KR20060075259A - The manufacturing method of mono-disperse functional crosslinked particles by dispersion polymerization - Google Patents
The manufacturing method of mono-disperse functional crosslinked particles by dispersion polymerization Download PDFInfo
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- KR20060075259A KR20060075259A KR1020040114029A KR20040114029A KR20060075259A KR 20060075259 A KR20060075259 A KR 20060075259A KR 1020040114029 A KR1020040114029 A KR 1020040114029A KR 20040114029 A KR20040114029 A KR 20040114029A KR 20060075259 A KR20060075259 A KR 20060075259A
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- 239000002245 particle Substances 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000012674 dispersion polymerization Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 230000008961 swelling Effects 0.000 claims abstract description 15
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- -1 inipher Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000013033 iniferter Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012986 chain transfer agent Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical group CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims 2
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims 1
- 230000002401 inhibitory effect Effects 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 239000012985 polymerization agent Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 8
- 239000000049 pigment Substances 0.000 abstract 2
- 239000002250 absorbent Substances 0.000 abstract 1
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000002537 cosmetic Substances 0.000 abstract 1
- 239000012776 electronic material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 206010042674 Swelling Diseases 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PTXBHUCBCQSAKC-UHFFFAOYSA-N S(=O)(=O)(O)O.C(CCCCCCCCCCC)Cl Chemical compound S(=O)(=O)(O)O.C(CCCCCCCCCCC)Cl PTXBHUCBCQSAKC-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 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
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- UAGGVDVXSRGPRP-UHFFFAOYSA-N diethylcarbamothioic s-acid Chemical compound CCN(CC)C(S)=O UAGGVDVXSRGPRP-UHFFFAOYSA-N 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004260 weight control 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
- C08F18/08—Vinyl acetate
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
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- Polymerisation Methods In General (AREA)
Abstract
본 발명은 리빙라디칼 개시제(iniferter)를 이용한 단분산성 기능성 입자의 중합방법에 관한 것으로서, 제조방법은 단량체, 이니퍼터, 안정제를 알콜상에서 녹인 후 분산중합하여 가교 시드(seed) 입자를 제조한 후, 단량체를 중합된 입자에 팽윤시켜 입자를 키우는 단량체 팽윤법과 중합된 고분자 입자를 시드로하여 다시 새로운 입자형성을 억제하면서 입자를 키우는 다단계 중합법을 이용하여 입자의 크기, 분자량 및 분포도 제어가 가능한 단분산성 기능성 가교 입자를 얻을 수 있다. 제조된 고분자 입자는 화장품안료, 페인트 안료, 산업용 흡수제등으로 다양한 용도로 사용될 수 있고 금속코팅에 의해 전자 소재 재료 등의 분야에 응용될 수 있다.
The present invention relates to a polymerization method of monodisperse functional particles using a living radical initiator (iniferter), and a method for preparing a crosslinked seed particle by dispersing and dispersing a monomer, an initiator and a stabilizer in an alcohol phase, Monodispersity which can control particle size, molecular weight and distribution by using monomer swelling method to swell monomer to polymerized particles and multi-step polymerization method to grow particles while suppressing new particle formation again with seeded polymerized polymer particles as seed Functional crosslinked particles can be obtained. The prepared polymer particles may be used for various purposes such as cosmetic pigments, paint pigments, industrial absorbents, etc., and may be applied to fields such as electronic material materials by metal coating.
단분산성 기능성 가교 입자, 이니퍼터, 가교제, 단량체 팽윤법, 다단계 중합법Monodisperse functional crosslinked particles, inipher, crosslinking agent, monomer swelling method, multistage polymerization method
Description
본 발명은 단분산성 기능성 가교입자의 제조방법에 관한 것으로, 보다 상세하기로는 기존의 분산중합에 이용하는 아조계나 벤조계 개시제를 대신하여 리빙라디칼 개시제(iniferter)를 이용하여 시드 폴리머를 제조한 후, 다단계 중합으로 균일한 기능성 고분자 입자를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing monodisperse functional crosslinked particles, and more specifically, to prepare a seed polymer using a living radical initiator (iniferter) in place of the azo or benzoic initiator used in the conventional dispersion polymerization, It relates to a method for producing uniform functional polymer particles by multi-step polymerization.
종래부터 현탁중합 방법과 관련하여, 미국특허 제4,017,670호, 제4,071,670호, 일본 특허공개 제90-261728 등에 현탁중합에 의한 폴리머 비드의 제조방법이 개시되어 있다. 그러나, 상기한 방법을 사용할 경우 공정이 복잡하고 분급장치에 대한 비용이 과다 소용 될 뿐만 아니라 생산성도 낮고 고분자 미립자의 입자크기 및 분포 조절이 어렵다는 단점이 있다.Conventionally, in connection with the suspension polymerization method, a method for producing polymer beads by suspension polymerization is disclosed in U.S. Patent Nos. 4,017,670, 4,071,670, and Japanese Patent Publication No. 90-261728. However, when the above method is used, the process is complicated, the cost of the classification apparatus is excessively used, the productivity is low, and the particle size and distribution of the polymer fine particles are difficult to control.
리빙라디칼 중합법은 용액중합이나 괴상중합에 의해 균일한 분자량 분포도를 갖는 괴상의 고분자물질, 혹은 이온중합법과 같은 분자구조의 설계를 위한 블록 코 폴리머를 제조하는데 사용되어왔으며, 유화중합에 접목하여 1 ㎛ 이하의 입자를 만든 예만이 있을 뿐이며 분산중합에 응용한 예는 없다.Living radical polymerization has been used to produce block copolymers for the design of bulk polymers with uniform molecular weight distribution by solution polymerization or bulk polymerization, or for the design of molecular structures such as ion polymerization. There are only examples where particles of 1 μm or less are made, and there are no examples of dispersion polymerization.
또한, 유화중합은 주로 submicron크기의 구상 고분자 미립자를 제조하는데 사용하지만 최근에 무유화제 유화중합, successive seeding 유화중합 및 무중력 하에서 유화중합에 의해 약 1∼100 ㎛ 크기의 단분산의 polystyrene(PS)미립자를 제조할 수 있는 방법이 보고된 바 있다. 그러나, 이 방법들은 제조과정이 복잡하고 장시간을 요하며 저 고형분에 한정한다는 단점을 갖는다. 또한, 분산중합법등을 이용해서 단분산성을 나타낼 수 있으나 고수율 획득을 위한 장시간 반응이 필요뿐 아니라, 제조 후 얻어진 입자의 계면활성제 등의 제거에 어려움이 있다.In addition, emulsion polymerization is mainly used to produce submicron-sized spherical polymer fine particles, but recently monodisperse polystyrene (PS) fine particles having a size of about 1 to 100 μm by emulsion-free emulsion polymerization, successive seeding emulsion polymerization and emulsion polymerization under zero gravity. It has been reported how to prepare. However, these methods have the disadvantage that the manufacturing process is complicated, takes a long time and is limited to low solids. In addition, monodispersity may be exhibited by using a dispersion polymerization method, but not only a long time reaction for obtaining a high yield is required, but it is difficult to remove surfactants and the like of the particles obtained after preparation.
또한, 아조계나 벤조계 개시제를 이용한 분산중합에 의해 단분산된 고분자 입자는 만들어지지만, 이 방법은 응집발생율이 높아 제조된 폴리머 비드의 가교도가 2%미만이므로 높은 가교도를 가진 폴리머 비드를 얻는 것이 어렵고, 분자량과 분자량 분포도를 조절하는데 어려움이 있다.
In addition, monodisperse polymer particles are produced by dispersion polymerization using an azo or benzoin initiator. However, in this method, polymer beads having a high crosslinking degree are obtained because the degree of aggregation is high and the degree of crosslinking of the prepared polymer beads is less than 2%. Difficult and difficult to control the molecular weight and molecular weight distribution.
본 발명은 상기와 같은 종래기술의 문제점을 해결하기 위한 것으로, 본 발명의 목적은 한 분자내에 개시제(iniferter)와 종결제가 결합되어 있는 리빙라디칼 개시제를 선택 사용하여 마이크론 크기의 고분자 입자를 제조한 후, 이 고분자 입자를 시드(seed)로 하여 점차적으로 중합시키는 단량체 팽윤법과 다단계 중합법을 이용하여 단분산성 기능성 입자를 제조한다. 이는, 리빙 라디칼 중합에 사용되어지 는 개시제를 이용하여 리빙라디칼 중합의 장점인 생성된 고분자의 분자량 및 분자량 분포도 조절함으로써 입자가 사용되는 분야에 따라 달라져야 하는 입도와 분자량 등의 물성을 조절할 수 있을 뿐 아니라 다단계 중합방법을 이용하거나, 단량체 팽윤법을 이용하여 가교도를 증가시킴으로써 단분산성 기능성 가교 입자의 제조방법을 제공하는 것이다.
The present invention is to solve the problems of the prior art as described above, the object of the present invention is to produce a micron-sized polymer particles by using a living radical initiator in which an initiator (iniferter) and terminator are combined in one molecule Monodisperse functional particles are prepared by using a monomer swelling method and a multistage polymerization method in which the polymer particles are seeded and gradually polymerized. By controlling the molecular weight and molecular weight distribution of the produced polymer, which is an advantage of living radical polymerization, by using an initiator used for living radical polymerization, it is possible to control physical properties such as particle size and molecular weight that should be varied depending on the field in which the particle is used. However, the present invention provides a method for producing monodisperse functional crosslinked particles by using a multistage polymerization method or by increasing the degree of crosslinking using a monomer swelling method.
본 발명의 단분산성 기능성 고분자입자의 제조방법은 (1)단량체, 리빙라디칼 개시제, 안정제를 알콜상에서 녹인 후 분산중합하여 가교 시드(seed)입자를 제조하는 제 1단계; (2)상기 제조된 고분자 입자를 시드로 하여 단량체를 중합된 입자에 팽윤시켜 입자를 키우는 단량체 팽윤법과 중합된 고분자 입자를 시드로 하여 다시 새로운 입자형성을 억제하면서 입자를 키우는 다단계 중합법을 이용해서 중합시키는 제 2단계로 이루어지는 것을 특징으로 한다. The method for producing monodisperse functional polymer particles of the present invention comprises the steps of: (1) dissolving a monomer, a living radical initiator, and a stabilizer in alcohol, followed by dispersion polymerization to prepare crosslinked seed particles; (2) By using the prepared polymer particles as a seed, the monomer swells the polymerized particles to grow the particles, and the polymerized polymer particles are used as the seed to suppress the formation of new particles again using a multi-step polymerization method to grow the particles. It is characterized by consisting of a second step of polymerization.
이하, 본 발명을 보다 상세하게 설명한다. Hereinafter, the present invention will be described in more detail.
(1) 제 1단계 : 시드 입자의 제조(1) Step 1: Preparation of Seed Particles
본 발명에서는 시드(seed)입자로 단분산성 시드입자를 사용한다. 먼저, 단량체, 리빙라디칼 중합 개시제, 안정제를 알콜상에서 녹인 후 적절한 UV 램프를 8시간정도 분산중합하고 원심분리를 이용하여 다수 세척 건조하여 분말상태의 시드(seed) 입자를 얻는다. In the present invention, monodisperse seed particles are used as seed particles. First, the monomer, the living radical polymerization initiator, and the stabilizer are dissolved in alcohol, and then, an appropriate UV lamp is dispersed and polymerized for about 8 hours and washed and dried by centrifugation to obtain seed particles in powder form.
본 발명은 유화, 분산 또는 현탁 중합하는 반응에 기존에 일반적으로 사용되 어온 퍼옥사이드계 또는 아조계 개시제를 대신하여 한 분자 구조 내에 개시제, 연쇄이동제(chain transfer) 및 종결제(terminator)의 기능을 모두 갖춘 리빙라디칼 중합개시제(iniferter)를 사용하므로써 0.1 ∼ 100 ㎛의 입자직경과 1 ∼ 2의 분자량 분포도(Mw/Mn)를 가지는 단분산성 고분자 입자를 중합하는 방법을 그 특징으로 한다. 즉, 개시제를 수마이크로미터의 입자를 얻을 수 있는 분산중합법과 시드중합법을 동시에 순차적으로 사용하여 1 ㎛ 이상의 고분자의 입자 크기 및 분자량 및 분자량 분포도가 균일한 입자를 제조하는 것이 가능한 것이다.The present invention replaces the functions of the initiator, chain transfer and terminator in one molecular structure in place of the peroxide-based or azo-based initiators generally used in emulsion, dispersion or suspension polymerization. It is characterized by a method of polymerizing monodisperse polymer particles having a particle diameter of 0.1 to 100 µm and a molecular weight distribution (Mw / Mn) of 1 to 2 by using a living radical polymerization initiator having all. That is, it is possible to produce particles having a uniform particle size, molecular weight and molecular weight distribution of a polymer of 1 µm or more by using a dispersion polymerization method and a seed polymerization method, which can simultaneously obtain particles of several micrometers, using an initiator.
상기 제 1단계에 있어서, 가교제를 첨가시켜 가교된 시드 입자를 사용할 수 있다. 가교 시드(seed) 제조의 경우에는 폴리디메틸실록산 계열의 장쇄형 가교제(PDMS-type crosslinker, 이하 PTC)를 상기 첨가물과 함께 일정 함량 이상 첨가시켜 제조될 수 있다. 그리고, 시드(seed) 고분자 입자의 제조에 사용되는 연속상은 알콜상으로서, 구체적으로는 메탄올, 에탄올, n-프로판올등을 포함하며 연속상의 용해력을 조절하기 위하여 증류수 또는 벤젠, 톨루엔, 크실렌과 같은 유기물을 상기 알코올과 혼합하여 사용하기도 한다.
In the first step, the cross-linking seed particles can be used by adding a crosslinking agent. In the case of cross-linked seed production, a polydimethylsiloxane-based long chain crosslinker (PDMS-type crosslinker, hereinafter PTC) may be prepared by adding a predetermined content or more with the additive. In addition, the continuous phase used to prepare the seed polymer particles is an alcohol phase, specifically, methanol, ethanol, n-propanol, and the like, and distilled water or organic substances such as benzene, toluene, and xylene in order to control the dissolving power of the continuous phase. It may be used in combination with the alcohol.
(2) 제 2단계 : 팽윤공정/다단계중합(2) Second Step: Swelling Process / Multi-Stage Polymerization
상기 제 1단계로부터 제조된 고분자 시드(seed) 입자를 0.1-0.5%의 유화제가 녹아 있는 수상에 초음파를 이용하여 재분산시킨다. 팽윤제로 선택된 올리고머를 먼저 유화제가 녹아있는 수상에서 기계식 교반기를 이용하여 일정시간 유화시켜 시드 분산체에 도입하여 팽윤시키고, 이어서 개시제가 녹아있는 단량체를 상기팽윤제 와 동일한 방법으로 유화시켜 팽윤제가 도입된 시드 분산체에 적하시켜 2차팽윤 시킨다.The polymer seed particles prepared from the first step are redispersed using ultrasonic waves in an aqueous phase in which 0.1-0.5% of an emulsifier is dissolved. The oligomer selected as the swelling agent is first emulsified in the aqueous phase in which the emulsifier is dissolved using a mechanical stirrer for a predetermined time and introduced into the seed dispersion, followed by swelling of the monomer in which the initiator is dissolved in the same manner as the swelling agent. The mixture was added dropwise to the seed dispersion and subjected to secondary swelling.
상기 제 2단계에서 단량체 팽윤이 완전히 끝난 후, 팽윤된 고분자 분산체를 분산 안정제를 이용하여 안정화시키고 적정한 시간동안 UV 램프를 가지고 중합한다. 제조된 고분자 입자는 시드(seed) 고분자 입자 제조와 동일한 과정으로 세척 건조시킨다. After the monomer swelling is completely completed in the second step, the swollen polymer dispersion is stabilized using a dispersion stabilizer and polymerized with a UV lamp for a suitable time. The prepared polymer particles are washed and dried in the same process as the preparation of seed polymer particles.
상기 제 1단계로부터 제조된 고분자 시드(seed) 입자에 단량체, 개시제를 첨가한 후 일정시간 UV 램프를 조사하며 반응기를 교반하여 새로운 입자형성을 억제하면서 가교되지 않은 중합부위가 가교 시드를 둘러싸는 형태로 입자를 얻었다. After adding monomers and initiators to the polymer seed particles prepared from the first step, irradiating a UV lamp for a predetermined time, stirring the reactor to inhibit formation of new particles, while the uncrosslinked polymerized site surrounds the crosslinked seed. Particles were obtained.
이하, 본 발명의 각 단계에서 사용되는 구성성분을 구체적으로 설명한다.Hereinafter, the components used in each step of the present invention will be described in detail.
본 발명에 따른 중합반응에 사용되는 단량체로는 라디칼중합이 가능한 단량체로, 구체적으로는 메틸아(메타)크릴레이트, 에틸아(메타)크릴레이트, 스티렌, 비닐 아세테이트 등이 있으며, 상기한 단량체는 1종 또는 2종 이상을 혼합하여 사용할 수 있다. 안정된 분산 입자가 얻어지기 위해서는 분산매 60-99중량%에 대하여 상기한 비닐계 단량체를 1 ∼ 40 중량% 범위 내에서 사용하며, 더욱 바람직하기로는 분산매 85 ∼ 90 중량%에 대하여 상기한 비닐계 단량체를 10 ∼ 15 중량% 범위내에서 사용하는 것이 적절하다.Monomers used in the polymerization reaction according to the present invention are monomers capable of radical polymerization, and specifically, methyl methacrylate, ethyl methacrylate, styrene, vinyl acetate, and the like. It can be used 1 type or in mixture of 2 or more types. In order to obtain stable dispersed particles, the above-described vinyl monomers are used in the range of 1 to 40% by weight based on 60-99% by weight of the dispersion medium, and more preferably, the vinyl monomers are used in the range of 85 to 90% by weight of the dispersion medium. It is appropriate to use within the range of 10 to 15% by weight.
본 발명에 따른 중합반응에 사용되는 가교제는 폴리디메틸실록산 계열의 가교제 이외에, 분자량(Mw)이 약 500-10,000 범위의 폴리옥시에틸렌글리콜계, 폴리옥시프로필렌글리콜계, 폴리테트라메틸렌글리콜계 등이 말단 비닐기 혹은 말단 아크 릴레이트된 가교제 및 에폭시아크릴레이트, 우레탄아크릴레이트등 의 반응성 가교제의 도입이 가능하다.In addition to the polydimethylsiloxane-based crosslinking agent, the crosslinking agent used in the polymerization reaction according to the present invention has a polyoxyethylene glycol-based, polyoxypropylene glycol-based, polytetramethylene glycol-based, etc. having a molecular weight (Mw) of about 500-10,000. It is possible to introduce a vinyl group or a terminally arcelated crosslinking agent and a reactive crosslinking agent such as epoxy acrylate and urethane acrylate.
본 발명에 따른 중합반응에 사용되는 개시제는 일반적으로 라디칼 중합에 사용되었던 아조계나 벤조계 개시제가 아니라, 한 분자 구조 내에 개시제, 연쇄이동제 및 종결제의 기능을 모둔 갖춘, 일명 이니퍼터(iniferter)로서, 이미 1982년 일본의 T.Otsu 등 [Macromolecular Rapid Community, 3, 127~132(1982)]에 의해 발표된 개시제로서 다음 화학식 1로 표시된다. 본 발명에 사용된 개시제는 벤질익디에틸티오카바메이트가 사용된다.
Initiators used in the polymerization reaction according to the present invention are not generally azo or benzoic initiators used for radical polymerization, but are called iniferters having all the functions of an initiator, a chain transfer agent and a terminator in one molecular structure. As an initiator, already disclosed by T.Otsu et al. (Macromolecular Rapid Community, 3, 127-132 (1982)) in Japan in 1982, it is represented by the following general formula (1). As the initiator used in the present invention, benzyl icyl diethylthio carbamate is used.
(상기 화학식 1에서, X1는 페닐기, 벤질기 및 톨루익산기가 포함되는 방향족기를 나타낸다.)(In Formula 1, X1 represents an aromatic group including a phenyl group, benzyl group and toluic acid group.)
본 발명에 따른 중합반응에 사용되는 분산매로서는 초기 단량체, 안정제, 개시제 등과 완전히 혼합될 수 있는 용매를 사용하는데, 알코올류(메틸알콜, 에틸알콜, 부틸알콜, 옥틸알콜 등), 다가 알코올류(에틸렌 글리콜, 프로필렌 글리콜, 글리세린 등), 물 등이 사용되며, 함께 사용되는 단량체, 안정제 등과 용해도 값이 비슷한 용매들 중 하나 또는 두개 이상을 혼합하여 사용함으로써 중합용매의 단량 체 용해도 값을 조절하거나 유기 폴리머의 입자 크기를 조절할 수 있다.As a dispersion medium used in the polymerization reaction according to the present invention, a solvent which can be completely mixed with an initial monomer, a stabilizer, an initiator, and the like is used. Alcohols (methyl alcohol, ethyl alcohol, butyl alcohol, octyl alcohol, etc.), polyhydric alcohols (ethylene Glycol, propylene glycol, glycerin, etc.), water, and the like, and one or two or more of the solvents having similar solubility values, such as monomers, stabilizers, and the like used together, are used to adjust the monomer solubility value of the polymerization solvent or Particle size can be controlled.
본 발명에 사용 가능한 안정제는 폴리비닐피롤리돈, 폴리비닐메틸에테르, 폴리에틸렌이민, 폴리아크릴산, 폴리비닐알콜, 비닐아세테이트 코폴리머, 에틸 셀룰로스 등이 있으며, 이들 중 하나 또는 두개 이상을 혼합하여 사용한다. 이 중 바람직하기로는 폴리비닐피롤리돈을 들 수 있다. 상기한 분산 안정제는 분산매 100 중량부에 대하여 0 ∼ 10 중량부 범위 내에서 사용되고, 더욱 바람직하기로는 2 ∼ 5 중량부 범위로 사용하는 것이 적절하다. Stabilizers usable in the present invention include polyvinylpyrrolidone, polyvinyl methyl ether, polyethyleneimine, polyacrylic acid, polyvinyl alcohol, vinyl acetate copolymer, ethyl cellulose, and the like. . Among these, polyvinylpyrrolidone is preferable. Said dispersion stabilizer is used within the range of 0-10 weight part with respect to 100 weight part of dispersion media, More preferably, it is suitable to use in the range of 2-5 weight part.
본 발명의 실시예는 아래와 같다.
An embodiment of the present invention is as follows.
<실시예 1><Example 1>
반응기에 질소 분위기하에서 개시제인 벤질익디에틸티오카바메이트 0.2g, 분산 안정화제인 폴리비닐피롤리돈 K-30 4g, 용매로 메탄올 86g을 20g의 메틸메타크릴레이트 단량체와 충분히 교반, 완전 용해시켰다. 이어서 350nm 파장대의 500W UV램프를 8시간 정도 조사하며 반응기를 교반하였다. 제조된 가교 폴리메틸메타크릴레이트 시드(seed)입자는 원심분리기를 이용하여 미반응물과 분산안정제를 제거한 후 진공 오븐에서 24시간 건조시켜 분말 형태로 얻었다.In the reactor under nitrogen atmosphere, 0.2 g of benzyl dimethylethylcarbamate as an initiator, 4 g of polyvinylpyrrolidone K-30 as a dispersion stabilizer, and 86 g of methanol as a solvent were sufficiently stirred and completely dissolved with 20 g of methyl methacrylate monomer. Subsequently, the reactor was stirred while irradiating a 500W UV lamp having a wavelength of 350 nm for 8 hours. The prepared crosslinked polymethyl methacrylate seed particles were removed in a centrifuge and then dried in a vacuum oven for 24 hours to obtain a powder form.
상기에서 제조된 폴리메타메타크릴레이트 입자를 광산란법과 전자현미경으로 분석한 결과, 지름이 0.54 ㎛ 정도의 단분산에 가교도가 91.5 mol/m3 인 입자임을 확인하였다.
As a result of analyzing the polymethacrylate methacrylate particles prepared above by light scattering method and electron microscope, it was confirmed that the particles having a crosslinking degree of 91.5 mol / m 3 with a monodispersity of about 0.54 ㎛ diameter.
<실시예 2> <Example 2>
상기 실시예 1에서 제조된 가교 입자를 팽윤법으로 팽윤시키고 중합시켰다. 구체적으로는 가교 폴리메틸메타크릴레이트 시드(seed) 입자 1.0g을 0.25% SLS(염화 라우릴 설페이트) 수용액 100.0g에 초음파를 10분간 조사하여 유리 반응기에서 재분산시켰다. 이어 동일 SLS 수용액 200.0g에 벤조일퍼록시드 개시제가 녹아있는 20.0g 이하의 메틸메타크릴레이트 단량체를 초음파 조사와 20000rpm 이상의 기계식 교반을 동시에 진행하여 10분간 유화시키고 시드입자 분산체에 적하시켜 상온에서 10시간 팽윤시켰다. 팽윤이 종료됨을 확인한 후, 역시 폴리비닐피롤리돈 10.0g 녹아있는 수용액을 이용하여 전체 함량이 500.0g이 되도록 조절하였다. The crosslinked particles prepared in Example 1 were swollen by a swelling method and polymerized. Specifically, 1.0 g of the cross-linked polymethyl methacrylate seed particles were irradiated with 100.0 g of an aqueous 0.25% SLS (lauryl chloride sulfate) solution for 10 minutes and redispersed in a glass reactor. Subsequently, 20.0 g or less methyl methacrylate monomer in which the benzoyl peroxide initiator is dissolved in 200.0 g of the same SLS aqueous solution is simultaneously emulsified for 10 minutes by ultrasonic irradiation and mechanical stirring of 20000 rpm or more, and dropped into the seed particle dispersion for 10 hours at room temperature. Swelling. After confirming that the swelling was finished, the total content was adjusted to 500.0g by using 10.0 g of polyvinylpyrrolidone dissolved aqueous solution.
이어서, 350 nm 파장대의 500 W UV 램프를 8시간 정도 조사하며 반응기를 교반하였다. 얻어진 라텍스를 여과하여 메탄올로 세척한 후 폴리비닐피롤리돈이 제거된 입자를 얻어, 광산란법과 전자현미경으로 분석한 결과, 지름 5.3 ㎛ 정도의 단분산된 가교 입자임을 확인 할 수 있었다.
Subsequently, the reactor was stirred while irradiating a 500 W UV lamp having a wavelength of 350 nm for about 8 hours. 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 monodisperse crosslinked particles having a diameter of about 5.3 μm.
<실시예 3><Example 3>
상기 실시예 1에서 제조된 가교 입자를 다단계중합법으로 중합시켰다. 구체적으로는 실시예 1에서 얻어진 라텍스 80g을 질소분위기 하에넣고, 메틸메타크릴레이트 10g을 첨가한 후, 350 nm 파장대의 500 W UV 램프를 8시간 정도 조사하며 반응기를 교반하였다. 제조된 입자를 세척 건조하여 분말 형태로 얻었다. The crosslinked particles prepared in Example 1 were polymerized by a multistage polymerization method. Specifically, 80 g of the latex obtained in Example 1 was put under a nitrogen atmosphere, 10 g of methyl methacrylate was added, and the reactor was stirred while irradiating a 500 W UV lamp having a wavelength of 350 nm for about 8 hours. The prepared particles were washed and dried to obtain a powder form.
상기에서 제조한 입자는 가교된 폴리머를 가교되지 않은 중합 부위가 둘러싸는 형태로 열가소성 수지와의 분산력을 향상시켜 우수한 투명도와 헤이즈를 갖는, 6.8 ㎛의 기능성 입자를 얻었다.
The particles prepared above improved the dispersibility with the thermoplastic resin in a form in which the crosslinked polymer was surrounded by an uncrosslinked polymerized site to obtain 6.8 μm functional particles having excellent transparency and haze.
이상에서 설명한 바와 같이, 본 발명에 따라 리빙성이 있는 개시제인 이니퍼터를 사용함으로써 분자량 조절 및 분자량 분포도가 좁으며 수마이크로미터 크기의 단분산된 가교 시드입자의 제조가 가능하다. 그리고, 단량체를 중합된 입자를 키우는 단량체 팽윤법으로 단분산된 기능성 가교입자의 제조방법과 중합된 고분자 입자를 시드로 하여 다시 새로운 입자형성을 억제하면서 입자를 키우는 방법인 다단계 중합법을 이용하여 가교된 입자를 가교되지 않은 중합 부위가 둘러싸는 형태로 단분산된 기능성 입자의 제조방법을 제공하는 효과가 있다.As described above, according to the present invention, the use of an initiator, which is a living initiator, makes it possible to prepare monodisperse crosslinked seed particles having a narrow molecular weight control and a molecular weight distribution and a size of several micrometers. In addition, crosslinking is carried out using a multistage polymerization method which is a method of preparing monodisperse functional crosslinked particles by monomer swelling method in which monomers are polymerized particles and growing particles while suppressing new particle formation by using polymerized polymer particles as seeds. There is an effect of providing a method for producing mono-dispersed functional particles in a form in which the crosslinked particles are surrounded by a non-crosslinked polymerization site.
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