CN110997743A - Method for producing block polymer - Google Patents
Method for producing block polymer Download PDFInfo
- Publication number
- CN110997743A CN110997743A CN201880051098.XA CN201880051098A CN110997743A CN 110997743 A CN110997743 A CN 110997743A CN 201880051098 A CN201880051098 A CN 201880051098A CN 110997743 A CN110997743 A CN 110997743A
- Authority
- CN
- China
- Prior art keywords
- block polymer
- producing
- mixer
- monomer
- polymer according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920000642 polymer Polymers 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 88
- 239000000178 monomer Substances 0.000 claims abstract description 69
- 238000002156 mixing Methods 0.000 claims abstract description 61
- 230000003068 static effect Effects 0.000 claims abstract description 52
- 239000003999 initiator Substances 0.000 claims abstract description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 238000003780 insertion Methods 0.000 claims description 47
- 230000037431 insertion Effects 0.000 claims description 47
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 3
- -1 Polytetrafluoroethylene Polymers 0.000 description 208
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 46
- 239000000243 solution Substances 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 7
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 6
- 239000004696 Poly ether ether ketone Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 229920002530 polyetherether ketone Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 229930182556 Polyacetal Natural products 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 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 2
- OXHSYXPNALRSME-UHFFFAOYSA-N (4-ethenylphenyl)-trimethylsilane Chemical compound C[Si](C)(C)C1=CC=C(C=C)C=C1 OXHSYXPNALRSME-UHFFFAOYSA-N 0.000 description 2
- GNHVCDAPMWHFKG-UHFFFAOYSA-N 1-ethenyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C=C)C(OC)=C1 GNHVCDAPMWHFKG-UHFFFAOYSA-N 0.000 description 2
- 125000006433 1-ethyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000006439 1-n-propyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000002900 organolithium compounds Chemical class 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- SOSNAIPTFXTNRU-UHFFFAOYSA-N (4-ethenylphenoxy)-trimethylsilane Chemical compound C[Si](C)(C)OC1=CC=C(C=C)C=C1 SOSNAIPTFXTNRU-UHFFFAOYSA-N 0.000 description 1
- LAGQCXVIXQYJHO-UHFFFAOYSA-N (4-ethenylphenyl)-dimethylsilane Chemical compound C[SiH](C)C1=CC=C(C=C)C=C1 LAGQCXVIXQYJHO-UHFFFAOYSA-N 0.000 description 1
- PCTZLSCYMRXUGW-UHFFFAOYSA-N 1,1,1,2,2-pentafluorobutane Chemical group [CH2]CC(F)(F)C(F)(F)F PCTZLSCYMRXUGW-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-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
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 description 1
- PECUPOXPPBBFLU-UHFFFAOYSA-N 1-ethenyl-3-methoxybenzene Chemical compound COC1=CC=CC(C=C)=C1 PECUPOXPPBBFLU-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
- OBRYRJYZWVLVLF-UHFFFAOYSA-N 1-ethenyl-4-ethoxybenzene Chemical compound CCOC1=CC=C(C=C)C=C1 OBRYRJYZWVLVLF-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
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- 125000000453 2,2,2-trichloroethyl group Chemical group [H]C([H])(*)C(Cl)(Cl)Cl 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- OWRKXOZFTROHSH-UHFFFAOYSA-N 2-ethenyl-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1C=C OWRKXOZFTROHSH-UHFFFAOYSA-N 0.000 description 1
- AHNYHYYIECFEQY-UHFFFAOYSA-N 2-phenylethenylsilicon Chemical compound [Si]C=CC1=CC=CC=C1 AHNYHYYIECFEQY-UHFFFAOYSA-N 0.000 description 1
- PMZXJPLGCUVUDN-UHFFFAOYSA-N 4-ethenyl-1,2-dimethylbenzene Chemical compound CC1=CC=C(C=C)C=C1C PMZXJPLGCUVUDN-UHFFFAOYSA-N 0.000 description 1
- DBEJPQQGEMWGRE-UHFFFAOYSA-N 5-ethenyl-1,2,3-trimethoxybenzene Chemical compound COC1=CC(C=C)=CC(OC)=C1OC DBEJPQQGEMWGRE-UHFFFAOYSA-N 0.000 description 1
- YBUSAOXTVKRWBM-UHFFFAOYSA-N 6-hydroxy-5-(2-methylprop-2-enoyloxy)bicyclo[2.2.1]hept-2-ene-2-carboxylic acid Chemical compound C(C(=C)C)(=O)OC1C2C=C(C(C1O)C2)C(=O)O YBUSAOXTVKRWBM-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- ICKXMDGNIZPYRS-UHFFFAOYSA-N [Li]CCCCCC[Li] Chemical compound [Li]CCCCCC[Li] ICKXMDGNIZPYRS-UHFFFAOYSA-N 0.000 description 1
- BZEZSORUWZUMNU-UHFFFAOYSA-N [Li]CCCC[Li] Chemical compound [Li]CCCC[Li] BZEZSORUWZUMNU-UHFFFAOYSA-N 0.000 description 1
- MXFRWBNCSXHXRE-UHFFFAOYSA-N [Li]\C=C\C Chemical compound [Li]\C=C\C MXFRWBNCSXHXRE-UHFFFAOYSA-N 0.000 description 1
- NAAFUPBXVBAGSC-UHFFFAOYSA-N [SiH3]OC=Cc1ccccc1 Chemical compound [SiH3]OC=Cc1ccccc1 NAAFUPBXVBAGSC-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000001352 cyclobutyloxy group Chemical group C1(CCC1)O* 0.000 description 1
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 0.000 description 1
- 125000000131 cyclopropyloxy group Chemical group C1(CC1)O* 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZEFNMRMJJKIGBT-UHFFFAOYSA-N dilithium;pentane Chemical compound [Li+].[Li+].[CH2-]CCC[CH2-] ZEFNMRMJJKIGBT-UHFFFAOYSA-N 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- AGUDKYVAXRDJLV-UHFFFAOYSA-N ethynyllithium Chemical compound [Li]C#C AGUDKYVAXRDJLV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-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
- SNHOZPMHMQQMNI-UHFFFAOYSA-N lithium;2h-thiophen-2-ide Chemical compound [Li+].C=1C=[C-]SC=1 SNHOZPMHMQQMNI-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 1
- VCPPTNDHEILJHD-UHFFFAOYSA-N lithium;prop-1-ene Chemical compound [Li+].[CH2-]C=C VCPPTNDHEILJHD-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- PGOLTJPQCISRTO-UHFFFAOYSA-N vinyllithium Chemical compound [Li]C=C PGOLTJPQCISRTO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
-
- 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
-
- 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
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- 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
- C08F20/00—Homopolymers and 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
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
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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)
- Inorganic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention provides a method for producing a block polymer, the method comprising: using a flow reactor including a two-liquid mixing mixer having a flow path capable of mixing a plurality of liquids, a step of synthesizing a polymer by anionically polymerizing a styrene-based monomer as a first monomer in the presence of an initiator, and a step of synthesizing a block polymer by polymerizing an acrylic monomer as a second monomer with the polymer block; the flow reactor comprises a mixer for two-liquid mixing comprising a joint member or a static mixer member having a double pipe inside.
Description
Technical Field
The present invention relates to a method for producing a block polymer.
Background
In recent years, mobile chemical synthesis has attracted attention, in which chemical synthesis is continuously performed while a solution is made to flow, using a reaction apparatus called a flow reactor or a microreactor. Compared with the batch mode which is carried out in the prior art, the flow chemical synthesis has the following advantages: since the reaction is carried out using a small reaction vessel, precise temperature control can be achieved and the mixing efficiency is also good.
In the two-liquid mixing type fluid synthesis, there are problems that insoluble substances are often precipitated in a mixing portion (mixer), a flow path is blocked, pressure fluctuation occurs, continuous operation for a long time is not possible, and the quality of the obtained composition is not stable. In particular, this problem is significant in a reaction system using an organolithium reagent such as anion polymerization of a polymer, and it is not easy to achieve both stable continuous operation for a long time and efficient mixing.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-067999
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a method capable of stably producing a block polymer for a long period of time.
Means for solving the problems
The present inventors have made extensive studies to achieve the above object, and as a result, have found that: when a block polymer comprising a polymer block derived from a styrenic monomer and a polymer block derived from an acrylic monomer is produced, a block polymer can be stably produced for a long period of time by using a predetermined flow reactor, and the present invention has been completed.
Accordingly, the present invention provides the following method for producing a block polymer.
1. A method for producing a block polymer, the method comprising: a step of synthesizing a polymer by anionic-polymerizing a styrene monomer as a first monomer in the presence of an initiator using a flow reactor including a mixer for two-liquid mixing including a flow path capable of mixing a plurality of liquids; and a step of polymerizing an acrylic monomer as a second monomer with the polymer block to synthesize a block polymer,
the flow reactor comprises a mixer for two-liquid mixing comprising a joint member or a static mixer member having a double pipe inside.
2.1A method for producing a block polymer, comprising: a step of reacting a non-separately polymerizable monomer after synthesizing a polymer by anion polymerization of a first monomer and before polymerizing a second monomer block.
The method for producing a block polymer according to claim 1 or 2, wherein the non-separately polymerizable monomer is 1, 1-diphenylethylene or a derivative thereof.
4.1 to 3, wherein the static mixer member comprises a cylindrical body and a unit body inserted therein.
5.1 to 4, wherein the mixer for two-liquid mixing comprises a joint member having a double pipe inside and a static mixer member.
The method for producing a block polymer according to 6.5, wherein the mixer for two-liquid mixing comprises a joint member having a double pipe inside and a static mixer member, the static mixer member comprises a tubular body and a unit body inserted therein, and the joint member and the static mixer member are connected so that an end surface of the tubular body on the double pipe side and an end surface of the double pipe on the static mixer member side abut against each other.
7.6A method for producing a block polymer, wherein the end of the double pipe on the static mixer member side is located inside the joint member.
8.5 to 7, wherein the joint member has an insertion hole for inserting an inner tube through which an initiator solution flows, and the double tube is formed by a space formed by the inner side of the inner tube and the outer wall of the inner tube and the inner wall of the insertion hole, at least in the vicinity of the tip of the inner tube, in a state where the inner tube is inserted.
The process for producing a block polymer according to 9.8, wherein the joint member has an introduction hole for introducing a monomer solution, and the introduction hole is connected to the insertion hole.
The method for producing a block polymer according to 10.9, wherein the insertion hole is formed so as to have a diameter substantially equal to the outer diameter of the inner tube in the vicinity of a connecting portion with the introduction hole, and is formed so as to have a diameter larger than the outer diameter of the inner tube from the connecting portion to the tip end of the inner tube.
11.8 to 10, wherein the joint member has a hole for connecting a static mixer member, and the insertion hole is connected to the hole for connecting.
12.4 to 11, wherein the unit cell is inserted into the tubular body so that one end thereof is substantially flush with the end surface of the tubular body on the double tube side.
13.4 to 12, wherein the unit cell has a shape in which a plurality of right twisted blades and left twisted blades are alternately connected in a twisted axis direction.
14.1-13, wherein the initiator is a mono-organolithium compound.
15.1 to 14 of the block polymer preparation method, wherein, the styrene monomer is represented by the following formula (1) compounds.
[ solution 1]
(in the formula, R1Is a hydrogen atom or a methyl group, R2～R6Each independently a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, -OSiR7 3or-SiR7 3，R7Each independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms or an alkylsilyl group having 1 to 5 carbon atoms. )
16.1 to 15, wherein the acrylic monomer is a compound represented by the following formula (2).
[ solution 2]
(in the formula, R11Is a hydrogen atom or a methyl group, R12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. )
ADVANTAGEOUS EFFECTS OF INVENTION
Since the two-liquid mixing mixer used in the flow reactor is not easily clogged and has good mixing efficiency, the polymer can be stably produced for a long time by the method for producing a polymer of the present invention using the mixer. In particular, the block polymer obtained by the production method of the present invention has a small dispersity (Mw/Mn) (narrow molecular weight distribution) and a highly controlled structure, and can be applied to semiconductor lithography using induced self-organization, other nano-patterning techniques, or production of high-functional elastomers and the like.
Drawings
Fig. 1 is a perspective view of a two-liquid mixing mixer used in the present invention.
Fig. 2 is an exploded perspective view of the two-liquid mixing mixer of fig. 1.
Fig. 3 is a cross-sectional view of the body taken along line III-III of fig. 2.
Fig. 4 is a sectional view taken along line IV-IV of fig. 1.
Fig. 5 is an enlarged sectional view of the double-walled pipe portion of fig. 4.
Fig. 6 is a bottom view of the main body in a state where the inner tube is inserted.
Fig. 7 is a view obtained by viewing the unit cell of the static mixer element from a direction orthogonal to the direction of its torsion axis.
Fig. 8 is a perspective view showing the form of the two-liquid mixing device used in the present invention.
FIG. 9 is a schematic view showing a form of a flow reactor used in the present invention.
FIG. 10 is a schematic view showing the constitution of a flow reactor used in examples.
FIG. 11 is a schematic view showing the structure of a flow reactor used in a comparative example.
Fig. 12 is a graph showing the pressure trend in the reaction in example 1.
FIG. 13 shows a view of a polymer obtained in example 11H-NMR chart.
Fig. 14 is a graph showing the pressure trend in the reaction in comparative example 1.
Fig. 15 is a graph showing the pressure trend in the reaction in comparative example 2.
Detailed Description
The method for producing a block polymer of the present invention comprises: a step of synthesizing a homopolymer by anionic polymerization of a styrene monomer as a first monomer in the presence of an initiator using a flow reactor including a mixer for two-liquid mixing including a flow path capable of mixing a plurality of liquids; and a step of block-polymerizing an acrylic monomer as a second monomer with the homopolymer to synthesize a block polymer.
[ flow reactor ]
The flow reactor is not particularly limited as long as it includes a mixer for two-liquid mixing having a double pipe inside, and preferably has the following configuration. That is, the two-liquid mixing mixer preferably includes a joint member or a static mixer member having a double pipe inside. The mixer for two-liquid mixing preferably includes both a joint member having a double pipe therein and a static mixer member, and more preferably the static mixer member includes a cylindrical body and a unit body inserted therein, and the joint member is connected to the static mixer member so that an end surface of the cylindrical body on the double pipe side abuts an end surface of the double pipe on the static mixer member side.
By connecting the joint member and the static mixer member in this manner so that the end surface on the double pipe side of the tubular body abuts against the end surface on the static mixer member side of the double pipe, the above-described two-liquid mixing mixer can be operated stably for a long time without being easily clogged while maintaining the mixing efficiency.
That is, the mixer is configured such that the double pipe and (the cylindrical body of) the static mixer are connected inside the joint, and thus the respective end surfaces can be more reliably brought into contact with each other as compared with the conventional microreactor structure, and as a result, the two liquids flowing out of the double pipe flow into the static mixer substantially simultaneously with the outflow of the two liquids, and thus the two liquids are more reliably mixed at the start of the reaction.
In the above-described mixer for two-liquid mixing, it is preferable that an end portion of the double pipe on the static mixer member side is located inside the joint member. With such a configuration, the construction of the double pipe is simplified, and as a result, the joint member can be easily manufactured, and the contact point between the joint member and the static mixer member can be easily confirmed.
In the above-described mixer for two-liquid mixing, it is preferable that the joint member has an insertion hole into which an inner tube through which the first liquid flows is inserted, and the double tube is formed by a space formed by an inner side of the inner tube and an inner wall of the insertion hole and an outer wall of the inner tube at least in the vicinity of a distal end portion of the inner tube in a state where the inner tube is inserted. With such a configuration, the construction of the double pipe is simplified, and as a result, the joint member can be easily manufactured.
The insertion hole can be formed by cutting, using a die including a die corresponding to the insertion hole, or the like. In this case, the inner tube may be fixed to the joint member body in a state where the insertion hole formed in the joint member is inserted, or may be detachably fixed from the joint member body, and preferably, may be detachably fixed from the joint member body, as long as it can maintain liquid-tightness. By forming the structure that the inner pipe can be detached in this way, the following advantages are achieved: the used double pipe portion can be easily cleaned, and the double pipe portion can be replaced when the inner pipe is damaged, closed or contaminated.
The fixing and fixing means for the inner tube is not particularly limited as long as it can maintain liquid-tightness as described above, and includes fixing with an adhesive, fixing with welding, or the like, and detachable fixing means with screw fastening or the like, and preferably, detachable fixing means with screw fastening or the like is used.
Preferably, the joint member has an introduction hole for introducing the second liquid, and the introduction hole is connected to the insertion hole. With such a configuration, the double pipe can be constructed inside the joint member body, and as a result, the length of the double pipe can be shortened, so that the joint member can be easily manufactured. The introduction hole can be formed by cutting or a method using a die, similarly to the insertion hole.
The position of the introduction hole in the joint member is not particularly limited, but is preferably formed in a direction orthogonal to the insertion hole, and further, if the length of the double tube is considered to be shortened, it is preferably formed at the following positions: the insertion hole can be connected to the proximal end portion of the insertion hole and the central portion of the terminal end portion at a position closer to the terminal end portion than the central portion.
Further, it is preferable that the insertion hole is formed so as to have a diameter substantially equal to the outer diameter of the inner tube in the vicinity of a connection portion with the introduction hole, and is formed so as to have a diameter larger than the outer diameter of the inner tube from the connection portion to the tip end of the inner tube. By having the hole structure with such different diameters, a gap is hardly formed between the inner tube and the insertion hole at the connection portion, and therefore, the second liquid flowing in from the introduction hole can be prevented from leaking to the base end portion side of the insertion hole, and the two liquids can be efficiently mixed.
Preferably, the joint member has a hole for connecting a static mixer member, and the insertion hole is connected to the hole for connecting. With such a configuration, since the joint member and the static mixer member can be individually designed, the internal structure of the two-liquid mixing mixer can be easily adjusted. The connecting hole can be formed by cutting or a method using a die, similarly to the above-described insertion hole.
The static mixer member may be fixed to the joint member body in a state inserted into a connecting hole formed in the joint member, may be detachably fixed from the joint member body, and is preferably detachably fixed from the joint member body as long as liquid tightness can be maintained, similarly to the above-described inner pipe. By making it detachable, the position of the unit body inside the static mixer member and the cleaning of the mixer after use become easy, and the replacement of each part becomes possible in the case of contamination, deterioration, and the like. Further, as the fixing and fixing means of the static mixer member, the same means as described in the inner pipe can be cited, and in this case, it is also preferable to use a detachable fixing means by screw fastening or the like.
Further, it is preferable that the unit body is inserted into the cylindrical body so that one end thereof is substantially flush with the end surface of the cylindrical body on the double tube side. In this way, by the end face of the cylindrical body substantially coinciding with the end of the unit cell, the two liquids flowing out of the double pipe flow into the unit cell substantially simultaneously with the outflow and are mixed, so that more efficient mixing and stirring are performed from the start of the reaction.
The shape of the cylindrical body is not particularly limited, but a cylindrical shape is preferable in consideration of fluidity, mixing property, and the like of the two liquids passing through the inside thereof.
The structure of the unit body is not particularly limited, and can be appropriately selected from the structures used as the unit bodies of the static mixer, and examples thereof include a unit body having a shape in which a plurality of right twisted blades and left twisted blades are alternately connected in the longitudinal direction (twisting axis direction), a unit body having a spiral shape in which the twisting direction is constant, a unit body in which a plurality of plates provided with 1 or 2 or more holes are stacked, and the like, and a unit body having a shape in which a plurality of right twisted blades and left twisted blades are alternately connected in the twisting axis direction is preferable. By using the unit body having such a shape, it is possible to more efficiently mix the components, and it becomes more difficult to cause the blockage of the mixer during the reaction.
The unit body may be a detachable structure that is simply inserted into the cylindrical body, or a non-detachable structure that is fixed to the cylindrical body after insertion, but a detachable structure that is simply inserted is preferable. By providing the detachable structure, the position of the inside of the cylindrical body of the unit body can be easily adjusted and the unit body can be easily replaced.
The diameter of the unit body is not particularly limited as long as it can be inserted into the cylindrical body, and preferably, the diameter (maximum diameter) thereof is substantially the same as the inner diameter of the cylindrical body. By doing so, even in the case where only the unit body is inserted into the cylindrical body, it is possible to prevent the position of the unit body from being varied in the longitudinal direction and the lateral direction inside the cylindrical body. In consideration of the use of the above-mentioned two-liquid mixer, the diameter of the unit body is preferably about 1 to 10mm, more preferably about 1.6 to 8mm, and still more preferably about 2 to 5 mm.
The length of the unit body is not particularly limited as long as it can be inserted into the tubular body, and is preferably substantially the same as the length of the tubular body. By doing so, the alignment of the end of the unit body and the end face of the double tube side of the cylindrical body becomes easy.
The flow reactor used in the present invention includes the above-mentioned two-liquid mixing mixer. The flow reactor may include one or more of the two-liquid mixing mixers. When two or more of the above-described two-liquid mixing mixers are included, multistage flow synthesis becomes possible. Since the above-mentioned two-liquid mixing mixer is not easily blocked, the pressure loss in the flow synthesis using a flow reactor is small, and a stable continuous operation can be performed for a long time, and the mixer is suitable for mass synthesis.
The flow reactor used in the present invention may include, in addition to the above-described two-liquid mixing mixer, various other members necessary for the reaction, such as a pump for feeding liquid, a pipe for forming a flow path, and a temperature adjusting device for adjusting temperature, as necessary.
The liquid feeding pump is not particularly limited, and a commonly used pump such as a plunger pump, a syringe pump, or a rotary pump can be used.
The material of the pipe for forming the flow path is not particularly limited, and may be stainless steel, metal such as titanium, iron, copper, nickel, or aluminum, or resin such as Polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), Perfluoroalkoxy Fluoride (PFA), polyether ether ketone (PEEK), or polypropylene (PP).
The inner diameter of the flow passage forming pipe may be appropriately set according to the purpose within a range not impairing the effect of the present invention, and is usually preferably about 0.5 to 10mm, more preferably about 0.7 to 4mm, and further preferably about 1 to 2 mm. The length of the flow passage forming pipe may be appropriately set according to the purpose within a range not impairing the effect of the present invention, and is usually preferably about 0.1 to 20m, more preferably about 0.2 to 10m, and further preferably about 0.3 to 5 m.
The mixer for two-liquid mixing and the flow reactor used in the present invention will be specifically described below based on the drawings. The two-fluid mixing mixer 1 is configured to include a joint member 2 and a static mixer member 3, as shown in fig. 1. The joint member 2 comprises a main body 21 made of stainless steel, and an inner pipe 22 (outer diameter 1.6mm, inner diameter 1.0mm) made of stainless steel for the first liquid flow.
As shown in fig. 2 and 3, the main body 21 has: an insertion hole 211 for inserting the inner tube 22; an introduction hole 212 for introducing the second liquid, which is orthogonal to the insertion hole 211 and is connected to the insertion hole 211 in the main body 21; and a static mixer member connecting hole 213. On the inner walls of the insertion hole 211, the introduction hole 212, and the connection hole 213, nut portions 211a, 212a, and 213a corresponding to bolt portions formed in each connector described later are formed so that the inner tube 22, the introduction tube through which the second liquid flows, and the static mixer element 3 can be fixed to the main body 21 by screw fastening.
The insertion hole 211 is formed from a proximal end portion side to a distal end portion side, and includes a nut portion 211a, a liquid-tight portion 211b having a trapezoidal cross section and a diameter reduced according to a shape of a distal end portion of a connector, which will be described later, and an inner tube passage portion 211c formed continuously thereto. As shown in fig. 5, the inner diameter b of the inner tube passage 211c of the insertion hole 211 is formed to have a diameter substantially equal to the outer diameter a of the inner tube 22 in the vicinity of the connection portion 214 with the introduction hole 212, and the inner diameter c of the inner tube passage 211c from the connection portion 214 to the connection hole 213 is formed to be larger than the outer diameter a of the inner tube 22. Thus, the connecting portion 214 is configured to have almost no gap between the inner tube 22 and the insertion hole 211, prevent the second liquid flowing in from the introduction hole 212 from leaking to the base end portion side of the insertion hole 211, and form the double tube 25 by the inner tube inner side 221 and the space 24 formed by the inner tube outer wall 222 and the insertion hole inner wall 211d, as shown in fig. 6.
In addition, as shown in fig. 3, the insertion hole 211 is connected at its base end portion to the connection hole 213, whereby the hole formed by the insertion hole 211 and the connection hole 213 penetrates the main body 21.
As shown in fig. 2, the inner tube 22 is attached to a connector 23 having a substantially hexagonal columnar head 232 for screw fixation and a bolt portion 231 and an inverted truncated cone-shaped seal portion 233 formed integrally therewith for holding the liquid-tightness inside the joint main body 21, while forming a hole (not shown) through which the inner tube 22 opens, and in this state, the inner tube is inserted into the insertion hole 211 having the nut portion 211a and fixed to the main body 21 by screw fastening.
As shown in fig. 3, the introduction hole 212 is composed of a nut portion 212a, a liquid-tight portion 212b having a rectangular cross section conforming to the shape of the distal end portion of the connector, which will be described later, formed continuously thereto, and a coupling portion 212c extending from the nut portion to a coupling portion 214 of the insertion hole 211. The insertion hole 211 and the introduction hole 212 are connected to the proximal end portion and the center of the terminal end portion of the insertion hole 211 on the terminal end portion side.
As shown in fig. 3, the static mixer connection hole 213 is formed from a base end portion side to a terminal end portion side by a nut portion 213a and a liquid-tight portion 213b having a rectangular cross section conforming to the shape of a connector tip portion described later and formed continuously thereto.
The static mixer member 3, as shown in fig. 1 and 2, includes a cylindrical body 31 (inner diameter 3.0mm) made of fluororesin or stainless steel and a unit body 32 (diameter 3 mm) made of polyacetal inserted inside thereof. As shown in fig. 2 and 4, the unit body 32 is inserted into the cylindrical body 31 with its base end on the same horizontal plane as the end surface of the cylindrical body 31 on the double pipe 25 side. Here, as shown in fig. 7, the unit body 32 has a shape in which a plurality of right twisted blades 321 and left twisted blades 322 are alternately connected in a twisted axis (central axis in the longitudinal direction) 323 direction.
As shown in fig. 2, a fluororesin connector 33 having a screw portion 331 and a hole (not shown) through which the cylindrical body 31 is passed is attached to an upper end portion of the cylindrical body 31 in the drawing, and in this state, the connector is inserted into the connecting hole 213 having the nut portion 213a and is fixed to the body 21 by screwing.
Next, the internal structure of the two-liquid mixing mixer 1 having the above-described configuration will be described with reference to fig. 4 to 6. As described above, the diameter of the insertion hole 211, specifically, the inner diameter b of the inner tube passage 211c near the connection portion 214 of the introduction hole 212 is made substantially the same as the outer diameter a of the inner tube 22. Further, the inner diameter c of the inner tube passage 211c from the connection portion 214 of the insertion hole 211 and the introduction hole 212 to the tip 223 of the inner tube 22 on the static mixer member 3 side is formed larger than the outer diameter a of the inner tube 22. Thereby, the double pipe 25 is formed by the inner side 221 of the inner pipe 22 and the space 24 constructed by the outer wall 222 of the inner pipe 22 and the inner wall 211d of the insertion hole 211.
Further, the end surface of the cylindrical body 31 on the double pipe 25 side of the static mixer element 3 abuts against the end surface of the double pipe 25 on the static mixer element 3 side, and in the present embodiment, as described above, the base end of the unit body 32 and the end surface of the cylindrical body 31 on the double pipe 25 side are on the same level, and therefore the end surface of the double pipe 25 on the static mixer element 3 side and the base end (upper end in fig. 4) of the unit body 32 also abut.
In this case, as shown in fig. 8, the introduction pipe 26 through which the second liquid flows is fixedly connected to the introduction hole 212 by screw fastening using a connector 27 having a sealing portion (not shown) for holding the liquid tightness of the inside of the joint main body 21 and a bolt portion 271, while forming a hole (not shown) through which the introduction pipe 26 passes, as the introduction pipe 26 is introduced.
Next, an embodiment of a flow reactor using the two-liquid mixing mixer configured as described above will be described with reference to fig. 9.
The flow reactor 4 is configured by connecting the first two-fluid mixing mixer 1a and the second two-fluid mixing mixer 1b disposed inside the thermostatic layer 43 in series using a PTFE tube 42d (inner diameter 1.5 mm).
The pump 41a for feeding the first liquid was connected to the inner tube 22a of the first mixer 1a for two-liquid mixing via a PTFE tube 42a (inner diameter 1.0 mm). On the other hand, a pump 41b for feeding the second liquid was connected to an introduction hole provided in the main body 21a of the joint member of the two-liquid mixing mixer 1a via a PTFE tube 42b (inner diameter 1.0mm) through which the second liquid having a connector provided at the distal end flowed.
A pump 41c for feeding the third liquid was connected to the introduction hole of the two-liquid mixing mixer 1b via a PTFE tube 42c (inner diameter 1.0mm) having a connector provided at the distal end thereof and through which the third liquid flowed, and a PTFE tube 42e (inner diameter 1.5mm) was connected to the terminal end of the static mixer member 3b of the two-liquid mixing mixer 1 b.
In the flow reactor 4 having such a configuration, the liquids fed from the first liquid feeding pump 41a and the second liquid feeding pump 41b flow into the joint member main body 21a of the first two-liquid mixing mixer 1a, pass through the double pipe constructed therein, flow into the static mixer member 3a in contact with the end of the double pipe, and are mixed and stirred in the unit bodies inside, and the first reaction occurs at the same time. The first reaction liquid after the reaction passes through the pipe 42d and then flows into the joint member main body 21b through the inner pipe 22b of the second two-liquid mixing mixer 1 b. The first reaction liquid passes through the double pipe inside the joint member main body 21b together with the third liquid fed from the third liquid feeding pump 41c and flows into the joint member main body 21b, and flows into the static mixer element 3b as in the case of the first two-liquid mixing mixer 1a, so that the second reaction proceeds.
The mixer for two-liquid mixing and the flow reactor used in the present invention are not limited to the above-described embodiments, and may be modified and improved within a range in which the object and effect of the present invention can be achieved.
That is, in the above-described two-liquid mixing mixer 1, the inner tube 22 and the static mixer member 3 are screwed so as to be detachable from the joint member main body 21, but they may be detachably configured by other fixing means, and may be connected and fixed in a state where they cannot be detached.
The inner tube 22 and the cylindrical body 31 may be provided with the separate connectors 23 and 33, or they may be omitted to form a suitable fixing means for the inner tube and the cylindrical body themselves.
Further, the introduction hole 212 is formed in the joint member main body 21 so as to be connected to the insertion hole 211 orthogonally, but may be connected to the insertion hole at another angle, and the position of the introduction hole 212 may be set at any position.
The material of the body 21, the inner tube 22, and the connector 23 is stainless steel, but is not limited thereto, and may be other metals such as titanium, iron, copper, nickel, and aluminum, or resins such as PTFE, FEP, PFA, PEEK, and PP.
The inner diameter of the inner tube 22 may be appropriately set in accordance with the purpose within a range not impairing the effect of the present invention, and is usually preferably about 0.1 to 3mm, more preferably about 0.5 to 2mm, and still more preferably about 0.5 to 1 mm. The outer diameter of the inner tube 22 may be appropriately set according to the purpose within a range not impairing the effect of the present invention, and is usually preferably about 0.8 to 4mm, more preferably about 0.8 to 3mm, and still more preferably about 0.8 to 1.6 mm.
The aperture c of the insertion hole 211 can be set appropriately according to the purpose within a range not impairing the effect of the present invention, and is usually preferably about 0.1 to 5mm, more preferably about 0.5 to 4mm, and still more preferably about 0.8 to 2 mm.
The material of the cylindrical body 31 is not limited to stainless steel, and may be other metals such as titanium, iron, copper, nickel, and aluminum, and resins such as PTFE, FEP, PFA, PEEK, and PP.
The material of the unit body 32 is not limited to polyacetal, and may be other resins such as PTFE, FEP, PFA, PEEK, PP, stainless steel, metals such as titanium, iron, copper, nickel, aluminum, ceramics, or the like.
The shape of the unit body 32 may be a shape having a spiral shape with a constant twisting direction, a shape in which a plurality of plates provided with 1 or 2 or more holes are laminated, or the like.
The material of the connector 33 is not limited to fluorine-based resin, and may be other resin such as PEEK and PP, or metal such as stainless steel, titanium, iron, copper, nickel, and aluminum.
The inner diameter of the cylindrical body 31 can be set as appropriate according to the purpose within a range not impairing the effect of the present invention, and is usually preferably about 1 to 10mm, more preferably about 1.6 to 8mm, and further preferably about 2 to 5 mm. The diameter of the unit body 32 may be set as appropriate according to the purpose within a range not impairing the effect of the present invention, and is usually preferably about 1 to 10mm, more preferably about 1.6 to 8mm, and still more preferably about 2 to 5 mm.
The flow reactor 4 includes 2 mixers for two-liquid mixing, and thus can perform two-stage flow synthesis, and in the case of one-stage flow synthesis, the number of mixers for two-liquid mixing may be 1, and in the case of n-stage flow synthesis, the flow reactor can be assembled as described above using n mixers for two-liquid mixing.
The inner diameters of the tubes 42a to 42e constituting the flow reactor 4 may be appropriately set according to the purpose within a range not impairing the effect of the present invention, and are usually preferably about 0.5 to 10mm, more preferably about 0.7 to 4mm, and further preferably about 1 to 2 mm. The length thereof may be set as appropriate in accordance with the purpose within a range not impairing the effect of the present invention, and is usually preferably about 0.1 to 20m, more preferably about 0.2 to 10m, and still more preferably about 0.3 to 5 m.
[ first monomer ]
The styrene monomer as the first monomer is not particularly limited as long as it is a styrene derivative, and a styrene derivative represented by the following formula (1) is preferable.
[ solution 3]
In the formula, R1Represents a hydrogen atom or a methyl group. R2～R6Each independently represents a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, -OSiR7 3or-SiR7 3。R7Each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms, or an alkylsilyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2-dimethyl-n-propyl, 1-ethyl-propyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2-ethyl-n-propyl, cyclopentyl, 1-methylcyclobutyl, 2-, 1, 2-dimethylcyclopropyl, 2, 3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 2, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1, 2, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1, 2-dimethylcyclobutyl, 1, 3-dimethylcyclobutyl, 2, 2-dimethylcyclobutyl, 2, 3-dimethylcyclobutyl, 2, 4-dimethylcyclobutyl, 3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1, 2, 2-trimethylcyclopropyl, 1, 2, 3-trimethylcyclopropyl, 2, 2, 3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, etc, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl, and the like. Of these, an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is even more preferable.
Examples of the above alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a cyclopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a cyclobutoxy group, a 1-methylcyclopropoxy group, a 2-methylcyclopropoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a1, 1-dimethyl-n-propoxy group, a1, 2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, a1, 1-diethyl-n-propoxy group, a cyclopentyloxy group, a 1-methyl-cyclobutoxy group, a 2-methyl-cyclobutoxy group, a 3-methyl-cyclobutoxy group, a1, 2-dimethyl-cyclopropoxy group, 2-ethyl cyclopropoxy, and the like. The structure of the alkoxy group is preferably straight or branched. Among these, alkoxy groups having 1 to 3 carbon atoms are preferable.
The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom or a chlorine atom.
As R4Preferably an alkoxy group having 1 to 5 carbon atoms or-SiR7 3More preferably methoxy or-Si (CH)3)3. In addition, as R2、R3、R5And R6Preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or-SiR7 3More preferably a hydrogen atom, methoxy group or-Si (CH)3)3。
Specific examples of the styrene derivative include styrene, α -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-ethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-tert-butylstyrene, 4-dimethylsilylstyrene, 4-trimethylsilylstyrene, 4-trimethylsiloxystyrene, 4-dimethyl (tert-butyl) silylstyrene, 4-dimethyl (tert-butyl) silyloxystyrene, 2-methoxystyrene, 3-methoxystyrene, 4-ethoxystyrene, 3, 4-dimethylstyrene, 2, 6-dimethylstyrene, 2, 4-dimethoxystyrene, 3, 4, 5-trimethoxystyrene and the like.
Among these, styrene monomers are preferably styrene, 4-t-butylstyrene, 4-methoxystyrene, 4-trimethylsilylstyrene, and the like, because monodisperse polymers are easily obtained even at relatively high temperatures.
[ second monomer ]
The acrylic monomer as the second monomer is not particularly limited as long as it is a compound having a (meth) acryloyl group, and preferably has one (meth) acryloyl group. As such a compound, a compound represented by the following formula (2) is particularly preferable.
[ solution 4]
In the formula, R11Is a hydrogen atom or a methyl group. R12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1, 2-dimethylcyclopropyl, 2, 3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, N-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 2, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1, 2, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 3-ethylcyclobutyl, 1, 2-dimethylcyclobutyl, 1, 3-dimethylcyclobutyl, 2, 2-dimethylcyclobutyl, 2, 3-dimethylcyclobutyl, 2, 4-dimethylcyclobutyl, 3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1, 2, 2-trimethylcyclopropyl, 1, 2, 3-trimethylcyclopropyl, 2, 2, 3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1-dimethyl-n-pentyl, 1, 2-dimethyl-n-pentyl, 1, 3-dimethyl-n-pentyl, 2-dimethyl-n-pentyl, 2, 3-dimethyl-n-pentyl, 3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1-dimethyl-n-hexyl, 1, 2-dimethyl-n-hexyl, 1, 3-dimethyl-n-hexyl, 2-dimethyl-n-hexyl, 2, 3-dimethyl-n-hexyl, 3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1-methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, isodecyl, n-undecyl, n-dodecyl, n-tridecyl, N-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, 16-methyl-n-octadecyl, n-nonadecyl, eicosyl, adamantyl, norbornyl, isobornyl, 2-methyl-2-adamantyl, and the like.
Examples of the haloalkyl group having 1 to 20 carbon atoms include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with a halogen atom such as fluorine, chlorine, bromine, or iodine. Specific examples thereof include trifluoromethyl, 2, 2, 2-trifluoroethyl, 1, 2, 2, 2-pentafluoroethyl, 3, 3, 3-trifluoropropyl, 2, 2, 3, 3, 3-pentafluoropropyl, 1, 2, 2, 3, 3, 3-heptafluoropropyl, 4, 4, 4-trifluorobutyl, 3, 3, 4, 4, 4-pentafluorobutyl, 2, 2, 3, 3, 4, 4-heptafluorobutyl, 1, 2, 2, 3, 3, 4, 4, 4-nonafluorobutyl and the like.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like.
Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a 2-phenylethyl group, an anthrylmethyl group and the like.
Among these, as R12The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms and the aralkyl group having 7 to 20 carbon atoms are preferable, and the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 14 carbon atoms and the aralkyl group having 7 to 15 carbon atoms are more preferable.
Examples of the (meth) acrylic compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, 16-methyl-n-heptadecyl (meth) acrylate, phenyl (meth) acrylate, and mixtures thereof, Naphthyl (meth) acrylate, anthracenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, anthracenylmethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 2-trichloroethyl (meth) acrylate, 2, 2, 3, 3, 4, 4, 4-heptafluorobutyl (meth) acrylate, methoxydiglycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, n-butoxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methyl-2, 2-ethyl-2-adamantyl (meth) acrylate, 2-propyl-2-adamantyl (meth) acrylate, 2-methoxybutyl-2-adamantyl (meth) acrylate, 8-methyl-8-tricyclodecanyl (meth) acrylate, 8-ethyl-8-tricyclodecanyl (meth) acrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, and the like.
Among these, tert-butyl (meth) acrylate and isopropyl (meth) acrylate are preferable as the acrylic monomer because a monodisperse polymer can be easily obtained even at a relatively high temperature.
[ initiator ]
The initiator used in the method for producing a polymer of the present invention is not particularly limited as long as it is an initiator generally used in anionic polymerization, and examples thereof include an organolithium compound.
Examples of the organolithium compounds include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, hexyllithium, methoxymethyllithium, ethoxymethyllithium, phenyllithium, naphthyllithium, benzyllithium, phenylethyllithium, α -methylphenyllithium, 1-diphenylhexyllithium, 1-diphenyl-3-methylpentyllithium, 3-methyl-1, 1-diphenylpentyllithium, vinyllithium, allyllithium, propenyl lithium, butenyl lithium, ethynyllithium, butynyllithium, pentynthium, hexynthium, 2-thienyllithium, 4-pyridylithium, 2-quinolylithium, and the like monoorganolithium compounds, such as 1, 4-dilithiobutane, 1, 5-dilithiopentane, 1, 6-dilithiohexane, 1, 10-dilithidecane, 1-dilithiylbiphenylbiphenyl, dilithiobutamylpolybutadiene, dilithiobutadienylpolydiene, 1, 4-dilithiobutyllithium, 1, 2-triethyllithium1, 3-triethyllithiumethyl-1, 3-triethyllithiumlithium, 1, 3-triethyllithiumlithium, 3-triethyllithiumobenzyllithium, 1, 2-triethyllithiumlithium, 3-triethyllithiumlithium, 2-lithium, and the like.
[ method for producing Block Polymer ]
By using a flow reactor having 2 or more mixers for two-liquid mixing, such as the flow reactor 4 described above, a block polymer having 2 or more monomer units can be synthesized.
The following describes a method for producing a block polymer of the present invention, taking as an example the synthesis of a binary block polymer. First, a first monomer solution containing the above-mentioned monomer is introduced into a flow reactor from an introduction hole of a first mixer, a solution containing the above-mentioned initiator is introduced into the flow reactor from an inner tube of the first mixer, and anion polymerization is performed to synthesize a homopolymer formed of the first monomer. In this case, by introducing the first monomer solution and the initiator solution as described above, the flow reactor is less likely to be closed, pressure loss is suppressed, and a polymer can be stably produced for a long period of time.
After the homopolymer formed from the first monomer is synthesized, in order to adjust the reactivity, a non-separately polymerizable monomer such as 1, 1-Diphenylethylene (DPE) or a derivative thereof may be reacted to modify the terminal of the polymer. Here, the non-separately polymerizable monomer means a monomer that does not cause anionic polymerization if it is the monomer alone.
The DPE was introduced into the flow reactor from the introduction hole of the second mixer. In this case, the DPE may be introduced directly into the flow reactor or may be diluted with a suitable solvent and introduced into the flow reactor. Examples of the solvent used for dilution include ether solvents such as Tetrahydrofuran (THF), 2-methyl THF, diethyl ether, Tetrahydropyran (THP), oxacyclohexane, and 1, 4-dioxane, and toluene, dichloromethane, and diethoxyethane. The concentration of DPE is preferably 0.1-5.7 mol/L.
After reacting a non-polymerizable monomer such as DPE, the second monomer solution is introduced into the flow reactor through the introduction hole of the third mixer, and a block polymer is synthesized.
The solvent for dissolving the first monomer and the second monomer is not particularly limited, but ether solvents such as THF, 2-methyl THF, diethyl ether, THP, oxacyclohexane, and 1, 4-dioxane, toluene, dichloromethane, and diethoxyethane are preferable.
The concentration of the first monomer is not particularly limited, and may be suitably set according to the purpose, and is preferably 0.1 to 5mol/L, more preferably 0.1 to 3mol/L, and particularly preferably 0.1 to 2 mol/L. The concentration of the second monomer is not particularly limited, and may be appropriately set according to the purpose, but is preferably 0.1 to 9.4mol/L, more preferably 1.0 to 9.4mol/L, and particularly preferably 2.0 to 9.4 mol/L. When the monomer concentration is in the above range, the flow reactor is less likely to be clogged, the pressure loss is suppressed, and the polymer can be stably produced for a long period of time.
The flow rate of the first monomer flowing through the flow path of the flow reactor is not particularly limited, and may be appropriately set according to the purpose, but is preferably 1 to 50 mL/min, more preferably 5 to 30mL/min, and particularly preferably 10 to 30 mL/min. The flow rate of the second monomer is not particularly limited, and may be appropriately set according to the purpose, but is preferably 0.1 to 50 mL/min, more preferably 0.1 to 30mL/min, and particularly preferably 0.1 to 20 mL/min. When the flow rate of the monomer is in the above range, the flow reactor is less likely to be closed, and the pressure loss is suppressed, so that the polymer can be stably produced for a long period of time.
As the initiator, n-butyllithium can be particularly preferably used. In the case of anionic polymerization, if it is carried out in a polar solvent (e.g., THF), the polymerization rate is accelerated, so the reaction is usually carried out at a low temperature. Therefore, if sec-butyllithium is not used as an initiator, there is a disadvantage that the initiation reaction is difficult to be uniform. On the other hand, if the reaction is carried out in a nonpolar solvent (e.g., toluene), the reaction rate is slow and heating becomes necessary. In this case, n-butyllithium having low reactivity may be used as the initiator. The process for producing a block polymer using the flow reactor of the present invention has a feature that n-butyllithium having low reactivity can be used as an initiator because the reaction can be carried out in a polar solvent at around room temperature.
The solvent for dissolving the initiator is not particularly limited, but ether solvents such as hexane, THF, 2-methyl THF, diethyl ether, THP, oxacyclohexane, and 1, 4-dioxane, toluene, dichloromethane, diethoxyethane, toluene, and diethyl ether are preferable.
The concentration of the initiator is not particularly limited, and may be suitably set in accordance with the kind of the monomer, and is preferably 0.01 to 0.5mol/L, more preferably 0.03 to 0.3mol/L, and particularly preferably 0.05 to 0.1 mol/L. When the concentration of the initiator is in the above range, the flow reactor is less likely to be clogged, the pressure loss is suppressed, and the polymer can be stably produced for a long period of time.
The flow rate of the initiator flowing through the flow path of the flow reactor is not particularly limited, and may be appropriately set according to the purpose, but is preferably 0.1 to 10mL/min, more preferably 0.5 to 8 mL/min, and particularly preferably 1 to 6 mL/min. When the flow rate of the initiator is in the above range, the flow reactor is less likely to be closed, the pressure loss is suppressed, and the polymer can be stably produced for a long period of time.
The reaction temperature (temperature of the flow reactor) in the production method of the present invention is not particularly limited, and can be appropriately set according to the purpose, and is preferably-80 ℃ or higher, more preferably-40 ℃ or higher, and further preferably-20 ℃ or higher, from the viewpoint of the reaction rate. The reaction temperature is preferably 100 ℃ or lower, more preferably 50 ℃ or lower, and still more preferably 30 ℃ or lower, from the viewpoint of suppressing side reactions and suppressing deactivation of growth ends.
Examples of the method for terminating the reaction include a method in which the polymerization reaction solution discharged from the flow reactor is recovered in a vessel containing an excessive amount of a reaction terminator such as methanol; a method of making a flow reactor have a configuration having 3 or more of the above-mentioned two-liquid mixing mixers, and flowing a reaction terminator such as methanol from the last two-liquid mixing mixer.
According to the production method of the present invention, a polymer having a small dispersity (Mw/Mn) (narrow molecular weight distribution) can be synthesized. The dispersion is preferably 1.5 or less, more preferably 1.3 or less, still more preferably 1.2 or less, and still more preferably 1.15 or less. Mw and Mn represent a weight average molecular weight and a number average molecular weight, respectively, and are measured values in terms of polystyrene by Gel Permeation Chromatography (GPC). The Mw of the polymer obtained by the production method of the present invention is not particularly limited, but is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000.
Examples
The present invention will be specifically explained below by way of synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.
A schematic diagram of a flow reactor (reaction apparatus) used in the following examples is shown in fig. 10. In fig. 10, arrows indicate the flow direction of the liquid. The plunger pump 1 (HP-12 manufactured by No. フ, No. ム) was used for feeding the first monomer solution, the plunger pump 1 and the mixer 1 were connected using a PTFE tube (inner diameter 1.0mm, outer diameter 1.6mm, length 2m), the Syringe pump 1 (1000D syring pump manufactured by TELEDYNE ISCO) was used for feeding the initiator solution, and the Syringe pump 1 and the mixer 1 were connected using a PTFE tube (inner diameter 1.0mm, outer diameter 1.6mm, length 2 m). The outlet of the mixer 1 and the inlet of the mixer 2 were connected by a PFA tube 1 (inner diameter: 2.0mm, outer diameter: 3mm, length: 1m), and the other inlet of the mixer 2 and the reaction control solution feeding syringe 2 (Keychem-L, manufactured by YMC, Ltd.) were connected by a PTFE tube (inner diameter: 1.0mm, outer diameter: 1.6mm, length: 2 m). The outlet of the mixer 2 and the inlet of the mixer 3 were connected by a PFA tube 2 (inner diameter: 2.0mm, outer diameter: 3mm, length: 1m), and the other inlet of the mixer 3 and the second monomer solution feeding plunger pump 2 (manufactured by JP フ, port ム, KP-12) were connected by a PTFE tube (inner diameter: 1.0mm, outer diameter: 1.6mm, length: 2 m). The outlet of the mixer 3 and the inlet of the mixer 4 were connected by a PFA tube 3 (inner diameter: 2.0mm, outer diameter: 3mm, length: 5m), and the other inlet of the mixer 4 and the reaction terminator solution feeding syringe 3 (Asia, Syrris) were connected by a PTFE tube (inner diameter: 1.0mm, outer diameter: 1.6mm, length: 2 m). A PFA tube 4 (inner diameter 2.0mm, outer diameter 3mm, length 0.7m) was connected to the outlet of the mixer 4. The flow path having a length of 90% from the forefront of each pump to the pipe 4 was immersed in a thermostatic bath at 24 ℃ to adjust the temperature. In addition, the record of the pressure sensor of the pump for sending the initiator solution is shown as a pressure trend.
A schematic diagram of a flow reactor used in the following comparative example is shown in fig. 11. In fig. 11, arrows indicate the flow direction of the liquid. Plunger pump 1 (HP-12, manufactured by フ, No. ム) was used for feeding the first monomer solution, plunger pump 1 and mixer 1 were connected using PTFE tube (inner diameter 1.0mm, outer diameter 1.6mm, length 2m), syringe pump 2 (Keychem-L, manufactured by YMC, Ltd.) was used for feeding the initiator solution, and syringe pump 2 and mixer 1 were connected using PTFE tube (inner diameter 1.0mm, outer diameter 1.6mm, length 2 m). The outlet of the mixer 1 and the inlet of the mixer 2 were connected to each other by a PTFE tube 1 (inner diameter: 1.5mm, outer diameter: 3mm, length: 1.3m (comparative example 1), length: 0.7m (comparative example 2)), and the other inlet of the mixer 2 was connected to a reaction terminator solution feeding syringe pump 3 (Asia, manufactured by Syrris) by a PTFE tube (inner diameter: 1.0mm, outer diameter: 1.6mm, length: 2 m). A PTFE tube 2 (inner diameter 1.5mm, outer diameter 3mm, length 1.3m (comparative example 1), 0.7m (comparative example 2)) was connected to the outlet of the mixer 2. The temperature of the flow path having a length of 90% from the foremost part of each pump to the pipe 2 was adjusted by immersing the flow path in a thermostat of 5 ℃ (comparative example 1) or 20 ℃ (comparative example 2). In addition, the record of the pressure sensor of the pump for sending the initiator solution is shown as a pressure trend.
The measurement conditions of GPC are as follows.
Column: PLgel 3 μm MIXED-E (manufactured by Agilent Technologies Co., Ltd.)
Mobile phase: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Column oven: 40 deg.C
A detector: UV detector
And (3) correcting a curve: standard polystyrene
In addition, the first and second substrates are,1the measurement conditions of H-NMR (300MHz) were as follows.
And (3) determination of a solvent: heavy chloroform
Reference substance: tetramethylsilane (TMS) (delta 0.0ppm)
[ example 1]
A0.25 mol/L styrene/THF solution as a first monomer and a 0.05mol/L n-butyllithium hexane solution as an initiator were mixed by a mixer 1 at flow rates of 30mL/min and 6mL/min, respectively, to polymerize the first monomer. As the joint member of the mixer 1, a joint member made of stainless steel was used, and as the cylindrical body, a cylindrical body made of stainless steel was used. In addition, as the static mixer unit, a product processed from NORITAKE CO., LIMITED DSP-MXA3-17 (polyacetal unit, number of twisted blades 17, diameter of 3 mm) was used. Subsequently, the reactivity with the second monomer was adjusted by mixing 1, 1-Diphenylethylene (DPE) with a mixer 2 at 56. mu.L/min. The mixer 2 used was the same mixer as the mixer 1. Subsequently, tert-butyl methacrylate as a second monomer was mixed at 1.2mL/min by a mixer 3, and block-polymerized. The mixer 3 used was the same mixer as the mixer 1. Next, as a polymerization terminator, a 0.25mol/L methanol/THF solution was mixed at 10mL/min by a mixer 4 to terminate the polymerization. A general simple double tube mixer was used as the mixer 4. A first monomer solution pipe was connected to the inlet of the introducing hole of the mixer 1, an initiator solution pipe was connected to the inlet of the inner pipe, the pipe 1 was connected to the inlet of the introducing hole of the mixer 2, a DPE liquid pipe was connected to the inlet of the inner pipe, the pipe 2 was connected to the inlet of the introducing hole of the mixer 3, a t-butyl methacrylate liquid pipe was connected to the inlet of the inner pipe, a polymerization terminator solution pipe was connected to the inlet of the introducing hole of the mixer 4, and the pipe 3 was connected to the inlet of the inner pipe. The solution is sent for 10 minutes, and effluent liquid is collected. The pressure trend in the reaction is shown in fig. 12. There was little pressure change during the 10 minutes.
The solvent was distilled off to 130g of the above-mentioned 387g effluent by an evaporator, and then the resultant was dropped into a mixed solution of 401g of methanol and 101g of water at room temperature. The resulting white suspension was filtered through a 0.5 μm membrane filter and washed with 201g of methanol. The obtained white solid was dried under reduced pressure (50 ℃ C., 2.5 hours) to obtain PS-b-PtBuMA17.51g. As a result of GPC analysis, Mn was 10,053 and Mw/Mn was 1.09. Of the polymer obtained1H-NMR is shown schematically in FIG. 13.
Comparative example 1
As the mixer 1 and the mixer 2, a T-shaped mixer (manufactured by Sanxinghui Co., Ltd., stainless steel, inner diameter 0.25mm) was used, and each pump was connected so that the first monomer solution and the initiator solution collided at 180 ℃. A1.0 mol/L4-methoxystyrene/THF solution as a first monomer and a 0.11mol/L sec-butyllithium hexane solution as an initiator were mixed by a mixer 1 at flow rates of 5mL/min and 1mL/min, respectively, to polymerize the first monomer. Subsequently, a solution of 0.25mol/L methanol/THF as a polymerization terminator was mixed with a mixer 2 at 6.3mL/min to terminate the polymerization.
The pressure trend at 10 minutes of liquid feeding is shown in fig. 14. A rapid pressure change was observed about 5 minutes after the liquid feeding.
Comparative example 2
コメツト X-01 (made of stainless steel) manufactured by テクノアプリケ - シヨンズ was used as the mixer 1 and the mixer 2. The first monomer solution pipe is connected to the inlet side of the outer pipe portion of the mixer 1, the initiator solution pipe is connected to the inlet side of the inner pipe portion, the polymerization terminator solution pipe is connected to the inlet side of the outer pipe portion of the mixer 2, and the pipe 1 is connected to the inlet side of the inner pipe portion. A2.0 mol/L styrene/THF solution as a first monomer and a 0.1mol/L sec-butyllithium hexane solution as an initiator were mixed by a mixer 1 at flow rates of 5mL/min and 1mL/min, respectively, to polymerize the first monomer. Subsequently, a solution of 0.25mol/L methanol/THF as a polymerization terminator was mixed with a mixer 2 at 6.1mL/min to terminate the polymerization.
The pressure trend at 35 minutes of liquid feeding is shown in fig. 15. Several pressure fluctuations and pressure rises over time were observed.
As described above, according to the method for producing a polymer of the present invention, since the flow path of the flow reactor is less likely to be closed, no pressure fluctuation is observed, and a polymer can be stably produced for a long time.
Description of reference numerals
1 double-liquid mixer
2 joint member
21 main body
211 is inserted into the hole
212 lead-in hole
213 connecting hole
22 inner pipe
Inner side of 221 inner tube
222 inner pipe outer wall
223 inner tube top end
24 space
25 double pipe
3 static mixer component
31 cylindrical body
32 unit body
321 right torsion blade
322 left-hand twisting blade
4 flow reactor
Claims (16)
1. A method for producing a block polymer, the method comprising: a step of synthesizing a polymer by anionic-polymerizing a styrene monomer as a first monomer in the presence of an initiator using a flow reactor including a mixer for two-liquid mixing including a flow path capable of mixing a plurality of liquids; and a step of polymerizing an acrylic monomer as a second monomer with the polymer block to synthesize a block polymer,
the flow reactor is provided with: a mixer for two-liquid mixing, comprising a joint member or a static mixer member having a double pipe inside.
2. The method for producing a block polymer according to claim 1, comprising: a step of reacting a non-separately polymerizable monomer after synthesizing a polymer by anion polymerization of a first monomer and before polymerizing a second monomer block.
3. The method for producing a block polymer according to claim 1 or 2, wherein the non-separately polymerizable monomer is 1, 1-diphenylethylene or a derivative thereof.
4. The method for producing a block polymer according to any one of claims 1 to 3, wherein the static mixer member comprises a cylindrical body and a unit body inserted therein.
5. The method for producing a block polymer according to any one of claims 1 to 4, wherein the mixer for two-liquid mixing comprises a static mixer member and a joint member having a double pipe inside.
6. The method for producing a block polymer according to claim 5, wherein the mixer for two-liquid mixing comprises a joint member having a double pipe inside and a static mixer member,
the static mixer member includes a cylindrical body and a unit body inserted therein,
the joint member is connected to the static mixer member so that the end surface of the cylindrical body on the double pipe side abuts against the end surface of the double pipe on the static mixer member side.
7. The method for producing a block polymer according to claim 6, wherein an end portion on the static mixer member side of the double pipe is located inside the joint member.
8. The method for producing a block polymer according to any one of claims 5 to 7, wherein the joint member has an insertion hole into which an inner tube through which an initiator solution flows is inserted, and the double tube is formed by a space formed by an inner side of the inner tube and an outer wall of the inner tube and an inner wall of the insertion hole, at least in the vicinity of a tip of the inner tube in a state where the inner tube is inserted.
9. The method for producing a block polymer according to claim 8, wherein the joint member has an introduction hole for introducing a monomer solution, and the introduction hole is joined to the insertion hole.
10. The method for producing a block polymer according to claim 9, wherein the insertion hole is formed so as to have a diameter substantially equal to an outer diameter of the inner tube in the vicinity of a connection portion with the introduction hole, and is formed so as to have a diameter larger than the outer diameter of the inner tube from the connection portion to a tip end of the inner tube.
11. The method for producing a block polymer according to any one of claims 8 to 10, wherein the joint member has a hole for connecting a static mixer member, and the insertion hole is connected to the hole for connecting.
12. The method for producing a block polymer according to any one of claims 4 to 11, wherein the unit cell is inserted into the tubular body so that one end thereof is substantially flush with an end surface of the tubular body on the double tube side.
13. The method for producing a block polymer according to any one of claims 4 to 12, wherein the unit cell has a shape in which a plurality of right twisted blades and left twisted blades are alternately connected in a twisting axis direction.
14. The method for producing a block polymer according to any one of claims 1 to 13, wherein the initiator is a mono-organolithium compound.
15. The method for producing a block polymer according to any one of claims 1 to 14, wherein the styrene monomer is a compound represented by the following formula (1):
[ solution 1]
In the formula, R1Is a hydrogen atom or a methyl group, R2～R6Each independently a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, -OSiR7 3or-SiR7 3，R7Each independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms or an alkylsilyl group having 1 to 5 carbon atoms.
16. The method for producing a block polymer according to any one of claims 1 to 15, wherein the acrylic monomer is a compound represented by the following formula (2):
[ solution 2]
In the formula, R11Is a hydrogen atom or a methyl group, R12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
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| JP2004332247A (en) * | 2003-04-30 | 2004-11-25 | Japan Found Eng Co Ltd | Chemical grouting method for reinforcing natural ground and its rock drill |
| CN101001884A (en) * | 2004-08-13 | 2007-07-18 | 可乐丽股份有限公司 | Process for continuously producing (meth)acrylic ester polymer or copolymer |
| CN101928371A (en) * | 2003-05-30 | 2010-12-29 | 日本曹达株式会社 | The manufacture method of polymkeric substance |
| JP2014193947A (en) * | 2013-03-28 | 2014-10-09 | Nippon Zeon Co Ltd | Coating liquid production apparatus |
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| US20170022300A1 (en) * | 2013-12-20 | 2017-01-26 | Horiba Stec, Co., Ltd. | Continuous reaction apparatus and method of continuous polymerization using the same |
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| US11059912B2 (en) * | 2016-02-04 | 2021-07-13 | Nissan Chemical Corporation | Polymer production method |
| JP6668792B2 (en) * | 2016-02-04 | 2020-03-18 | 日産化学株式会社 | Mixer for mixing two liquids |
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| JP2004332247A (en) * | 2003-04-30 | 2004-11-25 | Japan Found Eng Co Ltd | Chemical grouting method for reinforcing natural ground and its rock drill |
| CN101928371A (en) * | 2003-05-30 | 2010-12-29 | 日本曹达株式会社 | The manufacture method of polymkeric substance |
| CN101001884A (en) * | 2004-08-13 | 2007-07-18 | 可乐丽股份有限公司 | Process for continuously producing (meth)acrylic ester polymer or copolymer |
| JP2014193947A (en) * | 2013-03-28 | 2014-10-09 | Nippon Zeon Co Ltd | Coating liquid production apparatus |
| JP2015120642A (en) * | 2013-12-20 | 2015-07-02 | 株式会社堀場エステック | Continuous reaction apparatus, and continuous synthesis method using the same |
| US20170022300A1 (en) * | 2013-12-20 | 2017-01-26 | Horiba Stec, Co., Ltd. | Continuous reaction apparatus and method of continuous polymerization using the same |
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| JP7173013B2 (en) | 2022-11-16 |
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