KR20020078176A - Process for producing monodiserse polymer particles using iniferter - Google Patents
Process for producing monodiserse polymer particles using iniferter Download PDFInfo
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- KR20020078176A KR20020078176A KR1020010018196A KR20010018196A KR20020078176A KR 20020078176 A KR20020078176 A KR 20020078176A KR 1020010018196 A KR1020010018196 A KR 1020010018196A KR 20010018196 A KR20010018196 A KR 20010018196A KR 20020078176 A KR20020078176 A KR 20020078176A
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- particles
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- polymerization method
- dispersion polymerization
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- 239000002245 particle Substances 0.000 title claims abstract description 63
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000013033 iniferter Substances 0.000 title abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 5
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical group CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000012674 dispersion polymerization Methods 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- 239000011118 polyvinyl acetate Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 claims description 2
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 claims description 2
- YPHCUNZGBORYSA-UHFFFAOYSA-N 4-ethyloctan-2-yl 2-methylprop-2-enoate Chemical compound CCCCC(CC)CC(C)OC(=O)C(C)=C YPHCUNZGBORYSA-UHFFFAOYSA-N 0.000 claims description 2
- KQHMFMSQTXULEN-UHFFFAOYSA-N 4-ethyloctan-2-yl prop-2-enoate Chemical compound CCCCC(CC)CC(C)OC(=O)C=C KQHMFMSQTXULEN-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 6
- 239000004816 latex Substances 0.000 description 8
- 229920000126 latex Polymers 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- SBHOBKRCVFDBRL-UHFFFAOYSA-N benzyl n-tert-butylcarbamate Chemical compound CC(C)(C)NC(=O)OCC1=CC=CC=C1 SBHOBKRCVFDBRL-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- -1 diethylene Ether alcohols Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
-
- 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
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
- C08F2/08—Organic solvent with the aid of dispersing agents for the 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/124—Treatment for improving the free-flowing characteristics
Abstract
Description
본 발명은 단분산된 고분자 입자 제조 방법으로서, 더욱 상세하게는 한 분자내에 개시제와 종결제가 결합되어 있는 리빙라디칼 개시제(iniferter)를 이용해 비닐계 단량체를 분산중합으로 반응하여 균일한 고분자 입자를 제조하는 것으로, 얻어진 고분자 입자를 분산매에 재분산하여 단량체를 다시 첨가함으로써 입자의 크기와 구조를 조절할 수 있는 단분산된 고분자 입자 제조 방법에 관한 것이다.The present invention is a method for producing monodisperse polymer particles, and more specifically, using a living radical initiator in which an initiator and a terminator are combined in one molecule, vinyl monomers are reacted by dispersion polymerization to produce uniform polymer particles. The present invention relates to a method for producing monodisperse polymer particles which can control the size and structure of the particles by redispersing the obtained polymer particles in a dispersion medium and adding the monomers again.
입자가 구형이고 크기가 균일한 고분자는 기기를 검정할 때 사용되는 표준물질, 필터 기공의 크기와 효율 측정, 크로마토그래피용 칼럼의 충진물, 생화학에서 지지체, 생의학 분야, 코팅, 잉크, 복사용 건조 토너, 정보산업과 미세 전기기기등 고부가가치의 다양한 응용 분야에 사용되고 있다.Polymers with spherical particles and uniform size are the standard materials used to test the instrument, measurement of the size and efficiency of filter pores, filling of chromatography columns, supports in biochemistry, biomedical applications, coatings, inks, and dry toners for copying. It is used in a variety of high value-added applications, such as the information industry and microelectronics.
종래, 단분산된 고분자 입자의 제조는 비닐계 단량체를 현탁중합(suspension polymerization)을 통해 다양한 크기의 고분자 입자를 제조한 후 분급장치를 이용하여 입자의 크기에 따라 분리함으로써 제조하는 방법이 일본국 특허공개 제90-261728호에 개시되어 있다. 그러나 적수화학이 사용한 현탁중합에 의한 방법을 사용할 경우 공정이 복잡하고 분급장치에 대한 비용이 비쌀뿐 아니라 생산성도 낮다. 한편 WO-99/19375에는 현탁중합에 의한 단분산된 마이크론 크기의 고분자 입자 제조방법이 개시되어 있으나, 이 특허에는 고분자 입자의 구조 조절 등에 관하여는 언급되어 있지 않으며, 공정절차도 단순하지 않음을 볼 수 있다.Conventionally, the production of mono-dispersed polymer particles is a Japanese patent method for preparing polymer particles of various sizes through suspension polymerization and then separating them according to particle size using a classification apparatus. Publication No. 90-261728. However, the suspension polymerization method used by Integrity Chemistry is not only complicated and expensive, but also low in productivity. On the other hand, WO-99 / 19375 discloses a method for producing monodisperse micron-sized polymer particles by suspension polymerization, but this patent does not mention the structural control of the polymer particles, and the process procedure is not simple. Can be.
또한 유화중합에 의한 마이크론 크기의 고분자 입자 제조에 대하여 미국특허 제 6,031,051, 일본국 특허공개 제54-97582호 공보, 제63-137911호 및 제2-240108호에 개시되어 있다. 이 방법으로 제조할 시 반응에 참여되는 성분들이 많고 다단계 공정으로 제조해야 함으로 복잡하고, 시드 입자가 서브 마이크론이기 때문에 다양한 크기의 입자를 원활히 제조하기가 힘들뿐 아니라, 제조 후 얻어진 입자의 계면활성제 등의 제거에 어려움이 있다.Further, the preparation of micron-sized polymer particles by emulsion polymerization is disclosed in US Pat. No. 6,031,051, Japanese Patent Application Laid-Open Nos. 54-97582, 63-137911, and 2-240108. When manufacturing by this method, it is complicated to have many components involved in the reaction and must be manufactured in a multi-step process. Since seed particles are submicron, it is difficult to prepare particles of various sizes smoothly, and surfactants of particles obtained after preparation Has difficulty in removing.
또한 미국 특허 제4,459,378호에는 분산중합에 의한 단분산된 고분자 입자 제조에 관하여 개시되어 있으나 이 방법에 의하면 단분산된 고분자 입자는 얻을 수 있으나, 입자의 물성을 조절하기 위해 가교를 시킨다든지, 블록 중합체로 만드는 데 어려움이 있어 물성 변화에 대하여는 언급되어 있지 않다.In addition, U.S. Patent No. 4,459,378 discloses the production of monodisperse polymer particles by dispersion polymerization, but according to this method monodisperse polymer particles can be obtained, but the crosslinking or block polymer is used to control the physical properties of the particles. It is difficult to make it, so no change in properties is mentioned.
또한 미국 특허 제5,216,096호에는 가교가 가능한 단분산된 고분자 입자 제조 방법에 관하여 개시되어 있으나, 공정이 복잡하고 다양한 물성을 갖게 하기 위한 고분자의 구조 조절에 관한 언급은 되어 있지 않다.In addition, U.S. Patent No. 5,216,096 discloses a method for producing monodisperse polymer particles that can be crosslinked, but does not mention the structure control of the polymer to make the process complicated and various physical properties.
또한 미국특허 제5,708,102호, 제5,763,548호 등에는 리빙 라디칼 중합에 의한 고분자 용액 중합에 관하여 개시되어 있으나, 이는 단지 고분자의 물성을 조절할 수 있는 분자구조 설계에 초점을 맞춘 것으로 입자 제조에 관한 언급은 되어있지 않다.In addition, U.S. Patent Nos. 5,708,102, 5,763,548, etc. disclose a polymer solution polymerization by living radical polymerization, which focuses only on the molecular structure design that can control the physical properties of the polymer, which is referred to as particle production. Not.
따라서 본 발명의 목적은 상기와 같은 문제점과 한계점을 개선하여, 한 분자내에 개시제와 종결제가 결합되어 있는 리빙라디칼 개시제(iniferter)를 이용해 비닐계 단량체를 분산안정제 존재 하에 유기용매에서 분산중합함으로써 단분산된 마이크론 크기의 고분자 입자를 제조할 수 있고, 입자의 분자구조를 조절함으로써 입자가 사용되는 분야에 따라 달라져야 하는 내충격성, 변형율, 가교도 및 입도 등의 입자 물성을 조절할 수 있을 뿐 아니라 단량체만 첨가함으로 입자를 성장시킬 있 수는 단분산 고분자 입자 제조방법에 관한 것이다.Therefore, an object of the present invention is to improve the above problems and limitations, monodispersion by dispersing and polymerizing vinyl monomers in an organic solvent in the presence of a dispersion stabilizer using a living radical initiator (iniferter) in which an initiator and a terminator are combined in one molecule. Micron-sized polymer particles can be prepared, and by controlling the molecular structure of the particles, it is possible to control the particle properties such as impact resistance, strain, crosslinking degree and particle size, which should be varied depending on the field in which the particles are used, as well as adding monomers only. It relates to a method for producing monodisperse polymer particles that can grow particles.
즉, 본 발명의 목적은 한 분자내에 개시제와 종결제가 결합되어 있는 리빙라디칼 개시제를 이용하여 균일한 입도뿐 아니라 고분자 구조를 조절함으로써 물성을 제어할 수 있는 단분산된 고분자 입자 제조 방법을 제공하는 것이다.That is, an object of the present invention is to provide a method for producing monodisperse polymer particles that can control physical properties by controlling not only uniform particle size but also polymer structure by using a living radical initiator in which an initiator and a terminator are combined in one molecule. .
본 발명에 있어서 입자 제조방법은,The particle production method in the present invention,
분산안정제 0∼10 중량%를 함유한 유기 용매 중에 중합 가능한 비닐계 단량체 1종 또는 2종 이상 5∼30 중량%를 질소 분위기 하에 투입한 후, 기존 유화, 분산 또는 현탁 중합에 사용되는 퍼옥사이드계 또는 아조계 개시제가 아닌 한 분자 구조 내에 개시제(initiator), 연쇄이동(chain transfer)과 종결제(terminator)의 기능을 모두 갖춘, 일명 이니퍼터(iniferter) 0.01∼6 중량%를 리빙라디칼 중합 개시제로 사용하여 25∼130℃ 온도 또는 상온에서 자외선을 통해 개시 활성을 부여함으로써 단분산된 마이크론(0.1 - 500 ㎛)크기의 고분자 입자를 제조하는 것을 그 특징으로 한다.Peroxide type used for conventional emulsification, dispersion or suspension polymerization after adding one or two or more polymerizable vinyl monomers in an organic solvent containing 0 to 10% by weight of a dispersion stabilizer under nitrogen atmosphere. Or 0.01-6% by weight of an iniferter, which has both the functions of an initiator, chain transfer and terminator in a molecular structure, unless it is an azo initiator, as a living radical polymerization initiator. It is characterized by the production of mono-dispersed micron (0.1-500 ㎛) sized polymer particles by imparting the starting activity through ultraviolet light at a temperature of 25 ~ 130 ℃ or room temperature.
이하 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명에 사용되는 분산안정제는 수용성 또는 비수용성 용매에 용해되어 분산안정제 역할을 할 수 있는 것이면 모두 가능하다. 예를 들면, 폴리비닐피롤리돈, 폴리비닐메틸에테르, 폴리에틸렌아민, 폴리아크릴산, 폴리비닐알코올, 폴리비닐아세테이트, 폴리비닐아세테이트 공중합체, 폴리에틸셀룰로스 및 폴리히드록시프로필셀룰로스 등을 들 수 있다. 이 중 바람직하기로는 폴리비닐피롤리돈, 폴리아크릴산, 폴리비닐알코올, 폴리히드록시, 폴리프로필셀룰로스 등을 들수 있고, 특히 바람직하기로는 폴리비닐피롤리돈을 들 수 있다.The dispersion stabilizer used in the present invention may be any solvent that can dissolve in a water-soluble or non-aqueous solvent to serve as a dispersion stabilizer. For example, polyvinylpyrrolidone, polyvinyl methyl ether, polyethyleneamine, polyacrylic acid, polyvinyl alcohol, polyvinylacetate, polyvinylacetate copolymer, polyethyl cellulose, polyhydroxypropyl cellulose, etc. are mentioned. Among these, polyvinylpyrrolidone, polyacrylic acid, polyvinyl alcohol, polyhydroxy, polypropyl cellulose, and the like can be mentioned, and polyvinyl pyrrolidone is particularly preferable.
사용되는 분산안정제의 양은 0∼10 중량%가 바람직하고, 더욱 바람직하기로는 2∼5 중량%가 바람직하다.The amount of the dispersion stabilizer to be used is preferably 0 to 10% by weight, more preferably 2 to 5% by weight.
본 발명에 사용되는 비닐계 단량체로는 분산중합, 유화중합 또는 현탁중합으로 라디칼 개시가 가능한 것으로, 그 예를 들면 스티렌, 디비닐벤젠, 에틸비닐벤젠, 알파메틸스티렌, 플루오로스티렌 및 비닐피리딘 등의 방향족 비닐계 화합물; 아크릴로니트릴 및 메타크릴로니트릴 등의 시안계 비닐 화합물; 부틸아크릴레이트, 2-에틸헥실에틸아크릴레이트, 글리시딜아크릴레이트 및 N,N'-디메틸아미노에틸아크릴레이트 등의 아크릴레이트계 단량체; 부틸메타크릴레이트, 2-에틸헥실에틸메타크릴레이트, 메틸메타크릴레이트, 2-히드록시에틸메타크릴레이트 및 글리시딜메타크릴레이트 등의 메타크릴레이트계 단량체; 폴리에틸렌글리콜디아크릴레이트, 1,3-부틸렌글리콜디아크릴레이트, 1,6-헥산디아크릴레이트 등의 디아크릴레이트계 화합물; 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 폴리에틸렌글리콜디메타크릴레이트, 1,3-부틸렌글리콜디메타크릴레이트 등의 디메타크릴레이트계 화합물등을 들 수 있고 이들은 1종 또는 2종 이상을 혼합하여 사용할 수 있다.Vinyl monomers used in the present invention can be radically initiated by dispersion polymerization, emulsion polymerization or suspension polymerization, and examples thereof include styrene, divinylbenzene, ethylvinylbenzene, alphamethylstyrene, fluorostyrene and vinylpyridine. Aromatic vinyl compounds; Cyan vinyl compounds such as acrylonitrile and methacrylonitrile; Acrylate monomers such as butyl acrylate, 2-ethylhexylethyl acrylate, glycidyl acrylate, and N, N'-dimethylaminoethyl acrylate; Methacrylate monomers such as butyl methacrylate, 2-ethylhexylethyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate and glycidyl methacrylate; Diacrylate-based compounds such as polyethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,6-hexanediacrylate; Dimethacrylate type compounds, such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and 1, 3- butylene glycol dimethacrylate, etc. These can be used and these can be used 1 type or in mixture of 2 or more types.
안정된 분산 입자가 얻어지기에 바람직한 단량체 사용량은 5∼30 중량%이며, 더욱 바람직하기로는 10∼15 중량%이다.The amount of monomers preferably used is 5 to 30% by weight, more preferably 10 to 15% by weight, in order to obtain stable dispersed particles.
본 발명에 있어서, 유용한 유기용매로서는 상기의 분산안정제를 용해시킬 수 있는 것으로 그 예를 들면, 메탄올, 에탄올, 이소프로필알코올, 부틸알코올, 옥틸알코올, 벤질알코올, 시클로헥산올, 에틸렌글리콜, 글리네롤 및 디에틸렌글리콜 등의 알코올류, 메틸셀로솔브, 셀로솔브, 부틸셀로솔브, 이소프로필셀로솔브, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노메틸에테르 및 디에틸렌글리콜모노에틸에테르 등의 에테르 알코올류, 헥산, 옥탄, 페트롤륨에테르, 시클로헥산, 벤젠, 톨루엔 및 자이렌 등의 탄화수소류 용제, 아세톤, 메틸에틸케톤, 및 메틸이소부틸케톤 등의 케톤류를 들 수 있다. 이들 유기용매는 단독 또는 2종이상을 혼합하여 사용할 수 있다.In the present invention, useful organic solvents that can dissolve the above dispersion stabilizers include, for example, methanol, ethanol, isopropyl alcohol, butyl alcohol, octyl alcohol, benzyl alcohol, cyclohexanol, ethylene glycol, and grine Alcohols such as rolls and diethylene glycol, methyl cellosolve, cellosolve, butyl cellosolve, isopropyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene Ether alcohols such as glycol monoethyl ether, hydrocarbon solvents such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone have. These organic solvents can be used individually or in mixture of 2 or more types.
본 발명에 의하면 유기용매의 사용량은 70∼95 중량%가 좋으며, 바람직하기로는 85∼90 중량%가 좋다.According to the present invention, the amount of the organic solvent used is preferably 70 to 95% by weight, preferably 85 to 90% by weight.
본 발명에 사용되는 개시제는 일반적으로 라디칼 중합에 사용되었던 아조계나벤조계 개시제라 아니라, 한 분자 구조 내에 개시제(initiator), 연쇄이동(chain transfer)과 종결제(terminator)의 기능을 모두 갖춘, 일명 이니퍼터(iniferter)로서, 본 발명에 사용된 개시제는 다음과 같은 일반구조식을 갖는다.Initiators used in the present invention are not generally azo or benzoic initiators used for radical polymerization, but have all the functions of an initiator, chain transfer and terminator in one molecular structure. As an iniferter, the initiator used in the present invention has the following general structural formula.
(식중, X1은 페닐기, 벤질기, 톨루익산기 등을 나타낸다)(Wherein X 1 represents a phenyl group, benzyl group, toluic acid group, etc.)
이러한 이니퍼터는 이미 1982년 일본의 T. Otsu 등(맥크로몰리큘, 래피드 커뮤니티, 3, 127-132(1982))에 의해 발표된 개시제로서 그 동안 용액중합에 의한 블록중합체 연구에 많이 이용된 개시제이나, 이를 이용한 단분산된 고분자 입자 제조에 관하여는 아직 발표된 바가 없다.This initiator is an initiator already published by T. Otsu et al. (McChromolic, Rapid Community, 3, 127-132 (1982)) in Japan in 1982 and has been widely used for the study of block polymers by solution polymerization. Initiators, but the production of monodisperse polymer particles using the same have not been published yet.
개시제의 사용량은 0.01∼6 중량%가 바람직하며, 개시제의 활성은 열 또는 UV 등을 단독 또는 둘을 병행해 사용해도 좋다. 단분산된 입자 제조에 바람직한 개시온도는 40∼120℃이며, UV로도 개시 가능하다.The amount of the initiator is preferably 0.01 to 6% by weight, and the activity of the initiator may be used alone or in combination with heat or UV. Preferred starting temperatures for the production of monodisperse particles are 40 to 120 ° C. and can also be initiated by UV.
이상에서 설명한 내용을 다음의 실시예를 들어 보다 구체적으로 설명한다.The contents described above will be described in more detail with reference to the following examples.
[실시예1]Example 1
냉각기 있는 3구 둥근 플라스크 반응기에 메탄올 80 ml를 질소분위기 하에 넣고, 폴리비닐피롤리돈 2g을 넣은 뒤, 메틸메타크릴레이트 10g을 주사기로 첨가하였다. 반응기를 70℃ 유지시키고 개시제인 벤질익디에틸티오카바메이트 0.5g을 넣은 뒤, 7시간 교반하고, 얻어진 라텍스를 여과하여 메탄올로 세척한 후 폴리비닐피롤리돈이 제거된 입자를 얻어, 광산란법과 전자현미경으로 분석한 결과, 지름 0.8㎛ 정도의 단분산된 입자임을 확인하였다.Into a three-necked round-necked reactor, 80 ml of methanol was placed under nitrogen atmosphere, 2 g of polyvinylpyrrolidone was added, and 10 g of methyl methacrylate was added by syringe. The reactor was maintained at 70 DEG C, 0.5 g of benzyl dimethylethylcarbamate as an initiator was added thereto, and stirred for 7 hours. The resulting latex was filtered and washed with methanol to obtain particles from which polyvinylpyrrolidone was removed. As a result of microscopic analysis, it was confirmed that the particles were monodispersed particles having a diameter of about 0.8 μm.
[실시예2]Example 2
동일한 반응기에 메탄올, 폴리비닐피롤리돈, 메틸메타크릴레이트 및 개시제인 벤질익디에틸티오카바메이트를 질소 분위기 하에 동일한 양으로 첨가한 뒤, 350㎚ 파장대의 500W UV램프를 7시간 정도 조사하며 반응기를 교반하였다. 얻어진 라텍스를 여과하여 메탄올로 세척한 후 폴리비닐피롤리돈이 제거된 입자를 얻어, 광산란법과 전자현미경으로 분석한 결과, 지름 0.8㎛ 정도의 단분산된 입자임을 확인하였다.In the same reactor, methanol, polyvinylpyrrolidone, methyl methacrylate and the initiator benzyl dimethyl ethylcarbamate were added in the same amount under a nitrogen atmosphere, and the reactor was irradiated with a 500W UV lamp having a wavelength of 350 nm for about 7 hours. Stirred. The resulting latex was filtered and washed with methanol to obtain particles from which polyvinylpyrrolidone was removed, and analyzed by light scattering and electron microscopy to confirm that they were monodisperse particles having a diameter of about 0.8 μm.
[실시예3]Example 3
실시예 1 또는 2에서 얻어진 라텍스 80 g을 냉각기가 있는 3구 둥근 플라스크 반응기에 질소 분위기 하에 넣고, 메틸메타크릴레이트 10g을 첨가한 후, 350㎚ 파장대의 500W UV램프를 7시간 정도 조사하며 반응기를 교반하였다. 얻어진 라텍스를 여과하여 메탄올로 세척한 후 폴리비닐피롤리돈이 제거된 입자를 얻어, 광산란법과 전자현미경으로 분석한 결과, 지름 3.2㎛ 정도의 단분산된 입자임을 확인할 수 있었다.80 g of the latex obtained in Example 1 or 2 was placed in a three-necked round-necked flask reactor with a cooler under nitrogen atmosphere, and 10 g of methyl methacrylate was added, followed by irradiation of a 500 W UV lamp having a wavelength of 350 nm for about 7 hours. Stirred. The resulting latex was filtered and washed with methanol to obtain particles from which polyvinylpyrrolidone was removed, and analyzed by light scattering and electron microscopy. As a result, it was confirmed that the particles were monodispersed particles having a diameter of about 3.2 μm.
[실시예4]Example 4
실시예 3에서 얻어진 라텍스를 동일한 방법으로 반응하여, 고분자 입자를 얻은 뒤, 분석한 결과 지름 6.2㎛ 정도의 단분산된 입자임을 확인할 수 있었다.After reacting the latex obtained in Example 3 in the same manner to obtain a polymer particle, it was confirmed that the monodisperse particles having a diameter of about 6.2㎛.
[실시예5]Example 5
단량체인 메틸메타크릴레이트를 메틸메타크릴레이트 8g과 에틸렌글리콜디메틸아크릴레이트 2g으로 달리하고, 실시예 1과 동일한 방법으로 반응하여 얻어진 입자를 분석한 결과, 지름이 0.9㎛인 단분산된 입자임을 확인할 수 있었다.The particles obtained by reacting the monomer methyl methacrylate with 8 g of methyl methacrylate and 2 g of ethylene glycol dimethyl acrylate and reacting in the same manner as in Example 1 were identified as monodisperse particles having a diameter of 0.9 μm. Could.
얻어진 라텍스를 실시예 3과 동일하게 하여 단량체 메틸메타크릴레이트 8g과 에틸렌글리콜디메틸아크릴레이트 2g을 첨가한 후, 분석한 결과, 지름이 3.5㎛인 단분자된 입자임을 확인 할 수 있었다.In the same manner as in Example 3, the obtained latex was added with 8 g of monomer methyl methacrylate and 2 g of ethylene glycol dimethyl acrylate, and analyzed. As a result, it was confirmed that the particles were monomolecular particles having a diameter of 3.5 µm.
[실시예6]Example 6
실시예 2에서 얻어진 라텍스 80 g을 냉각기가 있는 3구 둥근 플라스크 반응기에 질소 분위기 하에 넣고, 부틸아타크릴레이트 10g을 첨가한 후, 350㎚ 파장대의 500W UV램프를 7시간 정도 조사하며 반응기를 교반하였다. 얻어진 라텍스를 여과하여 메탄올로 세척한 후 폴리비닐피롤리돈이 제거된 입자를 얻어, 광산란법과 전자현미경으로 분석한 결과, 지름 3.4㎛ 정도의 단분산된 점성이 있는 입자를 얻을 수 있었다.80 g of the latex obtained in Example 2 was placed in a three-neck round flask reactor with a cooler under nitrogen atmosphere, and 10 g of butyl atacacrylate was added, followed by irradiation of a 500 W UV lamp having a wavelength of 350 nm for about 7 hours to stir the reactor. . The resulting latex was filtered and washed with methanol to obtain particles from which polyvinylpyrrolidone was removed, and analyzed by light scattering method and electron microscope to obtain monodisperse viscous particles having a diameter of about 3.4 μm.
본 발명에서 제공하는 중합방법에 의해 리빙성이 있는 개시제인 이니퍼터를 사용함으로써 제조하기 힘들었던 마이크론 크기의 단분산된 고분자 입자를 제조할 수 있고, 입자의 분자 구조를 조절함으로써 내충격성, 변형률 및 가교도 등의 물성을 제어할 수 있는 단분산 고분자 입자의 제조가 가능하다.By using the polymerization method provided by the present invention, it is possible to produce micron-sized monodisperse polymer particles that have been difficult to produce by using an inferter which is a living initiator, and by controlling the molecular structure of the particles, impact resistance, strain and crosslinking can be prepared. It is possible to produce monodisperse polymer particles capable of controlling physical properties such as those of FIG.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100480329B1 (en) * | 2001-12-27 | 2005-04-06 | 제일모직주식회사 | Preparation of Highly Crosslinked Monodisperse Particles with a Diameter of a Micron Size |
| KR100761239B1 (en) * | 2006-05-17 | 2007-10-04 | 인하대학교 산학협력단 | Process for preparing monodisperse polymer particles by dispersion polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100480329B1 (en) * | 2001-12-27 | 2005-04-06 | 제일모직주식회사 | Preparation of Highly Crosslinked Monodisperse Particles with a Diameter of a Micron Size |
| KR100761239B1 (en) * | 2006-05-17 | 2007-10-04 | 인하대학교 산학협력단 | Process for preparing monodisperse polymer particles by dispersion polymerization |
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