KR20230072685A - Method for polymer preparation - Google Patents
Method for polymer preparation Download PDFInfo
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- KR20230072685A KR20230072685A KR1020210159182A KR20210159182A KR20230072685A KR 20230072685 A KR20230072685 A KR 20230072685A KR 1020210159182 A KR1020210159182 A KR 1020210159182A KR 20210159182 A KR20210159182 A KR 20210159182A KR 20230072685 A KR20230072685 A KR 20230072685A
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- flow reactor
- reactor
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- 229920000642 polymer Polymers 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 22
- -1 thiocarbonylthio group Chemical group 0.000 claims abstract description 22
- 150000003254 radicals Chemical class 0.000 claims abstract description 21
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical group [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims abstract description 16
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 33
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 7
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 238000013467 fragmentation Methods 0.000 claims description 5
- 238000006062 fragmentation reaction Methods 0.000 claims description 5
- 230000002441 reversible effect Effects 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 abstract description 10
- 239000000843 powder Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000009826 distribution Methods 0.000 description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 6
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000852 hydrogen donor Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000012989 trithiocarbonate Substances 0.000 description 4
- 239000007877 V-601 Substances 0.000 description 3
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 2
- 229920001774 Perfluoroether Polymers 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000004659 dithiocarbamates Chemical group 0.000 description 2
- 125000005022 dithioester group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- DKPACNKRVZMLAL-UHFFFAOYSA-N 2-[(2-cyano-3-methylpentan-2-yl)diazenyl]-2,3-dimethylpentanenitrile Chemical compound CCC(C)C(C)(C#N)N=NC(C)(C#N)C(C)CC DKPACNKRVZMLAL-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- LYPGJGCIPQYQBW-UHFFFAOYSA-N 2-methyl-2-[[2-methyl-1-oxo-1-(prop-2-enylamino)propan-2-yl]diazenyl]-n-prop-2-enylpropanamide Chemical compound C=CCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCC=C LYPGJGCIPQYQBW-UHFFFAOYSA-N 0.000 description 1
- NMZSJIQGMAGSSO-UHFFFAOYSA-N 3-[[1-amino-2-[[1-amino-1-(2-carboxyethylimino)-2-methylpropan-2-yl]diazenyl]-2-methylpropylidene]amino]propanoic acid Chemical compound OC(=O)CCNC(=N)C(C)(C)N=NC(C)(C)C(=N)NCCC(O)=O NMZSJIQGMAGSSO-UHFFFAOYSA-N 0.000 description 1
- CTLAWKZAJCYIFX-UHFFFAOYSA-N 4-(2-carboxyethylsulfanylcarbothioylsulfanyl)-4-cyanopentanoic acid Chemical compound C(=O)(O)CCSC(=S)SC(CCC(=O)O)(C)C#N CTLAWKZAJCYIFX-UHFFFAOYSA-N 0.000 description 1
- YNKQCPNHMVAWHN-UHFFFAOYSA-N 4-(benzenecarbonothioylsulfanyl)-4-cyanopentanoic acid Chemical compound OC(=O)CCC(C)(C#N)SC(=S)C1=CC=CC=C1 YNKQCPNHMVAWHN-UHFFFAOYSA-N 0.000 description 1
- RNTXYZIABJIFKQ-UHFFFAOYSA-N 4-cyano-4-dodecylsulfanylcarbothioylsulfanylpentanoic acid Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C#N)CCC(O)=O RNTXYZIABJIFKQ-UHFFFAOYSA-N 0.000 description 1
- KYLIZBIRMBGUOP-UHFFFAOYSA-N Anetholtrithion Chemical group C1=CC(OC)=CC=C1C1=CC(=S)SS1 KYLIZBIRMBGUOP-UHFFFAOYSA-N 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000005035 acylthio group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000005251 aryl acyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004475 heteroaralkyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005368 heteroarylthio group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004468 heterocyclylthio group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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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
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
본 발명은, 가역적 첨가-분절 연쇄이동(RAFT) 중합에 의해 제조된 고분자로부터 RAFT 물질 유래 관능기를 효율적으로 제거할 수 있는 고분자 제조 방법에 관한 것이다.The present invention relates to a method for preparing a polymer capable of efficiently removing a functional group derived from a RAFT material from a polymer prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization.
자유 라디칼 중합은 개시제의 분해시점이 중합 개시로부터 종료까지 넓게 분포되어 있고 단량체의 반응성 차이로 각각의 고분자 사슬마다 단량체의 조성이 불균일하게 중합되며 고분자 사슬간 종료반응이 영향을 끼쳐 넓은 분자량 분포 (PDI)를 가진 고분자를 수득하게 된다.In free radical polymerization, the decomposition point of the initiator is widely distributed from the start to the end of the polymerization, and the composition of the monomer is polymerized non-uniformly for each polymer chain due to the difference in the reactivity of the monomer, and the termination reaction between the polymer chains affects a wide molecular weight distribution (PDI) ) to obtain a polymer with
이러한 기존 자유 라디칼 중합의 단점을 개선하여 균일한 단량체 조성 및 낮은 PDI를 가지는 고분자를 중합하기 위해 가역적 첨가-분절 연쇄이동 (Reversible addition-fragmentation chain transfer, RAFT) 중합이 사용될 수 있다. RAFT 중합은 고분자를 합성할 때 원하는 분자량과 분자량 분포도를 정밀하게 콘트롤할 수 있는 리빙 라디칼 중합법(living radical polymerization) 중의 하나로서, 고분자 체인 끝에서 라디칼의 반응성을 조절해 원하는 분자량과 낮은 분자량 분포도의 고분자를 합성할 수 있는 방법이다.Reversible addition-fragmentation chain transfer (RAFT) polymerization can be used to improve the disadvantages of the existing free radical polymerization and polymerize a polymer having a uniform monomer composition and a low PDI. RAFT polymerization is one of the living radical polymerization methods that can precisely control the desired molecular weight and molecular weight distribution when synthesizing polymers. A method for synthesizing polymers.
RAFT 중합은 일반적으로 아래 반응식 1에 표시한 메커니즘에 따라 진행되는 것으로 알려져 있다.RAFT polymerization is generally known to proceed according to the mechanism shown in
[반응식 1][Scheme 1]
상기 반응식 1에 있어서, In
Initiator는 빛 혹은 열을 공급받아 분해되어 반응성 라디칼을 생성하는 종류의 개시제를 나타내며, R은 상기 개시제로부터 개시되어 생성된 반응성 라디칼이다.Initiator represents a kind of initiator generating reactive radicals by being decomposed by receiving light or heat, and R is a reactive radical initiated and generated from the initiator.
M은 반응성 라디칼에 의하여 폴리머를 생성하는 모노머이며 반응성 에틸렌기를 포함하는 모노머; 예를 들면 대표적으로 비닐기 혹은 (메타)아크릴레이트기를 포함하는 모노머이다. M is a monomer that generates a polymer by a reactive radical and includes a reactive ethylene group; For example, it is a monomer typically containing a vinyl group or a (meth)acrylate group.
Px, Py 는 전파단계에서 분자량이 증가하고 있는 폴리머이며, Px+y 는 종결단계에 의해 반응이 완료된 폴리머이다.P x and P y are polymers whose molecular weight is increasing in the propagation step, and P x+y is a polymer whose reaction has been completed by the termination step.
S는 황 원자를 나타낸다. S represents a sulfur atom.
RAFT 중합은 RAFT 물질의 존재 하에 진행되는데, RAFT 물질은 황 함유 관능기, 예를 들면, 트리티오카보네이트기, 다이티오카바메이트기, 다이티오에스터기, 티오카본일티오기 등을 포함하는 물질이다. 즉 RAFT 물질은 황 원자를 포함하고 있기 때문에, RAFT 중합에 의해 제조된 고분자는 고분자 사슬 이나 말단에 결합된 황 함유 관능기를 포함하고 있다. RAFT polymerization proceeds in the presence of a RAFT material, which is a material containing a sulfur-containing functional group, for example, a trithiocarbonate group, a dithiocarbamate group, a dithioester group, a thiocarbonylthio group, and the like. That is, since RAFT materials contain sulfur atoms, polymers produced by RAFT polymerization contain sulfur-containing functional groups attached to polymer chains or terminals.
고분자 사슬이나 말단에 포함된 황 함유 관능기들은 흡광에 의하여 의도하지 않은 발색을 일으켜 사용에 제한이 있을 수 있고 시간이 지남에 따라 분해되어 악취를 일으키는 원인이 될 수 있다. Sulfur-containing functional groups included in polymer chains or terminals may cause unintended color development by light absorption, which may limit their use, and may cause odor by decomposition over time.
따라서 고분자 사슬로부터 티오카본일티오기 혹은 트리티오카보네이트기가 제거될 필요가 있다. 이에, 대표적으로 하이포아인산염과 같은 수소공여체와 자유 라디칼 개시제를 적절히 사용하여 라디칼 유도 환원반응을 이용하거나 아민과 같은 수소공여체와 자유 라디칼 개시제를 사용하여 제거하는 방법 등이 알려져 있다. 이러한 방법은 반응식 2와 같은 메커니즘에 따라 진행되는 것으로 알려져 있다.Therefore, it is necessary to remove the thiocarbonylthio group or trithiocarbonate group from the polymer chain. Accordingly, representatively, a method of using a radical-induced reduction reaction by appropriately using a hydrogen donor such as hypophosphite and a free radical initiator, or a method of removing hydrogen using a hydrogen donor such as amine and a free radical initiator, and the like are known. It is known that this method proceeds according to the mechanism shown in Scheme 2.
[반응식 2][Scheme 2]
그러나 이러한 제거방법은 고분자에 인산염 또는 암모늄염이 잔류하게 되어 순도가 높은 고분자를 수득하기 어려우며 별도의 추가적인 정제공정을 도입하여 추가적인 시간과 비용을 들여 제거하지 않으면 그로 인한 고분자 물성의 저하나 경시 변화에 따른 악취 등 문제를 일으킬 수 있다.However, in this removal method, phosphate or ammonium salt remains in the polymer, making it difficult to obtain a high-purity polymer. It can cause problems such as bad smell.
따라서, 본 발명은 RAFT 반응을 통해 중합된 고분자의 사슬로부터 RAFT 물질 유래 관능기, 예를 들어 트리티오카보네이트기, 티오카본일티오기 등을 효율적으로 제거할 수 있는 방법을 제공하고자 한다. Accordingly, an object of the present invention is to provide a method capable of efficiently removing a functional group derived from a RAFT material, for example, a trithiocarbonate group, a thiocarbonylthio group, and the like, from a chain of a polymer polymerized through a RAFT reaction.
본 발명은 상기 기술적 과제를 해결하기 위하여, The present invention, in order to solve the above technical problem,
가역적 첨가-분절 연쇄이동 (Reversible addition-fragmentation chain transfer, RAFT) 중합에 의해 제조된 RAFT 고분자를 포함하는 용액을 제조하는 단계; preparing a solution containing a RAFT polymer prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization;
상기 RAFT 고분자를 포함하는 용액을 연속식 흐름 반응기 주입하여 반응시키는 단계; 및Reacting by injecting a solution containing the RAFT polymer into a continuous flow reactor; and
연속식 흐름 반응기로부터 수득되는 반응 용액을 비용매에 적가하여 침전시키는 단계를 포함하는 고분자의 제조 방법을 제공한다.Provided is a method for producing a polymer comprising the step of precipitating by dropwise adding a reaction solution obtained from a continuous flow reactor to a non-solvent.
일 구현예에 따르면, 상기 RAFT 고분자를 포함하는 용액은, According to one embodiment, the solution containing the RAFT polymer,
(i) 1종 이상의 RAFT 고분자,(i) one or more RAFT polymers;
(ii) 1종 이상의 자유 라디칼 개시제,(ii) one or more free radical initiators;
(iii) 1종 이상의 비알코올계 용제, 및(iii) one or more non-alcoholic solvents, and
(iv) 1종 이상의 알코올(iv) one or more alcohols;
을 포함하는 것일 수 있다. It may contain.
일 구현예에 따르면, 상기 RAFT 고분자는, 반응성 에틸렌기를 갖는 모노머, 자유 라디칼 개시제 및 RAFT 물질로 이루어지는 군으로부터 선택되는 하나 이상을 반응시켜 중합된 것일 수 있다. According to one embodiment, the RAFT polymer may be polymerized by reacting at least one selected from the group consisting of a monomer having a reactive ethylene group, a free radical initiator, and a RAFT material.
일 구현예에 따르면, 상기 RAFT 물질은 티오카본일티오기 혹은 트리티오카보네이트기를 갖는 물질일 수 있다. According to one embodiment, the RAFT material may be a material having a thiocarbonylthio group or a trithiocarbonate group.
일 구현예에 따르면, 상기 RAFT 고분자를 포함하는 용액은 총 중량을 기준으로 According to one embodiment, the solution containing the RAFT polymer is based on the total weight
(i) 1종 이상의 RAFT 고분자 1 내지 50 중량%,(i) 1 to 50% by weight of one or more RAFT polymers;
(ii) 1종 이상의 자유 라디칼 개시제 1 내지 10 중량%,(ii) 1 to 10% by weight of at least one free radical initiator;
(iii) 1종 이상의 비알코올계 용제 20 내지 80 중량%, 및(iii) 20 to 80% by weight of at least one non-alcoholic solvent, and
(iv) 1종 이상의 알코올 10 내지 50 중량%를 포함하는 것일 수 있다. (iv) 10 to 50% by weight of one or more alcohols.
일 구현예에 따르면, 상기 (iii) 비알코올계 용제는 테트라하이드로퓨란, 메틸에틸케톤, 톨루엔, 자일렌, 에틸아세테이트, 헥산, 시클로헥산, 헵탄 및 메틸렌클로라이드, 클로로포름으로 이루어지는 군으로부터 선택되는 1종 이상일 수 있다. According to one embodiment, the (iii) non-alcoholic solvent is one selected from the group consisting of tetrahydrofuran, methyl ethyl ketone, toluene, xylene, ethyl acetate, hexane, cyclohexane, heptane, methylene chloride, and chloroform may be ideal
일 구현예에 따르면, 상기 (iv) 알코올은 메탄올, 에탄올, 프로판올, 이소프로판올, 부탄올, 이소부탄올, 터셔리부탄올, 펜탄올, 이소펜탄올, 헥산올, 헵탄올, 에틸렌 글리콜 및 프로필렌 글리콜로 이루어지는 군으로부터 선택되는 1종 이상일 수 있다. According to one embodiment, the (iv) alcohol is a group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, heptanol, ethylene glycol and propylene glycol It may be one or more selected from.
일 구현예에 따르면, 상기 비용매는 헥산, 시클로헥산, 헵탄, 메탄올, 에탄올, 프로판올, 이소프로필알코올, 다이에틸에테르 및 증류수로 이루어지는 군에서 선택한 1종 이상일 수 있다. According to one embodiment, the non-solvent may be at least one selected from the group consisting of hexane, cyclohexane, heptane, methanol, ethanol, propanol, isopropyl alcohol, diethyl ether, and distilled water.
일 구현예에 따르면, 상기 연속식 흐름 반응기는 관 흐름 반응기, 미세유로 흐름 반응기, 또는 모세관 흐름 반응기일 수 있다. According to one embodiment, the continuous flow reactor may be a tubular flow reactor, a microchannel flow reactor, or a capillary flow reactor.
일 구현예에 따르면, 상기 연속식 흐름 반응기는 50℃ 내지 150℃ 온도로 가열되는 것일 수 있다. According to one embodiment, the continuous flow reactor may be heated to a temperature of 50 °C to 150 °C.
일 구현예에 따르면, 상기 연속식 흐름 반응기는 5 bar 내지 30 bar의 배압이 걸리는 것일 수 있다. According to one embodiment, the continuous flow reactor may have a back pressure of 5 bar to 30 bar.
본 발명에 의하면, RAFT 중합에 의해 중합된 RAFT 고분자로부터 RAFT 물질 유래 관능기, 예를 들어 트리티오카보네이트기, 티오카본일티오기 등을 효율적으로 제거할 수 있으며, 별도의 정제 공정 없이 불순물이 제거된 고분자 분말을 얻을 수 있어, 추가적인 시간과 비용을 들이지 않더라도 RAFT 고분자의 물성 저하나 경시 변화에 따른 악취 등 문제를 해결할 수 있다. According to the present invention, a functional group derived from a RAFT material, for example, a trithiocarbonate group, a thiocarbonylthio group, etc., can be efficiently removed from a RAFT polymer polymerized by RAFT polymerization, and a polymer from which impurities are removed without a separate purification process Since powder can be obtained, it is possible to solve problems such as deterioration of physical properties of RAFT polymer or odor due to change over time without additional time and cost.
도 1은 본 발명에 따른 방법을 실시하기 전과 후의 UV 스펙트럼 결과를 보여준다. Figure 1 shows the UV spectrum results before and after carrying out the method according to the present invention.
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는바, 특정 실시예를 상세히 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.Since the present invention can apply various transformations and have various embodiments, specific embodiments will be described in detail. However, it should be understood that this is not intended to limit the present invention to specific embodiments, and includes all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.
이하, 본 발명의 구현예에 RAFT 고분자로부터 RAFT 물질 유래 관능기, 예를 들어 트리티오카보네이트기 혹은 티오카본일티오기를 제거하는 방법 및 침전공정을 통해 불순물이 제거된 고분자의 제조방법에 대하여 상세하게 설명한다.Hereinafter, in an embodiment of the present invention, a method for removing a functional group derived from a RAFT material, for example, a trithiocarbonate group or a thiocarbonylthio group from a RAFT polymer, and a method for preparing a polymer from which impurities are removed through a precipitation process. Description in detail do.
본 발명에 따른 고분자 제조 방법은, The polymer manufacturing method according to the present invention,
가역적 첨가-분절 연쇄이동 (Reversible addition-fragmentation chain transfer, RAFT) 중합에 의해 제조된 RAFT 고분자를 포함하는 용액을 제조하는 단계; preparing a solution containing a RAFT polymer prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization;
상기 RAFT 고분자를 포함하는 용액을 연속식 흐름 반응기 주입하여 반응시키는 단계; 및Reacting by injecting a solution containing the RAFT polymer into a continuous flow reactor; and
연속식 흐름 반응기로부터 수득되는 반응 용액을 비용매에 적가하여 침전시키는 단계를 포함한다. and adding dropwise the reaction solution obtained from the continuous flow reactor to a non-solvent to precipitate it.
본 발명의 방법이 사용되는 RAFT 고분자는 일반적으로 알려진 RAFT 중합 방법으로 중합된 고분자며 그 방법은 특히 제한되지 않는다. 회분식 반응기 혹은 흐름 반응기를 사용한 중합 방식에 제한되지 않으며, 일반적으로 알려진 반응성 에틸렌기를 포함하는 모노머; 예를 들면 비닐기 혹은 (메타)아크릴레이트기를 포함하는 모노머와, 라디칼 개시제와, 티오카본일티오기 혹은 트리티오카보네이트기가 포함된 RAFT 물질을 사용하여 중합된 고분자이면 본 발명에 따른 방법을 제한 없이 실시할 수 있다.The RAFT polymer used in the method of the present invention is a polymer polymerized by a generally known RAFT polymerization method, and the method is not particularly limited. A monomer containing a generally known reactive ethylene group, which is not limited to a polymerization method using a batch reactor or a flow reactor; For example, if it is a polymer polymerized using a monomer containing a vinyl group or a (meth)acrylate group, a radical initiator, and a RAFT material containing a thiocarbonylthio group or a trithiocarbonate group, the method according to the present invention is carried out without limitation can do.
본 발명에서 '(메타)아크릴레이트기'라는 표현은 아크릴레이트기 또는 메타크릴레이트기를 지칭한다. In the present invention, the expression '(meth)acrylate group' refers to an acrylate group or a methacrylate group.
본 발명의 방법은 연속식 흐름 반응기를 사용한다. 연속식 흐름 반응기는 관 흐름 반응기, 미세유로 흐름 반응기, 모세관 흐름 반응기 등의 방식을 포함하는 것이며 반응기 내로 물질 혹은 혼합물이 주입되어 일련의 과정을 거친 후 결과물을 수득할 수 있는 일련의 흐름 반응기를 통칭하는 것이다. The process of the present invention uses a continuous flow reactor. The continuous flow reactor includes tubular flow reactors, microchannel flow reactors, capillary flow reactors, etc., and refers to a series of flow reactors in which a material or mixture is injected into the reactor and a result is obtained after a series of processes. is to do
반응기의 재질은 예를 들어 스테인레스강 혹은 하스텔로이(상표명) 등의 금속재질이 사용될 수 있고, 퍼플루오로알콕시(PFA) 수지, 폴리테트라플루오로에틸렌(PTFE) 수지, 폴리에테르에테르케톤(PEEK) 수지 혹은 유리 등의 비금속 재질도 사용될 수 있으며, 예시에 제한되지 않고 적절한 재질을 선택하여 사용할 수 있다.As the material of the reactor, metal materials such as stainless steel or Hastelloy (trade name) may be used, and perfluoroalkoxy (PFA) resin, polytetrafluoroethylene (PTFE) resin, and polyether ether ketone (PEEK) may be used. A non-metallic material such as resin or glass may also be used, and an appropriate material may be selected and used without being limited to the examples.
연속식 흐름 반응기의 라인은 그 형태에 제약을 받지 않으며 용액이 연속적으로 주입되어 라인 안을 흐름으로써 반응이 진행되고 반응액이 연속적으로 토출되어 수집할 수 있도록 반응속도, 시간당 처리량 등 필요에 따라 그 크기나 구조를 변형하여 사용할 수 있다. 또한 연속식 흐름 반응기는 배압(back pressure) 조절이 가능하기 때문에 반응 온도가 올라가더라도 반응기 내부에서 용제가 끓지 않도록 할 수 있어서 용제의 끓는점에 의해 반응온도가 제한되지 않으므로, RAFT 물질로부터 유래한 관능기들을 제거하는데 더욱 유리하다. The line of the continuous flow reactor is not limited in its shape, and the solution is continuously injected and flowed through the line so that the reaction proceeds and the reaction liquid is continuously discharged and collected. It can be used by modifying the structure. In addition, since the continuous flow reactor can control the back pressure, it is possible to prevent the solvent from boiling inside the reactor even if the reaction temperature rises, so that the reaction temperature is not limited by the boiling point of the solvent. It is better to remove
일 구현예에 따르면 연속식 반응기에 걸리는 배압을 5 내지 30 bar, 예를 들면 7 bar 이상 또는 10 bar 이상, 그리고 25 bar 이하 또는 20 bar 이하로 조절할 수 있다. 이렇게 함으로써 반응기 내에서 용제가 끓는 것을 방지할 수 있다.According to one embodiment, the back pressure applied to the continuous reactor may be adjusted to 5 to 30 bar, for example, 7 bar or more or 10 bar or more, and 25 bar or less or 20 bar or less. By doing so, boiling of the solvent in the reactor can be prevented.
본 발명의 반응에 사용되는 RAFT 고분자 용액은 (i) 1종 이상의 RAFT 고분자, (ii) 1종 이상의 자유 라디칼 개시제, (iii) 1종 이상의 비알코올계 용제, 및 (iv) 1종 이상의 알코올을 포함하는 것이다.The RAFT polymer solution used in the reaction of the present invention contains (i) one or more RAFT polymers, (ii) one or more free radical initiators, (iii) one or more non-alcoholic solvents, and (iv) one or more alcohols. to include
본 발명에 사용되는 RAFT 고분자는 일반적으로 알려진 방법으로 실시되어 중합된 고분자며 그 방법은 특히 제한되지 않는다. 예를 들면, 회분식 반응기 혹은 흐름 반응기를 사용한 중합 등 그 방식에 제한되지 않는다. 그리고 일반적으로 알려진 반응성 에틸렌기를 포함하는 모노머, 예를 들면 비닐기 혹은 (메타)아크릴레이트기를 포함하는 모노머와, 라디칼 개시제와, RAFT 물질을 사용하여 중합된 고분자이면 본 발명에 따른 방법을 제한 없이 실시할 수 있다. 이때, RAFT 물질은 티오카본일티오기 혹은 트리티오카보네이트기를 갖는 물질일 수 있다. The RAFT polymer used in the present invention is a polymer polymerized by a generally known method, and the method is not particularly limited. For example, polymerization using a batch reactor or a flow reactor is not limited thereto. And if it is a polymer polymerized using a monomer containing a generally known reactive ethylene group, for example, a monomer containing a vinyl group or a (meth)acrylate group, a radical initiator, and a RAFT material, the method according to the present invention is carried out without limitation can do. At this time, the RAFT material may be a material having a thiocarbonylthio group or a trithiocarbonate group.
일 구현예에 따르면, RAFT 고분자 용액 총 중량에 대하여 상기 RAFT 고분자의 함량은 1 중량% 내지 50중량%, 예를 들면 2중량% 이상, 3중량% 이상, 4중량% 이상, 또는 5 중량% 이상, 그리고 50중량% 이하, 30중량% 이하, 20중량% 이하, 또는 10 중량% 이하일 수 있다. According to one embodiment, the content of the RAFT polymer relative to the total weight of the RAFT polymer solution is 1% to 50% by weight, for example, 2% by weight or more, 3% by weight or more, 4% by weight or more, or 5% by weight or more , and may be 50 wt% or less, 30 wt% or less, 20 wt% or less, or 10 wt% or less.
본 발명에 사용되는 자유 라디칼 개시제는 2,2'-아조비스이소부티로니트릴, 4,4'-아조비스(4-시아노발레익산), 2,2'-아조비스(2-메틸부티로니트릴), 2,2'-아조비스(디메틸발레로니트릴), 2,2'-아조비스(4-메톡시-2,4-디메틸발레로니트릴), 1,1'-아조비스(시클로헥산카보니트릴), 디메틸 2,2-아조비스(2-메틸프로피오네이트), 2,2'-아조비스[2-메틸-N-(2-히드록시에틸)프로피온아미드], 2,2'-아조비스[N-(2-프로페닐)-2-메틸프로피온아미드], 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판]디하이드로클로라이드, 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판], 2,2'-아조비스(2-메틸프로피온아미딘)디하이드로클로라이드, 2,2'-아조비스[N-(2-카르복시에틸)-2-메틸프로피온아미딘] 등의 개시제로 가열 혹은 광개시 라디칼 개시제로 이루어진 군에서 선택한 1종 이상인 것이 바람직하다.The free radical initiator used in the present invention is 2,2'-azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleic acid), 2,2'-azobis (2-methylbutyro nitrile), 2,2'-azobis (dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexane) carbonitrile), dimethyl 2,2-azobis (2-methylpropionate), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'- Azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2' -Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis[N-( 2-carboxyethyl) -2-methylpropionamidine] and the like, preferably at least one selected from the group consisting of radical initiators initiated by heating or photoinitiation.
일 구현예에 따르면, RAFT 고분자 용액 총 중량에 대하여 상기 자유 라디칼 개시제의 함량은 1중량% 내지 10중량%, 예를 들면 1중량% 이상, 또는 2중량% 이상, 그리고 10중량% 이하, 8 중량% 이하, 6 중량% 이하 또는 4중량% 이하일 수 있다. According to one embodiment, the content of the free radical initiator relative to the total weight of the RAFT polymer solution is 1% to 10% by weight, for example, 1% by weight or more, or 2% by weight or more, and 10% by weight or less, 8% by weight % or less, 6% or less, or 4% or less.
또한 상기 비알코올계 용제는 테트라하이드로퓨란, 메틸에틸케톤, 톨루엔, 자일렌, 에틸아세테이트, 헥산, 시클로헥산, 헵탄, 메틸렌클로라이드, 클로로포름으로 이루어지는 군에서 선택한 1종 이상인 것이 바람직하다.In addition, the non-alcoholic solvent is preferably at least one selected from the group consisting of tetrahydrofuran, methyl ethyl ketone, toluene, xylene, ethyl acetate, hexane, cyclohexane, heptane, methylene chloride, and chloroform.
일 구현예에 따르면, RAFT 고분자 용액 총 중량에 대하여, 상기 비알코올계 용제의 함량은 20 내지 80 중량%, 예를 들면 30중량% 이상, 40 중량% 이상 또는 50중량% 이상, 그리고 70중량% 이하 또는 60중량% 이하일 수 있다. According to one embodiment, based on the total weight of the RAFT polymer solution, the content of the non-alcoholic solvent is 20 to 80% by weight, for example, 30% by weight or more, 40% by weight or more, or 50% by weight or more, and 70% by weight or less or 60% or less by weight.
또한 상기 알코올은 메탄올, 에탄올, 프로판올, 이소프로판올, 부탄올, 이소부탄올, 터셔리부탄올, 펜탄올, 이소펜탄올, 헥산올, 헵탄올, 에틸렌 글리콜, 프로필렌 글리콜로 이루어지는 군에서 선택한 1종 이상인 것이 바람직하다.In addition, the alcohol is preferably at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, heptanol, ethylene glycol, and propylene glycol. .
일 구현예에 따르면, RAFT 고분자 용액 총 중량에 대하여, 상기 알코올의 함량은 10 내지 50 중량%, 예를 들면 20 중량% 이상 또는 30 중량% 이상, 그리고 45 중량% 이하 또는 40 중량% 이하일 수 있다. According to one embodiment, based on the total weight of the RAFT polymer solution, the alcohol content may be 10 to 50% by weight, for example, 20% by weight or more or 30% by weight or more, and 45% by weight or less or 40% by weight or less. .
상기 RAFT 고분자, 자유 라디칼 개시제, 비알코올계 용제, 알코올 등은 상기 기재된 종류만으로 한정되는 것이 아니라, 필요에 따라 적절한 성분을 선택하여 이용하는 것도 가능할 것이다.The RAFT polymer, free radical initiator, non-alcoholic solvent, alcohol, etc. are not limited to the types described above, and appropriate components may be selected and used as needed.
본 발명에 따라, 자유 라디칼 개시제가 존재하는 비알코올계 용제 내에서 RAFT 고분자와 알코올을 혼합하여 흐름 반응기 내에서 반응시키면, 알코올이 수소공여체로 반응에 참가하여 RAFT 고분자 내의 티오카본일티오기 혹은 트리티오카보네이트기가 제거된다. According to the present invention, when a RAFT polymer and an alcohol are mixed in a non-alcoholic solvent in the presence of a free radical initiator and reacted in a flow reactor, the alcohol participates in the reaction as a hydrogen donor to form a thiocarbonylthio group or trithio group in the RAFT polymer. The carbonate group is removed.
본 발명에서 흐름 반응기로 주입된 용액의 반응을 촉진 시키기 위해 반응기의 온도를 증가시킬 수 있다. 일 구현예에 따르면 반응기의 온도는 50℃ 내지는 150℃, 예를 들면 70℃ 이상 또는 100℃ 이상, 예를 들면 150℃ 이하, 또는 130℃ 이하로 유지될 수 있다. 또한 흐름 반응기의 중간에 배관을 설치하여 개시제를 추가적으로 주입하여 반응을 더욱 촉진시킬 수 있다.In the present invention, the temperature of the reactor may be increased to promote the reaction of the solution injected into the flow reactor. According to one embodiment, the temperature of the reactor may be maintained at 50 °C to 150 °C, for example, 70 °C or higher or 100 °C or higher, for example, 150 °C or lower, or 130 °C or lower. In addition, a pipe may be installed in the middle of the flow reactor to additionally inject an initiator to further promote the reaction.
연속식 흐름 반응기 내의 반응물의 유속은 0.1 내지 1 ml/min 일 수 있으며, 예를 들면, 0.2 ml/min 이상 또는 0.3 ml/min 이상, 그리고 0.9 ml/min 이하, 0.8 ml/min 이하, 0.7 ml/min 이하, 0.6 ml/min 이하 또는 0.5 ml/min 일 수 있다.The flow rate of reactants in the continuous flow reactor can be from 0.1 to 1 ml/min, for example, 0.2 ml/min or more or 0.3 ml/min or more, and 0.9 ml/min or less, 0.8 ml/min or less, 0.7 ml /min or less, 0.6 ml/min or less, or 0.5 ml/min.
또한, 반응시간은 0.5 내지 5시간 일 수 있으며, 예를 들면 1시간 이상, 또는 1.5 시간 이상, 그리고 4시간 이하, 3시간 이하 또는 2.5 시간 이하일 수 있다. In addition, the reaction time may be 0.5 to 5 hours, for example, 1 hour or more, or 1.5 hours or more, and 4 hours or less, 3 hours or less, or 2.5 hours or less.
본 발명에서 반응이 완료된 용액으로부터 부산물을 제거하고 고분자를 분말의 형태로 가공하기 위해 비용매를 사용하여 침전시키는 과정을 통해 정제하는 단계를 포함할 수 있다.In the present invention, a purification step may be included through a process of precipitating using a non-solvent to remove by-products from the reaction-completed solution and process the polymer into a powder form.
상기 비용매는 고분자에 대하여 용해도가 없거나 매우 낮은 용제 중 선정하여 사용할 수 있으며, 예를 들면 헥산, 시클로헥산, 헵탄, 메탄올, 에탄올, 프로판올, 이소프로필알코올, 다이에틸에테르 및 증류수로 이루어지는 군에서 선택한 1종 이상인 것이 바람직하다.The non-solvent may be used by selecting a solvent having no or very low solubility in the polymer, for example, 1 selected from the group consisting of hexane, cyclohexane, heptane, methanol, ethanol, propanol, isopropyl alcohol, diethyl ether and distilled water More than one species is preferred.
비용매의 사용량은 반응용액에 대해 3 내지 10배 부피비로 사용할 수 있으며, 예를 들면, 4 배 이상, 5배 이상 또는 6배 이상, 그리고 9배 이하 또는 8배 이하의 부피비로 사용하는 것이 바람직할 수 있다. The amount of non-solvent can be used in a volume ratio of 3 to 10 times the reaction solution, and for example, it is preferable to use it in a volume ratio of 4 times or more, 5 times or more, 6 times or more, and 9 times or less or 8 times or less. can do.
이하에서는 본 발명의 실시예를 참조하여 보다 상세히 설명한다. 다만, 하기의 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 이들 실시예에 의해서 제한되는 것은 아니다.Hereinafter, it will be described in more detail with reference to embodiments of the present invention. However, the following examples are merely illustrative of the present invention, and the present invention is not limited by these examples.
[제조예] RAFT 고분자 합성[Production Example] Synthesis of RAFT polymer
메틸 메타아크릴레이트와 부틸 메타아크릴레이트는 TCI로부터 구입하였고, 메틸에틸케톤, 2,2'-아조비스이소부티로니트릴 및 메탄올은 대정화금으로부터 구입하여 추가적인 정제없이 사용하였다. Methyl methacrylate and butyl methacrylate were purchased from TCI, and methyl ethyl ketone, 2,2'-azobisisobutyronitrile and methanol were purchased from Daejung Chemical & Gold and used without further purification.
4-시아노-4-[[(도데실티오)카보노티오일]티오]펜타노익산과, 4-((((2-카르복시에틸)티오)카보노티오일)티오)-4-시아노펜타노익산은 합성하여 사용하였고, 4-cyano-4-[[(dodecylthio)carbonothioyl]thio]pentanoic acid, 4-((((2-carboxyethyl)thio)carbonothioyl)thio)-4-cyanopenta Noic acid was synthesized and used,
4-시아노-4-(페닐카보노티오일티오)펜타노익산은 시그마알드리치로부터 구입하여 추가적인 정제없이 사용하였다. 4-Cyano-4-(phenylcarbonothioylthio)pentanoic acid was purchased from Sigma-Aldrich and used without further purification.
제조예 1 - 고분자 1a의 제조 Preparation Example 1 - Preparation of Polymer 1a
250ml 3-neck flask에 메틸 메타아크릴레이트 11.3g, 부틸 메타아크릴레이트 13.2g, 메틸에틸케톤 60.86ml, 아조비스이소부티로니트릴 0.095g, 4-시아노-4-[[(도데실티오)카보노티오일]티오]펜타노익산 1.424g을 첨가하여 교반을 통해 혼합한 뒤 질소순환을 30분간 진행하여 탈기 하였다. 중합은 85℃까지 가온한 미네랄오일이 들어있는 수조에 반응기를 넣어 8hr동안 환류반응을 진행한 후 냉각하였다. 반응 후 노란색의 점성이 있는 액체를 수득하였으며 이를 메탄올에 침전시켜 여과 후 노란색의 고분자 분말을 얻었다. 고분자의 전환율과 평균분자량 및 분자량분포는 GPC로 측정하였다.In a 250ml 3-neck flask, 11.3 g of methyl methacrylate, 13.2 g of butyl methacrylate, 60.86 ml of methyl ethyl ketone, 0.095 g of azobisisobutyronitrile, 4-cyano-4-[[(dodecylthio)carbo 1.424 g of notioyl]thio]pentanoic acid was added and mixed by stirring, followed by degassing by nitrogen circulation for 30 minutes. Polymerization was performed by putting the reactor in a water bath containing mineral oil heated to 85° C., followed by a reflux reaction for 8 hr, and then cooled. After the reaction, a yellow viscous liquid was obtained, which was precipitated in methanol and filtered to obtain a yellow polymer powder. The conversion rate, average molecular weight and molecular weight distribution of the polymer were measured by GPC.
제조예 2 - 고분자 1b의 제조 Preparation Example 2 - Preparation of Polymer 1b
250ml 3-neck flask에 메틸 메타아크릴레이트 11.3g, 부틸 메타아크릴레이트 13.2g, 메틸에틸케톤 60.86ml, 아조비스이소부티로니트릴 0.095g, 4-((((2-카르복시에틸)티오)카보노티오일)티오)-4-시아노펜타노익산 1.424g을 첨가하여 교반을 통해 혼합한 뒤 질소순환을 30분간 진행하여 탈기 하였다. 중합은 85℃까지 가온한 미네랄오일이 들어있는 수조에 반응기를 넣어 8hr 동안 환류반응을 진행한 후 냉각하였다. 반응 후 노란색의 점성이 있는 액체를 수득하였으며 이를 메탄올에 침전시켜 여과 후 노란색의 고분자 분말을 얻었다. 고분자의 전환율과 평균분자량 및 분자량분포는 GPC로 측정하였다.In a 250ml 3-neck flask, 11.3 g of methyl methacrylate, 13.2 g of butyl methacrylate, 60.86 ml of methyl ethyl ketone, 0.095 g of azobisisobutyronitrile, 4-((((2-carboxyethyl)thio)carbonothio 1.424 g of oil) thio)-4-cyanopentanoic acid was added and mixed by stirring, followed by nitrogen circulation for 30 minutes to deaerate. The polymerization was performed by putting the reactor in a water bath containing mineral oil heated to 85° C., followed by a reflux reaction for 8 hr, and then cooled. After the reaction, a yellow viscous liquid was obtained, which was precipitated in methanol and filtered to obtain a yellow polymer powder. The conversion rate, average molecular weight and molecular weight distribution of the polymer were measured by GPC.
제조예 3 - 고분자 1c의 제조Preparation Example 3 - Preparation of Polymer 1c
250ml 3-neck flask에 메틸 메타아크릴레이트 11.3g, 부틸 메타아크릴레이트 13.2g, 메틸에틸케톤 60.86ml, 아조비스이소부티로니트릴 0.095g, 4-시아노-4-(페닐카보노티오일티오)펜타노익산 1.424g을 첨가하여 교반을 통해 혼합한 뒤 질소순환을 30분간 진행하여 탈기 하였다. 중합은 85℃까지 가온한 미네랄오일이 들어있는 수조에 반응기를 넣어 8hr 동안 환류반응을 진행한 후 냉각하였다. 반응 후 분홍색의 점성이 있는 액체를 수득하였으며 이를 메탄올에 침전시켜 여과 후 분홍색의 고분자 분말을 얻었다. 고분자의 전환율과 평균분자량 및 분자량분포는 GPC로 측정하였다.In a 250ml 3-neck flask, methyl methacrylate 11.3g, butyl methacrylate 13.2g, methyl ethyl ketone 60.86ml, azobisisobutyronitrile 0.095g, 4-cyano-4-(phenylcarbonothioylthio)penta 1.424 g of noic acid was added, mixed by stirring, and degassed by nitrogen circulation for 30 minutes. The polymerization was performed by putting the reactor in a water bath containing mineral oil heated to 85° C., followed by a reflux reaction for 8 hr, and then cooled. After the reaction, a pink viscous liquid was obtained, which was precipitated in methanol and filtered to obtain a pink polymer powder. The conversion rate, average molecular weight and molecular weight distribution of the polymer were measured by GPC.
[실시예][Example]
실시예에 사용된 1,1'-아조비스시클로헥산카보니트릴은 시그마알드리치로부터 구입하였고, 디메틸 2,2-아조비스(2-메틸프로피오네이트) (상품명 V-601), 2,2'-아조비스(디메틸발레로니트릴) (상품명 V-65)은 와코로부터 구입하여 추가적인 정제없이 사용하였다. 메틸에틸케톤, 메탄올, 이소프로필알코올, 부탄올, 터셔리부탄올은 대정화금으로부터 구입하여 추가적인 정제없이 사용하였다.The 1,1′-azobiscyclohexanecarbonitrile used in the examples was purchased from Sigma-Aldrich, and dimethyl 2,2-azobis(2-methylpropionate) (trade name V-601), 2,2′- Azobis(dimethylvaleronitrile) (trade name V-65) was purchased from Wako and used without further purification. Methyl ethyl ketone, methanol, isopropyl alcohol, butanol, and tert-butanol were purchased from Daejung Chemical Gold and used without further purification.
실시예 1. Example 1.
100ml 3-neck 반응기에 고분자1a 1.5g, 1,1'-아조비스시클로헥산카보니트릴 0.554g, 메틸에틸케톤 12.133g, 이소프로필알코올 8.089g을 투입 후 질소순환으로 탈기하며 30분간 교반하여 용해하였다. 모두 용해가 된 것을 확인 후 용액을 0.45μm 마이크로 필터로 여과하였다. 여과된 용액은 베이퍼텍(Vapourtec) R 흐름 반응기를 사용하여 반응을 진행하였다. 반응기는 스테인레스강으로 제작된 10ml 코일 4개가 연결되어 총 40ml의 용량으로 구성한 세트였으며, 각 코일은 유리 반응관 안에서 100℃로 가열하였다. 유속 0.333 ml/min으로 설정하여 120분 동안 반응기 코일을 거쳐 반응이 진행될 수 있도록 설정하였으며 코일의 말단에 15bar 배압 조절기를 설치하여 반응기 내부에서 용제가 끓지 않도록 하였다. 반응이 완료된 용액은 GPC로 측정하여 전환율을 측정하였고, 7배수의 메탄올에 적가하여 침전시키고 여과 후 백색의 고분자 분말을 얻었다. 얻어진 고분자 분말은 GPC로 평균 분자량 및 분자량 분포를 측정하였다.After adding 1.5 g of polymer 1a, 0.554 g of 1,1'-azobiscyclohexanecarbonitrile, 12.133 g of methyl ethyl ketone, and 8.089 g of isopropyl alcohol to a 100ml 3-neck reactor, the mixture was dissolved by stirring for 30 minutes while degassing with nitrogen circulation. . After confirming that all of the solution was dissolved, the solution was filtered through a 0.45 μm micro filter. The filtered solution was reacted using a Vapourtec R flow reactor. The reactor was a set composed of four 10 ml coils made of stainless steel connected to have a total capacity of 40 ml, and each coil was heated to 100° C. in a glass reaction tube. The flow rate was set at 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor. The reaction-completed solution was measured by GPC to measure the conversion rate, and was added dropwise to 7-fold methanol to precipitate, and after filtration, a white polymer powder was obtained. The obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
실시예 2. Example 2.
100ml 3-neck 반응기에 고분자1a 1.5g, 디메틸 2,2-아조비스(2-메틸프로피오네이트) (V-601, Wako) 0.668g, 메틸에틸케톤 12.133g, 터셔리부탄올 8.871g을 투입 후 질소순환으로 탈기하며 30분간 교반하여 용해하였다. 모두 용해가 된 것을 확인 후 용액을 0.45μm 마이크로 필터로 여과하였다. 여과된 용액은 베이퍼텍(Vapourtec) R 흐름 반응기를 사용하여 반응을 진행하였다. 반응기는 스테인레스강으로 제작된 10ml코일 4개가 연결되어 총 40ml의 용량으로 구성한 세트로 하였으며 각 코일은 유리 반응관 안에서 100℃로 가열하였다. 유속 0.333ml/min으로 설정하여 120분 동안 반응기 코일을 거쳐 반응이 진행될 수 있도록 설정하였으며 코일의 말단에 15bar 배압 조절기를 설치하여 반응기 내부에서 용제가 끓지 않도록 하였다. 반응이 완료된 용액은 GPC로 전환율을 측정하였고, 7배수의 메탄올에 적가하여 침전시키고, 여과 후 백색의 고분자 분말을 얻었다. 얻어진 고분자 분말은 GPC로 평균 분자량 및 분자량 분포를 측정하였다.After adding 1.5g of polymer 1a, 0.668g of dimethyl 2,2-azobis(2-methylpropionate) (V-601, Wako), 12.133g of methyl ethyl ketone, and 8.871g of tert-butanol to a 100ml 3-neck reactor, It was dissolved by stirring for 30 minutes while degassing with nitrogen circulation. After confirming that all of the solution was dissolved, the solution was filtered through a 0.45 μm micro filter. The filtered solution was reacted using a Vapourtec R flow reactor. The reactor was a set composed of four 10 ml coils made of stainless steel connected to a total capacity of 40 ml, and each coil was heated to 100 ° C in a glass reaction tube. The flow rate was set at 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor. The conversion rate of the reaction-completed solution was measured by GPC, precipitated by dropwise addition to 7-fold methanol, and after filtration, a white polymer powder was obtained. The obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
실시예 3. Example 3.
100ml 3-neck 반응기에 고분자1b 1.5g, 2,2'-아조비스(2,4-디메틸발레로니트릴) (V-65, Wako) 0.486g, 테트라하이드로퓨란 12.133g, 이소프로필알코올 7.514g을 투입 후 질소순환으로 탈기하며 30분간 교반하여 용해하였다. 모두 용해가 된 것을 확인 후 용액을 0.45μm 마이크로 필터로 여과하였다. 여과된 용액은 베이퍼텍(Vapourtec) R 흐름 반응기를 사용하여 반응을 진행하였다. 반응기는 스테인레스강으로 제작된 10ml코일 4개가 연결되어 총 40ml의 용량으로 구성한 세트로 하였으며 각 코일은 유리 반응관 안에서 100℃로 가열하였다. 반응기는 유속 0.333ml/min으로 설정하여 120분 동안 반응기 코일을 거쳐 반응이 진행될 수 있도록 설정하였으며, 코일의 말단에 15bar 배압 조절기를 설치하여 반응기 내부에서 용제가 끓지 않도록 하였다. 반응이 완료된 용액은 GPC로 전환율을 측정하였고, 7배수의 메탄올에 적가하여 침전시키고, 여과 후 백색의 고분자 분말을 얻었다. 얻어진 고분자 분말은 GPC로 평균 분자량 및 분자량 분포를 측정하였다.Polymer 1b 1.5g, 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, Wako) 0.486g, tetrahydrofuran 12.133g, isopropyl alcohol 7.514g were added to a 100ml 3-neck reactor. After the addition, the mixture was degassed by nitrogen circulation and dissolved by stirring for 30 minutes. After confirming that all of the solution was dissolved, the solution was filtered through a 0.45 μm micro filter. The filtered solution was reacted using a Vapourtec R flow reactor. The reactor was a set composed of four 10 ml coils made of stainless steel connected to a total capacity of 40 ml, and each coil was heated to 100 ° C in a glass reaction tube. The reactor was set at a flow rate of 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor. The conversion rate of the reaction-completed solution was measured by GPC, precipitated by dropwise addition to 7-fold methanol, and after filtration, a white polymer powder was obtained. The obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
실시예 4. Example 4.
100ml 3-neck 반응기에 고분자1b 1.5g, 2,2'-아조비스(2,4-디메틸발레로니트릴) (V-65, Wako) 0.486g, 테트라하이드로퓨란 12.133g, 이소프로필알코올 7.514g을 투입 후 질소순환으로 탈기하며 30분간 교반하여 용해하였다. 모두 용해가 된 것을 확인 후 용액을 0.45μm 마이크로 필터로 여과하였다. 여과된 용액은 베이퍼텍(Vapourtec) R 흐름 반응기를 사용하여 반응을 진행하였다. 반응기는 스테인레스강으로 제작된 10ml 코일 4개가 연결되어 총 40ml의 용량으로 구성한 세트로 하였으며, 각 코일은 유리 반응관 안에서 100℃로 가열하였다. 반응기는 유속 0.333ml/min으로 설정하여 120분 동안 반응기 코일을 거쳐 반응이 진행될 수 있도록 설정하였으며, 코일의 말단에 15bar 배압 조절기를 설치하여 반응기 내부에서 용제가 끓지 않도록 하였다. 반응이 완료된 용액은 GPC로 전환율을 측정하였고 7배수의 메탄올에 적가하여 침전시키고, 여과 후 백색의 고분자 분말을 얻었다. 얻어진 고분자 분말은 GPC로 평균 분자량 및 분자량 분포를 측정하였다.Polymer 1b 1.5g, 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, Wako) 0.486g, tetrahydrofuran 12.133g, isopropyl alcohol 7.514g were added to a 100ml 3-neck reactor. After the addition, the mixture was degassed by nitrogen circulation and dissolved by stirring for 30 minutes. After confirming that all of the solution was dissolved, the solution was filtered through a 0.45 μm micro filter. The filtered solution was reacted using a Vapourtec R flow reactor. The reactor was a set composed of four 10 ml coils made of stainless steel connected to a total capacity of 40 ml, and each coil was heated to 100 ° C in a glass reaction tube. The reactor was set at a flow rate of 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor. The reaction-completed solution was measured for conversion by GPC, added dropwise to 7-fold methanol, precipitated, and filtered to obtain a white polymer powder. The obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
실시예 5. Example 5.
100ml 3-neck 반응기에 고분자1c 1.5g, 디메틸 2,2-아조비스(2-메틸프로피오네이트) (V-601, Wako) 0.782g, 에틸아세테이트 12.133g, 부탄올 8.871g을 투입 후 질소순환으로 탈기하며 30분간 교반하여 용해하였다. 모두 용해가 된 것을 확인 후 용액을 0.45μm 마이크로 필터로 여과하였다. 여과된 용액은 베이퍼텍(Vapourtec) R 흐름 반응기를 사용하여 반응을 진행하였다. 반응기는 스테인레스강으로 제작된 10ml 코일 4개가 연결되어 총 40ml의 용량으로 구성한 세트로 하였으며, 각 코일은 유리 반응관 안에서 100℃로 가열하였다. 반응기는 유속 0.333ml/min으로 설정하여 120분 동안 반응기 코일을 거쳐 반응이 진행될 수 있도록 설정하였으며, 코일의 말단에 15bar 배압 조절기를 설치하여 반응기 내부에서 용제가 끓지 않도록 하였다. 반응이 완료된 용액은 GPC로 전환율을 측정하였고, 7배수의 메탄올에 적가하여 침전시키고, 여과 후 백색의 고분자 분말을 얻었다. 얻어진 고분자 분말은 GPC로 평균 분자량 및 분자량 분포를 측정하였다.After adding 1.5g of polymer 1c, 0.782g of dimethyl 2,2-azobis(2-methylpropionate) (V-601, Wako), 12.133g of ethyl acetate, and 8.871g of butanol to a 100ml 3-neck reactor, nitrogen cycle It was dissolved by stirring for 30 minutes while degassing. After confirming that all of the solution was dissolved, the solution was filtered through a 0.45 μm micro filter. The filtered solution was reacted using a Vapourtec R flow reactor. The reactor was a set composed of four 10 ml coils made of stainless steel connected to a total capacity of 40 ml, and each coil was heated to 100 ° C in a glass reaction tube. The reactor was set at a flow rate of 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor. The conversion rate of the reaction-completed solution was measured by GPC, precipitated by dropwise addition to 7-fold methanol, and after filtration, a white polymer powder was obtained. The obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
실시예 6. Example 6.
100ml 3-neck 반응기에 고분자1c 1.5g, 1,1'-아조비스시클로헥산카보니트릴 0.554g, 에틸아세테이트 12.133g, 이소프로필알코올 8.089g을 투입 후 질소순환으로 탈기하며 30분간 교반하여 용해하였다. 모두 용해가 된 것을 확인 후 용액을 0.45μm 마이크로 필터로 여과하였다. 여과된 용액은 베이퍼텍(Vapourtec) R 흐름 반응기를 사용하여 반응을 진행하였다. 반응기는 스테인레스강으로 제작된 10ml코일 4개가 연결되어 총 40ml의 용량으로 구성한 세트로 하였으며, 각 코일은 유리 반응관 안에서 100℃로 가열하였다. 반응기는 유속 0.333ml/min으로 설정하여 120분 동안 반응기 코일을 거쳐 반응이 진행될 수 있도록 설정하였으며, 코일의 말단에 15bar 배압 조절기를 설치하여 반응기 내부에서 용제가 끓지 않도록 하였다. 반응이 완료된 용액은 GPC로 전환율을 측정하였고, 7배수의 메탄올에 적가하여 침전시키고, 여과 후 백색의 고분자 분말을 얻었다. 얻어진 고분자 분말은 GPC로 평균 분자량 및 분자량 분포를 측정하였다.After putting 1.5 g of polymer 1c, 0.554 g of 1,1'-azobiscyclohexanecarbonitrile, 12.133 g of ethyl acetate, and 8.089 g of isopropyl alcohol into a 100ml 3-neck reactor, the mixture was degassed by nitrogen circulation and stirred for 30 minutes to dissolve. After confirming that all of the solution was dissolved, the solution was filtered through a 0.45 μm micro filter. The filtered solution was reacted using a Vapourtec R flow reactor. The reactor was a set composed of four 10 ml coils made of stainless steel connected to a total capacity of 40 ml, and each coil was heated to 100 ° C. in a glass reaction tube. The reactor was set at a flow rate of 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor. The conversion rate of the reaction-completed solution was measured by GPC, precipitated by dropwise addition to 7-fold methanol, and after filtration, a white polymer powder was obtained. The obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
비교예 1. Comparative Example 1.
100ml 3-neck 반응기에 고분자1a 1.5g, 1,1'-아조비스시클로헥산카보니트릴 0.022g, Toluene 21.36g, N-ethylpiperidine hypophosphite(EPHP) 0.257g을 투입 후 질소순환을 30분간 진행하여 탈기하였다. 용액은 100℃까지 가온한 미네랄오일이 들어있는 수조에 반응기를 넣어 2hr동안 가온한 후 냉각하였다. 반응 후 무색의 점성이 있는 액체를 수득하였으며 이를 메탄올에 침전시켜 여과 후 백색의 고분자 분말을 얻었다. 고분자의 평균분자량 및 분자량분포는 GPC로 측정하였으며 잔류 황 및 인의 함량을 ICP로 측정하였다. 고분자 사슬의 RAFT 물질 잔류는 UV를 측정하여 확인하였다.1.5g of polymer 1a, 0.022g of 1,1'-azobiscyclohexanecarbonitrile, 21.36g of toluene, and 0.257g of N-ethylpiperidine hypophosphite (EPHP) were added to a 100ml 3-neck reactor, followed by nitrogen circulation for 30 minutes to deaerate. . The solution was warmed for 2 hr by putting the reactor in a water bath containing mineral oil heated to 100 ° C, and then cooled. After the reaction, a colorless viscous liquid was obtained, which was precipitated in methanol and filtered to obtain a white polymer powder. The average molecular weight and molecular weight distribution of the polymer were measured by GPC, and the content of residual sulfur and phosphorus was measured by ICP. Residual RAFT material of the polymer chain was confirmed by measuring UV.
비교예 2. Comparative Example 2.
100ml 3-neck 반응기에 고분자1a 1.5g, 1,1'-아조비스시클로헥산카보니트릴 0.554g, 메틸에틸케톤 12.133g, 이소프로필알코올 8.089g을 투입 후 질소순환을 30분간 진행하여 탈기하였다. 용액은 85℃까지 가온한 미네랄오일이 들어있는 수조에 반응기를 넣어 8hr 동안 환류 반응 진행 후 냉각하였다. 반응 후 노란색의 점성이 있는 액체를 수득하였으며 이를 메탄올에 침전시켜 여과 후 노란색의 고분자 분말을 얻었다. 고분자의 평균분자량 및 분자량분포는 GPC로 측정하였으며 잔류 황 및 인의 함량을 ICP로 측정하였다. 고분자 사슬의 RAFT 물질 잔류는 UV를 측정하여 확인하였다.1.5 g of polymer 1a, 0.554 g of 1,1'-azobiscyclohexanecarbonitrile, 12.133 g of methyl ethyl ketone, and 8.089 g of isopropyl alcohol were added to a 100 ml 3-neck reactor, followed by nitrogen circulation for 30 minutes to degas. The solution was put in a reactor in a water bath containing mineral oil heated to 85° C., and then cooled under reflux for 8 hr. After the reaction, a yellow viscous liquid was obtained, which was precipitated in methanol and filtered to obtain a yellow polymer powder. The average molecular weight and molecular weight distribution of the polymer were measured by GPC, and the content of residual sulfur and phosphorus was measured by ICP. Residual RAFT material of the polymer chain was confirmed by measuring UV.
실시예 1 내지 6에서 사용된 고분자 용액의 성분들의 함량을 정리하면 표 1과 같다. Table 1 summarizes the contents of the components of the polymer solutions used in Examples 1 to 6.
[시험방법][Test Methods]
(1) GPC: 워터스 GPC e2695 분리모듈을 사용하여 이동상으로 테트라하이드로퓨란을 1.0ml/min의 속도로 컬럼에 흘려 분리한 후 워터스 2414 RI 탐지기로 측정하였다. 분리에 사용된 컬럼은 쇼덱스 KF-803, KF-802.5, KF802, KF-801을 연속으로 연결하여 사용하였으며 컬럼 온도는 40℃로 설정하였다. 얻어진 스펙트럼은 Shodex standard polystyrene kit SM-105으로 검정한 교정곡선을 사용하여 Mw 및 PDI를 계산하였다.(1) GPC: Using a Waters GPC e2695 separation module, tetrahydrofuran as a mobile phase was flowed through a column at a rate of 1.0 ml/min, followed by separation and measurement with a Waters 2414 RI detector. The columns used for the separation were Shodex KF-803, KF-802.5, KF802, and KF-801 connected in series, and the column temperature was set at 40 °C. Mw and PDI of the obtained spectrum were calculated using a calibration curve verified by Shodex standard polystyrene kit SM-105.
(2) UV: Agilent 8453 UV 분광기를 사용하여 파장별 흡광 스펙트럼을 측정하였다. 각 고분자의 g흡광계수는 티오카본일티오기 혹은 트리티오카보네이트로 인한 흡광이 가장 크게 일어나는 파장에서 계산하였으며, 도 1의 결과에 근거하여 고분자 1a, 1b 및 실시예 1 내지 4, 비교예 1 내지 2는 312nm, 고분자 1c 및 실시예 5 내지 6은 300nm의 g흡광계수를 계산하였다. (2) UV: The absorption spectrum for each wavelength was measured using an Agilent 8453 UV spectrometer. The g-absorption coefficient of each polymer was calculated at the wavelength at which the absorption due to the thiocarbonylthio group or trithiocarbonate is greatest, and based on the results of FIG. 1, polymers 1a and 1b and Examples 1 to 4 and Comparative Examples 1 to 2 Calculated the g extinction coefficient of 312nm, polymer 1c and Examples 5 to 6 at 300nm.
(3) ICP: Agilent Technologies 5100 ICP-OES 기기를 사용하여 측정하였다. 샘플은 산 분해 방식으로 전처리 진행한 후 황 및 인 원소에 대하여 측정하였다.(3) ICP: measured using an Agilent Technologies 5100 ICP-OES instrument. The samples were pretreated by acid decomposition and then sulfur and phosphorus elements were measured.
RAFT 물질 제거 전과 제거 후 고분자 물성 측정 결과는 표 2에 나타내었다. Table 2 shows the results of measuring polymer properties before and after removing the RAFT material.
실시예 1 내지 6에서 침전 후 건조까지 진행한 고분자 분말을 분석한 결과 RAFT 물질 제거 후 분자량이 크게 변하지 않으며, ICP 측정결과 고분자 분말 내 황 함유율이 최대 99.97%까지 감소함을 확인할 수 있다. 또한 UV 측정 결과에서 트리티오카보네이트 혹은 티오카본일티오기로 인한 312nm 혹은 300nm의 g흡광계수가 0.01 이하로 고분자 사슬 내 RAFT 물질은 거의 모두 제거된 것을 확인할 수 있다.As a result of analyzing the polymer powders from precipitation to drying in Examples 1 to 6, the molecular weight did not change significantly after the RAFT material was removed, and as a result of ICP measurement, it was confirmed that the sulfur content in the polymer powders decreased up to 99.97%. In addition, from the UV measurement results, it can be seen that the RAFT material in the polymer chain is almost all removed with a g absorption coefficient of 312 nm or 300 nm due to trithiocarbonate or thiocarbonylthio group of 0.01 or less.
일반적으로 잘 알려진 N-ethylpiperidine hypophosphite을 수소공여체로 사용하여 반응을 진행한 비교예 1의 경우, 고분자 사슬로부터 트리티오카보네이트가 제거되어 황의 함량이 161ppm으로 99.95% 제거되었고 312nm에서 g흡광계수가 0.001로 고분자 사슬 내 RAFT 물질이 거의 모두 제거된 것을 확인할 수 있으나, 고분자 분말의 잔류 인이 479ppm으로 측정되어 필요에 따라 추가적인 제거공정이 필요함을 알 수 있다. In the case of Comparative Example 1 in which the reaction was carried out using generally well-known N-ethylpiperidine hypophosphite as a hydrogen donor, trithiocarbonate was removed from the polymer chain, the sulfur content was 161 ppm and 99.95% was removed, and the g extinction coefficient at 312 nm was 0.001. It can be seen that almost all of the RAFT materials in the polymer chain have been removed, but the residual phosphorus in the polymer powder is measured at 479 ppm, indicating that an additional removal process is required as needed.
또한 실시예 1과 동일한 비율의 용액을 제조하여 회분식 반응기에서 반응을 진행한 비교예 2의 경우 연속식 흐름 반응기와 달리 반응온도가 사용한 용제의 끓는점에 의하여 제한되기 때문에 제거 반응이 거의 일어나지 않음을 확인할 수 있다. In addition, in the case of Comparative Example 2, in which a solution of the same ratio as Example 1 was prepared and the reaction was carried out in a batch reactor, it was confirmed that the elimination reaction hardly occurred because the reaction temperature was limited by the boiling point of the solvent used, unlike the continuous flow reactor. can
이상, 실시예 1 내지 6을 통해 흐름 반응기를 사용하여 고분자 사슬로부터 효과적으로 트리티오카보네이트 혹은 티오카본일티오기를 제거할 수 있음을 확인하였다. 또한 수소공여체로서 알코올을 도입함으로 인하여 다른 원소에 오염되지 않아 별도의 추가적인 정제공정을 진행하지 않고도 순도 높은 고분자 분말을 수득할 수 있음을 확인하였다.As described above, it was confirmed through Examples 1 to 6 that a trithiocarbonate or thiocarbonylthio group can be effectively removed from a polymer chain using a flow reactor. In addition, it was confirmed that high-purity polymer powder could be obtained without performing an additional purification process because it was not contaminated by other elements due to the introduction of alcohol as a hydrogen donor.
Claims (11)
상기 RAFT 고분자를 포함하는 용액을 연속식 흐름 반응기 주입하여 반응시키는 단계; 및
연속식 흐름 반응기로부터 수득되는 반응 용액을 비용매에 적가하여 침전시키는 단계를 포함하는 고분자의 제조 방법.preparing a solution containing a RAFT polymer prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization;
Reacting by injecting a solution containing the RAFT polymer into a continuous flow reactor; and
A method for producing a polymer comprising the step of precipitating by dropwise adding a reaction solution obtained from a continuous flow reactor to a non-solvent.
(i) 1종 이상의 RAFT 고분자,
(ii) 1종 이상의 자유 라디칼 개시제,
(iii) 1종 이상의 비알코올계 용제, 및
(iv) 1종 이상의 알코올
을 포함하는 것인, 고분자의 제조 방법. The method of claim 1, wherein the solution containing the RAFT polymer,
(i) one or more RAFT polymers;
(ii) one or more free radical initiators;
(iii) one or more non-alcoholic solvents, and
(iv) one or more alcohols;
A method for producing a polymer comprising a.
(i) 1종 이상의 RAFT 고분자 1 내지 50 중량%,
(ii) 1종 이상의 자유 라디칼 개시제 1 내지 10 중량%,
(iii) 1종 이상의 비알코올계 용제 20 내지 80 중량%, 및
(iv) 1종 이상의 알코올 10 내지 50 중량%를 포함하는 것인, 고분자의 제조 방법.The method of claim 1, wherein the solution containing the RAFT polymer is based on the total weight
(i) 1 to 50% by weight of one or more RAFT polymers;
(ii) 1 to 10% by weight of at least one free radical initiator;
(iii) 20 to 80% by weight of at least one non-alcoholic solvent, and
(iv) a method for producing a polymer comprising 10 to 50% by weight of at least one alcohol.
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| KR1020210159182A KR20230072685A (en) | 2021-11-18 | 2021-11-18 | Method for polymer preparation |
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| US7807755B2 (en) * | 2004-05-12 | 2010-10-05 | Commonwealth Scientific And Industrial Research Organisation | Method for removing sulfur-containing end groups |
| JP2006002096A (en) * | 2004-06-18 | 2006-01-05 | Toho Chem Ind Co Ltd | Conversion of polymer terminal group |
| CN104105718B (en) * | 2011-12-14 | 2017-05-10 | 联邦科学和工业研究组织 | RAFT polymers |
| KR20190064794A (en) * | 2017-12-01 | 2019-06-11 | 현대자동차주식회사 | Method for producing methacrylates block copolymers |
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