CN117362556A - Method for producing block polymer - Google Patents
Method for producing block polymer Download PDFInfo
- Publication number
- CN117362556A CN117362556A CN202311467938.XA CN202311467938A CN117362556A CN 117362556 A CN117362556 A CN 117362556A CN 202311467938 A CN202311467938 A CN 202311467938A CN 117362556 A CN117362556 A CN 117362556A
- Authority
- CN
- China
- Prior art keywords
- monomer
- block polymer
- producing
- mixer
- inner tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 80
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 238000002156 mixing Methods 0.000 claims abstract description 63
- 230000003068 static effect Effects 0.000 claims abstract description 47
- 239000003999 initiator Substances 0.000 claims abstract description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003780 insertion Methods 0.000 claims description 56
- 230000037431 insertion Effects 0.000 claims description 56
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 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
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 claims description 3
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 abstract description 5
- -1 Polytetrafluoroethylene Polymers 0.000 description 184
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 43
- 239000000243 solution Substances 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 28
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-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
- 230000000694 effects Effects 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 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
- 239000012530 fluid Substances 0.000 description 7
- 239000002904 solvent Substances 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
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 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
- 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
- 230000000903 blocking effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 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
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 4
- 238000010539 anionic addition polymerization reaction 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
- 150000002739 metals Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 125000006433 1-ethyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229930182556 Polyacetal Natural products 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
- 238000010586 diagram Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 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
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- 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
- 150000002900 organolithium compounds Chemical class 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
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 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
- 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 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
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 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
- 238000004140 cleaning Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011109 contamination 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([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
- 238000009826 distribution Methods 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 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
- 239000002798 polar solvent Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 230000001629 suppression Effects 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
- 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
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- PYWOMDDOXZOOJZ-UHFFFAOYSA-N [Li]C1=CC=C([Li])C=C1 Chemical compound [Li]C1=CC=C([Li])C=C1 PYWOMDDOXZOOJZ-UHFFFAOYSA-N 0.000 description 1
- LXXUYORAHKLDLS-UHFFFAOYSA-N [Li]C1CCC([Li])C(CC)C1 Chemical compound [Li]C1CCC([Li])C(CC)C1 LXXUYORAHKLDLS-UHFFFAOYSA-N 0.000 description 1
- QWFRFVPEFDDMQD-UHFFFAOYSA-N [Li]CCCCCCCCCC[Li] Chemical compound [Li]CCCCCCCCCC[Li] QWFRFVPEFDDMQD-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
- KWOQMYVNZIAJTI-UHFFFAOYSA-N [Li]c1c(CC)c([Li])c(CC)c([Li])c1CC Chemical compound [Li]c1c(CC)c([Li])c(CC)c([Li])c1CC KWOQMYVNZIAJTI-UHFFFAOYSA-N 0.000 description 1
- ARCHVGRSBFXDTP-UHFFFAOYSA-N [Li]c1cc([Li])cc([Li])c1 Chemical compound [Li]c1cc([Li])cc([Li])c1 ARCHVGRSBFXDTP-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
- 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
- 238000011088 calibration curve Methods 0.000 description 1
- 230000015556 catabolic process Effects 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
- 229920001577 copolymer Polymers 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ZEFNMRMJJKIGBT-UHFFFAOYSA-N dilithium;pentane Chemical compound [Li+].[Li+].[CH2-]CCC[CH2-] ZEFNMRMJJKIGBT-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 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
- 238000005194 fractionation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011630 iodine Substances 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-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
- IMRCWTBBTYVQHZ-UHFFFAOYSA-N lithium;4h-pyridin-4-ide Chemical compound [Li+].C1=CN=CC=[C-]1 IMRCWTBBTYVQHZ-UHFFFAOYSA-N 0.000 description 1
- ORTGOOBLGHYKOV-UHFFFAOYSA-N lithium;hex-1-yne Chemical compound [Li+].CCCCC#[C-] ORTGOOBLGHYKOV-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
- WTTUTKBXMMXKBQ-UHFFFAOYSA-N lithium;stilbene Chemical compound C=1C=CC=CC=1C([Li])C([Li])C1=CC=CC=C1 WTTUTKBXMMXKBQ-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
- 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
- 239000013307 optical fiber Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 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
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013558 reference substance Substances 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
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000725 suspension Substances 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention provides a method for producing a block polymer, comprising: a step of anionically polymerizing a styrene monomer as a first monomer in the presence of an initiator to synthesize a polymer, and a step of block polymerizing an acrylic monomer as a second monomer with the polymer to synthesize a block polymer, using a flow reactor comprising a two-liquid mixing mixer having a flow path capable of mixing a plurality of liquids; the flow reactor includes a dual liquid mixing mixer including a joint member or a static mixer member having a dual pipe inside.
Description
The present application is a divisional application of patent application having application date of 2018, 08 and 06, application number of 201880051098.X, and the name of the patent application "method for producing a block polymer".
Technical Field
The present invention relates to a method for producing a block polymer.
Background
In recent years, attention has been paid to flow chemical synthesis in which chemical synthesis is continuously performed while a solution is caused to flow, using a reaction apparatus called a flow reactor or a microreactor. Compared with the batch mode implemented in the prior art, the flow chemical synthesis has the following advantages: since the reaction is performed using a small reaction vessel, precise temperature control can be achieved and mixing efficiency is also good.
In the two-liquid mixing type flow synthesis, there are often problems that insoluble substances precipitate in the mixing section (mixer), the flow path is blocked, pressure fluctuation occurs, continuous operation is not possible for a long period of time, and the quality of the obtained composition is unstable. In particular, this problem is remarkable in a reaction system using an organolithium reagent such as an anionic polymerization of a polymer, and it is not easy to achieve both stable continuous operation for a long period of time and efficient mixing.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2009-067999
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a method for stably producing a block polymer for a long period of time.
Means for solving the problems
The present inventors have intensively studied to achieve the above object, and as a result, found that: in the production of a block polymer comprising a polymer block derived from a styrene monomer and a polymer block derived from an acrylic monomer, the present invention has been completed by using a predetermined flow reactor, whereby a block polymer can be stably produced for a long period of time.
Accordingly, the present invention provides a method for producing the following block polymer.
1. A method for producing a block polymer, which comprises: a step of synthesizing a polymer by anionically polymerizing a styrene monomer as a first monomer in the presence of an initiator using a flow reactor including a two-liquid mixing mixer having 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 to synthesize a block polymer,
the flow reactor includes a dual liquid mixing mixer including a joint member or a static mixer member having a dual pipe inside.
2.1, comprising: and a step of reacting the non-independently polymerizable monomer after anionically polymerizing the first monomer to synthesize the polymer and before the second monomer is polymerized.
3.1 or 2, wherein the non-independently polymerizable monomer is 1, 1-diphenylethylene or a derivative thereof.
The method for producing a block polymer according to any one of 4.1 to 3, wherein the static mixer member comprises a cylindrical body and a unit body inserted therein.
The method for producing a block polymer according to any one of 5.1 to 4, wherein the two-fluid mixing mixer comprises a joint member having a double pipe therein and a static mixer member.
The block polymer production method of 6.5, wherein the two-liquid mixing mixer comprises a joint member having a double pipe inside and a static mixer member comprising a cylindrical body and a unit body inserted into the interior thereof, and the joint member is connected to the static mixer member so that an end face of the cylindrical body on the double pipe side abuts against an end face of the double pipe on the static mixer member side.
7.6, wherein the end of the double tube on the static mixer member side is located inside the joint member.
The method for producing a block polymer according to any one of 8.5 to 7, wherein the joint member has an insertion hole for inserting an inner tube into which an initiator solution flows, and the double tube is formed by a space formed between the inner tube inner side and the outer wall of the inner tube and the inner wall of the insertion hole at least in the vicinity of the distal end of the inner tube in a state where the inner tube is inserted.
The method 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 that a diameter of the insertion hole is substantially equal to an outer diameter of the inner tube in the vicinity of a connection portion with the insertion hole, and a diameter of the insertion hole is larger than the outer diameter of the inner tube from the connection portion to a distal end of the inner tube.
The method for producing a block polymer according to any one of 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.
The method for producing a block polymer according to any one of 12.4 to 11, wherein the unit body is inserted into the tubular body so that one end thereof is substantially on the same horizontal plane as the end face of the tubular body on the double pipe side.
The method for producing a block polymer according to any one of claims 4 to 12, wherein the unit body has a shape in which a plurality of right torsion blades and left torsion blades are alternately connected in the torsion axis direction.
The method for producing a block polymer according to any one of claims 1 to 13, wherein the initiator is a mono-organolithium compound.
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).
[ chemical 1]
(wherein R is 1 Is a hydrogen atom or methyl group, R 2 ~R 6 Each independently represents a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or a halogen atomAtomic substituted alkyl group with 1-10 carbon atoms, -OSiR 7 3 or-SiR 7 3 ,R 7 Each 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 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).
[ chemical 2]
(wherein R is 11 Is a hydrogen atom or methyl group, R 12 Each 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
The mixer for mixing two liquids used in the above-mentioned flow reactor is not easy to be blocked and has good mixing efficiency, so according to the method for producing a polymer of the present invention using the same, a polymer can be stably produced for a long period of time. In particular, the block polymer obtained by the production method of the present invention has a small dispersity (Mw/Mn) (a narrow molecular weight distribution) and a highly controlled structure, and can be suitably used for the production of high-functional elastomers or the like by using a semiconductor lithography technique for inducing self-organization and other nanopatterning techniques.
Drawings
Fig. 1 is an oblique view of the mode of the mixer for mixing two liquids used in the present invention.
Fig. 2 is an exploded perspective view of the dual liquid mixing mixer of fig. 1.
Fig. 3 is a cross-sectional view of the body along line III-III of fig. 2.
Fig. 4 is a cross-sectional view taken along line IV-IV of fig. 1.
Fig. 5 is an enlarged cross-sectional view of the double tube 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 of the unit body of the static mixer member as seen from the direction orthogonal to the torsion axis direction thereof.
Fig. 8 is an oblique view showing the mode of the mixer for mixing two liquids used in the present invention.
FIG. 9 is a schematic view showing the configuration 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 diagram showing the structure of a flow reactor used in the comparative example.
FIG. 12 is a graph showing the trend of pressure in the reaction in example 1.
FIG. 13 shows the polymer obtained in example 1 1 H-NMR chart.
Fig. 14 is a graph showing the trend of the pressure in the reaction in comparative example 1.
Fig. 15 is a graph showing the trend of the pressure 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 anionically polymerizing a styrene monomer as a first monomer in the presence of an initiator using a flow reactor comprising a two-liquid mixing mixer having a flow path capable of mixing a plurality of liquids; and a step of polymerizing the acrylic monomer as the 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 double-liquid mixing mixer having a double pipe therein, and preferably has the following configuration. That is, the above-mentioned two-fluid mixing mixer preferably includes a joint member or a static mixer member having a double pipe inside. The double-liquid mixing mixer further preferably includes both a joint member having a double pipe therein and a static mixer member, and the static mixer member preferably 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 face of the cylindrical body on the double pipe side is brought into contact with an end face of the double pipe on the static mixer member side.
By connecting the joint member and the static mixer member in this way so that the end face of the tubular body on the double pipe side is brought into contact with the end face of the double pipe on the static mixer member side, the above-mentioned double-liquid mixing mixer is maintained in mixing efficiency, and is less likely to be blocked, and stable continuous operation can be performed for a long period of time.
That is, the above-described mixer is configured such that the double pipe and (the tubular body of) the static mixer are connected inside the joint, and thus, the end surfaces can be more reliably brought into contact with each other than in the conventional microreactor structure, and as a result, the two liquids flowing out from the double pipe flow into the static mixer at substantially the same time as the two liquids flow out, so that more reliable mixing of the two liquids is performed at the start of the reaction.
In the above-described two-fluid mixing mixer, it is preferable that an end portion of the double pipe on the static mixer member side is located inside the joint member. By adopting 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 between the joint member and the static mixer member can be easily confirmed.
In the above-described two-fluid mixing mixer, it is preferable that the joint member has an insertion hole for inserting an inner tube through which the first fluid flows, and the double tube is formed by a space formed between an outer wall of the inner tube and an inner wall of the insertion hole and an inner side 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. By adopting 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 mold 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 of being inserted into an insertion hole formed in the joint member, or may be detachably fixed from the joint member body, preferably, may be detachably fixed from the joint member body, as long as the inner tube can be kept liquid-tight. By forming the structure capable of detaching the inner tube in this way, the following advantages are achieved: the cleaning of the double tube portion after use is facilitated and replacement is possible in case of breakage or occlusion of the inner tube and contamination.
The fixing and fixing means of the inner tube is not particularly limited as long as it can be kept liquid-tight as described above, and includes fixing by an adhesive, fixing by welding, and the like, detachable fixing means by screw fastening and the like, and the detachable fixing means by screw fastening and the like is preferably 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 in the joint member main body, and as a result, the length of the double pipe can be shortened, and thus the joint member can be easily manufactured. The introduction hole can be formed by a cutting process using a die, similarly to the insertion hole.
The position of forming the introduction hole in the joint member is not particularly limited, and is preferably formed in a direction perpendicular to the insertion hole, and if the length of the double tube is to be shortened, it is preferably formed at the following position: the insertion hole can be connected to a position closer to the terminal portion than to the base end portion and the central portion of the terminal portion of the insertion hole.
Further, the insertion hole is preferably formed so that a diameter of the insertion hole is substantially equal to an outer diameter of the inner tube in the vicinity of a connection portion with the insertion hole, and so that a diameter of the insertion hole is larger than the outer diameter of the inner tube from the connection portion to a distal end of the inner tube. By forming the hole structures having such different diameters, almost no gap is formed between the inner tube and the insertion hole at the connecting portion, and thus leakage of the second liquid flowing in from the introduction hole to the base end portion side of the insertion hole can be prevented, and the two liquids can be efficiently mixed.
Preferably, the joint member has a static mixer member connection hole, and the insertion hole is connected to the connection hole. With such a configuration, the joint member and the static mixer member can be individually designed, and thus the internal structure of the mixer for mixing two liquids can be easily adjusted. The connecting hole can be formed by a cutting process using a die, similarly to the 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, or may be detachably fixed to the joint member body, preferably to the joint member body, as long as the static mixer member can be kept liquid-tight, as in the inner tube described above. By making it detachable, the position adjustment of the unit body inside the static mixer member and the cleaning of the mixer after use become easy, and replacement of each part becomes possible in the case of contamination, degradation, and the like. The fixing and fixing means of the static mixer member may be the same as those described above for the inner tube, and in this case, a detachable fixing means using screw fastening or the like is preferably used.
Further, it is preferable that the unit body is inserted into the cylindrical body so that one end thereof is substantially on the same horizontal plane as the end face of the cylindrical body on the double pipe side. In this way, by the end face of the cylindrical body being substantially coincident with the end of the unit body, the two liquids flowing out of the double pipe flow into the unit body 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, miscibility, and the like of the biliquid passing through the inside thereof.
The structure of the unit is not particularly limited, and a unit having a shape in which a plurality of right-turn blades and left-turn blades are alternately connected in the longitudinal direction (torsion axis direction), a unit having a spiral shape in which the torsion direction is constant, a unit having a shape in which a plurality of holes having 1 or 2 or more holes are laminated, or the like is preferably used, and a unit having a shape in which a plurality of right-turn blades and left-turn blades are alternately connected in the torsion axis direction is suitable. By using the unit body having such a shape, it is possible to more efficiently perform mixing, and clogging of the mixer at the time of reaction becomes more difficult to occur.
The unit body may be a detachable structure simply inserted into the cylindrical body, or may be a non-detachable structure fixed to the cylindrical body after insertion, but is preferably a detachable structure simply inserted. By the detachable structure, the position inside the cylindrical body of the unit body can be adjusted and the unit body can be replaced easily.
The diameter of the unit body is not particularly limited as long as the unit body can be inserted into the cylindrical body, and the diameter (maximum diameter) is preferably substantially the same as the inner diameter of the cylindrical body. By so doing, even in the case where only the unit body is inserted into the inside of the cylindrical body, the position of the unit body can be prevented from varying in the longitudinal direction and the lateral direction inside the cylindrical body. Further, in consideration of the use of the above-mentioned mixer for mixing two liquids, the diameter of the unit body is preferably about 1 to 10mm, more preferably about 1.6 to 8mm, and even more preferably about 2 to 5 mm.
The length of the unit body is not particularly limited as long as the unit body can be inserted into the cylindrical body, and is preferably set to be substantially the same as the length of the cylindrical body. By doing so, the alignment of the unit body end portion and the end face of the tubular body on the double pipe side 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 than two of the above-described mixers for mixing two liquids. In the case of including two or more of the above-described mixers for mixing two liquids, multistage flow synthesis is possible. Since the above-mentioned two-liquid mixing mixer is not easily blocked, the pressure loss in the case of flow synthesis using a flow reactor is small, and stable continuous operation for a long period of time is possible, and the mixer is suitable for mass synthesis.
The flow reactor used in the present invention may include, in addition to the above-described mixer for mixing two liquids, various other components necessary for the reaction such as a pump for feeding the liquid, a pipe for forming a flow path, a temperature adjusting device for adjusting the temperature, and the like, as required.
The liquid feeding pump is not particularly limited, and commonly used pumps such as a plunger pump, a syringe pump, and a rotary pump can be used.
The material of the pipe for forming the flow path is not particularly limited, and may be a metal such as stainless steel, titanium, iron, copper, nickel, aluminum, etc., a resin such as Polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), perfluoroalkoxy Fluorine (PFA), polyether ether ketone (PEEK), polypropylene (PP), etc.
The inner diameter of the pipe for forming the flow path can be set appropriately according to the purpose within a range that does not impair the effect of the present invention, and is usually about 0.5 to 10mm, more preferably about 0.7 to 4mm, and still more preferably about 1 to 2 mm. The length of the pipe for forming the flow path may be set appropriately according to the purpose within a range that does not impair the effect of the present invention, and is usually about 0.1 to 20m, more preferably about 0.2 to 10m, and still more preferably about 0.3 to 5 m.
The mixer and the flow reactor for two-liquid mixing used in the present invention will be specifically described below based on the drawings. As shown in fig. 1, the two-liquid mixing mixer 1 includes a joint member 2 and a static mixer member 3. The joint member 2 includes a main body 21 made of stainless steel, and an inner tube 22 (outer diameter 1.6mm, inner diameter 1.0 mm) made of stainless steel through which the first liquid flows.
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 orthogonal thereto and connected to the insertion hole 211 in the main body 21 for introducing the second liquid; and a static mixer member connection hole 213. Nut portions 211a, 212a, 213a corresponding to bolt portions formed in connectors described later are formed in the inner walls of the insertion hole 211, the introduction hole 212, and the connection hole 213, so that the inner tube 22, the introduction tube through which the second liquid flows, and the static mixer member 3 can be fastened to the main body 21 by screws.
The insertion hole 211 is formed from the base end portion side to the terminal end portion side by a nut portion 211a, a liquid-tight portion 211b having a trapezoidal cross section formed continuously thereto and having a reduced diameter according to the shape of the connector tip portion described later, and an inner tube passing portion 211c formed continuously thereto. As shown in fig. 5, the inner diameter b of the inner tube passing portion 211c of the insertion hole 211 is formed so as to have a diameter substantially equal to the outer diameter a of the inner tube 22 in the vicinity of the connection portion 214 of the introduction hole 212, and the inner diameter c of the inner tube passing portion 211c from the connection portion 214 to the connection hole 213 is formed so as to be larger than the outer diameter a of the inner tube 22. In this way, the connection portion 214 has a structure in which almost no space is formed between the inner tube 22 and the insertion hole 211, so that the second liquid flowing in from the introduction hole 212 is prevented from leaking out to the base end portion side of the insertion hole 211, and the double tube 25 is constructed by the inner tube inner side 221 and the space 24 formed by the inner tube outer wall 222 and the inner wall 211d of the insertion hole as shown in fig. 6.
As shown in fig. 3, the insertion hole 211 is connected to the connection hole 213 at the base end portion thereof, 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 hole (not shown) that forms the inside of the inner tube 22, and the connector 23 is provided with a substantially hexagonal prism-shaped head 232 for screw fixation, a bolt 231 integrally formed therewith, and an inverted truncated cone-shaped sealing portion 233 for retaining the liquid-tightness of the inside of the joint main body 21, and in this state, is inserted into the insertion hole 211 having the nut 211a, and is fastened and fixed to the main body 21 by screw fixation.
As shown in fig. 3, the introduction hole 212 is formed from the base end portion side to the terminal end portion side by a nut portion 212a, a liquid-tight portion 212b having a rectangular cross-section and formed continuously thereto and conforming to the shape of the tip end portion of a connector to be described later, and a connecting portion 212c extending therefrom to the connecting portion 214 of the insertion hole 211. The insertion hole 211 and the introduction hole 212 are connected to each other on the terminal side with respect to the center of the base end portion and the terminal portion of the insertion hole 211.
As shown in fig. 3, the static mixer connection hole 213 is formed from the base end portion side to the terminal end portion side by a nut portion 213a and a liquid-tight portion 213b having a rectangular cross section and conforming to the shape of the connector tip portion described later, which is formed continuously thereto.
As shown in fig. 1 and 2, the static mixer member 3 includes a cylindrical tubular body 31 (inner diameter 3.0 mm) made of fluororesin or stainless steel and a polyacetal unit body 32 (diameter 3 mm) inserted therein. As shown in fig. 2 and 4, the unit body 32 is inserted into the cylindrical body 31 in a state that the base end thereof is on the same horizontal plane as the end surface of the cylindrical body 31 on the double pipe 25 side. As shown in fig. 7, the unit body 32 has a shape in which right torsion blades 321 and left torsion blades 322 are alternately connected in a plurality in the torsion axis (central axis in the longitudinal direction) 323 direction.
As shown in fig. 2, a fluororesin-made connector 33 having a bolt 331 is attached to an upper end portion of the tubular body 31 in the drawing, and in this state, the above-mentioned connection hole 213 having a nut 213a is inserted and fastened by a screw, thereby fixing the connector to the main body 21.
Next, the internal structure of the two-fluid 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 passing portion 211c near the connection portion 214 of the introduction hole 212 is made substantially equal to the outer diameter a of the inner tube 22. In addition, an inner diameter c of the inner tube passing portion 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 an outer diameter a of the inner tube 22. Thus, the double pipe 25 is formed by the inner side 221 of the inner pipe 22 and the space 24 constituted by the outer wall 222 of the inner pipe 22 and the inner wall 211d of the insertion hole 211.
In the present embodiment, since the end face of the tubular body 31 of the static mixer member 3 on the double pipe 25 side is in contact with the end face of the double pipe 25 on the static mixer member 3 side, and the base end of the unit body 32 and the end face of the tubular body 31 on the double pipe 25 side are on the same level as described above, the end face of the double pipe 25 on the static mixer member 3 side is also in contact with the base end (upper end in fig. 4) of the unit body 32.
In this case, as shown in fig. 8, the second liquid is introduced from the introduction hole 212, and in the introduction pipe 26 through which the second liquid flows, a connector 27 having a hole (not shown) for forming the introduction pipe 26 to be introduced into the interior thereof and a sealing portion (not shown) and a bolt portion 271 for keeping the interior of the joint main body 21 liquid-tight is used, and is fixedly connected to the introduction hole 212 by screw fastening.
Next, an embodiment of a flow reactor using the double-liquid mixing mixer having the above-described configuration will be described with reference to fig. 9.
The flow reactor 4 is configured by connecting a first double-liquid mixing mixer 1a and a second double-liquid mixing mixer 1b disposed inside a constant temperature layer 43 in series by using a PTFE tube 42d (inner diameter 1.5 mm).
The first liquid-feeding pump 41a is connected to the inner tube 22a of the first two-liquid mixing mixer 1a via a PTFE tube 42a (inner diameter 1.0 mm). On the other hand, the second liquid feeding pump 41b is connected to an introduction hole provided in the main body 21a of the joint member of the two-liquid mixing mixer 1a via a second liquid flowing PTFE pipe 42b (inner diameter 1.0 mm) provided with a connector at the tip.
The third liquid feeding pump 41c is connected to the introduction hole of the double liquid mixing mixer 1b via a third liquid flowing PTFE pipe 42c (inner diameter 1.0 mm) provided with a connector at the tip end thereof, and the PTFE pipe 42e (inner diameter 1.5 mm) is connected to the terminal end portion of the static mixer member 3b of the double liquid mixing mixer 1b.
In the flow reactor 4 having such a configuration, the respective 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 inside thereof, flow into the static mixer member 3a abutted against the end of the double pipe, and mix and agitate the unit bodies inside thereof, and simultaneously the first reaction occurs. After passing through the pipe 42d, the first reaction liquid after the reaction flows into the joint member main body 21b through the inner pipe 22b of the second double-liquid mixing mixer 1b. 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 flowing into the inside of the joint member main body 21b, and flows into the inside of the static mixer member 3b as in the case of the first two-liquid mixing mixer 1a, so that the second reaction proceeds.
The mixer and the flow reactor for mixing two liquids used in the present invention are not limited to the above embodiments, and may be modified and improved within a range that can achieve the objects and effects of the present invention.
That is, in the above-described two-fluid mixing mixer 1, the inner pipe 22 and the static mixer member 3 are detachably screwed to each other from the joint member main body 21, but they may be detachably constituted by other fixing means, and may be connected and fixed in a non-detachable state.
The separate connectors 23 and 33 are provided in the inner tube 22 and the tubular body 31, and a suitable fixing means may be formed in the inner tube and the tubular body itself without providing them.
Further, the introduction hole 212 is formed in the joint member main body 21 so as to be connected to the insertion hole 211 in an orthogonal manner, but may be connected to the insertion hole at another angle, and the position of the introduction hole 212 may be set at any place.
The material of the main body 21, the inner tube 22 and the connector 23 is stainless steel, but the material is not limited thereto, and may be other metals such as titanium, iron, copper, nickel, aluminum, or resins such as PTFE, FEP, PFA, PEEK, PP.
The inner diameter of the inner tube 22 may be appropriately set according to the purpose within a range that does not impair the effect of the present invention, and is usually 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 that does not impair the effect of the present invention, and is usually 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 is set appropriately according to the purpose within a range that does not impair the effect of the present invention, and is usually 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, resins such as PTFE, FEP, PFA, PEEK, PP, and the like.
The material of the unit body 32 is not limited to polyacetal, and may be other resins such as PTFE, FEP, PFA, PEEK, PP, metals such as stainless steel, titanium, iron, copper, nickel, aluminum, ceramics, or the like.
The unit body 32 may have a spiral shape with a constant twisting direction, a plate formed by stacking a plurality of holes having 1 or 2 or more holes, or the like.
The material of the connector 33 is not limited to the fluorine resin, and may be other resins such as PEEK and PP, metals such as stainless steel, titanium, iron, copper, nickel, and aluminum.
The inner diameter of the tubular body 31 may be set appropriately according to the purpose within a range that does not impair the effect of the present invention, and is usually about 1 to 10mm, more preferably about 1.6 to 8mm, and still more preferably about 2 to 5 mm. The diameter of the unit body 32 may be appropriately set according to the purpose within a range that does not impair the effect of the present invention, and is usually about 1 to 10mm, more preferably about 1.6 to 8mm, and still more preferably about 2 to 5 mm.
Since the flow reactor 4 includes 2 mixers for two-liquid mixing, two-stage flow synthesis can be performed, and in the case of performing one-stage flow synthesis, 1 mixer for two-liquid mixing may be used, and in the case of performing n-stage flow synthesis, n mixers for two-liquid mixing may be used, and the flow reactor may be assembled as described above.
The inner diameters of the tubes 42a to 42e constituting the flow reactor 4 may be set appropriately according to the purpose within a range that does not impair the effect of the present invention, and are usually about 0.5 to 10mm, more preferably about 0.7 to 4mm, and still more preferably about 1 to 2 mm. The length thereof may be set appropriately according to the purpose within a range that does not impair the effect of the present invention, and is usually 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.
[ chemical 3]
Wherein R is 1 Represents a hydrogen atom or a methyl group. R is R 2 ~R 6 Each 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, -OSiR 7 3 or-SiR 7 3 。R 7 Each 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 straight-chain, branched or cyclic, 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-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-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1, 2-trimethyl-n-propyl, 1, 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-dimethylcyclobutyl, 2, 3-dimethylcyclobutyl, 2, 4-dimethylcyclobutyl, 3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1, 2-trimethylcyclopropyl, 1,2, 3-trimethylcyclopropyl, 2, 3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 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 still more preferable.
Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropyloxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclobutoxy, 1-methylcyclopropoxy, 2-methylcyclopropoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1-dimethyl-n-propoxy, 1, 2-dimethyl-n-propoxy, 2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, 1-diethyl-n-propoxy, cyclopentyloxy, 1-methylcyclobutoxy, 2-methylcyclobutoxy, 3-methylcyclobutoxy, 1, 2-dimethylcyclopropoxy, 2, 3-dimethylcyclopropoxy, 1-ethylcyclopropoxy and 2-ethylcyclopropoxy. The structure of the alkoxy group is preferably linear or branched. Among these, an alkoxy group having 1 to 3 carbon atoms is 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 R 4 Preferably an alkoxy group having 1 to 5 carbon atoms or-SiR 7 3 More preferably methoxy or-Si (CH) 3 ) 3 . In addition, as R 2 、R 3 、R 5 And R is 6 Preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or-SiR 7 3 More 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-t-butylstyrene, 4-dimethylsilylstyrene, 4-trimethylsilyl styrene, 4-trimethylsiloxystyrene, 4-dimethyl (t-butyl) silylhydrostyrene, 4-dimethyl (t-butyl) siloxystyrene, 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, 4-t-butylstyrene, 4-methoxystyrene, 4-trimethylsilylstyrene and the like are preferable as the styrene-based monomer because a monodisperse polymer is easily obtained even at relatively high temperatures.
[ second monomer ]
The second monomer, that is, the acrylic monomer, is not particularly limited as long as it is a compound having a (meth) acryloyl group, and preferably has a (meth) acryloyl group. As such a compound, a compound represented by the following formula (2) is particularly preferable.
[ chemical 4]
Wherein R is 11 Is a hydrogen atom or a methyl group. R is R 12 Each 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 straight-chain, branched or cyclic, 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-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-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-trimethylcyclopropyl, 1,2, 3-trimethylcyclopropyl, 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, 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-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, 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 those wherein part or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms such as fluorine, chlorine, bromine and iodine. As a specific example thereof, examples thereof include trifluoromethyl, 2-trifluoroethyl, 1, 2-pentafluoroethyl, and 3, 3-trifluoropropyl group, 2, 3-pentafluoropropyl group 3, 3-trifluoropropyl group 2, 3-pentafluoropropyl.
Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl and the like.
Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl, 2-phenylethyl, and anthrylmethyl.
Of these, R is 12 The 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.
As the above (meth) acrylic compound, examples thereof 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, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, and mixtures thereof n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, 16-methyl-n-heptadecyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracene (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate anthrylmethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-trifluoroethyl (meth) acrylate, 2-trichloroethyl (meth) acrylate, 2,3, 4-heptafluorobutyl (meth) acrylate, methoxy diglycol (meth) acrylate, methoxy polyethylene 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, 2-ethyl-2-adamantyl (meth) acrylate, 2-propyl-2-adamantyl (meth) acrylate, 2-methoxybutyl-2-adamantyl (meth) acrylate, 8-methyl-8-tricyclodecyl (meth) acrylate, 8-ethyl-8-tricyclodecyl (meth) acrylate, 5-methacryloyloxy-6-hydroxy norbornene-2-carboxylic acid-6-lactone and the like.
Among these, t-butyl (meth) acrylate and isopropyl (meth) acrylate are preferable as the acrylic monomer because a monodisperse polymer is easily obtained even at 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 organolithium compounds.
Examples of the organolithium compound include monoorganolithium compounds such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, pentyyllithium, hexyllithium, methoxymethyllithium, ethoxymethyllithium, phenyllithium, naphthyllithium, benzyllithium, phenylethyllithium, α -methylstyrene-based lithium, 1-diphenylhexyllithium, 1-diphenyl-3-methylpentyllithium, 3-methyl-1, 1-diphenylpentyyllithium, vinyllithium, allyllithium, propenyl lithium, butenyllithium, ethynyllithium, butynyllithium, pentynyllithium, hexynyllithium, 2-thienyl lithium, 4-pyridyllithium, and 2-quinolinyllithium; polyfunctional organolithium compounds such as 1, 4-dilithiobutane, 1, 5-dilithiopentane, 1, 6-dilithiohexane, 1, 10-dilithiodecane, 1-dilithiobiphenyl, dilithiopolybutadiene, dilithiopolyisoprene, 1, 4-dilithiobenzene, 1, 2-dilithio1, 2-diphenylethane, 1, 4-dilithio2-ethylcyclohexane, 1,3, 5-trilithiobenzene, and 1,3, 5-trilithio2, 4, 6-triethylbenzene. Among these, preferred are mono-organolithium compounds such as n-butyllithium, sec-butyllithium and tert-butyllithium.
[ method for producing Block Polymer ]
By using a flow reactor having 2 or more mixers for mixing two liquids as in the flow reactor 4 described above, a block polymer having 2 or more monomer units can be synthesized.
The method for producing a block polymer according to the present invention will be described below by taking the synthesis of a diblock polymer as an example. First, a first monomer solution containing the above-mentioned monomer is introduced into a flow reactor from an introduction hole of a first mixer, and a solution containing the above-mentioned initiator is introduced into the flow reactor from an inner pipe of the first mixer, and the solution is anionically polymerized 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 blocking of the flow reactor is less likely to occur, and the pressure loss is suppressed, so that the polymer can be stably produced for a long period of time.
After the synthesis of the homopolymer formed from the first monomer, in order to adjust the reactivity thereof, a non-independently polymerizable monomer such as 1, 1-Diphenylethylene (DPE) or a derivative thereof may be reacted to modify the terminal of the polymer. Here, the term "non-solely polymerizable monomer" refers to a monomer that does not cause anionic polymerization if it is only the monomer.
DPE is introduced into the flow reactor from the introduction hole of the second mixer. In this case, DPE may be introduced directly into the flow reactor or may be introduced into the flow reactor after diluted with an appropriate solvent. Examples of the solvent used for dilution include ether solvents such as Tetrahydrofuran (THF), 2-methyl THF, diethyl ether, tetrahydropyran (THP), cyclohexane, 1, 4-dioxane, toluene, methylene chloride, and diethoxyethane. The concentration of DPE is preferably 0.1 to 5.7mol/L.
After the non-polymerizable monomer such as DPE is reacted, the second monomer solution is introduced into the flow reactor from the introduction hole of the third mixer to synthesize a block polymer.
The solvent in which the first monomer and the second monomer are dissolved is not particularly limited, but an ether-based solvent such as THF, 2-methyl THF, diethyl ether, THP, cyclohexane, 1, 4-dioxane, toluene, methylene chloride, diethoxyethane, or the like is preferable.
The concentration of the first monomer is not particularly limited and may be appropriately set according to the purpose, but is preferably 0.1 to 5mol/L, more preferably 0.1 to 3mol/L, and particularly preferably 0.1 to 2mol/L. The concentration of the second monomer is not particularly limited, and may be appropriately set according to the purpose, and is preferably 0.1 to 9.4mol/L, more preferably 1.0 to 9.4mol/L, and particularly preferably 2.0 to 9.4mol/L. If the monomer concentration is in the above range, the blocking of the flow reactor is less likely to occur, 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, and is preferably 1 to 50 mL/min, more preferably 5 to 30 mL/min, and particularly preferably 10 to 30 mL/min. The flow rate of the second monomer is also not particularly limited, and may be appropriately set according to the purpose, and is preferably 0.1 to 50 mL/min, more preferably 0.1 to 30 mL/min, and particularly preferably 0.1 to 20 mL/min. If the flow rate of the monomer is in the above range, the blocking of the flow reactor is less likely to occur, the pressure loss is suppressed, and 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, and thus the reaction is usually carried out at a low temperature. Therefore, if sec-butyllithium is not used as an initiator, there is a disadvantage in that the initiation reaction is difficult to be consistent. On the other hand, if it 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 an initiator. The method 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 performed in a polar solvent at around room temperature.
The solvent in which the initiator is dissolved is not particularly limited, but is preferably an ether solvent such as hexane, THF, 2-methyl THF, diethyl ether, THP, cyclohexane, 1, 4-dioxane, toluene, methylene chloride, diethoxyethane, toluene, diethyl ether, or the like.
The concentration of the initiator is not particularly limited and may be appropriately set according to the type of monomer, but is preferably 0.01 to 0.5mol/L, more preferably 0.03 to 0.3mol/L, and particularly preferably 0.05 to 0.1mol/L. If the initiator concentration is in the above range, the blocking of the flow reactor is less likely to occur, 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, and is preferably 0.1 to 10 mL/min, more preferably 0.5 to 8 mL/min, and particularly preferably 1 to 6 mL/min. If the flow rate of the initiator is in the above range, the blocking of the flow reactor is less likely to occur, 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. In addition, the reaction temperature is preferably 100℃or lower, more preferably 50℃or lower, and still more preferably 30℃or lower, from the viewpoints of suppression of side reactions and suppression of deactivation of the 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 in which the flow reactor is provided with 3 or more mixers for mixing two liquids, and a reaction terminator such as methanol is introduced from the last mixer for mixing two liquids.
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 dispersity is preferably 1.5 or less, more preferably 1.3 or less, further preferably 1.2 or less, and still further preferably 1.15 or less. Mw and Mn represent weight average molecular weight and 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 ~ 100,000, more preferably 1,000 to 50,000.
Examples
The present invention will be specifically described below with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the 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. Plunger pump 1 (manufactured by TELEDONE ISCO., LTD. 1000D Syringe pump) was used for the first monomer solution feed, plunger pump 1 was connected to mixer 1 using PTFE tubing (inner diameter 1.0mm, outer diameter 1.6mm, length 2 m), syringe pump 1 (manufactured by TELEDONE ISCO., LTD. 1000D Syringe pump) was used for the initiator solution feed, and Syringe pump 1 was connected to mixer 1 using PTFE tubing (inner diameter 1.0mm, outer diameter 1.6mm, length 2 m). The outlet of the mixer 1 was connected to the inlet of the mixer 2 by a PFA pipe 1 (inner diameter 2.0mm, outer diameter 3mm, length 1 m), and the other inlet of the mixer 2 was connected to a reaction regulator solution feed syringe pump 2 (Keychem-L, YMC) by a PTFE pipe (inner diameter 1.0mm, outer diameter 1.6mm, length 2 m). The outlet of the mixer 2 was connected to an inlet of the mixer 3 by a PFA tube 2 (inner diameter 2.0mm, outer diameter 3mm, length 1 m), and the other inlet of the mixer 3 was connected to a second monomer solution feeding plunger pump 2 (KP-12, fjor.) by a PTFE tube (inner diameter 1.0mm, outer diameter 1.6mm, length 2 m). The outlet of the mixer 3 was connected to an inlet of the mixer 4 by a PFA pipe 3 (inner diameter 2.0mm, outer diameter 3mm, length 5 m), and the other inlet of the mixer 4 was connected to a reaction terminator solution feed syringe pump 3 (As ia, syrris Co., ltd.) by a PTFE pipe (inner diameter 1.0mm, outer diameter 1.6mm, length 2 m). The PFA tube 4 (inner diameter 2.0mm, outer diameter 3mm, length 0.7 m) was connected to the outlet of the mixer 4. The flow path from the forefront of each pump to 90% of the length of the tube 4 was immersed in a constant temperature bath at 24 ℃ to adjust the temperature. In addition, the record of the pressure sensor of the pump for feeding 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 (manufactured by fem, ltd.) was used for feeding the first monomer solution, plunger pump 1 was connected to mixer 1 using PTFE tubing (inner diameter 1.0mm, outer diameter 1.6mm, length 2 m), syringe pump 2 (manufactured by YMC, ltd.) was used for feeding the initiator solution, and syringe pump 2 was connected to mixer 1 using PTFE tubing (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 PTFE pipe 1 (inner diameter 1.5mm, outer diameter 3mm, length 1.3m (comparative example 1), 0.7m (comparative example 2)), and the other inlet of the mixer 2 was connected by a PTFE pipe (inner diameter 1.0mm, outer diameter 1.6mm, length 2 m) by an injection pump 3 (As ia, manufactured by Syrris Co.). 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 flow path from the forefront of each pump to 90% of the length of the tube 2 was immersed in a constant temperature bath of 5 ℃ (comparative example 1) and-20 ℃ (comparative example 2), and the temperature was adjusted. In addition, the record of the pressure sensor of the pump for feeding the initiator solution is shown as a pressure trend.
GPC measurement conditions were as follows.
Column: PLgel 3 μm MIXED-E (manufactured by Agi lent Technologies Co., ltd.)
Mobile phase: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Column oven: 40 DEG C
A detector: UV detector
Calibration curve: standard polystyrene
In addition, in the case of the optical fiber, 1 the measurement conditions of H-NMR (300 MHz) were as follows.
Measuring solvent: heavy chloroform
Reference substance: tetramethylsilane (TMS) (δ0.0ppm)
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 with a mixer 1 at a flow rate 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. As a static mixer unit, a product obtained by processing DSP-MXA3-17 (polyacetal unit, number of torsional blades 17, 3mm diameter) manufactured by LIMITED was used. Next, 1-Diphenylethylene (DPE) was mixed with a mixer 2 at 56. Mu.L/min to adjust the reactivity with the second monomer. The same mixer as the mixer 1 was used for the mixer 2. Next, t-butyl methacrylate as a second monomer was mixed at 1.2mL/min with a mixer 3 to block the polymer. The same mixer as the mixer 1 was used for the mixer 3. Next, as a polymerization terminator, 0.25mol/L methanol/THF solution was mixed with 10mL/min by a mixer 4 to terminate the polymerization. The mixer 4 is a general simple double-tube mixer. The first monomer solution tube was connected to the inlet of the inlet port of the mixer 1, the initiator solution tube was connected to the inlet port of the inner tube, the tube 1 was connected to the inlet port of the mixer 2, the DPE solution tube was connected to the inlet port of the inner tube, the tube 2 was connected to the inlet port of the mixer 3, the t-butyl methacrylate solution tube was connected to the inlet port of the inner tube, the polymerization terminator solution tube was connected to the inlet port of the mixer 4, and the tube 3 was connected to the inlet port of the inner tube. Delivering the liquid for 10 minutes, and collecting effluent liquid. The trend of the pressure in the reaction is shown in fig. 12. There was little pressure change during 10 minutes.
Further, the solvent was distilled off from 387g of the effluent by an evaporator to 130g, and then dropped into a mixture 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 then washed with 201g of methanol. The white solid obtained was dried under reduced pressure (50 ℃ C., 2.5 hours) to give 17.51g of PS-b-PtBuMA17. Fractionation by GPCAnalysis gave mn= 10,053 and Mw/mn=1.09. The polymer obtained 1 The H-NMR chart is shown in FIG. 13.
Comparative example 1
As mixer 1 and mixer 2, a T-shaped mixer ((manufactured by Sank refiner industry, stainless steel, inner diameter 0.25 mm)) was used, and each pump was connected to collide the first monomer solution and the initiator solution at 180 °. A1.0 mol/L solution of 4-methoxystyrene in THF as the first monomer and a 0.11mol/L solution of sec-butyllithium in hexane as the initiator were mixed with a mixer 1 at a flow rate of 5mL/min and 1mL/min, respectively, to polymerize the first monomer. Next, a 0.25mol/L methanol/THF solution as a polymerization terminator was mixed with 6.3mL/min by a mixer 2 to terminate the polymerization.
The trend of the pressure at 10 minutes of liquid feeding is shown in fig. 14. About 5 minutes after the liquid feeding, a rapid pressure change was found.
Comparative example 2
As the mixer 1 and the mixer 2, a device made of (a) tek X-01 (made of stainless steel) manufactured by コ b. The first monomer solution tube was connected to the inlet side of the outer tube of the mixer 1, the initiator solution tube was connected to the inlet of the inner tube, the polymerization terminator solution tube was connected to the inlet side of the outer tube of the mixer 2, and the tube 1 was connected to the inlet of the inner tube. 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 with a mixer 1 at a flow rate of 5mL/min and 1mL/min, respectively, to polymerize the first monomer. Next, a 0.25mol/L methanol/THF solution as a polymerization terminator was mixed with 6.1mL/min by a mixer 2 to terminate the polymerization.
The trend of the pressure at 35 minutes of liquid feeding is shown in fig. 15. Several pressure fluctuations and pressure increases over time were found.
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 blocked, no pressure fluctuation is found, and a polymer can be stably produced for a long period of time.
Description of the reference numerals
1. Mixer for mixing double liquids
2. Joint member
21. Main body
211. Insertion hole
212. Inlet hole
213. Connecting hole
22. Inner pipe
221. Inner side of inner tube
222. Outer wall of inner pipe
223. The top end of the inner tube
24. Space of
25. Double pipe
3. Static mixer component
31. Cylindrical body
32. Unit body
321. Right torsion blade
322. Left-turning vane
4. Flow reactor
Claims (13)
1. A method for producing a block polymer, which comprises: a step of synthesizing a polymer by anionically polymerizing a styrene monomer as a first monomer in the presence of an initiator using a flow reactor including a two-liquid mixing mixer having 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 to synthesize a block polymer using a flow reactor comprising a two-liquid mixing mixer having a flow path capable of mixing a plurality of liquids,
the flow reactor is provided with a double-liquid mixing mixer including a joint member having a double pipe therein and a static mixer member including a cylindrical body and a unit body inserted therein, and the joint member is connected to the static mixer member so that an end face of the cylindrical body on the double pipe side is brought into contact with an end face of the double pipe on the static mixer member side.
2. The method for producing a block polymer according to claim 1, comprising: and a step of reacting the non-independently polymerizable monomer after anionically polymerizing the first monomer to synthesize the polymer and before the second monomer is polymerized.
3. The method for producing a block polymer according to claim 1 or 2, wherein the non-independently polymerizable monomer is 1, 1-diphenylethylene or a derivative thereof.
4. The method for producing a block polymer according to claim 1, wherein the end of the double pipe on the static mixer member side is located inside the joint member.
5. The method for producing a block polymer according to claim 3 or 4, wherein the joint member has an insertion hole for inserting an inner tube into which an initiator solution flows, and the double tube is formed by a space formed between an outer wall of the inner tube and an inner wall of the insertion hole with an inner side of the inner tube at least in the vicinity of a distal end of the inner tube in a state where the inner tube is inserted.
6. The method for producing a block polymer according to claim 5, wherein the joint member has an introduction hole for introducing a monomer solution, and the introduction hole is connected to the insertion hole.
7. The method for producing a block polymer according to claim 6, wherein the insertion hole is formed so that a diameter of the insertion hole is substantially equal to an outer diameter of the inner tube in the vicinity of a connection portion with the insertion hole, and a diameter of the insertion hole is larger than the outer diameter of the inner tube from the connection portion to a distal end of the inner tube.
8. The method for producing a block polymer according to any one of claims 5 to 7, wherein the joint member has a static mixer member connecting hole, and the insertion hole is connected to the connecting hole.
9. The method for producing a block polymer according to any one of claims 1 to 8, wherein the unit body is inserted into the cylindrical body so that one end thereof is substantially on the same horizontal plane as the end face of the cylindrical body on the double pipe side.
10. The method for producing a block polymer according to any one of claims 1 to 9, wherein the unit body has a shape in which right-hand twist blades and left-hand twist blades are alternately connected in a twist axis direction.
11. The method for producing a block polymer according to any one of claims 1 to 10, wherein the initiator is a mono-organolithium compound.
12. The method for producing a block polymer according to any one of claims 1 to 11, wherein the styrene monomer is a compound represented by the following formula (1):
[ chemical 1]
Wherein R is 1 Is a hydrogen atom or methyl group, R 2 ~R 6 Each 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, -OSiR 7 3 or-SiR 7 3 ,R 7 Each 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.
13. The method for producing a block polymer according to any one of claims 1 to 12, wherein the acrylic monomer is a compound represented by the following formula (2):
[ chemical 2]
Wherein R is 11 Is a hydrogen atom or methyl group, R 12 Each 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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PCT/JP2018/029368 WO2019031435A1 (en) | 2017-08-08 | 2018-08-06 | Method for producing block polymer |
CN201880051098.XA CN110997743A (en) | 2017-08-08 | 2018-08-06 | Method for producing block polymer |
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