JP6145685B2 - (Meth) acrylic acid ester and polymer thereof - Google Patents
(Meth) acrylic acid ester and polymer thereof Download PDFInfo
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- JP6145685B2 JP6145685B2 JP2012105900A JP2012105900A JP6145685B2 JP 6145685 B2 JP6145685 B2 JP 6145685B2 JP 2012105900 A JP2012105900 A JP 2012105900A JP 2012105900 A JP2012105900 A JP 2012105900A JP 6145685 B2 JP6145685 B2 JP 6145685B2
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- Prior art keywords
- polymer
- meth
- monomer
- acid ester
- acrylic acid
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- 229920000642 polymer Polymers 0.000 title claims description 116
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims description 45
- 239000000178 monomer Substances 0.000 claims description 83
- 239000011347 resin Substances 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 230000015572 biosynthetic process Effects 0.000 description 25
- 238000003786 synthesis reaction Methods 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000005259 measurement Methods 0.000 description 17
- -1 2-ethoxy Chemical group 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 125000005262 alkoxyamine group Chemical group 0.000 description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- QOSDTVGLRFAKKU-UHFFFAOYSA-N CC(=C)C(=O)OC1CC(N(C(C1)(C)C)OC(=O)OC)(C)C Chemical compound CC(=C)C(=O)OC1CC(N(C(C1)(C)C)OC(=O)OC)(C)C QOSDTVGLRFAKKU-UHFFFAOYSA-N 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- BSWUJWQHAYAXFJ-UHFFFAOYSA-N CC(=C)C(=O)OC1CC(N(C(C1)(C)C)OC(F)(F)F)(C)C Chemical compound CC(=C)C(=O)OC1CC(N(C(C1)(C)C)OC(F)(F)F)(C)C BSWUJWQHAYAXFJ-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 9
- 238000010526 radical polymerization reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- FAPCFNWEPHTUQK-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)[NH+]1[O-] FAPCFNWEPHTUQK-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WPMYAEUPKDDTBR-UHFFFAOYSA-N (1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CON1C(C)(C)CC(OC(=O)C(C)=C)CC1(C)C WPMYAEUPKDDTBR-UHFFFAOYSA-N 0.000 description 5
- LRZVDTCXTZWZMB-UHFFFAOYSA-N (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) methyl carbonate Chemical compound COC(=O)ON1C(C)(C)CC(O)CC1(C)C LRZVDTCXTZWZMB-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 230000010354 integration Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- CTAIUGVBDKBXSG-UHFFFAOYSA-N (1,2,2,3-tetramethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CC1C(OC(=O)C(C)=C)CCN(C)C1(C)C CTAIUGVBDKBXSG-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- KAEPCNRUMVMDSQ-UHFFFAOYSA-N CC1(CC(CC(N1OC(F)(F)F)(C)C)O)C Chemical compound CC1(CC(CC(N1OC(F)(F)F)(C)C)O)C KAEPCNRUMVMDSQ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- NYNSFQBRQGSYKP-UHFFFAOYSA-N 1-methoxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CON1C(C)(C)CC(O)CC1(C)C NYNSFQBRQGSYKP-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- CJBXCCWMQNVWNJ-UHFFFAOYSA-N (1-methylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CN1CCC(OC(=O)C(C)=C)CC1 CJBXCCWMQNVWNJ-UHFFFAOYSA-N 0.000 description 1
- UFLXKQBCEYNCDU-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CC(C)(C)NC(C)(C)C1 UFLXKQBCEYNCDU-UHFFFAOYSA-N 0.000 description 1
- SNZAEUWCEHDROX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-one;trihydrate Chemical compound O.O.O.FC(F)(F)C(=O)C(F)(F)F SNZAEUWCEHDROX-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VTGXVUQXDHXADV-UHFFFAOYSA-N 1-methyl-1-oxidopiperidin-1-ium Chemical compound C[N+]1([O-])CCCCC1 VTGXVUQXDHXADV-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、（メタ）アクリル酸エステルに関する。また本発明は、前記（メタ）アクリル酸エステルを含む単量体成分を重合して得られる重合体に関する。また本発明は、前記重合体にエネルギーを与え安定ラジカルを有する重合体を得る製造方法に関する。また本発明は、前記製造方法で得られた安定ラジカルを有する重合体を用いた有機ラジカル電池に関する。また本発明は、前記製造方法で得られた安定ラジカルを有する重合体と樹脂を含む樹脂組成物に関する。また本発明は、前記樹脂組成物を成形して得られた成形体に関する。 The present invention relates to (meth) acrylic acid esters. Moreover, this invention relates to the polymer obtained by superposing | polymerizing the monomer component containing the said (meth) acrylic acid ester. The present invention also relates to a production method for obtaining a polymer having stable radicals by applying energy to the polymer. Moreover, this invention relates to the organic radical battery using the polymer which has the stable radical obtained by the said manufacturing method. Moreover, this invention relates to the resin composition containing the polymer and resin which have the stable radical obtained by the said manufacturing method. Moreover, this invention relates to the molded object obtained by shape | molding the said resin composition.
有機ラジカル電池は、充放電が可能な二次電池の一つで、従来の二次電池のようにカドミウムや鉛のような重金属を用いることがないので、人体や環境に及ぼす影響は少なく、また、充放電の高速化や柔軟性に優れることから、近年研究が盛んに行われている。有機ラジカル電池の材料としては、ニトロキシドラジカルのように安定ラジカルを有する重合体が一般に用いられる。ニトロキシドラジカルを有する重合体を得る方法としては、例えば、特許文献１に記載されている炭素−炭素不飽和二重結合とアルコキシアミン骨格を有する単量体（以下、重合性アルコキシアミンという。）を含む単量体成分を重合した重合体を前駆体として用いる方法が考えられる。 Organic radical batteries are one of the secondary batteries that can be charged and discharged, and do not use heavy metals such as cadmium and lead unlike conventional secondary batteries. In recent years, research has been actively conducted because of its high charge-discharge speed and excellent flexibility. As a material for the organic radical battery, a polymer having a stable radical such as a nitroxide radical is generally used. As a method for obtaining a polymer having a nitroxide radical, for example, a monomer having a carbon-carbon unsaturated double bond and an alkoxyamine skeleton described in Patent Document 1 (hereinafter referred to as polymerizable alkoxyamine) is used. A method is conceivable in which a polymer obtained by polymerizing a monomer component is used as a precursor.
しかしながら、特許文献１で提案されている重合性アルコキシアミンを用いる方法は、ニトロキシドラジカルに３級炭素でなく１級炭素が結合しているため、ニトロキシドラジカルに付加した置換基が脱離しにくく、側鎖に安定ラジカルを有する重合体を得ることが困難であるという課題を有する。これらを解決する方法として、特許文献２には、ニトロキシドラジカルに脱離しやすい３級炭素が結合した、特定の重合性アルコキシアミンを用いる方法が開示されている。
However, in the method using the polymerizable alkoxyamine proposed in
しかし、特許文献１または特許文献２で提案されている重合性アルコキシアミンは、製造時の収率がやや低いという課題を有する。
However, the polymerizable alkoxyamine proposed in
そこで、本発明の目的は、合成が容易であり、且つ、側鎖に安定ラジカルを有する重合体を効率的に得る製造方法を提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to provide a production method for efficiently obtaining a polymer that is easy to synthesize and has a stable radical in the side chain.
本発明の一は、下記式（１）または（２）で表される（メタ）アクリル酸エステル（ａ）である。 One aspect of the present invention is a (meth) acrylic acid ester (a) represented by the following formula (1) or (2).
（式（１）中、Ｒ1は、水素原子又はメチル基を表す。Ｒ2は、置換基を有していてもよい総炭素数１〜５のアルキル基、又は置換基を有していてもよい総炭素数６〜１０のアリール基を表す。） (In the formula (1), R 1 is .R 2 represents a hydrogen atom or a methyl group, have an alkyl group, or a substituent of the optionally several total or carbon with 1 to 5 have a substituent And represents an aryl group having 6 to 10 carbon atoms in total.)
（式（２）中、Ｒ1は、水素原子又はメチル基を表す。Ｘ1、Ｘ2、及びＸ3は、ハロゲン原子を表し、互いに同一であっても異なっていてもよい。） (In Formula (2), R 1 represents a hydrogen atom or a methyl group. X 1 , X 2 , and X 3 represent a halogen atom and may be the same or different from each other.)
また、本発明の一は、前記（メタ）アクリル酸エステル（ａ）を含む単量体成分を重合して得られる重合体である。 Another aspect of the present invention is a polymer obtained by polymerizing a monomer component containing the (meth) acrylic acid ester (a).
また、本発明の一は、前記重合体にエネルギーを与え、下記式（３）で表される単量体（ａ’）構造単位を含む重合体を得る製造方法である。 Another aspect of the present invention is a method for producing a polymer containing a monomer (a ′) structural unit represented by the following formula (3) by applying energy to the polymer.
（式（３）中、Ｒ1は、水素原子又はメチル基を表す。） (In formula (3), R 1 represents a hydrogen atom or a methyl group.)
また、本発明の一は、前記製造方法で得られた単量体（ａ’）構造単位を含む重合体を用いた有機ラジカル電池である。 Another aspect of the present invention is an organic radical battery using a polymer containing the monomer (a ′) structural unit obtained by the production method.
また、本発明の一は、前記重合体からなる難燃剤である。 Another aspect of the present invention is a flame retardant comprising the polymer.
また、本発明の一は、前記製造方法で得られた単量体（ａ’）構造単位を含む重合体からなる難燃剤である。 Another aspect of the present invention is a flame retardant comprising a polymer containing the monomer (a ′) structural unit obtained by the production method.
また、本発明の一は、前記製造方法で得られた単量体（ａ’）構造単位を含む重合体と樹脂を含む樹脂組成物である。 Another aspect of the present invention is a resin composition comprising a polymer containing a monomer (a ′) structural unit obtained by the above production method and a resin.
また、本発明の一は、前記難燃剤と樹脂を含む樹脂組成物である。 Another aspect of the present invention is a resin composition containing the flame retardant and a resin.
更に、本発明の一は、前記樹脂組成物を成形して得られる成形体である。 Furthermore, one aspect of the present invention is a molded body obtained by molding the resin composition.
本発明の（メタ）アクリル酸エステル（ａ）は、ニトロキシドラジカルに付加した置換基が解離することなく、ラジカル重合を行うことが可能である。また、前記（メタ）アクリル酸エステル（ａ）を含む単量体成分を重合して得られた重合体は、エネルギーを与えることで安定ラジカルである単量体（ａ’）構造単位を含む重合体を得ることができる。得られる単量体（ａ’）構造単位を含む重合体は、安定ラジカルを有するため、有機ラジカル電池として有用であり、更に、樹脂に配合することにより、樹脂の耐候性を向上させることが可能である。また、本発明の（メタ）アクリル酸エステル（ａ）を含む単量体成分を重合して得られる重合体は、樹脂の熱分解を向上させることができ、難燃剤として用いることができる。 The (meth) acrylic acid ester (a) of the present invention can perform radical polymerization without dissociating the substituent added to the nitroxide radical. In addition, the polymer obtained by polymerizing the monomer component containing the (meth) acrylic acid ester (a) is a polymer containing a monomer (a ′) structural unit which is a stable radical by applying energy. Coalescence can be obtained. The resulting polymer containing the monomer (a ′) structural unit has a stable radical, and thus is useful as an organic radical battery. Further, by adding it to the resin, it is possible to improve the weather resistance of the resin. It is. Moreover, the polymer obtained by superposing | polymerizing the monomer component containing the (meth) acrylic acid ester (a) of this invention can improve the thermal decomposition of resin, and can be used as a flame retardant.
本発明の（メタ）アクリル酸エステル（ａ）は、下記式（１）または（２）で表される。 The (meth) acrylic acid ester (a) of the present invention is represented by the following formula (1) or (2).
式（１）中、Ｒ1は、水素又はメチル基を表す。Ｒ2は、置換基を有していてもよい総炭素数１〜５のアルキル基、又は置換基を有していてもよい総炭素数６〜１０のアリール基を表す。 In formula (1), R 1 represents hydrogen or a methyl group. R 2 represents an alkyl group having 1 to 5 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent.
Ｒ2の置換基を有していてもよい総炭素数１〜５のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、２−メトキシエチル基、２−エトキシエチル基が挙げられる。 Examples of the alkyl group having 1 to 5 carbon atoms that may have a substituent of R 2 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a 2-methoxyethyl group, and 2-ethoxy. An ethyl group is mentioned.
Ｒ2の置換基を有していてもよい総炭素数６〜１０のアリール基としては、例えば、フェニル基、ｐ−メチルフェニル基、ｐ−メトキシフェニル基、２，５−ジメチルフェニル基が挙げられる。 Examples of the aryl group having 6 to 10 carbon atoms that may have a substituent of R 2 include a phenyl group, a p-methylphenyl group, a p-methoxyphenyl group, and a 2,5-dimethylphenyl group. It is done.
Ｒ2における置換基としては、例えば、アルキル基、アルコキシ基が挙げられる。 Examples of the substituent for R 2 include an alkyl group and an alkoxy group.
式（２）中、Ｒ1は、水素又はメチル基を表す。Ｘ1、Ｘ2、及びＸ3はハロゲン原子を表し、互いに同一であっても異なっていてもよい。 In formula (2), R 1 represents hydrogen or a methyl group. X 1 , X 2 , and X 3 represent a halogen atom and may be the same or different from each other.
Ｘ1、Ｘ2、Ｘ3としては、例えば、Ｘ1＝Ｘ2＝Ｘ3＝フッ素原子または塩素原子、Ｘ1＝Ｘ2＝フッ素原子、Ｘ3＝塩素原子や、Ｘ1＝Ｘ2＝塩素原子、Ｘ3＝フッ素原子が挙げられる。Ｘ1＝Ｘ2＝Ｘ3＝フッ素原子または塩素原子の場合、それぞれトリフルオロメチル基またはトリクロロメチル基がニトロキサイドの酸素原子と結合したことになる。 X 1 , X 2 , X 3 are, for example, X 1 = X 2 = X 3 = fluorine atom or chlorine atom, X 1 = X 2 = fluorine atom, X 3 = chlorine atom, X 1 = X 2 = A chlorine atom and X 3 = fluorine atom may be mentioned. When X 1 = X 2 = X 3 = fluorine atom or chlorine atom, this means that the trifluoromethyl group or trichloromethyl group is bonded to the oxygen atom of nitroxide, respectively.
これらの（メタ）アクリル酸エステル（ａ）の中でも、合成が容易であることから、１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン、１−エトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン、１−プロポキシカルボニルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン、１−フェノキシカルボニルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン、１−（トリフルオロメチル）オキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン、１−（トリクロロメチル）オキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジンが好ましく、原料の入手のし易さから、１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン、１−（トリフルオロメチル）オキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジンがより好ましい。 Among these (meth) acrylic acid esters (a), since they are easy to synthesize, 1-methoxycarbonyloxy-2,2,6,6-tetramethyl-4-methacryloyloxypiperidine, 1-ethoxycarbonyloxy -2,2,6,6-tetramethyl-4-methacryloyloxypiperidine, 1-propoxycarbonyloxy-2,2,6,6-tetramethyl-4-methacryloyloxypiperidine, 1-phenoxycarbonyloxy-2,2 , 6,6-tetramethyl-4-methacryloyloxypiperidine, 1- (trifluoromethyl) oxy-2,2,6,6-tetramethyl-4-methacryloyloxypiperidine, 1- (trichloromethyl) oxy-2, 2,6,6-tetramethyl-4-methacryloyloxypiperidine is preferred From the availability of raw materials, 1-methoxycarbonyloxy-2,2,6,6-tetramethyl-4-methacryloyloxypiperidine, 1- (trifluoromethyl) oxy-2,2,6,6 -Tetramethyl-4-methacryloyloxypiperidine is more preferred.
本発明の（メタ）アクリル酸エステル（ａ）は、ニトロキシドラジカルに結合した置換基が脱離しやすく、効率的に単量体（ａ’）構造単位を含む重合体を得ることができる。 In the (meth) acrylic acid ester (a) of the present invention, the substituent bonded to the nitroxide radical is easily removed, and a polymer containing the monomer (a ′) structural unit can be obtained efficiently.
本発明の（メタ）アクリル酸エステル（ａ）の合成方法としては、特に制限されることはなく、例えば、以下に示すような公知の合成手法を応用することができる。 The method for synthesizing the (meth) acrylic acid ester (a) of the present invention is not particularly limited, and for example, a known synthesis method as shown below can be applied.
式（１）で表される（メタ）アクリル酸エステル（ａ）の中でも、Ｒ1がメチル基、Ｒ2がメチル基である１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジンは、特表２００９−５４１４２８号公報に記載の方法に従い、１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−ヒドロキシピペリジンを合成した後、メタクリロイルクロリドと反応させて合成することができる。 Among the (meth) acrylic acid esters (a) represented by the formula (1), 1-methoxycarbonyloxy-2,2,6,6-tetramethyl- wherein R 1 is a methyl group and R 2 is a methyl group 4-Methacryloyloxypiperidine is synthesized with 1-methoxycarbonyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine according to the method described in JP-T-2009-541428, and then reacted with methacryloyl chloride. Can be synthesized.
具体的には、２，２，６，６−テトラメチル−４−ヒドロキシピペリジン−Ｎ−オキシドを、塩化銅（Ｉ）の存在下、ピルビン酸メチル及び３０％過酸化水素水溶液と反応させて、１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−ヒドロキシピペリジンを得る。そして、得られた１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−ヒドロキシピペリジンを、メタクリロイルクロリドと反応させることで１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジンを合成することができる。 Specifically, 2,2,6,6-tetramethyl-4-hydroxypiperidine-N-oxide is reacted with methyl pyruvate and 30% aqueous hydrogen peroxide in the presence of copper (I) chloride, 1-methoxycarbonyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine is obtained. Then, the obtained 1-methoxycarbonyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine is reacted with methacryloyl chloride to give 1-methoxycarbonyloxy-2,2,6,6-tetra. Methyl-4-methacryloyloxypiperidine can be synthesized.
また、２，２，６，６−テトラメチル−４−ヒドロキシピペリジン−Ｎ−オキシドの４位のアルコールに、トリメチルシリル保護を行い、還元して１−ヒドロキシ−２，２，６，６−テトラメチル−４−トリメチルシリルオキシピペリジンに変換した後、炭酸ジメチルとのエステル交換により、１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−トリメチルシリルオキシピペリジンを合成し、トリメチルシリル保護を脱保護した後にメタクリロイルクロリドと反応させて合成することもできる。 In addition, trimethylsilyl protection is performed on the alcohol at the 4-position of 2,2,6,6-tetramethyl-4-hydroxypiperidine-N-oxide and reduced to give 1-hydroxy-2,2,6,6-tetramethyl. After conversion to -4-trimethylsilyloxypiperidine, 1-methoxycarbonyloxy-2,2,6,6-tetramethyl-4-trimethylsilyloxypiperidine was synthesized by transesterification with dimethyl carbonate, and the trimethylsilyl protection was deprotected. Then, it can be synthesized by reacting with methacryloyl chloride.
式（２）で表される（メタ）アクリル酸エステル（ａ）の中でも、Ｒ1がメチル基、Ｘ1、Ｘ2及びＸ3がいずれもフッ素原子である１−（トリフルオロメチル）オキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジンは、例えば、２，２，６，６−テトラメチル−４−ヒドロキシピペリジン−Ｎ−オキシドを、塩化銅（Ｉ）の存在下、ヘキサフルオロアセトン及び３０％過酸化水素水溶液と反応させ、得られた１−トリフルオロメチルオキシ−２，２，６，６−テトラメチル−４−ヒドロキシピペリジンをメタクリロイルクロリドと反応させることで合成することができる。 Among the (meth) acrylic acid esters (a) represented by the formula (2), 1- (trifluoromethyl) oxy- in which R 1 is a methyl group, and X 1 , X 2 and X 3 are all fluorine atoms. 2,2,6,6-tetramethyl-4-methacryloyloxypiperidine is, for example, 2,2,6,6-tetramethyl-4-hydroxypiperidine-N-oxide in the presence of copper (I) chloride, Synthesis by reacting 1-trifluoromethyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine with methacryloyl chloride by reacting with hexafluoroacetone and 30% aqueous hydrogen peroxide. Can do.
また、２，２，６，６−テトラメチル−４−ヒドロキシピペリジン−Ｎ−オキシドを、塩化銅（Ｉ）の存在下、２，２，２−トリフルオロエタノール及び３０％過酸化水素水溶液と反応させ、得られた１−トリフルオロメチルオキシ−２，２，６，６−テトラメチル−４−ヒドロキシピペリジンを、メタクリロイルクロリドと反応させることで１−（トリフルオロメチル）オキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジンを合成することもできる。 Also, 2,2,6,6-tetramethyl-4-hydroxypiperidine-N-oxide is reacted with 2,2,2-trifluoroethanol and 30% aqueous hydrogen peroxide in the presence of copper (I) chloride. The resulting 1-trifluoromethyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine is reacted with methacryloyl chloride to give 1- (trifluoromethyl) oxy-2,2,6. , 6-tetramethyl-4-methacryloyloxypiperidine can also be synthesized.
また、２，２，６，６−テトラメチル−４−ヒドロキシピペリジン−Ｎ−オキシドに、無水酢酸によるアセチル保護を行い、４，４’−ｔ−ブチル−２，２’−ビピリジン又はＮ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’−ペンタメチルジエチレントリアミン、並びに臭化銅（Ｉ）存在下、トリフルオロヨードメタンと反応させ、アセチル保護を脱保護した後、メタクリロイルクロリドと反応させることで合成することができる。 Further, 2,2,6,6-tetramethyl-4-hydroxypiperidine-N-oxide is subjected to acetyl protection with acetic anhydride, and 4,4′-t-butyl-2,2′-bipyridine or N, N , N ′, N ″, N ″ -pentamethyldiethylenetriamine and copper (I) bromide in the presence of trifluoroiodomethane, deprotecting the acetyl protection, and then reacting with methacryloyl chloride can do.
本発明の重合体は、（メタ）アクリル酸エステル（ａ）を含む単量体成分を重合して得られる。 The polymer of the present invention is obtained by polymerizing a monomer component containing the (meth) acrylic acid ester (a).
（メタ）アクリル酸エステル（ａ）は、１種を単独で用いてもよく、２種以上を併用してもよい。 (Meth) acrylic acid ester (a) may be used individually by 1 type, and may use 2 or more types together.
単量体成分は、（メタ）アクリル酸エステル（ａ）以外にも共重合可能なその他の単量体（ｂ）を含んでもよい。 The monomer component may contain other monomers (b) that can be copolymerized in addition to the (meth) acrylic acid ester (a).
その他の単量体（ｂ）は、得られる重合体の用途に応じて適宜設定することができ、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸−２−エチルヘキシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸−２−ヒドロキシエチル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸−２−アミノエチル等の（メタ）アクリル酸エステル；スチレン、ビニルトルエン、α−メチルスチレン、スチレンスルホン酸及びその塩等の芳香族ビニル単量体；パーフルオロエチレン、弗化ビニリデン等の弗素含有単量体；塩化ビニル、塩化ビニリデン等の塩素含有単量体；ビニルトリメトキシシラン、ビニルトリエトキシシラン等の珪素含有単量体；無水マレイン酸、マレイン酸、マレイン酸モノアルキルエステル又はジアルキルエステル等のマレイン酸系単量体；フマル酸、フマル酸モノアルキルエステル又はジアルキルエステル等のフマル酸系単量体；マレイミド、Ｎ−メチルマレイミド、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド等のマレイミド系単量体；（メタ）アクリロニトリル等のシアノ基含有単量体；（メタ）アクリルアミド等のアミド基含有単量体；酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、安息香酸ビニル等のビニルエステル；エチレン、プロピレン等のアルケン；ブタジエン、イソプレン等の共役ジエンが挙げられる。これらのその他の単量体（ｂ）は、１種を単独で用いてもよく、２種以上を併用してもよい。その他の単量体（ｂ）の中でも、得られる重合体の特性の観点から、メタクリル酸メチル、アクリル酸ｎ−ブチル等の（メタ）アクリル酸エステル、スチレン等の芳香族ビニル単量体、（メタ）アクリロニトリル等のシアノ基含有単量体が好ましく、（メタ）アクリル酸エステル及びシアノ基含有単量体がより好ましい。 The other monomer (b) can be appropriately set according to the intended use of the polymer to be obtained. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate , T-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, (meth ) (Meth) acrylate esters such as phenyl acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and 2-aminoethyl (meth) acrylate; styrene Aromatic vinyl monomers such as vinyltoluene, α-methylstyrene, styrenesulfonic acid and salts thereof; perfluoro Fluorine-containing monomers such as ethylene and vinylidene fluoride; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; silicon-containing monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, Maleic acid monomers such as maleic acid monoalkyl ester or dialkyl ester; fumaric acid monomers such as fumaric acid, fumaric acid monoalkyl ester or dialkyl ester; maleimide, N-methylmaleimide, N-phenylmaleimide, N -Maleimide monomers such as cyclohexylmaleimide; Cyano group-containing monomers such as (meth) acrylonitrile; Amide group-containing monomers such as (meth) acrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, benzoic acid Vinyl esters such as vinyl; alkenes such as ethylene and propylene; Examples thereof include conjugated dienes such as butadiene and isoprene. These other monomers (b) may be used individually by 1 type, and may use 2 or more types together. Among other monomers (b), from the viewpoint of the properties of the resulting polymer, (meth) acrylic acid esters such as methyl methacrylate and n-butyl acrylate, aromatic vinyl monomers such as styrene, ( Cyano group-containing monomers such as (meth) acrylonitrile are preferred, and (meth) acrylic acid esters and cyano group-containing monomers are more preferred.
尚、本発明において、「（メタ）アクリル」とは、「アクリル」又は「メタクリル」を表す。 In the present invention, “(meth) acryl” means “acryl” or “methacryl”.
重合体中の（メタ）アクリル酸エステル（ａ）単位とその他の単量体（ｂ）単位の組成比としては、得られる重合体の用途に応じて適宜設定することができ、全単量体単位１００ｍｏｌ％中、（メタ）アクリル酸エステル（ａ）単位が１〜１００ｍｏｌ％、その他の単量体（ｂ）単位が０〜９９ｍｏｌ％であることが好ましく、（メタ）アクリル酸エステル（ａ）単位が１０〜１００ｍｏｌ％、その他の単量体（ｂ）単位が０〜９０ｍｏｌ％であることがより好ましく、（メタ）アクリル酸エステル（ａ）単位が５０〜１００ｍｏｌ％、その他の単量体（ｂ）単位が０〜５０ｍｏｌ％であることが更に好ましい。（メタ）アクリル酸エステル（ａ）単位の含有率が、１ｍｏｌ％以上であれば、有機ラジカル電池としての効果を有し、樹脂に配合したときの樹脂の耐候性に優れる。その他の単量体（ｂ）単位の含有率が、９９ｍｏｌ％以下であれば、有機ラジカル電池としての効果を有し、樹脂に配合したときの樹脂の耐候性に優れる。 The composition ratio of the (meth) acrylic acid ester (a) unit and the other monomer (b) unit in the polymer can be appropriately set according to the intended use of the polymer obtained, and all monomers In 100 mol% unit, (meth) acrylic acid ester (a) unit is preferably 1 to 100 mol%, and other monomer (b) units are preferably 0 to 99 mol%, (meth) acrylic acid ester (a) More preferably, the unit is 10 to 100 mol%, the other monomer (b) unit is 0 to 90 mol%, the (meth) acrylic acid ester (a) unit is 50 to 100 mol%, and the other monomer ( b) More preferably, the unit is 0 to 50 mol%. If the content rate of a (meth) acrylic acid ester (a) unit is 1 mol% or more, it has the effect as an organic radical battery, and is excellent in the weather resistance of resin when it mix | blends with resin. If the content rate of other monomer (b) units is 99 mol% or less, it has an effect as an organic radical battery and is excellent in the weather resistance of the resin when blended with the resin.
単量体成分の重合方法としては、例えば、ラジカル重合、イオン重合等の公知の重合方法が挙げられる。これらの重合方法の中でも、重合効率に優れることから、ラジカル重合が好ましい。また、ラジカル重合としては、原子移動ラジカル重合、可逆的付加開裂型連鎖移動重合等の公知の制御ラジカル重合も用いることができる。 Examples of the polymerization method of the monomer component include known polymerization methods such as radical polymerization and ionic polymerization. Among these polymerization methods, radical polymerization is preferable because of excellent polymerization efficiency. As the radical polymerization, known controlled radical polymerization such as atom transfer radical polymerization and reversible addition-fragmentation chain transfer polymerization can also be used.
単量体成分の重合形態としては、例えば、塊状重合法、溶液重合法、乳化重合法、懸濁重合法等の公知の重合形態が挙げられる。 Examples of the polymerization form of the monomer component include known polymerization forms such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization.
単量体成分の重合媒体としては、例えば、無溶媒、各種溶媒、水等の分散媒、超臨界二酸化炭素が挙げられる。溶媒としては、例えば、ベンゼン、トルエン等の炭化水素系溶媒；ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒；ジクロロメタン、クロロホルム等のハロゲン化炭化水素系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒；メタノール、エタノール、１−プロパノール、２−プロパノール、ｎ−ブチルアルコール、ｔ−ブチルアルコール等のアルコール系溶媒；アセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル系溶媒；酢酸エチル、酢酸ｎ−ブチル等のエステル系溶媒；エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒が挙げられる。これらの溶媒は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the monomer component polymerization medium include solvent-free, various solvents, dispersion media such as water, and supercritical carbon dioxide. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as dichloromethane and chloroform; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. ; Alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, t-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ethyl acetate, n-butyl acetate, etc. And ester solvents such as carbonate solvents such as ethylene carbonate and propylene carbonate. These solvents may be used alone or in combination of two or more.
単量体成分の重合におけるラジカル重合開始剤としては、例えば、ベンゾイルパーオキシド、ジ−ｔ−ブチルパーオキシド等の過酸化物系開始剤；２，２’−アゾビスイソブチロニトリル、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−（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス−（２−メチルブチロニトリル）等のアゾ系開始剤が挙げられる。これらのラジカル重合開始剤は、１種を単独で用いてもよく、２種以上を併用してもよい。これらのラジカル重合開始剤の中でも、重合効率に優れ、取扱性に優れることから、ベンゾイルパーオキシド、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス−（２，４−ジメチルバレロニトリル）が好ましい。 Examples of radical polymerization initiators in the polymerization of monomer components include peroxide initiators such as benzoyl peroxide and di-t-butyl peroxide; 2,2′-azobisisobutyronitrile, 2, 2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (2-methylbutyronitrile) And azo initiators such as These radical polymerization initiators may be used alone or in combination of two or more. Among these radical polymerization initiators, benzoyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethyl) are excellent in polymerization efficiency and handleability. Valeronitrile) is preferred.
単量体成分の重合におけるラジカル重合開始剤の使用量としては、得られる重合体の用途に応じて適宜設定することができ、単量体成分１ｍｏｌに対して、０．００００１〜０．０１ｍｏｌであることが好ましく、０．０００１〜０．０１ｍｏｌであることがより好ましい。 The amount of radical polymerization initiator used in the polymerization of the monomer component can be appropriately set according to the intended use of the polymer obtained, and is 0.00001 to 0.01 mol with respect to 1 mol of the monomer component. It is preferable that it is 0.0001-0.01 mol.
単量体成分の重合における雰囲気としては、特に制限されることはないが、ラジカル重合の場合、酸素はラジカルと容易に反応し重合を阻害するため、酸素不存在雰囲気であることが好ましい。 The atmosphere in the polymerization of the monomer component is not particularly limited, but in the case of radical polymerization, oxygen is preferably an atmosphere in the absence of oxygen because it easily reacts with the radical and inhibits the polymerization.
単量体成分の重合温度としては、−５０〜５０℃であることが好ましく、０〜３０℃であることがより好ましい。重合温度が５０℃以下であれば、重合時にニトロキシドラジカルに付加した置換基が解離することが抑制され、−５０℃以上であれば、重合反応が停止し難くなる。 The polymerization temperature of the monomer component is preferably −50 to 50 ° C., and more preferably 0 to 30 ° C. When the polymerization temperature is 50 ° C. or lower, dissociation of the substituent added to the nitroxide radical during polymerization is suppressed, and when it is −50 ° C. or higher, the polymerization reaction is difficult to stop.
本発明の重合体の数平均分子量としては、１０００〜１００万であることが好ましく、２０００〜５０万であることがより好ましい。重合体の数平均分子量が１０００以上であれば、重合体が大気中に揮発することが抑制され、１００万以下であれば、溶融成形等の成形が容易となる。また、重合体の数平均分子量を調節するために、重合時にメルカプタン等の連鎖移動剤を用いることもできる。 As a number average molecular weight of the polymer of this invention, it is preferable that it is 1000-1 million, and it is more preferable that it is 2000-500,000. If the number average molecular weight of the polymer is 1000 or more, the polymer is suppressed from volatilizing in the atmosphere, and if it is 1 million or less, molding such as melt molding becomes easy. In order to adjust the number average molecular weight of the polymer, a chain transfer agent such as mercaptan can be used during the polymerization.
本発明の重合体は、エネルギーを与えることで、下記式（３）で表される単量体（ａ’）構造単位を含む重合体を得ることができる。 The polymer of this invention can obtain the polymer containing the monomer (a ') structural unit represented by following formula (3) by giving energy.
式（３）中、Ｒ1は、水素又はメチル基を表す。 In formula (3), R 1 represents hydrogen or a methyl group.
エネルギーとしては、（メタ）アクリル酸エステル（ａ）単位の窒素−酸素−炭素結合における酸素−炭素結合を解離させることができれば特に制限されることはなく、例えば、熱エネルギー、紫外線等の光エネルギーが挙げられる。 The energy is not particularly limited as long as the oxygen-carbon bond in the nitrogen-oxygen-carbon bond of the (meth) acrylic acid ester (a) unit can be dissociated. For example, heat energy, light energy such as ultraviolet light, etc. Is mentioned.
これらのエネルギーの中でも、（メタ）アクリル酸エステル（ａ）単位の窒素−酸素−炭素結合における酸素−炭素結合を効率的に解離させることができることから、熱エネルギーが好ましい。 Among these energies, thermal energy is preferable because the oxygen-carbon bond in the nitrogen-oxygen-carbon bond of the (meth) acrylic acid ester (a) unit can be efficiently dissociated.
熱エネルギーを与える方法としては、（メタ）アクリル酸エステル（ａ）単位の窒素−酸素−炭素結合における酸素−炭素結合を解離させることができれば特に制限されることはなく、例えば、（メタ）アクリル酸エステル（ａ）を含む単量体成分を重合した後、そのまま加熱する方法や、重合体を単離した後、重合体を溶剤に溶解させ、加熱する方法が挙げられる。 The method for applying thermal energy is not particularly limited as long as the oxygen-carbon bond in the nitrogen-oxygen-carbon bond of the (meth) acrylic acid ester (a) unit can be dissociated. For example, (meth) acrylic Examples include a method in which the monomer component containing the acid ester (a) is polymerized and then heated as it is, and a method in which the polymer is isolated and then dissolved in a solvent and heated.
これらの熱エネルギーを与える方法の中でも、（メタ）アクリル酸エステル（ａ）単位を含む重合体のアルコキシアミン部位から脱離したＲ2、ＣＸ1Ｘ2Ｘ3を含む化合物等の不純物の除去が容易であることから、重合体を単離した後、重合体を溶剤に溶解させ、加熱する方法が好ましい。 Among these methods of applying thermal energy, removal of impurities such as compounds containing R 2 and CX 1 X 2 X 3 desorbed from the alkoxyamine moiety of the polymer containing the (meth) acrylate (a) unit is possible. Since it is easy, after isolating a polymer, the method of dissolving a polymer in a solvent and heating is preferable.
溶剤としては、重合体を溶解させることができる溶剤であれば特に制限されることはなく、例えば、ベンゼン、トルエン等の炭化水素系溶媒；ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒；塩化メチレン、クロロホルム等のハロゲン化炭化水素系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒；メタノール、エタノール、プロパノール、イソプロパノール、ｎ−ブチルアルコール、ｔ−ブチルアルコール等のアルコール系溶媒；アセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル系溶媒；酢酸エチル、酢酸ｎ−ブチル等のエステル系溶媒；エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒が挙げられる。これらの溶剤は１種を単独で用いてもよく、２種以上を併用してもよい。 The solvent is not particularly limited as long as it is a solvent capable of dissolving the polymer. For example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; methylene chloride and chloroform Halogenated hydrocarbon solvents such as acetone; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, and t-butyl alcohol; acetonitrile, propionitrile And nitrile solvents such as benzonitrile; ester solvents such as ethyl acetate and n-butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate. These solvents may be used alone or in combination of two or more.
尚、単量体（ａ’）構造単位を含む重合体を製造する際に生成する（メタ）アクリル酸エステル（ａ）単位を含む重合体のアルコキシアミン部位から脱離したＲ2、ＣＸ1Ｘ2Ｘ3を含む化合物は、低分子の化合物であるため、エネルギーを与えている間又はエネルギーを与えた後に、除去することができる。具体的には、沸点の高い溶媒中で（メタ）アクリル酸エステル（ａ）を含む単量体成分を重合した後、減圧下で加熱しながら化合物を揮発させ除去する方法や（メタ）アクリル酸エステル（ａ）を含む単量体成分を加熱した後、再沈殿により化合物を除去する方法が挙げられる。 R 2 and CX 1 X desorbed from the alkoxyamine moiety of the polymer containing the (meth) acrylic acid ester (a) unit produced when the polymer containing the monomer (a ′) structural unit is produced. Since the compound containing 2 X 3 is a low-molecular compound, it can be removed during energy application or after energy application. Specifically, a method of polymerizing a monomer component containing (meth) acrylic acid ester (a) in a solvent having a high boiling point and then volatilizing and removing the compound while heating under reduced pressure or (meth) acrylic acid The method of removing the compound by reprecipitation after heating the monomer component containing ester (a) is mentioned.
熱エネルギーを与える際の加熱温度としては、（メタ）アクリル酸エステル（ａ）単位の窒素−酸素−炭素結合における酸素−炭素結合を解離させることができれば特に制限されることはなく、１％質量減少温度より高い温度であれば、効率的に単量体（ａ’）構造単位を含む重合体を得ることができる。具体的には、７０〜２００℃であることが好ましく、７０〜１７０℃であることがより好ましい。加熱温度が７０℃以上であれば、（メタ）アクリル酸エステル（ａ）単位の窒素−酸素−炭素結合における酸素−炭素結合を効率的に解離させることができ、２００℃以下であれば、重合体を分解させることが少ない。 The heating temperature for applying thermal energy is not particularly limited as long as the oxygen-carbon bond in the nitrogen-oxygen-carbon bond of the (meth) acrylic acid ester (a) unit can be dissociated, and is 1% by mass. When the temperature is higher than the decrease temperature, a polymer containing the monomer (a ′) structural unit can be obtained efficiently. Specifically, it is preferable that it is 70-200 degreeC, and it is more preferable that it is 70-170 degreeC. If heating temperature is 70 degreeC or more, the oxygen-carbon bond in the nitrogen-oxygen-carbon bond of a (meth) acrylic acid ester (a) unit can be dissociated efficiently, and if it is 200 degrees C or less, heavy Less likely to break up coalescence.
本発明の単量体（ａ’）構造単位を含む重合体の製造方法は、下記式（４）で表される従来の単量体（ａ’）をアニオン重合して得る方法に比べて、安価に合成することが可能であることから好ましい。単量体（ａ’）は安定ラジカル部位を有することから、強いラジカル重合阻害作用を持ち、ラジカル重合により重合体を得ることは困難である。そのため、従来技術においては単量体（ａ’）構造単位を含む重合体を得る際にアニオン重合を行う必要が有った。 The method for producing a polymer containing the monomer (a ′) structural unit of the present invention is compared with a method obtained by anionic polymerization of a conventional monomer (a ′) represented by the following formula (4): It is preferable because it can be synthesized at low cost. Since the monomer (a ′) has a stable radical site, it has a strong radical polymerization inhibitory action, and it is difficult to obtain a polymer by radical polymerization. Therefore, in the prior art, it was necessary to perform anionic polymerization when obtaining a polymer containing the monomer (a ′) structural unit.
式（４）中、Ｒ1は、水素原子又はメチル基を表す。 In formula (4), R 1 represents a hydrogen atom or a methyl group.
本発明の製造方法により得られた単量体（ａ’）構造単位を含む重合体は、側鎖に安定ラジカルを有することから、有機ラジカル電池として有用である。 Since the polymer containing the monomer (a ′) structural unit obtained by the production method of the present invention has a stable radical in the side chain, it is useful as an organic radical battery.
有機ラジカル電池は、軽量かつ大出力を可能とする蓄電デバイスであり、正極、負極の少なくとも一方の活物質がラジカル化合物を含有することを特徴としており、前記ラジカル化合物として、単量体（ａ’）構造単位を含む重合体を用いることができる。単量体（ａ’）構造単位を含む重合体は、正極活物質、負極活物質のいずれにも用いることができるが、金属酸化物系の活物質に比べて比重が小さく、エネルギー密度に優れることから、正極活物質に用いることが好ましい。 An organic radical battery is an electricity storage device that is lightweight and capable of high output, and is characterized in that at least one active material of a positive electrode and a negative electrode contains a radical compound. As the radical compound, a monomer (a ′ ) A polymer containing a structural unit can be used. The polymer containing the monomer (a ′) structural unit can be used for both the positive electrode active material and the negative electrode active material, but has a lower specific gravity and excellent energy density than the metal oxide active material. Therefore, it is preferably used for the positive electrode active material.
正極での電極反応としては、高速充放電が可能となることから、放電時の電極反応が安定ラジカルを有する単量体（ａ’）構造単位を含む重合体を反応物とする電極反応であることが好ましい。また、前記反応の生成物が電解質カチオンとの結合を形成する反応であれば、更なる高速充放電が期待される。電解質カチオンとしては、特に制限されるもので
はないが、容量の観点から、リチウムイオンが好ましい。
As the electrode reaction at the positive electrode, high-speed charge / discharge is possible, and therefore the electrode reaction during discharge is an electrode reaction using a polymer containing a monomer (a ′) structural unit having a stable radical as a reactant. It is preferable. Further, if the reaction product forms a bond with an electrolyte cation, further rapid charge / discharge is expected. The electrolyte cation is not particularly limited, but lithium ion is preferable from the viewpoint of capacity.
尚、前記反応物とは、化学反応を起こす物質であり、長時間に亘って安定に存在する物質のことである。一方、前記生成物とは化学反応の結果生じる物質であり、長時間に亘って安定に存在する物質のことである。 The reactant is a substance that causes a chemical reaction and is a substance that exists stably for a long time. On the other hand, the product is a substance resulting from a chemical reaction, and is a substance that exists stably over a long period of time.
本発明の有機ラジカル電池の形状としては、公知の形状が挙げられる。二次電池の形状としては、例えば、電極積層体又は巻回体を、金属ケース、樹脂ケース又はアルミニウム箔等の金属箔と合成樹脂フィルムからなるラミネートフィルム等により封止したものが挙げられる。 As the shape of the organic radical battery of the present invention, known shapes can be mentioned. Examples of the shape of the secondary battery include those in which the electrode laminate or the wound body is sealed with a metal film such as a metal case, a resin case, or an aluminum foil and a laminate film made of a synthetic resin film.
本発明の有機ラジカル電池の製造方法としては、公知の製造方法が挙げられる。例えば、本発明の製造方法で得られた単量体（ａ’）構造単位を含む重合体に溶剤を加えスラリー状にして電極集電体に塗布し、セパレータを介して対極と積層する方法、本発明の製造方法で得られた単量体（ａ’）構造単位を含む重合体に溶剤を加えスラリー状にして電極集電体を巻回したものを外装体で包み、電解液を注入して封止する方法が挙げられる。 As the method for producing the organic radical battery of the present invention, known production methods can be mentioned. For example, a method in which a solvent is added to a polymer containing the monomer (a ′) structural unit obtained by the production method of the present invention and applied to an electrode current collector, and laminated with a counter electrode via a separator, A polymer containing the monomer (a ′) structural unit obtained by the production method of the present invention is added with a solvent to form a slurry and is wrapped with an electrode current collector. And sealing it.
本発明の実施形態の難燃剤は、単独で成形材料として用いても良いが、他の樹脂と混合して用いても良い。他の樹脂としては、特に限定されるものではないが、難燃性が求められる樹脂であることが好ましく、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、ポリスチレン、（メタ）アクリル酸エステル・スチレン共重合体、スチレン・アクリロニトリル等のスチレン系樹脂、ポリメタクリル酸メチル等のアクリル系樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン等の塩化ビニル系樹脂が挙げられる。これらの樹脂は、用途に応じて１種を単独で用いてもよく、２種以上を併用してもよい。 Although the flame retardant of the embodiment of the present invention may be used alone as a molding material, it may be used by mixing with other resins. The other resin is not particularly limited, but is preferably a resin that requires flame retardancy. For example, polyolefin resin such as polyethylene and polypropylene, polystyrene, (meth) acrylic acid ester / styrene Examples thereof include polymers, styrene resins such as styrene / acrylonitrile, acrylic resins such as polymethyl methacrylate, and vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride. These resins may be used individually by 1 type according to a use, and may use 2 or more types together.
これらの樹脂と混合する本発明の難燃剤の添加量は特に限定されないが、単量体（ａ）構造単位または単量体（ａ’）構造単位が樹脂組成物総量に対し、０．２５〜１０重量％であることが好ましく、０．５〜８重量％であることがより好ましく、０．５〜３重量％であることがさらに好ましい。 Although the addition amount of the flame retardant of the present invention mixed with these resins is not particularly limited, the monomer (a) structural unit or monomer (a ′) structural unit is 0.25 to 0.25 based on the total amount of the resin composition. It is preferably 10% by weight, more preferably 0.5 to 8% by weight, and even more preferably 0.5 to 3% by weight.
本発明の成形体は、重合体中に立体障害アルコキシアミンが化学結合で導入されていることから、長期間の屋外暴露によるブリードアウトが抑制され、屋外等の過酷な環境下で用いられる高分子材料の難燃性付与に好適である。 Since the sterically hindered alkoxyamine is introduced into the polymer by a chemical bond, the molded product of the present invention is a polymer that can be used in harsh environments such as outdoors because bleedout due to long-term outdoor exposure is suppressed. Suitable for imparting flame retardancy of materials.
本発明の製造方法により得られた単量体（ａ’）構造単位を含む重合体は、側鎖に安定ラジカルを有することから、樹脂に配合することにより、樹脂の耐候性を向上させることが可能である。 Since the polymer containing the monomer (a ′) structural unit obtained by the production method of the present invention has a stable radical in the side chain, it can improve the weather resistance of the resin by blending with the resin. Is possible.
樹脂としては、単量体（ａ’）構造単位を含む重合体がラジカル捕捉剤としての機能を有し樹脂の分解を抑制することから、ラジカル重合で得られた樹脂がよく、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、ポリスチレン、（メタ）アクリル酸エステル・スチレン共重合体、スチレン・アクリロニトリル等のスチレン系樹脂、ポリメタクリル酸メチル等のアクリル系樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン等の塩化ビニル系樹脂が挙げられる。これらの樹脂は、１種を単独で用いてもよく、２種以上を併用してもよい。 As the resin, since the polymer containing the monomer (a ′) structural unit has a function as a radical scavenger and suppresses the decomposition of the resin, a resin obtained by radical polymerization is preferable, for example, polyethylene, Polyolefin resins such as polypropylene, polystyrene, (meth) acrylic acid ester / styrene copolymers, styrene resins such as styrene / acrylonitrile, acrylic resins such as polymethyl methacrylate, chlorides such as polyvinyl chloride and polyvinylidene chloride Vinyl resin is mentioned. These resins may be used alone or in combination of two or more.
本発明の樹脂組成物を成形する方法としては、例えば、カレンダー成形、押出成形、押出ブロー成形、射出成形等の公知の成形方法が挙げられる。 Examples of the method for molding the resin composition of the present invention include known molding methods such as calendar molding, extrusion molding, extrusion blow molding, and injection molding.
本発明の成形体は、樹脂の耐候性に優れることから、屋外等の過酷な環境下で用いられる高分子材料に好適である。 Since the molded article of the present invention is excellent in the weather resistance of the resin, it is suitable for a polymer material used in harsh environments such as outdoors.
以下、実施例により本発明について具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
実施例、比較例における各評価は、以下に示す方法により実施した。 Each evaluation in Examples and Comparative Examples was carried out by the following methods.
（１）（メタ）アクリル酸エステル（ａ）の同定
測定には、1Ｈ−ＮＭＲ及び13Ｃ−ＮＭＲ（機種名「ＪＮＭ−ＥＸ２７０」、日本電子（株）製）を用いた。合成したメタクリル酸エステルを重水素化クロロホルムに溶解し、基準物質にテトラメチルシランを用い、測定温度２５℃、積算回数１６回で測定した。ピーク強度の積分比及びピーク位置から、（メタ）アクリル酸エステル（ａ）を同定した。
(1) Identification of (meth) acrylic acid ester (a) For the measurement, 1H-NMR and 13C-NMR (model name “JNM-EX270”, manufactured by JEOL Ltd.) were used. The synthesized methacrylic acid ester was dissolved in deuterated chloroform, and tetramethylsilane was used as a reference material, and measurement was performed at a measurement temperature of 25 ° C. and 16 integrations. The (meth) acrylic acid ester (a) was identified from the integration ratio of the peak intensity and the peak position.
（２）重合転化率
測定には、1Ｈ−ＮＭＲ（機種名「ＪＮＭ−ＥＸ２７０」、日本電子（株）製）を用いた。合成した重合体を重水素化クロロホルムに溶解し、基準物質にテトラメチルシランを用い、測定温度２５℃、積算回数１６回で測定した。（メタ）アクリル酸エステル（ａ）を含む単量体に由来するピーク強度と重合体に由来するピーク強度の積分比から、重合体の重合転化率を計算した。
(2) Polymerization conversion rate For the measurement, 1H-NMR (model name “JNM-EX270”, manufactured by JEOL Ltd.) was used. The synthesized polymer was dissolved in deuterated chloroform, and tetramethylsilane was used as a reference substance, and measurement was performed at a measurement temperature of 25 ° C. and 16 times of integration. The polymerization conversion rate of the polymer was calculated from the integral ratio of the peak intensity derived from the monomer containing the (meth) acrylic acid ester (a) and the peak intensity derived from the polymer.
（３）共重合体の組成比
測定には、1Ｈ−ＮＭＲ（機種名「ＪＮＭ−ＥＸ２７０」、日本電子（株）製）を用いた。合成した重合体を重水素化クロロホルムに溶解し、基準物質にテトラメチルシランを用い、測定温度２５℃、積算回数１６回で測定した。（メタ）アクリル酸エステル（ａ）に由来するピーク強度とその他の単量体（ｂ）に由来するピーク強度の積分比から、共重合体の組成比を計算した。
(3) Composition ratio of copolymer 1H-NMR (model name “JNM-EX270”, manufactured by JEOL Ltd.) was used for measurement. The synthesized polymer was dissolved in deuterated chloroform, and tetramethylsilane was used as a reference substance, and measurement was performed at a measurement temperature of 25 ° C. and 16 times of integration. The composition ratio of the copolymer was calculated from the integral ratio of the peak intensity derived from the (meth) acrylic acid ester (a) and the peak intensity derived from the other monomer (b).
（４）重合体の数平均分子量及び分子量分布
重合体の数平均分子量及び分子量分布（質量平均分子量／数平均分子量）は、ポリメタクリル酸メチルをスタンダードとして、ゲルパーミエーションクロマトグラフィーを用い、以下の条件により測定した。
(4) Number average molecular weight and molecular weight distribution of polymer The number average molecular weight and molecular weight distribution (mass average molecular weight / number average molecular weight) of the polymer are as follows, using polymethyl methacrylate as a standard, and gel permeation chromatography. Measured according to conditions.
機種名 ：ＨＬＣ−８２２０（東ソー（株）製）
カラム ：ＴＳＫ ＧＵＡＲＤ ＣＯＬＵＭＮ ＳＵＰＥＲ ＨＺ−Ｌ（東ソー（株）製、４．６×３５ｍｍ）、ＴＳＫ−ＧＥＬ ＳＵＰＥＲ ＨＺＭ−Ｎ（東ソー（株）製、６．０×１５０ｍｍ）、２直列接続
溶離液 ：クロロホルム
測定温度：４０℃
流速 ：０．６ｍｌ／分
Model name: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSK GUARD COLUMN SUPER HZ-L (manufactured by Tosoh Corp., 4.6 × 35 mm), TSK-GEL SUPER HZM-N (manufactured by Tosoh Corp., 6.0 × 150 mm), 2 series connection Eluent: Chloroform Measurement temperature: 40 ° C
Flow rate: 0.6 ml / min
（５）重合体の熱分解性（１％質量減少温度）
測定には、熱分析装置（機種名「ＴＧ／ＤＴＡ６３００」、エスアイアイ・ナノテクノロジー（株）製）を用いた。
(5) Thermal decomposability of polymer (1% mass loss temperature)
For the measurement, a thermal analyzer (model name “TG / DTA6300”, manufactured by SII Nano Technology Co., Ltd.) was used.
十分乾燥させた重合体を所定量計り取り、空気中、３０〜５００℃の温度範囲で、１０℃／分で昇温させ、１％質量減少温度を測定した。 A predetermined amount of the sufficiently dried polymer was weighed and heated in air at a temperature range of 30 to 500 ° C. at a rate of 10 ° C./min, and a 1% mass reduction temperature was measured.
（６）重合体のラジカル濃度
測定には、電子スピン共鳴測定装置（機種名「ＪＥＳ ＴＥ−２００」、日本電子（株）製）を用い、以下の条件により測定した。
(6) Polymer Radical Concentration For measurement, an electron spin resonance measuring device (model name “JES TE-200”, manufactured by JEOL Ltd.) was used and measured under the following conditions.
中心磁場 ：３３４６±５０ガウス
モジュレーション：１００ＫＨｚ、１．０ガウス
パワー ：２０ｍＷ
ゲイン ：１×１００、５×１０
レスポンス ：０．１秒
Central magnetic field: 3346 ± 50 Gauss Modulation: 100 KHz, 1.0 Gauss Power: 20 mW
Gain: 1 × 100, 5 × 10
Response: 0.1 seconds
尚、ラジカル濃度の決定には、予め定量しておいた２，２，６，６−テトラメチルピペリジン−Ｎ−オキシドを用い、スペクトルの二回積分により定量し検量線を作成し、作成した検量線からラジカル濃度を算出した。 The radical concentration was determined using 2,2,6,6-tetramethylpiperidine-N-oxide, which had been quantified in advance, and quantified by two-time integration of the spectrum to prepare a calibration curve. The radical concentration was calculated from the line.
［実施例１］１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン（ａ１）の合成
２，２，６，６−テトラメチル−４−ヒドロキシピペリジン−Ｎ−オキシド ３．４ｇ（２０ｍｍｏｌ）、ピルビン酸メチル ２０ｇ（２００ｍｍｏｌ）、３０％過酸化水素 ４．５ｇ（４０ｍｍｏｌ）を投入し、５℃に冷却した。塩化銅（Ｉ） ０．１ｇ（１ｍｍｏｌ）を添加し、適宜氷浴で冷却しつつ、３０℃付近で２時間反応させた。２時間後、４ｍｏｌ／Ｌの重亜硫酸ナトリウム水溶液２０ｍｌ、飽和炭酸水素カリウム水溶液１０ｍｌを加え、１００ｍｌの酢酸エチルで抽出した。有機層を回転エバポレーターで濃縮し、白色固体の、１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−ヒドロキシピペリジン ４．４ｇ（収率：９５％）を得た。
[Example 1] Synthesis of 1-methoxycarbonyloxy-2,2,6,6-tetramethyl-4-methacryloyloxypiperidine (a1) 2,2,6,6-tetramethyl-4-hydroxypiperidine-N- 3.4 g (20 mmol) of oxide, 20 g (200 mmol) of methyl pyruvate and 4.5 g (40 mmol) of 30% hydrogen peroxide were added and cooled to 5 ° C. Copper (I) chloride 0.1g (1mmol) was added, and it was made to react at 30 degreeC vicinity for 2 hours, cooling with an ice bath suitably. Two hours later, 20 ml of 4 mol / L aqueous sodium bisulfite solution and 10 ml of saturated aqueous potassium hydrogen carbonate solution were added, and the mixture was extracted with 100 ml of ethyl acetate. The organic layer was concentrated by a rotary evaporator to obtain 4.4 g (yield: 95%) of 1-methoxycarbonyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine as a white solid.
得られた１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−ヒドロキシピペリジン ２．３ｇ（１０ｍｍｏｌ）をジクロロメタン１０ｍｌ、トリエチルアミン４ｍｌに溶解し、メタクリロイルクロリド１．３ｇ（１２ｍｍｏｌ）を０℃にてゆっくり添加した。徐々に室温まで昇温しつつ、１時間反応させた。１時間後、反応混合物を回転エバポレーターで濃縮し、残渣に水１５０ｍｌを加え、合計２００ｍｌの酢酸エチルで抽出した。有機層を回転エバポレーターで濃縮し、残渣をカラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル＝１０／１体積比）によって精製して、無色液体の１−メトキシカルボニルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン（ａ１）を１．９ｇ得た（収率６２％）。 2.3 g (10 mmol) of 1-methoxycarbonyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine obtained was dissolved in 10 ml of dichloromethane and 4 ml of triethylamine, and 1.3 g (12 mmol) of methacryloyl chloride was dissolved in 0 ml. Slowly added at ° C. The reaction was allowed to proceed for 1 hour while gradually warming to room temperature. After 1 hour, the reaction mixture was concentrated on a rotary evaporator, 150 ml of water was added to the residue, and the mixture was extracted with a total of 200 ml of ethyl acetate. The organic layer is concentrated on a rotary evaporator, and the residue is purified by column chromatography (silica gel, hexane / ethyl acetate = 10/1 volume ratio) to give 1-methoxycarbonyloxy-2,2,6,6- 1.9 g of tetramethyl-4-methacryloyloxypiperidine (a1) was obtained (yield 62%).
1Ｈ−ＮＭＲ及び13Ｃ−ＮＭＲの測定により、生成物が式（１）で表される単量体（ａ１）であることを確認した。 It was confirmed by measurement of 1H-NMR and 13C-NMR that the product was a monomer (a1) represented by the formula (1).
1Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ（ｐｐｍ）：１．１０（ｓ、６Ｈ），１．２０（ｓ、６Ｈ），１．７４（ｔ、２Ｈ），１．８５（ｓ、３Ｈ），１．９０（ｍ、２Ｈ），３．７５（ｓ、３Ｈ），５．０６（ｍ、１Ｈ），５．４８（ｓ、１Ｈ），６．００（ｓ、１Ｈ） 1H-NMR (CDCl3): δ (ppm): 1.10 (s, 6H), 1.20 (s, 6H), 1.74 (t, 2H), 1.85 (s, 3H), 1. 90 (m, 2H), 3.75 (s, 3H), 5.06 (m, 1H), 5.48 (s, 1H), 6.00 (s, 1H)
13Ｃ−ＮＭＲ（ＣＤＣｌ3）：δ（ｐｐｍ）：１８．０３，２０．９８，３１．３６，４３．４３，５４．９３，６０．５５，６６．０７，１２５．３２，１３６．２６，１６６．７０ 13 C-NMR (CDCl 3): δ (ppm): 18.03, 20.98, 31.36, 43.43, 54.93, 60.55, 66.07, 125.32, 136.26, 166. 70
［実施例２］１−トリフルオロメチルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン（ａ２）の合成
２，２，６，６−テトラメチル−４−ヒドロキシピペリジン−Ｎ−オキシド ２．６ｇ（１５ｍｍｏｌ）、ヘキサフルオロアセトン・３水和物 ２２ｇ（２２０ｍｍｏｌ）、３０％過酸化水素 ５．７ｇ（３４ｍｍｏｌ）を投入し、０℃に氷冷した。塩化銅（Ｉ） ０．０５ｇ（０．５ｍｍｏｌ）を添加し、濃塩酸３滴を加え、適宜氷浴で冷却しつつ、１時間反応させた。４ｍｏｌ／Ｌの重亜硫酸ナトリウム水溶液１０ｍｌ、飽和炭酸水素カリウム水溶液２０ｍｌを加え、１００ｍｌの酢酸エチルで抽出した。有機層を回転エバポレーターで濃縮し、残渣をカラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル＝５／１体積比）によって精製して、１−トリフルオロメチルオキシ−２，２，６，６−テトラメチル−４−ヒドロキシピペリジン １．６ｇ（収率：４４％）を得た。
Example 2 Synthesis of 1-trifluoromethyloxy-2,2,6,6-tetramethyl-4-methacryloyloxypiperidine (a2) 2,2,6,6-tetramethyl-4-hydroxypiperidine-N -Oxide 2.6 g (15 mmol), hexafluoroacetone trihydrate 22 g (220 mmol), 30% hydrogen peroxide 5.7 g (34 mmol) were added, and the mixture was ice-cooled to 0 ° C. 0.05 g (0.5 mmol) of copper (I) chloride was added, 3 drops of concentrated hydrochloric acid was added, and the mixture was allowed to react for 1 hour while appropriately cooling in an ice bath. 10 ml of 4 mol / L sodium bisulfite aqueous solution and 20 ml of saturated potassium hydrogen carbonate aqueous solution were added, and the mixture was extracted with 100 ml of ethyl acetate. The organic layer is concentrated on a rotary evaporator, and the residue is purified by column chromatography (silica gel, hexane / ethyl acetate = 5/1 volume ratio) to give 1-trifluoromethyloxy-2,2,6,6-tetramethyl. 1.6 g (yield: 44%) of -4-hydroxypiperidine was obtained.
得られた１−トリフルオロメチルオキシ−２，２，６，６−テトラメチル−４−ヒドロキシピペリジン １．４ｇ（６ｍｍｏｌ）をジクロロメタン３ｍｌ、トリエチルアミン２ｍｌに溶解し、メタクリロイルクロリド０．８ｇ（８ｍｍｏｌ）を０℃にてゆっくり添加した。徐々に室温まで昇温しつつ、１時間反応させた。１時間後、反応混合物を回転エバポレーターで濃縮し、残渣に水５０ｍｌを加え、酢酸エチル５０ｍｌで抽出した。有機層を回転エバポレーターで濃縮し、残渣をカラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル＝１５／１体積比）によって精製して、無色液体の１−トリフルオロメチルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン（ａ２）を１．４ｇ得た（収率７６％）。 The obtained 1-trifluoromethyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine (1.4 g, 6 mmol) was dissolved in 3 ml of dichloromethane and 2 ml of triethylamine, and 0.8 g (8 mmol) of methacryloyl chloride was dissolved. Slowly added at 0 ° C. The reaction was allowed to proceed for 1 hour while gradually warming to room temperature. After 1 hour, the reaction mixture was concentrated on a rotary evaporator, 50 ml of water was added to the residue, and the mixture was extracted with 50 ml of ethyl acetate. The organic layer is concentrated on a rotary evaporator, and the residue is purified by column chromatography (silica gel, hexane / ethyl acetate = 15/1 volume ratio) to give 1-trifluoromethyloxy-2,2,6,6 as a colorless liquid. 1.4 g of tetramethyl-4-methacryloyloxypiperidine (a2) was obtained (76% yield).
1Ｈ−ＮＭＲ及び13Ｃ−ＮＭＲの測定により、生成物が式（２）で表される単量体（ａ２）であることを確認した。 It was confirmed by measurement of 1H-NMR and 13C-NMR that the product was a monomer (a2) represented by the formula (2).
1Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ（ｐｐｍ）：１．２３（ｓ、６Ｈ），１．３０（ｓ、６Ｈ），１．７１（ｔ、２Ｈ），１．９２（ｓ、３Ｈ），１．９８（ｍ、２Ｈ），５．１１（ｍ、１Ｈ），５．５６（ｓ、１Ｈ），６．０８（ｓ、１Ｈ） 1H-NMR (CDCl3): δ (ppm): 1.23 (s, 6H), 1.30 (s, 6H), 1.71 (t, 2H), 1.92 (s, 3H), 1. 98 (m, 2H), 5.11 (m, 1H), 5.56 (s, 1H), 6.08 (s, 1H)
13Ｃ−ＮＭＲ（ＣＤＣｌ3）：δ（ｐｐｍ）：１８．１５，２１．１７，３２．６９，４４．１５，６１．６９，６５．９９，１２３．５３，１２５．４７，１３６．３５，１６６．８６ 13 C-NMR (CDCl 3): δ (ppm): 18.15, 21.17, 32.69, 44.15, 61.69, 65.9, 123.53, 125.47, 136.35, 166. 86
［実施例３］メタクリル酸エステル（ａ１）／メタクリル酸メチル（ＭＭＡ）共重合体の合成 [Example 3] Synthesis of methacrylate ester (a1) / methyl methacrylate (MMA) copolymer
実施例１で得られたメタクリル酸エステル（ａ１）０．６０ｇ（２．０ｍｍｏｌ）及びＭＭＡ（３８．０ｍｍｏｌ）の単量体成分に、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）（商品名「Ｖ−７０」、和光純薬（株）製）０．０６ｇ（０．２ｍｍｏｌ）とトルエン１０ｍｌを加え単量体溶液を調製した後、窒素バブリングを２０分行った。ついで、内温を２５℃に昇温し、そのまま２４時間保持した。その後、得られた重合体を大量のメタノール中に注ぎ、再沈殿させ、白色の粉末の重合体を得た。 To the monomer components of 0.60 g (2.0 mmol) and MMA (38.0 mmol) of the methacrylic acid ester (a1) obtained in Example 1, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile) (trade name “V-70”, manufactured by Wako Pure Chemical Industries, Ltd.) 0.06 g (0.2 mmol) and 10 ml of toluene were added to prepare a monomer solution, and nitrogen bubbling was performed for 20 minutes. . Subsequently, the internal temperature was raised to 25 ° C. and kept as it was for 24 hours. Thereafter, the obtained polymer was poured into a large amount of methanol and reprecipitated to obtain a white powder polymer.
［実施例４］メタクリル酸エステル（ａ２）／ＭＭＡ共重合体の合成
メタアクリル酸エステル（ａ１）０．６０ｇ（２．０ｍｍｏｌ）の代わりに、実施例２で得られたメタクリル酸エステル（ａ２）０．６２ｇ（２．０ｍｍｏｌ）を加えたこと以外は、実施例３と同様に行い、白色の粉末の重合体を得た。
[Example 4] Synthesis of methacrylic acid ester (a2) / MMA copolymer Methacrylic acid ester (a2) obtained in Example 2 instead of 0.60 g (2.0 mmol) of methacrylic acid ester (a1) A white powder polymer was obtained in the same manner as in Example 3 except that 0.62 g (2.0 mmol) was added.
［実施例５］メタクリル酸エステル（ａ１）単独重合体の合成
メタクリル酸エステル（ａ１）０．６０ｇ（２．０ｍｍｏｌ）及びＭＭＡ３．８１ｇ（３８．０ｍｍｏｌ）の代わりに、メタクリル酸エステル（ａ１）１１．９７ｇ（４０．０ｍｍｏｌ）を加えたこと以外は、実施例３と同様に行い、白色の粉末の重合体を得た。
[Example 5] Synthesis of methacrylic acid ester (a1) homopolymer Methacrylic acid ester (a1) 11 instead of 0.60 g (2.0 mmol) of methacrylic acid ester (a1) and 3.81 g (38.0 mmol) of MMA Except that .97 g (40.0 mmol) was added, the same procedure as in Example 3 was performed to obtain a white powder polymer.
［実施例６］メタクリル酸エステル（ａ２）単独重合体の合成
メタクリル酸エステル（ａ１）０．６０ｇ（２．０ｍｍｏｌ）及びＭＭＡ３．８１ｇ（３８．０ｍｍｏｌ）の代わりに、メタクリル酸エステル（ａ２）１２．３７ｇ（４０．０ｍｍｏｌ）を加えたこと以外は、実施例３と同様に行い、白色の粉末の重合体を得た。
[Example 6] Synthesis of methacrylic acid ester (a2) homopolymer Methacrylic acid ester (a2) 12 instead of 0.60 g (2.0 mmol) of methacrylic acid ester (a1) and 3.81 g (38.0 mmol) of MMA Except that .37 g (40.0 mmol) was added, the same procedure as in Example 3 was performed to obtain a white powder polymer.
［実施例７］単量体（ａ’）構造単位を含む重合体の合成
実施例４で得られた重合体１ｇを２０ｍｌのアンプル管に注入し、トルエン３ｍｌに溶解させ、窒素雰囲気下、１００℃のオイルバスに浸漬し、４時間加熱した。得られた溶液を１００ｍｌのメタノールに沈殿させ、０．８ｇの赤色粉末を得た。
[Example 7] Synthesis of polymer containing monomer (a ') structural unit 1 g of the polymer obtained in Example 4 was poured into a 20 ml ampoule tube and dissolved in 3 ml of toluene. It was immersed in an oil bath at 0 ° C. and heated for 4 hours. The obtained solution was precipitated in 100 ml of methanol to obtain 0.8 g of red powder.
得られた赤色粉末０．２２ｇをトルエン溶解させ、１０ｍｌの溶液調製し、電子スピン共鳴測定を行ったところ、ニトロキシドラジカルに特徴的な３本線が観測され、予め２，２，６，６−テトラメチルピペリジン−Ｎ−オキシドを用いた検量線から見積もったラジカル濃度は３．５８ｍｍｏｌ／ｌであった。尚、実施例４で得られた重合体中のトリフルオロメチル基が１００ｍｏｌ％脱離した場合、ラジカル濃度は１０．０ｍｍｏｌ／ｌとなることから、実施例７において、重合体中のトリフルオロメチル基が３５．８ｍｏｌ％脱離し、安定ラジカルである単量体（ａ’）構造単位を含む重合体が得られていることが確認された。 0.22 g of the obtained red powder was dissolved in toluene, 10 ml of solution was prepared, and electron spin resonance measurement was performed. As a result, three lines characteristic of the nitroxide radical were observed, and 2,2,6,6-tetra The radical concentration estimated from the calibration curve using methylpiperidine-N-oxide was 3.58 mmol / l. Incidentally, when 100 mol% of the trifluoromethyl group in the polymer obtained in Example 4 was eliminated, the radical concentration was 10.0 mmol / l. Therefore, in Example 7, the trifluoromethyl group in the polymer was It was confirmed that a polymer containing the monomer (a ′) structural unit, which is a stable radical, was obtained by removing 35.8 mol% of the group.
実施例３〜６における重合転化率、重合体の組成、数平均分子量、分子量分布（質量平均分子量／数平均分子量）、１％質量減少温度を、表１に示す。 Table 1 shows the polymerization conversion ratio, polymer composition, number average molecular weight, molecular weight distribution (mass average molecular weight / number average molecular weight), and 1% mass reduction temperature in Examples 3 to 6.
表１中の略号を、以下に示す。
ＭＭＡ：メタクリル酸メチル
Abbreviations in Table 1 are shown below.
MMA: Methyl methacrylate
実施例３〜６において１％質量減少温度を測定しているが、この質量減少は、重合体中の（メタ）アクリル酸エステル（ａ）単位の窒素−酸素−炭素結合における酸素−炭素結合が熱エネルギーにより切断され、炭素側の部位が揮発し失われたことに起因している。表１の結果から明らかなように、実施例３〜６の重合体の１％質量減少温度は２２０℃以下であり、熱処理により容易に単量体（ａ’）構造単位を含む重合体を製造することが可能である。 In Examples 3 to 6, the 1% mass reduction temperature is measured. This mass reduction is caused by the oxygen-carbon bond in the nitrogen-oxygen-carbon bond of the (meth) acrylic acid ester (a) unit in the polymer. This is due to the fact that the carbon side portion was volatilized and lost by being cut by thermal energy. As is apparent from the results in Table 1, the polymers of Examples 3 to 6 have a 1% mass reduction temperature of 220 ° C. or less, and easily produce a polymer containing the monomer (a ′) structural unit by heat treatment. Is possible.
実施例１〜２により、本発明の（メタ）アクリル酸エステル（ａ）を合成することができた。また、実施例３〜６により、アルコキシアミン構造を有する（メタ）アクリル酸エステル（ａ）単位含む重合体を得ることができた。また、実施例７により、効率的に単量体（ａ’）構造単位を含む重合体を得ることができた。得られた重合体は、側鎖に安定ラジカルを有することから、有機ラジカル電池として有用であり、更に、樹脂に配合することにより、樹脂の耐候性を向上させることが可能である。 According to Examples 1 and 2, the (meth) acrylic acid ester (a) of the present invention could be synthesized. Moreover, the polymer containing the (meth) acrylic acid ester (a) unit which has an alkoxyamine structure was able to be obtained by Examples 3-6. Further, according to Example 7, a polymer containing the monomer (a ′) structural unit was efficiently obtained. Since the obtained polymer has a stable radical in the side chain, it is useful as an organic radical battery, and further, it is possible to improve the weather resistance of the resin by blending with the resin.
[合成例１] １−メチルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン（ａ３）の合成
２，２，６，６−テトラメチル−４−ヒドロキシピペリジン−Ｎ−オキシド１７．８ｇ（１００ｍｍｏｌ）をアセトン１００ｍｌに溶解し、３０％過酸化水素水溶液３４ｇ（３００ｍｍｏｌ）を１０分以上かけてゆっくり添加した。５℃まで冷却しながら、塩化銅（Ｉ）０．４９ｇ（５．０ｍｏｌ％）を添加し、反応混合物の温度を５℃から５５℃の間に保持した。１５分後、３５％塩酸を０．５ｇ添加し、反応混合物を室温において２時間撹拌した。２時間後、４ｍｏｌ／Ｌの重亜硫酸ナトリウム水溶液５０ｍｌ、飽和炭酸水素カリウム水溶液１００ｍｌを加え、３００ｍｌの酢酸エチルで抽出した。有機層を回転エバポレーターで濃縮し、１−メチルオキシ−２，２，６，６−テトラメチル−４−ヒドロキシピペリジンを得た。
[Synthesis Example 1] Synthesis of 1-methyloxy-2,2,6,6-tetramethyl-4-methacryloyloxypiperidine (a3) 2,2,6,6-tetramethyl-4-hydroxypiperidine-N-oxide 17.8 g (100 mmol) was dissolved in 100 ml of acetone, and 34 g (300 mmol) of a 30% aqueous hydrogen peroxide solution was slowly added over 10 minutes. While cooling to 5 ° C., 0.49 g (5.0 mol%) of copper (I) chloride was added and the temperature of the reaction mixture was maintained between 5 ° C. and 55 ° C. After 15 minutes, 0.5 g of 35% hydrochloric acid was added and the reaction mixture was stirred at room temperature for 2 hours. Two hours later, 50 ml of 4 mol / L aqueous sodium bisulfite solution and 100 ml of saturated aqueous potassium hydrogen carbonate solution were added, and the mixture was extracted with 300 ml of ethyl acetate. The organic layer was concentrated with a rotary evaporator to obtain 1-methyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine.
得られた１−メチルオキシ−２，２，６，６−テトラメチル−４−ヒドロキシピペリジンをジクロロメタン５０ｍｌ、トリエチルアミン５０ｍｌに溶解し、メタクリロイルクロリド１０．４ｇ（１００ｍｍｏｌ）を０℃にてゆっくり添加した。徐々に室温まで昇温しつつ、１時間反応させた。１時間後、反応混合物を回転エバポレーターで濃縮し、残渣に水３００ｍｌを加え、酢酸エチル３００ｍｌで抽出した。有機層を回転エバポレーターで濃縮し、残渣をカラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル＝１０／１体積比）によって精製して、無色の液体である１−メチルオキシ−２，２，６，６−テトラメチル−４−メタクリロイルオキシピペリジン（ａ３）を１９．０ｇ得た。（収率７４．３％） The obtained 1-methyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine was dissolved in 50 ml of dichloromethane and 50 ml of triethylamine, and 10.4 g (100 mmol) of methacryloyl chloride was slowly added at 0 ° C. The reaction was allowed to proceed for 1 hour while gradually warming to room temperature. After 1 hour, the reaction mixture was concentrated on a rotary evaporator, 300 ml of water was added to the residue, and the mixture was extracted with 300 ml of ethyl acetate. The organic layer was concentrated on a rotary evaporator, and the residue was purified by column chromatography (silica gel, hexane / ethyl acetate = 10/1 volume ratio) to give a colorless liquid 1-methyloxy-2,2,6,6. 19.0 g of tetramethyl-4-methacryloyloxypiperidine (a3) was obtained. (Yield 74.3%)
１Ｈ−ＮＭＲの測定により、生成物がビニル単量体（ａ３）であることを確認した。 The product was confirmed to be a vinyl monomer (a3) by 1H-NMR measurement.
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：δ（ｐｐｍ）：１．１９（ｓ、６Ｈ），１．２３（ｓ、６Ｈ），１．６０（ｍ、２Ｈ），１．８７（ｍ、２Ｈ），１．９２（ｓ、３Ｈ），３．６２（ｓ、３Ｈ），５．０７（ｍ、１Ｈ），５．５３（ｓ、１Ｈ），６．０６（ｓ、１Ｈ） 1H-NMR (CDCl3): δ (ppm): 1.19 (s, 6H), 1.23 (s, 6H), 1.60 (m, 2H), 1.87 (m, 2H), 1. 92 (s, 3H), 3.62 (s, 3H), 5.07 (m, 1H), 5.53 (s, 1H), 6.06 (s, 1H)
［合成例２］メタクリル酸エステル（ａ３）／メタクリル酸メチル（ＭＭＡ）／アクリル酸メチル（ＭＡ）共重合体の合成
合成例１で得られたメタクリル酸エステル（ａ３）０．２５５ｇ（１．０ｍｍｏｌ）、ＭＭＡ４．８１ｇ（４８．０ｍｍｏｌ）、ＭＡ０．８６１ｇ（１．０ｍｍｏｌ）の単量体成分に、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）（商品名「Ｖ−７０」、和光純薬（株）製）０．０６ｇ（０．２ｍｍｏｌ）とトルエン１０ｍｌを加えて単量体溶液を調製した後、窒素バブリングを２０分行った。次いで、内温を２５℃に昇温し、そのまま２４時間保持した。その後、得られた重合体を大量のメタノール中に注ぎ、再沈殿させ、白色の粉末の重合体（Ａ−１）を得た。
[Synthesis Example 2] Synthesis of methacrylate ester (a3) / methyl methacrylate (MMA) / methyl acrylate (MA) copolymer 0.255 g (1.0 mmol) of methacrylate ester (a3) obtained in Synthesis Example 1 ), MMA 4.81 g (48.0 mmol), MA 0.861 g (1.0 mmol) monomer component and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (trade name “V -70 ", Wako Pure Chemical Industries, Ltd.) 0.06 g (0.2 mmol) and 10 ml of toluene were added to prepare a monomer solution, and nitrogen bubbling was performed for 20 minutes. Next, the internal temperature was raised to 25 ° C. and maintained as it was for 24 hours. Thereafter, the obtained polymer was poured into a large amount of methanol and reprecipitated to obtain a white powder polymer (A-1).
［実施例８］メタクリル酸エステル（ａ２）／ＭＭＡ／ＭＡ共重合体の合成
メタクリル酸エステル（ａ３）０．２５５ｇの代わりに、実施例２で得られたメタクリル酸エステル（ａ２）０．３０９ｇ（１．０ｍｍｏｌ）を加えたこと以外は、合成例２と同様に行い、白色の粉末の重合体（Ａ−２）を得た。
[Example 8] Synthesis of methacrylic acid ester (a2) / MMA / MA copolymer Instead of 0.255 g of methacrylic acid ester (a3), 0.309 g of methacrylic acid ester (a2) obtained in Example 2 ( A white powder polymer (A-2) was obtained in the same manner as in Synthesis Example 2 except that 1.0 mmol) was added.
［実施例９］メタクリル酸エステル（ａ２）／ＭＡ共重合体の合成
メタクリル酸エステル（ａ３）０．２５５ｇ（１．０ｍｍｏｌ）及びＭＭＡ４．８１ｇ（４８．０ｍｍｏｌ）の代わりに、メタクリル酸エステル（ａ２）１２．５ｇ（４９．０ｍｍｏｌ）を加えたこと以外は、合成例２と同様に行い、白色の粉末の重合体（Ａ−３）を得た。
Example 9 Synthesis of Methacrylate (a2) / MA Copolymer Methacrylate (a2) instead of 0.255 g (1.0 mmol) and 4.81 g (48.0 mmol) of MMA ) A white powder polymer (A-3) was obtained in the same manner as in Synthesis Example 2 except that 12.5 g (49.0 mmol) was added.
（合成例３）ＭＭＡ／ＭＡ共重合体の合成
メタクリル酸エステル（ａ３）０．２５５ｇ（１．０ｍｍｏｌ）及びＭＭＡ４．８１ｇ（４８．０ｍｍｏｌ）の代わりに、ＭＭＡ４．９１ｇ（４９．０ｍｍｏｌ）を加えたこと以外は、合成例２と同様に行い、白色の粉末の重合体（Ａ−４）を得た。
(Synthesis Example 3) Synthesis of MMA / MA copolymer Instead of 0.255 g (1.0 mmol) of methacrylic acid ester (a3) and 4.81 g (48.0 mmol) of MMA, 4.91 g (49.0 mmol) of MMA was added. The white powder polymer (A-4) was obtained in the same manner as in Synthesis Example 2.
実施例８、９および合成例２、３における収率、重合体の組成、数平均分子量、分子量分布（質量平均分子量／数平均分子量）を、表２に示す。 Table 2 shows the yield, polymer composition, number average molecular weight, and molecular weight distribution (mass average molecular weight / number average molecular weight) in Examples 8 and 9 and Synthesis Examples 2 and 3.
実施例８で得られた重合体（Ａ−２）の空気中および窒素中での熱重量分析を行った。結果を図１、２に示す。併せて、重合体（Ａ−２）を加熱（２６０℃にて３分間溶融加熱)し、クロロホルムに溶解し、メタノールで再沈精製した重合体を用いて同様に熱重量分析を行った。結果を同じく図１，２に示す。 The polymer (A-2) obtained in Example 8 was subjected to thermogravimetric analysis in air and nitrogen. The results are shown in FIGS. In addition, the polymer (A-2) was heated (melted and heated at 260 ° C. for 3 minutes), dissolved in chloroform, and subjected to thermogravimetric analysis in the same manner using the polymer purified by reprecipitation with methanol. The results are also shown in FIGS.
［比較例］
合成例２および合成例３で得られた重合体（Ａ−１）および（Ａ−４）の窒素中および空気中における熱重量分析を行った。結果をそれぞれ図１（窒素中）、２（空気中）に併せて示す。
[Comparative example]
Thermogravimetric analysis of the polymers (A-1) and (A-4) obtained in Synthesis Example 2 and Synthesis Example 3 in nitrogen and air was performed. The results are also shown in FIGS. 1 (in nitrogen) and 2 (in air).
図１が示すように、実施例８で得られた特定の立体障害アルコキシアミン単位を含む重合体（Ａ−２）については、立体障害アルコキシアミン単位を含むにもかかわらず、合成例２で得られた重合体（Ａ−１）に見られる、窒素中における３００℃付近からの重量減少は確認されていない。そのことから、重合体（Ａ−２）については、熱分解が抑制されていることが分かる。また合成例３で得られた、式（１）または（２）で表される（メタ）アクリル酸エステル由来の立体障害アルコキシアミン単位を含まない重合体（Ａ−４）は耐熱分解性が不良であった。以上の結果は図２で示す空気中での測定結果でも同様であり、特定の立体障害アルコキシアミン単位を含む重合体は熱分解性が向上していることがわかる。 As shown in FIG. 1, the polymer (A-2) containing the specific sterically hindered alkoxyamine unit obtained in Example 8 was obtained in Synthesis Example 2 even though it contained a sterically hindered alkoxyamine unit. The weight reduction from about 300 degreeC in nitrogen seen in the obtained polymer (A-1) is not confirmed. From this, it can be seen that the thermal decomposition of the polymer (A-2) is suppressed. In addition, the polymer (A-4) obtained in Synthesis Example 3 that does not contain a sterically hindered alkoxyamine unit derived from the (meth) acrylic acid ester represented by the formula (1) or (2) has poor thermal decomposition resistance. Met. The above results are the same in the measurement results in air shown in FIG. 2, and it is understood that the polymer containing a specific sterically hindered alkoxyamine unit has improved thermal decomposability.
また、実施例８で得られた重合体（Ａ−２）を熱処理したサンプルも、窒素中および空気中のいずれにおいても耐熱分解性は重合体（Ａ−２）の熱分解挙動と同様の分解挙動を示している。以上の結果より、重合体（Ａ−２）は分解温度が高く、３００℃以上では速やかにＮ−オキシル体へ変換されていると考えられる。重合体（Ａ−２）の分解により生成したニトロキシドラジカルによるラジカルトラップ効果により、ポリマーの分解が抑制されているものと考えられる。 Further, in the sample obtained by heat-treating the polymer (A-2) obtained in Example 8, the thermal decomposition resistance in both nitrogen and air is the same as the thermal decomposition behavior of the polymer (A-2). The behavior is shown. From the above results, it is considered that the polymer (A-2) has a high decomposition temperature and is promptly converted to the N-oxyl form at 300 ° C. or higher. It is considered that the decomposition of the polymer is suppressed by the radical trap effect by the nitroxide radical generated by the decomposition of the polymer (A-2).
本発明の、特定の立体障害アルコキシアミンを含む（メタ）アクリル酸エステル単量体重合して得られる重合体は、重合体にエネルギーを与えることで、側鎖に安定ラジカルを有する重合体を効率的に得ることができ、有機ラジカル電池への応用が可能である。更に、長期間難燃性を付与することが可能であり、難燃性が求められる樹脂として使用できるだけでなく、難燃性が求められる樹脂に添加することが可能である。 The polymer obtained by polymerizing a (meth) acrylic acid ester monomer containing a specific sterically hindered alkoxyamine according to the present invention efficiently gives a polymer having a stable radical in the side chain by applying energy to the polymer. And can be applied to organic radical batteries. Furthermore, it is possible to impart flame retardancy for a long period of time, and not only can it be used as a resin that requires flame retardancy, but it can also be added to a resin that requires flame retardancy.
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| MXPA04006095A (en) * | 2001-12-21 | 2004-11-01 | Ciba Sc Holding Ag | Poly(vinylalcohol)-co-poly(vinylamine) polymers comprising functioal moieties. |
| WO2003085039A1 (en) * | 2002-04-10 | 2003-10-16 | Ciba Specialty Chemicals Holding Inc. | Flame retardant coatings |
| JP5429596B2 (en) * | 2008-11-10 | 2014-02-26 | 日本電気株式会社 | Secondary battery and manufacturing method thereof |
| JP5366854B2 (en) * | 2009-02-19 | 2013-12-11 | 三菱レイヨン株式会社 | (Meth) acrylic acid ester |
| KR101766504B1 (en) * | 2009-12-01 | 2017-08-08 | 미쯔비시 케미컬 주식회사 | Method of producing a polymer using monomers having a piperidine skeleton, and molded body |
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