JPWO2014087644A1 - Method for producing polymer - Google Patents
Method for producing polymer Download PDFInfo
- Publication number
- JPWO2014087644A1 JPWO2014087644A1 JP2014550927A JP2014550927A JPWO2014087644A1 JP WO2014087644 A1 JPWO2014087644 A1 JP WO2014087644A1 JP 2014550927 A JP2014550927 A JP 2014550927A JP 2014550927 A JP2014550927 A JP 2014550927A JP WO2014087644 A1 JPWO2014087644 A1 JP WO2014087644A1
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- carbon atoms
- meth
- acrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000009826 distribution Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000003505 polymerization initiator Substances 0.000 claims description 11
- 238000010551 living anionic polymerization reaction Methods 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 125000005647 linker group Chemical group 0.000 claims description 7
- 239000000178 monomer Substances 0.000 abstract description 28
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract description 13
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 74
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 26
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- -1 nitroxide structure Chemical group 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 16
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 13
- 239000004926 polymethyl methacrylate Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000008034 disappearance Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 150000003335 secondary amines Chemical class 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 229940043279 diisopropylamine Drugs 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000005529 alkyleneoxy group Chemical group 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- 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
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- GBVSONMCEKNESD-UHFFFAOYSA-N 1,1'-biphenyl;lithium Chemical group [Li].C1=CC=CC=C1C1=CC=CC=C1 GBVSONMCEKNESD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- QQHQTCGEZWTSEJ-UHFFFAOYSA-N 1-ethenyl-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(C=C)C=C1 QQHQTCGEZWTSEJ-UHFFFAOYSA-N 0.000 description 1
- HVBADOTWUFBZMF-UHFFFAOYSA-N 1-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOC(C)OC(=O)C(C)=C HVBADOTWUFBZMF-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- STPRYPLHPUMXIF-UHFFFAOYSA-N 2,2,6,6-tetramethyl-4-(oxiran-2-ylmethoxy)piperidine Chemical compound C1C(C)(C)NC(C)(C)CC1OCC1OC1 STPRYPLHPUMXIF-UHFFFAOYSA-N 0.000 description 1
- FXRQXYSJYZPGJZ-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethenylbenzene Chemical compound CC(C)(C)OC=CC1=CC=CC=C1 FXRQXYSJYZPGJZ-UHFFFAOYSA-N 0.000 description 1
- DGAWPXLUGCQPIK-UHFFFAOYSA-N 2-ethenyl-1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=C(C=C)C(C(C)C)=C1 DGAWPXLUGCQPIK-UHFFFAOYSA-N 0.000 description 1
- DBWWINQJTZYDFK-UHFFFAOYSA-N 2-ethenyl-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(C=C)=C1 DBWWINQJTZYDFK-UHFFFAOYSA-N 0.000 description 1
- 125000004819 2-methylbutylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:1])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- YKVAWSVTEWXJGJ-UHFFFAOYSA-N 4-chloro-2-methylsulfanylthieno[3,2-d]pyrimidine Chemical compound CSC1=NC(Cl)=C2SC=CC2=N1 YKVAWSVTEWXJGJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 0 CCC(C)(*)C(OC1CC(C)(C)NC(C)(C)C1)=O Chemical compound CCC(C)(*)C(OC1CC(C)(C)NC(C)(C)C1)=O 0.000 description 1
- IEKZHTQJUQCDDF-UHFFFAOYSA-N CCC(COC1CC(C)(C)NC(C)(C)C1)OC Chemical compound CCC(COC1CC(C)(C)NC(C)(C)C1)OC IEKZHTQJUQCDDF-UHFFFAOYSA-N 0.000 description 1
- FLAKGKCBSLMHQU-UHFFFAOYSA-N CC[Mg] Chemical compound CC[Mg] FLAKGKCBSLMHQU-UHFFFAOYSA-N 0.000 description 1
- NTZRDKVFLPLTPU-UHFFFAOYSA-N CC[Na] Chemical compound CC[Na] NTZRDKVFLPLTPU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical class [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- URMHJZVLKKDTOJ-UHFFFAOYSA-N lithium;(3-methyl-1-phenylpentyl)benzene Chemical compound [Li+].C=1C=CC=CC=1[C-](CC(C)CC)C1=CC=CC=C1 URMHJZVLKKDTOJ-UHFFFAOYSA-N 0.000 description 1
- UUQLCJCZFWUWHH-UHFFFAOYSA-N lithium;1-phenylhexylbenzene Chemical compound [Li+].C=1C=CC=CC=1[C-](CCCCC)C1=CC=CC=C1 UUQLCJCZFWUWHH-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- SQCMCIWNVXFWQF-UHFFFAOYSA-N piperidin-4-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCNCC1 SQCMCIWNVXFWQF-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- ODBSOAATZFAZCB-UHFFFAOYSA-N prop-1-en-2-ylbenzene;sodium Chemical compound [Na].CC(=C)C1=CC=CC=C1 ODBSOAATZFAZCB-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
- C08F220/346—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links and further oxygen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
高立体障害性の二級アミノ基または高立体障害性ハロアミノ基を有する（メタ）アクリル酸エステル系重合体の新たな製造方法、特に、二級アミンを保護基で保護する必要がない簡便な製造方法が望まれている。立体障害性の二級アミノ基または高立体障害性ハロアミノ基を有する特定の（メタ）アクリル酸エステル単量体は、当該二級アミンを保護することなく、リビングアニオン重合法により重合でき、本発明の製造方法によれば、分子量分布が狭い（メタ）アクリル酸エステル重合体を得ることができる。A new method for producing a (meth) acrylic acid ester-based polymer having a highly sterically hindered secondary amino group or a highly sterically hindered haloamino group. A method is desired. A specific (meth) acrylic acid ester monomer having a sterically hindered secondary amino group or a highly sterically hindered haloamino group can be polymerized by a living anion polymerization method without protecting the secondary amine, and the present invention. According to this production method, a (meth) acrylic acid ester polymer having a narrow molecular weight distribution can be obtained.
Description
本発明は、立体障害性二級アミノ基又は立体障害性ハロアミノ基を有する（メタ）アクリル酸エステルをリビングアニオン重合法により重合する製造方法、および当該製造方法により得られる重合体に関する。
本願は、２０１２年１２月７日に出願された日本国特許出願第２０１２−２６８４６１号に対し優先権を主張し、その内容をここに援用する。The present invention relates to a production method for polymerizing a (meth) acrylic acid ester having a sterically hindered secondary amino group or a sterically hindered haloamino group by a living anion polymerization method, and a polymer obtained by the production method.
This application claims priority with respect to the Japan patent application 2012-268461 for which it applied on December 7, 2012, and uses the content here.
重合体の側鎖に、ヒンダートアミンなどの高立体障害性の二級アミンを導入することにより、重合体の光安定性を改善できることが知られている。例えば、特許文献１では立体障害性のアミン側鎖を含有するポリエーテルが提案されている。特許文献１の段落０１２８では、２，２，６，６−テトラメチル−４−（２，３−エポキシプロポキシ）ピペリジンを、カリウム第三ブトキシドおよび１８−クラウン−６を用いてアニオン重合することにより、高立体障害性の二級アミン側鎖を含有するポリエーテル（１）を製造している。 It is known that the light stability of a polymer can be improved by introducing a highly sterically hindered secondary amine such as a hindered amine into the side chain of the polymer. For example, Patent Document 1 proposes a polyether containing a sterically hindered amine side chain. In paragraph 0128 of Patent Document 1, 2,2,6,6-tetramethyl-4- (2,3-epoxypropoxy) piperidine is subjected to anionic polymerization using potassium tert-butoxide and 18-crown-6. A polyether (1) containing a highly sterically hindered secondary amine side chain is produced.
また、ヒンダートアミンなどの高立体障害性の二級アミンを有する重合体は、ニトロキシド構造を含有する重合体を得るための中間体としても有用である。例えば、特許文献２では、２，２，６，６−テトラメチル−４−ピペリジニルメタクリレートを架橋剤の存在下で、ラジカル重合することにより、下記式（２）で表される繰り返し単位を有する（メタ）アクリル酸イミノ重合体を得ている。 A polymer having a highly sterically hindered secondary amine such as a hindered amine is also useful as an intermediate for obtaining a polymer containing a nitroxide structure. For example, in Patent Document 2, a repeating unit represented by the following formula (2) is obtained by radical polymerization of 2,2,6,6-tetramethyl-4-piperidinyl methacrylate in the presence of a crosslinking agent. A (meth) acrylic acid imino polymer is obtained.
しかし、ヒンダートアミンなどの高立体障害性の二級アミン又は高立体障害性ハロアミノ基を有する（メタ）アクリル酸エステルを、リビングアニオン重合法により重合する製造方法は知られていなかった。 However, a production method for polymerizing a highly sterically hindered secondary amine such as a hindered amine or a (meth) acrylic acid ester having a highly sterically hindered haloamino group by a living anion polymerization method has not been known.
高立体障害性の二級アミン又は高立体障害性のハロアミノ基を有する（メタ）アクリル酸エステル系重合体の新たな製造方法が望まれていた。特に、二級アミンを保護基で保護する必要がない簡便な製造方法が望まれていた。 A new method for producing a (meth) acrylic acid ester polymer having a highly sterically hindered secondary amine or a highly sterically hindered haloamino group has been desired. In particular, there has been a demand for a simple production method that does not require the secondary amine to be protected with a protecting group.
本発明者らは、上記課題を解決するために鋭意研究した結果、立体障害性の二級アミンを有する特定の（メタ）アクリル酸エステル単量体は、当該二級アミンを保護することなく、リビングアニオン重合法により重合できることを見出した。また、立体障害性のハロアミノ基を有する特定の（メタ）アクリル酸エステル単量体を、リビングアニオン重合法により重合できることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have found that a specific (meth) acrylic acid ester monomer having a sterically hindered secondary amine does not protect the secondary amine, It was found that polymerization can be performed by a living anionic polymerization method. Moreover, it discovered that the specific (meth) acrylic acid ester monomer which has a sterically hindered haloamino group can be superposed | polymerized by the living anion polymerization method.
すなわち本発明は、
（１）重合開始剤を使用するリビングアニオン重合法により、式〔Ｉ〕That is, the present invention
(1) By the living anionic polymerization method using a polymerization initiator, the formula [I]
（式中、Ｒ１、Ｒ２、Ｒ３、及びＲ４は、それぞれ独立に水素原子又は炭素数１〜６のアルキル基を示す。ただし、Ｒ１、Ｒ２、Ｒ３、及びＲ４のうち、少なくとも２つが炭素数１〜６のアルキル基であり、炭素数１〜６のアルキル基同士は、それぞれ同一又は相異なっていてもよく、また、相互に結合して環を形成していてもよい。ｒは、炭素数１〜６のアルキル基を示し、ｍは、０又は１を示し、Ｒ１１は水素原子又はメチル基を示し、Ｘは２価の連結基を示し、ｎは、０又は１を示す。Ｚは、水素原子又はハロゲン原子を示す。）、又は、式〔ＩＩ〕 (Wherein, R 1, R 2, R 3, and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. However, R 1, R 2, R 3, and R 4 Among them, at least two are alkyl groups having 1 to 6 carbon atoms, and the alkyl groups having 1 to 6 carbon atoms may be the same or different from each other, and are bonded to each other to form a ring. R represents an alkyl group having 1 to 6 carbon atoms, m represents 0 or 1, R 11 represents a hydrogen atom or a methyl group, X represents a divalent linking group, and n represents Represents 0 or 1. Z represents a hydrogen atom or a halogen atom.) Or the formula [II]
（式中、Ｒ５、Ｒ６、Ｒ７、Ｒ８、及びＲ９は、それぞれ独立に水素原子又は炭素数１〜６のアルキル基を示す。ただし、Ｒ５、Ｒ６、Ｒ７、Ｒ８、及びＲ９のうち、少なくとも３つが炭素数１〜６のアルキル基であり、炭素数１〜６のアルキル基同士は、それぞれ同一又は相異なっていてもよく、また、相互に結合して環を形成していてもよい。Ｒ１２は水素原子又はメチル基を示し、Ｙは２価の連結基を示す。Ｑは、水素原子又はハロゲン原子を示す。）
で表される（メタ）アクリル酸エステルを重合させることを特徴とする重合体の製造方法 (Wherein, R 5, R 6, R 7, R 8, and R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. However, R 5, R 6, R 7, R 8 and R 9 are at least three alkyl groups having 1 to 6 carbon atoms, and the alkyl groups having 1 to 6 carbon atoms may be the same or different from each other, and may be bonded to each other. (R 12 represents a hydrogen atom or a methyl group, Y represents a divalent linking group, and Q represents a hydrogen atom or a halogen atom.)
A method for producing a polymer, characterized by polymerizing a (meth) acrylic acid ester represented by
（２）式〔ＩＩＩ〕
で表される繰り返し単位を含み、分子量分布が１．００〜１．５０であることを特徴とする重合体(2) Formula [III]
And a polymer having a molecular weight distribution of 1.00 to 1.50.
（３）式〔ＩＶ〕
で表される繰り返し単位を含み、分子量分布が１．００〜１．５０であることを特徴とする重合体に関する。(3) Formula [IV]
And a polymer having a molecular weight distribution of 1.00 to 1.50.
立体障害性二級アミノ基又は立体障害性ハロアミノ基を側鎖に有する重合体の新たな製造方法が提供される。本発明の製造方法では、特定の立体障害性二級アミノ基又は立体障害性ハロアミノ基を有する（メタ）アクリル酸エステルを用いて、リビングアニオン重合することができる。また、本発明の製造方法によれば、分子量分布が狭い重合体を得ることができる。 A new method for producing a polymer having a sterically hindered secondary amino group or a sterically hindered haloamino group in the side chain is provided. In the production method of the present invention, living anion polymerization can be performed using a (meth) acrylic acid ester having a specific sterically hindered secondary amino group or sterically hindered haloamino group. Moreover, according to the production method of the present invention, a polymer having a narrow molecular weight distribution can be obtained.
（（メタ）アクリル酸エステル）
本発明において使用される（メタ）アクリル酸エステルは、式〔Ｉ〕または式〔ＩＩ〕で表される。((Meth) acrylic acid ester)
The (meth) acrylic acid ester used in the present invention is represented by the formula [I] or the formula [II].
式〔Ｉ〕
式〔Ｉ〕中、Ｒ１、Ｒ２、Ｒ３、及びＲ４は、それぞれ独立に水素原子又は炭素数１〜６のアルキル基を示す。In the formula [I], R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Ｒ１、Ｒ２、Ｒ３、及びＲ４における炭素数１〜６のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、イソブチル基、ヘキシル基等が挙げられる。これらのうち、炭素数１〜３のアルキル基が好ましく、メチル基又はエチル基がより好ましい。Examples of the alkyl group having 1 to 6 carbon atoms in R 1 , R 2 , R 3 , and R 4 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, t- A butyl group, an isobutyl group, a hexyl group, etc. are mentioned. Among these, a C1-C3 alkyl group is preferable and a methyl group or an ethyl group is more preferable.
Ｒ１、Ｒ２、Ｒ３、及びＲ４のうち、少なくとも２つは炭素数１〜６のアルキル基である。また、少なくとも３つが炭素数１〜６のアルキル基であるのがより好ましく、４つすべてが炭素数１〜６のアルキル基であるのがさらに好ましい。Of R 1 , R 2 , R 3 , and R 4 , at least two are alkyl groups having 1 to 6 carbon atoms. Moreover, it is more preferable that at least three are alkyl groups having 1 to 6 carbon atoms, and it is more preferable that all four are alkyl groups having 1 to 6 carbon atoms.
Ｒ１、Ｒ２、Ｒ３、及びＲ４の炭素数１〜６のアルキル基同士は、それぞれ同一又は相異なっていてもよいが、それぞれ同一であるのが好ましく、Ｒ１、Ｒ２、Ｒ３、及びＲ４がメチル基であるのがより好ましい。The alkyl groups having 1 to 6 carbon atoms of R 1 , R 2 , R 3 , and R 4 may be the same or different, but are preferably the same, and R 1 , R 2 , R More preferably, 3 and R 4 are methyl groups.
Ｒ１、Ｒ２、Ｒ３、及びＲ４の炭素数１〜６のアルキル基同士は、相互に結合して環を形成していてもよい。Ｒ１、Ｒ２のいずれかと、Ｒ３、Ｒ４のいずれかが相互に結合して架橋構造を形成してもよく、Ｒ１とＲ２が相互に結合して、又は、Ｒ３とＲ４が相互に結合してスピロ環構造を形成してもよい。The alkyl groups having 1 to 6 carbon atoms of R 1 , R 2 , R 3 , and R 4 may be bonded to each other to form a ring. Either R 1 , R 2 and R 3 , R 4 may be bonded to each other to form a crosslinked structure, R 1 and R 2 may be bonded to each other, or R 3 and R 2 4 may be bonded to each other to form a spiro ring structure.
式〔Ｉ〕中、ｒは、炭素数１〜６のアルキル基を示し、ｍは、０又は１を示す。 In the formula [I], r represents an alkyl group having 1 to 6 carbon atoms, and m represents 0 or 1.
ｒにおける炭素数１〜６のアルキル基としては、Ｒ１、Ｒ２、Ｒ３、及びＲ４における炭素数１〜６のアルキル基と同様のものを挙げることができる。The alkyl group having 1 to 6 carbon atoms in the r, R 1, R 2, R 3, and may be the same as the alkyl group having 1 to 6 carbon atoms in R 4.
式〔Ｉ〕中、Ｒ１１は水素原子又はメチル基を示し、メチル基が好ましい。In the formula [I], R 11 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
式〔Ｉ〕中、Ｘは２価の連結基を示す。２価の連結基としては、リビングアニオン重合を阻害しない構造であれば特に限定されないが、単結合、炭素数１〜６のアルキレン基、又は、炭素数２〜６のアルキレンオキシ基が好ましく、単結合、炭素数１〜６のアルキレンオキシ基がより好ましく、単結合が特に好ましい。 In formula [I], X represents a divalent linking group. The divalent linking group is not particularly limited as long as it does not inhibit living anion polymerization, but is preferably a single bond, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 2 to 6 carbon atoms. A bond and an alkyleneoxy group having 1 to 6 carbon atoms are more preferable, and a single bond is particularly preferable.
炭素数１〜６のアルキレン基としては、メチレン、エチレン、プロピレン、メチルエチレン、ブチレン、１，２−ジメチルエチレン、ペンチレン、１−メチルブチレン、２−メチルブチレン等が挙げられる。 Examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethylene, propylene, methylethylene, butylene, 1,2-dimethylethylene, pentylene, 1-methylbutylene and 2-methylbutylene.
炭素数２〜６のアルキレンオキシ基としては、エチレンオキシ基、１，２−プロピレンオキシ基、１，３−プロピレンオキシ基、１，２−ブチレンオキシ基、１，４−ブチレンオキシ基および１，６−へキシレンオキシ基などが挙げられる。 Examples of the alkyleneoxy group having 2 to 6 carbon atoms include ethyleneoxy group, 1,2-propyleneoxy group, 1,3-propyleneoxy group, 1,2-butyleneoxy group, 1,4-butyleneoxy group, and 1, Examples include 6-hexyleneoxy group.
式〔Ｉ〕中、ｎは、０又は１を示す。 In the formula [I], n represents 0 or 1.
式〔Ｉ〕中、Ｚは水素原子、又はハロゲン原子を示す。 In formula [I], Z represents a hydrogen atom or a halogen atom.
式〔Ｉ〕で表される化合物として具体的には、表１で表される化合物を挙げることができる。 Specific examples of the compound represented by the formula [I] include compounds represented by Table 1.
式〔ＩＩ〕
式〔ＩＩ〕中、Ｒ５、Ｒ６、Ｒ７、Ｒ８、及びＲ９は、それぞれ独立に水素原子又は炭素数１〜６のアルキル基を示す。In the formula [II], R 5 , R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Ｒ５、Ｒ６、Ｒ７、Ｒ８、及びＲ９における炭素数１〜６のアルキル基としては、式〔Ｉ〕における炭素数１〜６のアルキル基と同様のものを挙げることができる。The R 5, R 6, R 7 , R 8, and an alkyl group having 1 to 6 carbon atoms in R 9, may be mentioned the same alkyl groups having 1 to 6 carbon atoms in the formula [I].
Ｒ５、Ｒ６、Ｒ７、Ｒ８、及びＲ９のうち、少なくとも３つは炭素数１〜６のアルキル基であるのが好ましい。Of R 5 , R 6 , R 7 , R 8 , and R 9 , at least three are preferably alkyl groups having 1 to 6 carbon atoms.
Ｒ５、Ｒ６、Ｒ７、Ｒ８、及びＲ９の炭素数１〜６のアルキル基同士は、それぞれ同一又は相異なっていてもよいが、それぞれ同一であるのが好ましい。The alkyl groups having 1 to 6 carbon atoms of R 5 , R 6 , R 7 , R 8 and R 9 may be the same or different from each other, but are preferably the same.
Ｒ５、Ｒ６、Ｒ７、Ｒ８、及びＲ９の炭素数１〜６のアルキル基同士は、相互に結合して環を形成していてもよい。The alkyl groups having 1 to 6 carbon atoms of R 5 , R 6 , R 7 , R 8 , and R 9 may be bonded to each other to form a ring.
式〔ＩＩ〕中、Ｒ１２は水素原子又はメチル基を示し、メチル基が好ましい。In the formula [II], R 12 represents a hydrogen atom or a methyl group, preferably a methyl group.
式〔ＩＩ〕中、Ｙは２価の連結基を示す。２価の連結基としては、リビングアニオン重合を阻害しない構造であれば特に限定されないが、炭素数１〜６のアルキレン基が好ましく、エチレン基、プロピレン基がより好ましい。 In formula [II], Y represents a divalent linking group. Although it will not specifically limit if it is a structure which does not inhibit living anion polymerization as a bivalent coupling group, A C1-C6 alkylene group is preferable and an ethylene group and a propylene group are more preferable.
炭素数１〜６のアルキレン基としては、式〔Ｉ〕における炭素数１〜６のアルキレン基と同様のものを挙げることができる。 Examples of the alkylene group having 1 to 6 carbon atoms include those similar to the alkylene group having 1 to 6 carbon atoms in the formula [I].
式〔ＩＩ〕中、Ｑは水素原子、又はハロゲン原子を示す。 In formula [II], Q represents a hydrogen atom or a halogen atom.
式〔ＩＩ〕で表される化合物として具体的には、表２で表される化合物を挙げることができる。 Specific examples of the compound represented by the formula [II] include compounds represented by Table 2.
（リビングアニオン重合法）
本発明の製造方法は、式〔Ｉ〕又は式〔ＩＩ〕で表される（メタ）アクリル酸エステルを、重合開始剤を使用してリビングアニオン重合する方法である。本発明の製造方法では、式〔Ｉ〕で表される（メタ）アクリル酸エステルのみを重合しても良いし、式〔ＩＩ〕で表される（メタ）アクリル酸エステルのみを重合しても良いし、式〔Ｉ〕で表される（メタ）アクリル酸エステルと、式（〔ＩＩ〕で表される（メタ）アクリル酸エステルを共重合してもよい。また、式〔Ｉ〕及び／又は式〔ＩＩ〕で表される（メタ）アクリル酸エステルと他のモノマーを共重合してもよい。また、式〔Ｉ〕及び式〔ＩＩ〕で表される（メタ）アクリル酸エステルは、それぞれ、１種又は２種以上の混合物を使用することができる。(Living anion polymerization method)
The production method of the present invention is a method in which a (meth) acrylic acid ester represented by the formula [I] or the formula [II] is subjected to living anion polymerization using a polymerization initiator. In the production method of the present invention, only the (meth) acrylic acid ester represented by the formula [I] may be polymerized, or only the (meth) acrylic acid ester represented by the formula [II] may be polymerized. The (meth) acrylic acid ester represented by the formula [I] and the (meth) acrylic acid ester represented by the formula ([II]) may be copolymerized. Alternatively, the (meth) acrylate represented by the formula [II] may be copolymerized with another monomer, and the (meth) acrylate represented by the formula [I] and the formula [II] In each case, one or a mixture of two or more can be used.
（重合開始剤）
本発明の製造方法で使用する重合開始剤は、公知のリビングアニオン重合開始剤を用いることができる。
リビングアニオン重合開始剤としては、求核剤であって、リビングアニオン重合性単量体の重合を開始させる働きを有するものであれば特に制限されるものではない。(Polymerization initiator)
As the polymerization initiator used in the production method of the present invention, a known living anionic polymerization initiator can be used.
The living anion polymerization initiator is not particularly limited as long as it is a nucleophile and has a function of initiating polymerization of the living anion polymerizable monomer.
具体的には、金属リチウム、金属ナトリウム、金属カリウム、金属セシウム等のアルカリ金属；メチルリチウム、エチルリチウム、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔ−ブチルリチウム、エチルナトリウム、リチウムビフェニル、リチウムナフタレン、リチウムトリフェニル、ナトリウムナフタレン、α-メチルスチレンナトリウムジアニオン、１，１−ジフェニルヘキシルリチウム、１，１−ジフェニル−３−メチルペンチルリチウム、リチウムジイソプロピルアミド等の有機アルカリ金属；メチルマグネシウムブロミド、エチルマグネシウムブロミド、フェニルマグネシウムブロミド等の有機アルカリ土類金属；等を挙げることができる。これらのうち、有機アルカリ金属が好ましく、有機リチウムがより好ましく、ｎ−ブチルリチウム、リチウムジイソプロピルアミドが特に好ましい。
これらのリビングアニオン重合開始剤は１種単独で、あるいは２種以上を組み合わせて用いることができる。Specifically, alkali metals such as metallic lithium, metallic sodium, metallic potassium, metallic cesium; methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, ethylsodium, lithium biphenyl, lithium naphthalene Organic alkali metals such as lithium triphenyl, sodium naphthalene, α-methylstyrene sodium dianion, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, lithium diisopropylamide; methyl magnesium bromide, ethyl magnesium And organic alkaline earth metals such as bromide and phenylmagnesium bromide. Of these, organic alkali metals are preferable, organic lithium is more preferable, and n-butyl lithium and lithium diisopropylamide are particularly preferable.
These living anionic polymerization initiators can be used alone or in combination of two or more.
リビングアニオン重合開始剤の使用量は、使用するモノマーに対して、通常０．００１〜０．２当量、好ましくは０．００５〜０．１当量である。この範囲のリビングアニオン重合開始剤を用いることによって、目的とする重合体を収率よく製造することができる。 The usage-amount of a living anion polymerization initiator is 0.001-0.2 equivalent normally with respect to the monomer to be used, Preferably it is 0.005-0.1 equivalent. By using a living anionic polymerization initiator in this range, the target polymer can be produced with high yield.
（リビングアニオン重合の条件）
本発明における重合温度は、移動反応や停止反応などの副反応が起こらず、モノマーが消費され重合が完結する温度範囲であれば特に制限されないが、−１００℃〜０℃の温度範囲で行われるのが好ましい。さらに好ましくは−８０℃〜−３０℃の温度範囲で行われることが好ましい。(Conditions for living anionic polymerization)
The polymerization temperature in the present invention is not particularly limited as long as it does not cause side reactions such as transfer reaction and termination reaction, and the monomer is consumed and the polymerization is completed, but it is carried out in a temperature range of −100 ° C. to 0 ° C. Is preferred. More preferably, it is carried out in a temperature range of −80 ° C. to −30 ° C.
リビングアニオン重合反応は、適当な重合溶媒中で行うことができる。用いる重合溶媒は、重合反応に関与せず、かつ重合体と相溶性のある溶媒であれば、特に制限されない。 The living anionic polymerization reaction can be performed in a suitable polymerization solvent. The polymerization solvent to be used is not particularly limited as long as it does not participate in the polymerization reaction and is compatible with the polymer.
具体的には、ｎ−ヘキサン、ｎ−ヘプタン等の脂肪族炭化水素類、シクロヘキサン、シクロペンタン等の脂環族炭化水素類、ベンゼン、トルエン等の芳香族炭化水素類、ジエチルエーテル、テトラヒドロフラン（ＴＨＦ）、ジオキサン等のエーテル類の他、アニソール、ヘキサメチルホスホルアミド等のリビングアニオン重合において通常使用される有機溶媒を挙げることができ、これらは１種単独溶媒又は２種以上の混合溶媒として使用することができる。 Specifically, aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane and cyclopentane, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran (THF) ), Ethers such as dioxane, and organic solvents usually used in living anionic polymerization such as anisole and hexamethylphosphoramide can be used, and these can be used as a single solvent or a mixed solvent of two or more. can do.
溶媒の使用量は、特に制限されないが、アニオン重合性単量体の重合溶媒に対する濃度が、通常１〜４０重量％の範囲となる量、好ましくは１０〜３０重量％の範囲となる量である。 The amount of the solvent used is not particularly limited, but is an amount such that the concentration of the anionic polymerizable monomer with respect to the polymerization solvent is usually in the range of 1 to 40% by weight, preferably in the range of 10 to 30% by weight. .
（他のモノマー）
本発明に使用することができる他のモノマーとしては、リビングアニオン重合性不飽和結合を有するものであれば特に限定されないが、具体的には、スチレン及びその誘導体、ブタジエン及びその誘導体、式（Ｉ）又は式（ＩＩ）で表される（メタ）アクリル酸エステル以外の（メタ）アクリル酸エステル誘導体等を好ましく例示することができる。(Other monomers)
The other monomer that can be used in the present invention is not particularly limited as long as it has a living anion polymerizable unsaturated bond. Specifically, styrene and its derivatives, butadiene and its derivatives, and formula (I ) Or (meth) acrylic acid ester derivatives other than the (meth) acrylic acid ester represented by the formula (II).
スチレン及びその誘導体として具体的には、スチレン、α−アルキルスチレン、核置換基を有するスチレン等を例示することができる。 Specific examples of styrene and derivatives thereof include styrene, α-alkylstyrene, and styrene having a nuclear substituent.
核置換基としては、重合開始能力があるアニオン種、及び重合開始能力がないアニオン種に対して不活性な基であれば特に制限されない。具体的には、アルキル基、アルコキシアルキル基、アルコキシ基、アルコキシアルコキシ基、ｔ−ブトキシカルボニル基、ｔ−ブトキシカルボニルメチル基、テトラヒドロピラニル基等を例示することができる。 The nuclear substituent is not particularly limited as long as it is an inactive group with respect to an anionic species having a polymerization initiating ability and an anionic species having no ability to initiate polymerization. Specific examples include an alkyl group, an alkoxyalkyl group, an alkoxy group, an alkoxyalkoxy group, a t-butoxycarbonyl group, a t-butoxycarbonylmethyl group, a tetrahydropyranyl group, and the like.
α−アルキルスチレン、核置換基を有するスチレンの具体例としては、α−メチルスチレン、α−メチル−ｐ−メチルスチレン、ｐ−メチルスチレン、ｍ−メチルスチレン、ｏ−メチルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、２，５−ジメチルスチレン、ｐ−イソプロピルスチレン、２，４，６−トリイソプロピルスチレン、ｐ−ｔ−ブトキシスチレン、ｐ−ｔ−ブトキシ−α−メチルスチレン、ｍ−ｔ−ブトキシスチレンなどが挙げられる。 Specific examples of α-alkyl styrene and styrene having a nuclear substituent include α-methyl styrene, α-methyl-p-methyl styrene, p-methyl styrene, m-methyl styrene, o-methyl styrene, p-ethyl styrene. 2,4-dimethylstyrene, 2,5-dimethylstyrene, p-isopropylstyrene, 2,4,6-triisopropylstyrene, pt-butoxystyrene, pt-butoxy-α-methylstyrene, m- Examples include t-butoxystyrene.
ブタジエン及びその誘導体としては、１，３−ブタジエン、イソプレン、２，３−ジメチルブタジエン、２−エチル−１，３−ブタジエン、１，３−ペンタジエンなどが挙げられる。 Examples of butadiene and its derivatives include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and the like.
式（Ｉ）又は式（ＩＩ）で表される（メタ）アクリル酸エステル以外の（メタ）アクリル酸エステル誘導体は、エステルのアルコール残基の炭素数が１〜２０のものが反応性の観点より好ましい。このような（メタ）アクリル酸エステル誘導体としては、メチルエステル、エチルエステル、イソプロピルエステル、ｎ−ブチルエステル等を例示することができる。 The (meth) acrylic acid ester derivative other than the (meth) acrylic acid ester represented by the formula (I) or the formula (II) has an alcohol residue of 1 to 20 carbon atoms from the viewpoint of reactivity. preferable. Examples of such (meth) acrylic acid ester derivatives include methyl ester, ethyl ester, isopropyl ester, n-butyl ester and the like.
これらの他のモノマーは１種単独で、あるいは２種以上を組み合わせて用いることができる。本発明の製造方法は、ブロック共重合体、ランダム共重合体などの共重合体の製造においても適用が可能である。 These other monomers can be used alone or in combination of two or more. The production method of the present invention can also be applied to the production of copolymers such as block copolymers and random copolymers.
（その他）
本発明においては、必要に応じて添加剤を重合開始時、又は、重合中に添加することができる。そのような添加剤として、具体的には、ナトリウム、カリウム、バリウム、マグネシウムの硫酸塩、硝酸塩、ホウ酸塩などの鉱酸塩やハロゲン化物を例示することができ、より具体的にはリチウムやバリウムの塩化物、臭化物、ヨウ化物や、ホウ酸リチウム、硝酸マグネシウム、塩化ナトリウム、塩化カリウム、などを挙げることができるが、これらの中でも、リチウムのハロゲン化物、例えば塩化リチウム、臭化リチウム、ヨウ化リチウム又はフッ化リチウム、特に塩化リチウムを使用するのが好ましい。(Other)
In the present invention, if necessary, an additive can be added at the start of polymerization or during polymerization. Specific examples of such additives include mineral salts and halides such as sodium, potassium, barium, and magnesium sulfates, nitrates, and borates. Examples include barium chloride, bromide, iodide, lithium borate, magnesium nitrate, sodium chloride, potassium chloride, and the like. Among these, lithium halides such as lithium chloride, lithium bromide, iodine Preference is given to using lithium fluoride or lithium fluoride, in particular lithium chloride.
（重合体）
本発明の重合体は、式〔ＩＩＩ〕又は式〔ＩＶ〕で表される繰り返し単位を含有する限り特に制限されない。(Polymer)
The polymer of the present invention is not particularly limited as long as it contains a repeating unit represented by formula [III] or formula [IV].
本発明の重合体は、重合開始剤を使用するリビングアニオン重合法により、式〔Ｉ〕、又は、式〔ＩＩ〕で表される（メタ）アクリル酸エステルを重合させることにより製造することができる。
なお、式〔ＩＩＩ〕、又は、式〔ＩＶ〕で表される繰り返し単位のＺ又はＱがハロゲン原子の場合は、Ｚ又はＱがハロゲン原子である式〔Ｉ〕、又は、式〔ＩＩ〕で表される（メタ）アクリル酸エステルを重合させることができるが、Ｚ又はＱが水素原子である式〔Ｉ〕又は式〔ＩＩ〕で表される（メタ）アクリル酸エステルを重合させた後、ハロゲン化剤でＮ原子をハロゲン化してもよい。The polymer of the present invention can be produced by polymerizing the (meth) acrylic acid ester represented by the formula [I] or the formula [II] by a living anion polymerization method using a polymerization initiator. .
In addition, when Z or Q of the repeating unit represented by the formula [III] or the formula [IV] is a halogen atom, the formula [I] or the formula [II] in which Z or Q is a halogen atom The (meth) acrylic acid ester represented can be polymerized, but after polymerizing the (meth) acrylic acid ester represented by the formula [I] or the formula [II] wherein Z or Q is a hydrogen atom, The N atom may be halogenated with a halogenating agent.
ハロゲン化剤として、具体的には、塩素、臭素、ヨウ素、フッ素等のハロゲン、ジハロイソシアヌル酸ナトリウム、次亜ハロゲン酸ナトリウム、Ｎ−ハロスクシンイミド、１，３−ジハロヒダントイン及び次亜ハロゲン酸カルシウム等を挙げることができる。 Specific examples of halogenating agents include halogens such as chlorine, bromine, iodine and fluorine, sodium dihaloisocyanurate, sodium hypohalite, N-halosuccinimide, 1,3-dihalohydantoin and hypohalous acid. Calcium etc. can be mentioned.
式〔ＩＩＩ〕中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ１１、ｎ、Ｘ、ｒ、ｍ及びＺは、前記と同じである。
式〔ＩＶ〕中、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１２、Ｙ、及びＱは、前記と同じである。In the formula [III], R 1 , R 2 , R 3 , R 4 , R 11 , n, X, r, m and Z are the same as described above.
In formula [IV], R 5 , R 6 , R 7 , R 8 , R 9 , R 12 , Y, and Q are the same as described above.
本発明の重合体は、式〔Ｉ〕で表される（メタ）アクリル酸エステルを重合したホモポリマー、式〔ＩＩ〕で表される（メタ）アクリル酸エステルを重合したホモポリマー、式〔Ｉ〕で表される（メタ）アクリル酸エステルと式〔ＩＩ〕で表される（メタ）アクリル酸エステルを共重合したコポリマー、及び、式〔Ｉ〕及び／又は式〔ＩＩ〕で表される（メタ）アクリル酸エステル単量体と他のモノマーを共重合したコポリマーを包含する。 The polymer of the present invention includes a homopolymer obtained by polymerizing a (meth) acrylic acid ester represented by the formula [I], a homopolymer obtained by polymerizing a (meth) acrylic acid ester represented by the formula [II], and a formula [I A copolymer obtained by copolymerizing a (meth) acrylic acid ester represented by the formula (II) and a (meth) acrylic acid ester represented by the formula [II], and the formula [I] and / or the formula [II] ( It includes a copolymer obtained by copolymerizing a (meth) acrylate monomer with another monomer.
本発明の重合体のＧＰＣ（Gel Permeation Chromatography：移動相ＤＭＦ又はＴＨＦ，ＰＭＭＡスタンダード）を用いて測定した数平均分子量（Ｍｎ）は特に制限されないが、１，０００〜５０，０００であるのが好ましく、１,５００〜２０，０００であるのがより好ましく、２，０００〜１０，０００であるのが特に好ましい。さらに、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比である分子量分布（Ｍｗ／Ｍｎ）は、特に制限されないが、１．００〜１．５０であるのが好ましく、１．００〜１．４０であるのがより好ましく、１．００〜１．３５であるのが特に好ましい。 The number average molecular weight (Mn) measured using GPC (Gel Permeation Chromatography: mobile phase DMF or THF, PMMA standard) of the polymer of the present invention is not particularly limited, but is preferably 1,000 to 50,000. More preferably, it is 1,500 to 20,000, and particularly preferably 2,000 to 10,000. Furthermore, the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is not particularly limited, but is preferably 1.00 to 1.50, preferably 1.00 It is more preferably 1.40, and particularly preferably 1.00 to 1.35.
以下実施例を用いて本発明を詳細に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, the technical scope of this invention is not limited to these illustrations.
（実施例１）
２００ｍＬフラスコにＴＨＦ９８．９ｇ、塩化リチウム０．１ｇを加え、−６０℃まで冷却した。ｎ−ブチルリチウム２．０ｇ（１５．４重量％濃度ヘキサン溶液）、次いで、ジイソプロピルアミン０．６ｇを加えて１０分間撹拌した。ＴＨＦに溶解したメタクリル酸２，２，６，６−テトラメチル−４−ピペリジル（以下、ＴＭＰＭＡと略す）４３．７ｇ（４７．０％ＴＨＦ溶液）を３０分間かけて滴下し、１５分間撹拌した。一部をサンプリングし、ＧＣ測定によりモノマー消失を確認した後、メタノール０．８ｇを加えて反応を停止した。
得られた重合体をＧＰＣ（移動相ＤＭＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が３，９２０、分子量分布（Ｍｗ／Ｍｎ）が１．１５であることを確認した。Example 1
To a 200 mL flask, 98.9 g of THF and 0.1 g of lithium chloride were added and cooled to −60 ° C. 2.0 g of n-butyllithium (15.4 wt% hexane solution) and then 0.6 g of diisopropylamine were added and stirred for 10 minutes. 43.7 g (47.0% THF solution) of 2,2,6,6-tetramethyl-4-piperidyl methacrylate (hereinafter abbreviated as TMPMA) dissolved in THF was added dropwise over 30 minutes and stirred for 15 minutes. . A part was sampled, and after confirming the disappearance of the monomer by GC measurement, 0.8 g of methanol was added to stop the reaction.
The obtained polymer was analyzed by GPC (mobile phase DMF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 3,920 and the molecular weight distribution (Mw / Mn) was 1.15.
（実施例２）
２００ｍＬフラスコにＴＨＦ１０５．６ｇ、塩化リチウム０．１ｇを加え、−６０℃まで冷却した。ｎ−ブチルリチウム２．０ｇ（１５．４重量％濃度ヘキサン溶液）、次いで、ジフェニルエチレン１．０ｇを加えて３０分間撹拌した。ＴＨＦに溶解したＴＭＰＭＡ３８．３ｇ（５３．３％ＴＨＦ溶液）を３０分間かけて滴下し、１５分間撹拌した。一部をサンプリングし、ＧＣ測定によりモノマー消失を確認した後、メタノール０．８ｇを加えて反応を停止した。
得られた重合体をＧＰＣ（移動相ＤＭＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が４，９２０、分子量分布（Ｍｗ／Ｍｎ）が１．１３であることを確認した。(Example 2)
To a 200 mL flask, 105.6 g of THF and 0.1 g of lithium chloride were added, and cooled to −60 ° C. 2.0 g of n-butyllithium (15.4 wt% hexane solution) and then 1.0 g of diphenylethylene were added and stirred for 30 minutes. TMPMA 38.3g (53.3% THF solution) melt | dissolved in THF was dripped over 30 minutes, and it stirred for 15 minutes. A part was sampled, and after confirming the disappearance of the monomer by GC measurement, 0.8 g of methanol was added to stop the reaction.
The obtained polymer was analyzed by GPC (mobile phase DMF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 4,920 and the molecular weight distribution (Mw / Mn) was 1.13.
（実施例３）
３００ｍＬフラスコにＴＨＦ１１３．８ｇ、塩化リチウム０．２ｇを加え、−６０℃まで冷却した。ｎ−ブチルリチウム４．０ｇ（１５．４重量％濃度ヘキサン溶液）、次いで、ジイソプロピルアミン０．９ｇを加えて３０分間撹拌した。メタクリル酸２−（ｔ−ブチルアミノ）エチル１４．７ｇを３０分間かけて滴下し、１５分間撹拌した。一部をサンプリングし、ＧＣ測定によりモノマー消失を確認した後、メタノール０．７ｇを加えて反応を停止した。
得られた重合体をＧＰＣ（移動相ＤＭＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が１，８４０、分子量分布（Ｍｗ／Ｍｎ）が１．３１であることを確認した。(Example 3)
To a 300 mL flask, THF 113.8 g and lithium chloride 0.2 g were added and cooled to -60 ° C. After adding 4.0 g of n-butyllithium (15.4 wt% hexane solution) and then 0.9 g of diisopropylamine, the mixture was stirred for 30 minutes. 14.7 g of 2- (t-butylamino) ethyl methacrylate was added dropwise over 30 minutes and stirred for 15 minutes. A part was sampled, and after confirming disappearance of the monomer by GC measurement, 0.7 g of methanol was added to stop the reaction.
The obtained polymer was analyzed by GPC (mobile phase DMF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 1,840 and the molecular weight distribution (Mw / Mn) was 1.31.
（比較例１）
モノマーとしてメタクリル酸４−ピペリジルを用い、実施例３と同様に重合を行ったが、重合は進行しなかった。(Comparative Example 1)
Polymerization was carried out in the same manner as in Example 3 using 4-piperidyl methacrylate as the monomer, but the polymerization did not proceed.
（実施例４）
２００ｍＬフラスコに、ＴＨＦ１０４．３３ｇ、塩化リチウム０．１７ｇを仕込み、−６０℃に冷却後、ｎ−ブチルリチウム３．３７ｇ（１５．４重量％濃度ヘキサン溶液）、ジイソプロピルアミン０．８１ｇを仕込み、１５分間撹拌した。次いでイソ酪酸メチル０．８７ｇを仕込み、１５分間撹拌した。ＴＨＦ２８．９２ｇに溶解したＴＭＰＭＡ１５．３８ｇ、メタクリル酸アリル１５．３８ｇを４０分間かけて滴下し、１５分間熟成した。一部をサンプリングし、ＧＣ測定によりモノマー消失を確認した後、メタノール１．２ｇを加えて反応を停止した。
得られた共重合体をＧＰＣ（移動相ＴＨＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が３，８６０、分子量分布（Ｍｗ／Ｍｎ）が１．１１であることを確認した。Example 4
A 200 mL flask was charged with 104.33 g of THF and 0.17 g of lithium chloride. After cooling to −60 ° C., 3.37 g of n-butyllithium (15.4 wt% hexane solution) and 0.81 g of diisopropylamine were charged. Stir for minutes. Next, 0.87 g of methyl isobutyrate was charged and stirred for 15 minutes. 15.38 g of TMPMA and 15.38 g of allyl methacrylate dissolved in 28.92 g of THF were added dropwise over 40 minutes and aged for 15 minutes. A part was sampled, and after confirming disappearance of the monomer by GC measurement, 1.2 g of methanol was added to stop the reaction.
The obtained copolymer was analyzed by GPC (mobile phase THF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 3,860 and the molecular weight distribution (Mw / Mn) was 1.11.
モノマーの１．２５倍の水、ＴＨＦの１／９量の酢酸エチルを加え、分液した。次亜塩素酸ナトリウム溶液７６．３ｇを加え、室温で１時間熟成することにより、塩素化反応を行った。分液後、有機層を三回水洗した。有機層を濃縮後、３０％ＴＨＦ溶液に調整し、大量の水で再沈した。得られた共重合体を真空乾燥することにより白色粉末３２．７６ｇを得た。
得られた重合体をＧＰＣ（移動相ＴＨＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が４，８５０、分子量分布（Ｍｗ／Ｍｎ）が１．１１であることを確認した。
ＩＣＰ−ＡＥＳ分析より、共重合体中の塩素濃度は６．８％（理論値７．３％）であった。1.25 times as much water as the monomer and 1/9 amount of ethyl acetate in THF were added to separate the layers. Chlorination reaction was performed by adding 76.3 g of sodium hypochlorite solution and aging for 1 hour at room temperature. After liquid separation, the organic layer was washed with water three times. The organic layer was concentrated, adjusted to a 30% THF solution, and reprecipitated with a large amount of water. The obtained copolymer was vacuum-dried to obtain 32.76 g of white powder.
The obtained polymer was analyzed by GPC (mobile phase THF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 4,850 and the molecular weight distribution (Mw / Mn) was 1.11.
From the ICP-AES analysis, the chlorine concentration in the copolymer was 6.8% (theoretical value: 7.3%).
（実施例５）
２００ｍＬフラスコにＴＨＦ９０．３０ｇ、塩化リチウム０．１６ｇを加え、−６０℃まで冷却した。ｎ−ブチルリチウム３．２５ｇ（１５．４重量％濃度ヘキサン溶液）、ジイソプロピルアミン０．８３ｇを仕込み、１５分間撹拌した。次いでイソ酪酸メチル０．８４ｇを仕込み、１５分間撹拌した。ＴＨＦ２８．２６ｇに溶解したＴＭＰＭＡ１５．２１ｇ、メタクリル酸グリシジル１５．２１ｇを４０分間かけて滴下し、１５分間熟成した。一部をサンプリングし、ＧＣ測定によりモノマー消失を確認した後、メタノール１．２ｇを加えて反応を停止した。
得られた共重合体をＧＰＣ（移動相ＴＨＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が３，４１０、分子量分布（Ｍｗ／Ｍｎ）が１．２４であることを確認した。(Example 5)
90.30 g of THF and 0.16 g of lithium chloride were added to a 200 mL flask and cooled to −60 ° C. n-Butyllithium 3.25g (15.4 wt% concentration hexane solution) and diisopropylamine 0.83g were charged and stirred for 15 minutes. Next, 0.84 g of methyl isobutyrate was charged and stirred for 15 minutes. 15.21 g of TMPMA and 15.21 g of glycidyl methacrylate dissolved in 28.26 g of THF were added dropwise over 40 minutes and aged for 15 minutes. A part was sampled, and after confirming disappearance of the monomer by GC measurement, 1.2 g of methanol was added to stop the reaction.
The obtained copolymer was analyzed by GPC (mobile phase THF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 3,410 and the molecular weight distribution (Mw / Mn) was 1.24.
モノマーの１．２５倍の水、ＴＨＦの１／９量の酢酸エチルを加え、分液した。次亜塩素酸ナトリウム溶液６０．２ｇを加え、室温で１時間熟成することにより、クロロ化反応を行った。分液後、有機層を三回水洗した。有機層を濃縮後、３０％ＴＨＦ溶液に調整し、大量の水で再沈した。得られた共重合体を真空乾燥することにより白色粉末３２．１１ｇを得た。
得られた共重合体をＧＰＣ（移動相ＴＨＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が５，１８０、分子量分布（Ｍｗ／Ｍｎ）が１．３３であることを確認した。
ＩＣＰ−ＡＥＳ分析より、共重合体中の塩素濃度は７．７％（理論値７．３％）であった。1.25 times as much water as the monomer and 1/9 amount of ethyl acetate in THF were added to separate the layers. Chlorination reaction was performed by adding 60.2 g of sodium hypochlorite solution and aging for 1 hour at room temperature. After liquid separation, the organic layer was washed with water three times. The organic layer was concentrated, adjusted to a 30% THF solution, and reprecipitated with a large amount of water. The obtained copolymer was vacuum-dried to obtain 32.11 g of a white powder.
The obtained copolymer was analyzed by GPC (mobile phase THF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 5,180 and the molecular weight distribution (Mw / Mn) was 1.33.
From the ICP-AES analysis, the chlorine concentration in the copolymer was 7.7% (theoretical value: 7.3%).
（実施例６）
２００ｍＬフラスコに、ＴＨＦ９７．２３ｇ、塩化リチウム０．３４ｇを仕込み、−６０℃に冷却後、ｎ−ブチルリチウム４．８ｍＬ（１５．４重量％濃度ヘキサン溶液）、ジイソプロピルアミン０．８０ｇを仕込み、１５分間撹拌した。次いでイソ酪酸メチル０．８２ｇを仕込み、１５分間撹拌した。ＴＨＦ９．２４ｇに溶解したメタクリル酸Ｎ−クロロ−２，２，６，６−テトラメチル−４−ピペリジン９．２４ｇ、メタクリル酸１−エトキシエチル１６．７８ｇを３０分間かけて滴下し、４５分間熟成した。一部をサンプリングし、ＧＣ測定によりモノマー消失を確認した後、メタノール１．２１ｇおよび酢酸０．３７ｇを加えて反応を停止した。
得られた重合体をＧＰＣ（移動相ＴＨＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が３，７２０、分子量分布（Ｍｗ／Ｍｎ）が１．１４であることを確認した。(Example 6)
A 200 mL flask was charged with 97.23 g of THF and 0.34 g of lithium chloride, cooled to −60 ° C., and then charged with 4.8 mL of n-butyllithium (15.4 wt% hexane solution) and 0.80 g of diisopropylamine, 15 Stir for minutes. Next, 0.82 g of methyl isobutyrate was charged and stirred for 15 minutes. 9.24 g of N-chloro-2,2,6,6-tetramethyl-4-piperidine methacrylate and 16.78 g of 1-ethoxyethyl methacrylate dissolved in 9.24 g of THF were added dropwise over 30 minutes and aged for 45 minutes. did. A part was sampled and the disappearance of the monomer was confirmed by GC measurement. Then, 1.21 g of methanol and 0.37 g of acetic acid were added to stop the reaction.
The obtained polymer was analyzed by GPC (mobile phase THF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 3,720 and the molecular weight distribution (Mw / Mn) was 1.14.
ＴＨＦの１／２量の酢酸エチルおよび同重量の水を加え、分液した。有機層を濃縮後、３０％ＴＨＦ溶液に調整し、モノマーと同重量のメタノールおよび１モル／Ｌ濃度塩酸を加えて室温で３時間撹拌した。酢酸エチル３７０ｇおよび水１００ｇを加え、分液した。水層を濃縮後、大量のアセトンに滴下し、沈殿として析出させた。得られた沈殿を真空乾燥することにより白色粉末８．９ｇを得た。
ＩＣＰ−ＡＥＳ分析より、共重合体中の塩素濃度は４．８％（理論値５．６％）であった。A half amount of THF in ethyl acetate and the same weight of water were added to separate the layers. The organic layer was concentrated, adjusted to a 30% THF solution, methanol and 1 mol / L hydrochloric acid having the same weight as the monomer were added, and the mixture was stirred at room temperature for 3 hours. Ethyl acetate (370 g) and water (100 g) were added and the layers were separated. The aqueous layer was concentrated and then dropped into a large amount of acetone to precipitate as a precipitate. The obtained precipitate was vacuum-dried to obtain 8.9 g of a white powder.
From the ICP-AES analysis, the chlorine concentration in the copolymer was 4.8% (theoretical value: 5.6%).
（実施例７）
２００ｍＬフラスコにＴＨＦ７５．３０ｇ、塩化リチウム０．１１ｇを加え、−６０℃まで冷却した。ｎ−ブチルリチウム２．０３ｇ（１５．４重量％濃度ヘキサン溶液）、次いで、ジイソプロピルアミン０．６３ｇを加えて１０分間撹拌した。ＴＨＦに溶解したＴＭＰＭＡ１２．２４ｇ（５０％ＴＨＦ溶液）を１５分間かけて滴下し、２０分間撹拌した。一部をサンプリングし、ＧＣ測定によりモノマー消失を確認した。また、得られた重合体をＧＰＣ（移動相ＤＭＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が２３４０、分子量分布（Ｍｗ／Ｍｎ）が１．１７であることを確認した。
次いで、メタクリル酸グリシジル（以下、ＧＭＡと略す）７．７５ｇを１０分間かけて滴下し、１５分間撹拌した。一部をサンプリングし、ＧＣ測定によりモノマー消失を確認した後、メタノール０．８ｇを加えて反応を停止した。得られた共重合体をＧＰＣ（移動相ＤＭＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が４，３４０、分子量分布（Ｍｗ／Ｍｎ）が１．１９であることを確認した。(Example 7)
75.30 g of THF and 0.11 g of lithium chloride were added to a 200 mL flask and cooled to −60 ° C. 2.03 g of n-butyllithium (15.4 wt% hexane solution) and then 0.63 g of diisopropylamine were added and stirred for 10 minutes. 12.24 g of TMPMA dissolved in THF (50% THF solution) was added dropwise over 15 minutes and stirred for 20 minutes. A part was sampled and monomer disappearance was confirmed by GC measurement. The obtained polymer was analyzed by GPC (mobile phase DMF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 2340 and the molecular weight distribution (Mw / Mn) was 1.17.
Next, 7.75 g of glycidyl methacrylate (hereinafter abbreviated as GMA) was added dropwise over 10 minutes and stirred for 15 minutes. A part was sampled, and after confirming the disappearance of the monomer by GC measurement, 0.8 g of methanol was added to stop the reaction. The obtained copolymer was analyzed by GPC (mobile phase DMF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 4,340 and the molecular weight distribution (Mw / Mn) was 1.19.
モノマーの１．２５倍の水、ＴＨＦの１／９量の酢酸エチルを加え、分液した。次亜塩素酸ナトリウム溶液４８．５ｇを加え、室温で１時間熟成することにより、クロロ化反応を行った。分液後、有機層を三回水洗した。有機層を濃縮後、３０％ＴＨＦ溶液に調整し、大量のメタノールで再沈した。得られた共重合体を真空乾燥することにより白色粉末２０．８５ｇを得た。
得られた共重合体をＧＰＣ（移動相ＤＭＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が５，５２０、分子量分布（Ｍｗ／Ｍｎ）が１．２０であることを確認した。
ＩＣＰ−ＡＥＳ分析より、共重合体中の塩素濃度は９．０％（理論値８．８％）であった。1.25 times as much water as the monomer and 1/9 amount of ethyl acetate in THF were added to separate the layers. Chlorination reaction was performed by adding 48.5 g of sodium hypochlorite solution and aging for 1 hour at room temperature. After liquid separation, the organic layer was washed with water three times. The organic layer was concentrated, adjusted to a 30% THF solution, and reprecipitated with a large amount of methanol. The obtained copolymer was vacuum-dried to obtain 20.85 g of a white powder.
The obtained copolymer was analyzed by GPC (mobile phase DMF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 5,520 and the molecular weight distribution (Mw / Mn) was 1.20.
From the ICP-AES analysis, the chlorine concentration in the copolymer was 9.0% (theoretical value: 8.8%).
（実施例８）
２００ｍＬフラスコに、ＴＨＦ８９．３７ｇ、塩化リチウム０．１４ｇを仕込み、−６０℃に冷却後、ｎ−ブチルリチウム２．０５ｇ（１５．４重量％濃度ヘキサン溶液）、ジイソプロピルアミン０．６０ｇを仕込み、１５分間撹拌した。次いでイソ酪酸メチル０．５５ｇを仕込み、１５分間撹拌した。ＴＨＦ５．８２ｇに溶解したメタクリル酸Ｎ−クロロ−２，２，６，６−テトラメチル−４−ピペリジン９．５３ｇ、メタクリル酸アリル９．５３ｇを１５分間かけて滴下し、３０分間熟成した。一部をサンプリングし、ＧＣ測定によりモノマー消失を確認した後、メタノール０．８ｇを加えて反応を停止した。
得られた重合体をＧＰＣ（移動相ＴＨＦ、ＰＭＭＡスタンダード）により分析し、分子量（Ｍｎ）が４，７６０、分子量分布（Ｍｗ／Ｍｎ）が１．２２であることを確認した。(Example 8)
A 200 mL flask was charged with 89.37 g of THF and 0.14 g of lithium chloride. After cooling to −60 ° C., 2.05 g of n-butyllithium (15.4 wt% hexane solution) and 0.60 g of diisopropylamine were charged. Stir for minutes. Next, 0.55 g of methyl isobutyrate was charged and stirred for 15 minutes. 9.53 g of N-chloro-2,2,6,6-tetramethyl-4-piperidine methacrylate and 9.53 g of allyl methacrylate dissolved in 5.82 g of THF were added dropwise over 15 minutes and aged for 30 minutes. A part was sampled, and after confirming the disappearance of the monomer by GC measurement, 0.8 g of methanol was added to stop the reaction.
The obtained polymer was analyzed by GPC (mobile phase THF, PMMA standard), and it was confirmed that the molecular weight (Mn) was 4,760 and the molecular weight distribution (Mw / Mn) was 1.22.
モノマーの１．２５倍の水、ＴＨＦの１／９量の酢酸エチルを加え、分液した。有機層を濃縮後、３０％ＴＨＦ溶液に調整し、大量の水で再沈した。得られたポリマーを真空乾燥することにより白色粉末１８．８８ｇを得た。
ＩＣＰ−ＡＥＳ分析より、共重合体中の塩素濃度は６．６％（理論値６．８％）であった。1.25 times as much water as the monomer and 1/9 amount of ethyl acetate in THF were added to separate the layers. The organic layer was concentrated, adjusted to a 30% THF solution, and reprecipitated with a large amount of water. The obtained polymer was vacuum-dried to obtain 18.88 g of a white powder.
From the ICP-AES analysis, the chlorine concentration in the copolymer was 6.6% (theoretical value: 6.8%).
Claims (3)
で表される（メタ）アクリル酸エステルを重合させることを特徴とする重合体の製造方法。By the living anionic polymerization method using a polymerization initiator, the formula [I]
A method for producing a polymer, characterized by polymerizing a (meth) acrylic acid ester represented by the formula:
で表される繰り返し単位を含み、分子量分布が１．００〜１．５０であることを特徴とする重合体。Formula [III]
The polymer characterized by having a molecular weight distribution of 1.00 to 1.50.
で表される繰り返し単位を含み、分子量分布が１．００〜１．５０であることを特徴とする重合体。Formula [IV]
The polymer characterized by having a molecular weight distribution of 1.00 to 1.50.
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| CN1219542A (en) * | 1997-12-12 | 1999-06-16 | 中国科学院化学研究所 | Preparation method for polymerized hindered amine |
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| US6699933B2 (en) * | 2001-08-07 | 2004-03-02 | Ppg Industries Ohio, Inc. | Method of coating coils using a high solids fluorocarbon coating composition |
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| CN104822714A (en) | 2015-08-05 |
| CN104822714B (en) | 2017-10-13 |
| WO2014087644A1 (en) | 2014-06-12 |
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