prior art keywords
- alkoxyamine
- nitroxide
- group
- polymerization
- temperature
- Prior art date
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- 125000005262 alkoxyamine group Chemical group 0.000 title claims description 36
- 238000010526 radical polymerization reaction Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000010146 3D printing Methods 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 239000002966 varnish Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- -1 N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide Chemical class 0.000 description 27
- 150000003254 radicals Chemical class 0.000 description 25
- 125000000217 alkyl group Chemical group 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 12
- 229920001400 block copolymer Polymers 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- 150000002978 peroxides Chemical class 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 238000000089 atomic force micrograph Methods 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Chemical class OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- YPAURZBMECSUPE-UHFFFAOYSA-N 1-(2-hydroxyethyl)imidazolidin-2-one;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OCCN1CCNC1=O YPAURZBMECSUPE-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical class OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical class C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-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
- PFPUZMSQZJFLBK-UHFFFAOYSA-N 2-(2-oxoimidazolidin-1-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCNC1=O PFPUZMSQZJFLBK-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical class FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 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
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- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- VALXVSHDOMUUIC-UHFFFAOYSA-N 2-methylprop-2-enoic acid;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(O)=O VALXVSHDOMUUIC-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
- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-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
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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- WQBCAASPALGAKX-UHFFFAOYSA-N Benzenemethanol, 4-(dimethylamino)- Chemical compound CN(C)C1=CC=C(CO)C=C1 WQBCAASPALGAKX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- JIJFDVNVQIXRLZ-UHFFFAOYSA-N CC(C(O)=O)=C.CC(C(O)=O)=C.CC(C(O)=O)=C.P Chemical class CC(C(O)=O)=C.CC(C(O)=O)=C.CC(C(O)=O)=C.P JIJFDVNVQIXRLZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical class OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
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- YACTZEZVNPAVGJ-UHFFFAOYSA-N P.C(=O)(O)C=C.C(=O)(O)C=C.C(=O)(O)C=C Chemical class P.C(=O)(O)C=C.C(=O)(O)C=C.C(=O)(O)C=C YACTZEZVNPAVGJ-UHFFFAOYSA-N 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- XQMLSYSRQSWOCA-UHFFFAOYSA-H [Ce+3].C(C)C(C(=O)[O-])(C(=O)[O-])CC.C(C)C(C(=O)[O-])(C(=O)[O-])CC.C(C)C(C(=O)[O-])(C(=O)[O-])CC.[Ce+3] Chemical compound [Ce+3].C(C)C(C(=O)[O-])(C(=O)[O-])CC.C(C)C(C(=O)[O-])(C(=O)[O-])CC.C(C)C(C(=O)[O-])(C(=O)[O-])CC.[Ce+3] XQMLSYSRQSWOCA-UHFFFAOYSA-H 0.000 description 1
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 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
- 239000012933 diacyl peroxide Substances 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
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- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])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])C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011976 maleic acid 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
- 230000007246 mechanism Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DUVTXUGBACWHBP-UHFFFAOYSA-N methyl 2-(1h-benzimidazol-2-ylmethoxy)benzoate Chemical compound COC(=O)C1=CC=CC=C1OCC1=NC2=CC=CC=C2N1 DUVTXUGBACWHBP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical class CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- HVYCQBKSRWZZGX-UHFFFAOYSA-N naphthalen-1-yl 2-methylprop-2-enoate Chemical compound C1=CC=C2C(OC(=O)C(=C)C)=CC=CC2=C1 HVYCQBKSRWZZGX-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 230000002085 persistent effect Effects 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- AHIHJODVQGBOND-UHFFFAOYSA-M propan-2-yl carbonate Chemical compound CC(C)OC([O-])=O AHIHJODVQGBOND-UHFFFAOYSA-M 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
- 238000007342 radical addition reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- WIJVUKXVPNVPAQ-UHFFFAOYSA-N silyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)O[SiH3] WIJVUKXVPNVPAQ-UHFFFAOYSA-N 0.000 description 1
- GRJISGHXMUQUMC-UHFFFAOYSA-N silyl prop-2-enoate Chemical class [SiH3]OC(=O)C=C GRJISGHXMUQUMC-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 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
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-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
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
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- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Description
で想起され、より詳細には欧州特許第0760824号に記載される。
本発明は、以下の工程:
− 少なくとも1種のニトロキシド還元剤及び少なくとも1種のアルコキシアミンの存在下で、少なくとも1種のモノマーを含む混合物を調製する工程と、
− モノマーが完全に転化されるまで−50℃〜80℃の温度で混合物を重合させる工程と
を含むラジカル重合方法に関する。
nはアルコキシアミンの官能価、すなわち、メカニズム:
にしたがってアルコキシアミンにより放出され得るニトロキシドラジカルTの数を表す。
(式中、R3及びR4は、同一又は異なっていてもよく、1〜10個の範囲のいくつかの炭素原子を含有する直鎖又は分岐アルキル基、F、Cl、若しくはBrなどのハロゲン原子によって、或いは1〜4個の範囲のいくつかの炭素原子を含有する直鎖若しくは分岐アルキル基によって、或いはニトロ、アルコキシ、アリールオキシ、カルボニル、若しくはカルボキシル基によって置換されていてもよいフェニル又はチエニル基;ベンジル基、3〜12個の範囲のいくつかの炭素原子を含有するシクロアルキル基、1つ又は複数の不飽和部分を含む基を表し;Bは1〜20個の範囲のいくつかの炭素原子を含有する直鎖又は分岐アルキレン基を表し;mは1〜10の範囲の整数である);
(式中、R5及びR6は、同一又は異なっていてもよく、F、Cl、若しくはBrなどのハロゲン原子によって、或いは1〜4個の範囲のいくつかの炭素原子を含有する直鎖若しくは分岐アルキル基によって、或いはニトロ、アルコキシ、アリールオキシ、カルボニル、若しくはカルボキシル基によって置換されていてもよい、アリール、ピリジル、フリル、又はチエニル基を表し;Dは1〜6個の範囲のいくつかの炭素原子を含有する直鎖若しくは分岐アルキレン基、フェニレン基、又はシクロアルキレン基を表し;pは1〜10の範囲の整数である);
(式中、R7、R8、及びR9は、同一又は異なっていてもよく、式(I)のR3及びR4と同じ意味を有し、q、r、及びsは1〜10の範囲の整数である);
(式中、R10は式(II)のR5及びR6と同じ意味を有し、tは1〜4の範囲の整数であり、uは2〜6の整数である(芳香族基は置換されている));
(式中、R11は式(IV)の基R10と同じ意味を有し、vは2〜6の整数である);
式中、R12、R13、及びR14は、同一又は異なっていてもよく、Cl又はBrなどのハロゲン原子によって、或いは1〜10個の範囲のいくつかの炭素原子を含有する直鎖若しくは分岐アルキル基によって置換されていてもよいフェニル基を表し;Wは酸素、硫黄、又はセレン原子を表し、wは0又は1に等しい。
(式中、R15は式(I)のR3と同じ意味を有し、R16は式(II)のR5又はR6と同じ意味を有する);
(式中、R17及びR18は、同一又は異なっていてもよく、水素原子、又は1〜10個の範囲のいくつかの炭素原子を含有する直鎖若しくは分岐アルキル基、ハロゲン原子又はヘテロ原子で置換されていてもよいアリール基を表す)。
[式中、
R19、R20、R21、R22、R23、及びR24は
− 直鎖又は分岐C1−C20、好ましくはC1−C10アルキル、例えば置換又は非置換のメチル、エチル、プロピル、ブチル、イソプロピル、イソブチル、tert−ブチル、又はネオペンチルなど、
− 置換又は非置換のC6−C30アリール、例えばベンジル又はアリール(フェニル)など、
− 飽和C1−C30環状基
の中からの基を表し、
基R19及びR22は、
(式中、xは1〜12の整数を表す)
から選択してもよい、置換されていてもよい環状構造R19−CNC−R22の一部を形成していてもよい]
により表される。
のニトロキシドが使用され、
Ra及びRbは1〜40個の炭素原子を有する同一又は異なるアルキル基を表し、任意選択的に環を形成するように互いに結合しており、ヒドロキシル、アルコキシ、又はアミノ基で置換されていてもよく、
RLはモル質量が15.42g/molを超え、好ましくは30g/molを超える一価基を表す。基RLは、例えば40〜450g/molのモル質量を有していてもよい。これは好ましくは一般式(XI):
(式中、X及びYは、同一又は異なっていてもよく、アルキル、シクロアルキル、アルコキシル、アリールオキシル、アリール、アラルキルオキシル、ペルフルオロアルキル、及びアラルキル基から選択されてもよく、1〜20個の炭素原子を含んでいてもよい。X及び/又はYはまた、塩素、臭素、又はフッ素原子などのハロゲン原子であってもよい)
のリン含有基である。
(式中、Rc及びRdは2つの同一又は異なるアルキル基であり、任意選択的に環を形成するように結合しており、1〜40個の置換されていてもよい又は非置換の炭素原子を含む)
のホスホナート基である。
(式中、
Zは多価基を表し;
Ra及びRbは、1〜40個の炭素原子を有する同一又は異なるアルキル基を表し、任意選択的に環を形成するように互いに結合しており、ヒドロキシル、アルコキシ、又はアミノ基で置換されていてもよく;
RLはモル質量が15.042g/molを超え、好ましくは30g/molを超える一価基を表す)
のアルコキシアミンが好ましい。基RLは、例えば40〜450g/molのモル質量を有していてもよい。これは好ましくは一般式(XI):
(式中、X及びYは、同一又は異なっていてもよく、アルキル、シクロアルキル、アルコキシル、アリールオキシル、アリール、アラルキルオキシル、ペルフルオロアルキル、及びアラルキル基から選択されてもよく、1〜20個の炭素原子を含んでいてもよい;X及び/又はYはまた、塩素、臭素、又はフッ素原子などのハロゲン原子であってもよい)
のリン含有基である。
(式中、Rc及びRdは2つの同一又は異なるアルキル基であり、任意選択的に環を形成するように結合しており、1〜40個の置換されていてもよい又は非置換の炭素原子を含む)
のホスホナート基である。
− N−tert−ブチル−1−フェニル−2−メチルプロピルニトロキシド、
− N−(2−ヒドロキシメチルプロピル)−1−フェニル−2−メチルプロピルニトロキシド、
− N−tert−ブチル−1−ジベンジルホスホノ−2,2−ジメチルプロピルニトロキシド、
− N−tert−ブチル−1−ビス(2,2,2−トリフルオロエチル)ホスホノ−2,2−ジメチルプロピルニトロキシド、
− N−tert−ブチル[(1−ジエチルホスホノ)−2−メチルプロピル]ニトロキシド、
− N−(1−メチルエチル)−1−シクロヘキシル−1−(ジエチルホスホノ)ニトロキシド、
− N−(1−フェニルベンジル)−[(1−ジエチルホスホノ)−1−メチルエチル]ニトロキシド、
− N−フェニル−1−ジエチルホスホノ−2,2−ジメチルプロピルニトロキシド、
− N−フェニル−1−ジエチルホスホノ−1−メチルエチルニトロキシド、
− N−(1−フェニル−2−メチルプロピル)−1−ジエチルホスホノメチルエチルニトロキシド、
− 或いは式
のニトロキシド
を挙げることができる。
アルコキシアミンTRIAMINSの合成
206gのエタノール、100gのBlocBuilder(登録商標)(Arkema)、及び26.5gのトリアクリル酸ペンタエリトリトール(Sartomer SR 444D)を500mLの反応器中に入れる。混合物を撹拌しながら80℃で4時間加熱する。次いで反応混合物を取り出し、ロータリーエバポレーターを使用してエタノールを蒸発させて除く。126gのTRIAMINSが定量的に得られる。
マクロ開始剤ポリアルコキシアミンの合成
羽根車撹拌機、油の循環によって加熱するためのジャケット、及び真空/窒素入口を備えた2リットルの金属反応器中に、以下を入れる:
・ 643gのアクリル酸ブチル
・ 96gのスチレン
・ 6gのTRIAMINS。
非開始剤コポリマー(ラジカルBuPA/スチレン)の合成
500gのアクリル酸ブチル、70gのスチレン、966gのトルエン、0.1854gのAIBN(Vazo64、DuPont社)、及び0.6gのn−ドデシルメルカプタンで構成される混合物を、当業者が一般的に使用する撹拌されたステンレス鋼反応器中に入れる。2barの窒素の圧力下に反応器を置き、85℃の温度で3時間加熱する。次いで混合物を室温(20℃)まで冷却し、次いで125℃及び100mbarの絶対圧力においてオーブンで16時間真空乾燥させる。ポリアクリル酸ブチル−co−スチレンの乾燥非開始剤コポリマーが得られる。
バルクで、溶媒を使用せず、室温、25℃において、大気圧で重合を行う。これらの実施例において、実施例2のマクロ開始剤ポリアルコキシアミンでメタクリル酸メチルを重合させることが求められる。選択される過酸化物は過酸化ベンゾイル(BPO)であり、アミンはジメチル−パラ−トルイジン(DMPT)である。磁気撹拌により溶液(過酸化物を含まない)を調製し、次いで重合に悪影響を及ぼす場合がある溶解ガスを除去するために、真空下で15分脱気する。溶液(20gの反応混合物)を30mLのガラス瓶へ注ぐ。過酸化物を加え、次いで漏れ止めカプセルを使用して瓶を閉じる。
エポキシ樹脂混合物中の、マクロ開始剤の存在下でのメタクリル酸メチルの重合
工程1:エポキシ樹脂DGEBA(ビス(4−(2,3−エポキシプロポキシ)フェニル)プロパン、エポキシ当量=186g/eq、商品名:LY556 Huntsman)中の溶液中、室温、25℃、大気圧において、重合を行う。
1.5gの実施例2のマクロ開始剤であるポリアルコキシアミン
8.5gのメタクリル酸メチル
0.1gの過酸化ベンゾイル
90gのDGEBA樹脂
硬化剤Jeffamine(ポリオキシプロピレントリアミン、M=400g/mol、商品名:T403 Huntsman)を使用して樹脂DGEBAを重合させる。
Claims (6)
- 以下の工程:
− 少なくとも1種のニトロキシド還元剤及び少なくとも1種のアルコキシアミンの存在下で、少なくとも1種のモノマーを含む混合物を調製する工程と、
− モノマーが完全に転化されるまで0℃〜50℃の温度で混合物を重合させる工程と
を含む、ラジカル重合方法であって、
重合がホスト材料の存在下で行われる、方法。 - ホスト材料が織物繊維又は不織繊維、ポリエステル、ポリウレタン、及びエポキシ樹脂から選択される、請求項1に記載の方法。
- 結合剤、複合材料部品、及びニスの製造のための、請求項1又は2に記載の方法の使用。
- コーティングのための、請求項1又は2に記載の方法の使用。
- 3D印刷のための、請求項1又は2に記載の方法の使用。
- 請求項3から5の何れか一項に記載の使用によって得られる物体。
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FR1462678A FR3030525B1 (fr) | 2014-12-18 | 2014-12-18 | Polymerisation radicalaire d'alcoxyamines a basse temperature |
FR1462678 | 2014-12-18 | ||
PCT/FR2015/053625 WO2016097649A1 (fr) | 2014-12-18 | 2015-12-18 | Polymerisation radicalaire d'alcoxyamines a basse temperature |
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CN (2) | CN110396147B (ja) |
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FR3075212B1 (fr) * | 2017-12-18 | 2020-11-20 | Arkema France | Composition de polymere (meth)acrylique, son procede de preparation et utilisation |
FR3075211B1 (fr) * | 2017-12-18 | 2020-11-20 | Arkema France | Composition de polymere (meth)acrylique, son procede de preparation et utilisation |
FR3088329B1 (fr) * | 2018-11-08 | 2022-01-07 | Arkema France | Compositions d'alcoxyamines |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4666978A (en) * | 1985-11-27 | 1987-05-19 | First Chemical Corporation | Method of curing unsaturated polyester resins at low temperatures |
FR2730240A1 (fr) | 1995-02-07 | 1996-08-09 | Atochem Elf Sa | Stabilisation d'un polymere par un radical libre stable |
CA2229978A1 (fr) * | 1996-06-04 | 1997-12-11 | Elf Atochem S.A. | Procede de preparation d'oligomeres de 1,3-diene telecheliques par polymerisation radicalaire controlee de 1,3-dienes en presence d'un radical libre stable |
AU750626B2 (en) * | 1997-01-10 | 2002-07-25 | Commonwealth Scientific And Industrial Research Organisation | Method of controlling polymer molecular weight and structure |
EP0996643B1 (en) * | 1997-07-15 | 2003-03-26 | Ciba SC Holding AG | Polymerizable compositions containing alkoxyamine compounds derived from nitroso- or nitrone compounds |
FR2791979B1 (fr) | 1999-04-08 | 2003-05-16 | Atochem Elf Sa | Procede de preparation d'alcoxyamines a partir de nitroxydes |
JP4505698B2 (ja) * | 2000-01-17 | 2010-07-21 | 日油株式会社 | ビニル基含有アルコキシアミン、その用途および製造方法 |
FR2804118B1 (fr) * | 2000-01-26 | 2003-08-22 | Atofina | Procede de polymerisation ou copolymerisation radicalaire controlee de l'ethylene sous haute pression en presence de radicaux libres amorceurs et de radicaux nitroxydes indoliniques controleurs |
FR2807439B1 (fr) * | 2000-04-07 | 2003-06-13 | Atofina | Polymeres multimodaux par polymerisation radicalaire controlee en presence d'alcoxyamines |
TWI236482B (en) * | 2000-11-13 | 2005-07-21 | Ciba Sc Holding Ag | Process for the (co)polymerization of vinyl chloride in the presence of a stable free nitroxyl radical |
CN100455614C (zh) | 2002-01-22 | 2009-01-28 | 阿托菲纳公司 | 抗冲击性增强且含有在氮氧化物存在下由受控的自由基聚合获得的嵌段共聚物材料的生产和使用方法 |
US6762263B2 (en) * | 2002-02-01 | 2004-07-13 | Atofina Chemicals, Inc. | High-solids coatings resins via controlled radical polymerization |
AU2003212272A1 (en) | 2002-03-05 | 2003-09-16 | Ciba Specialty Chemicals Holding Inc. | Open-chain alkoxyamines and their corresponding nitroxides for controlled low temperature radical polymerization |
JP2004156005A (ja) * | 2002-03-28 | 2004-06-03 | Djk Kenkyusho:Kk | 常温硬化可能な樹脂組成物、該樹脂組成物の硬化方法及び該樹脂組成物の硬化物 |
JP2004027172A (ja) * | 2002-05-08 | 2004-01-29 | Djk Kenkyusho:Kk | ラジカル硬化型樹脂組成物の硬化助促進化合物、該硬化助促進化合物を含むラジカル硬化型樹脂組成物、及び該樹脂組成物の硬化方法 |
FR2859476B1 (fr) * | 2003-09-10 | 2005-11-11 | Specific Polymers | Copolymeres triblocs formes d'un bloc hydrophile encadre par deux blocs hydrophobes et structurants utilises a titre d'agents gelifiants ou epaississants de systemes aqueux |
JP2005113058A (ja) * | 2003-10-09 | 2005-04-28 | Mitsubishi Rayon Co Ltd | 水溶性高分子開始剤を用いた乳化重合法 |
US20080318931A1 (en) | 2004-07-08 | 2008-12-25 | Moshe Arkin | Treatment of Disorders and Diseases of the Colon |
JP4691986B2 (ja) | 2004-12-27 | 2011-06-01 | 住友化学株式会社 | 樹脂接着体の製造方法 |
ATE439386T1 (de) * | 2005-05-03 | 2009-08-15 | Basf Se | Verfahren zur herstellung von kammblockcopolymeren aus epoxidfunktionalisierten nitroxylethern und anionisch polymerisierbaren monomeren |
FR2889703A1 (fr) * | 2005-08-09 | 2007-02-16 | Arkema Sa | Procede de preparation d'un materiau polymerique comprenant un copolymere multibloc obtenu par polymerisation radicalaire controlee |
JP5399071B2 (ja) * | 2005-08-30 | 2014-01-29 | チバ ホールディング インコーポレーテッド | ニトロキシルラジカル重合により得られるポリマー |
US20090065737A1 (en) * | 2007-09-11 | 2009-03-12 | Arkema Inc. | Polymerization controllers for composites cured by organic peroxide initiators |
JP5527036B2 (ja) * | 2010-04-15 | 2014-06-18 | Dic株式会社 | モルタル組成物、コンクリート構造体及び補修方法 |
JP4821916B1 (ja) * | 2010-05-07 | 2011-11-24 | 横浜ゴム株式会社 | 変性ポリマーの製造法 |
US9434837B2 (en) * | 2010-09-01 | 2016-09-06 | Arkema Inc. | Method of producing fluoropolymers using acid-functionalized monomers |
FR2969633B1 (fr) * | 2010-12-23 | 2015-02-06 | Arkema France | Composition pour des plaques coulees nanostructurees reticulees |
JP5333975B2 (ja) * | 2011-05-23 | 2013-11-06 | 電気化学工業株式会社 | (メタ)アクリル酸エステル共重合体およびこれを含んでなる粘着剤組成物ならびに(メタ)アクリル酸エステル共重合体の製造方法 |
ES2646778T3 (es) * | 2012-02-10 | 2017-12-15 | Arkema, Inc. | Aglutinantes de látex útiles en composiciones de recubrimiento con bajo contenido de VOC o contenido cero |
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