KR100615346B1 - Process for Preparing of Monodisperse Cross-linked Polymer Particles Using Monomers Comprising Silan Group and Unsaturated Carbon - Google Patents
Process for Preparing of Monodisperse Cross-linked Polymer Particles Using Monomers Comprising Silan Group and Unsaturated Carbon Download PDFInfo
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- KR100615346B1 KR100615346B1 KR1020030070006A KR20030070006A KR100615346B1 KR 100615346 B1 KR100615346 B1 KR 100615346B1 KR 1020030070006 A KR1020030070006 A KR 1020030070006A KR 20030070006 A KR20030070006 A KR 20030070006A KR 100615346 B1 KR100615346 B1 KR 100615346B1
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- Prior art keywords
- monomer
- unsaturated carbon
- formula
- silane group
- fine particles
- Prior art date
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- 239000000178 monomer Substances 0.000 title claims abstract description 43
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 150000001721 carbon Chemical class 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 title description 39
- 229920006037 cross link polymer Polymers 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 239000010419 fine particle Substances 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000000376 reactant Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 125000005395 methacrylic acid group Chemical group 0.000 claims abstract description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- -1 acryl Chemical group 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims 1
- 238000012674 dispersion polymerization Methods 0.000 abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- 239000003431 cross linking reagent Substances 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 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
- 230000007246 mechanism Effects 0.000 description 3
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 3
- 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 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- JMYZLRSSLFFUQN-UHFFFAOYSA-N (2-chlorobenzoyl) 2-chlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1Cl JMYZLRSSLFFUQN-UHFFFAOYSA-N 0.000 description 1
- WOTCBNVQQFUGLX-UHFFFAOYSA-N (2-methoxybenzoyl) 2-methoxybenzenecarboperoxoate Chemical compound COC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1OC WOTCBNVQQFUGLX-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- IBTLFDCPAJLATQ-UHFFFAOYSA-N 1-prop-2-enoxybutane Chemical compound CCCCOCC=C IBTLFDCPAJLATQ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 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-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C08F112/00—Homopolymers 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
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
본 발명에 따른 단분산성 고분자 가교 미립자의 제조 방법은 실란기 및 불포화 탄소를 포함하는 단량체, 개시제, 및 중합을 원하는 단량체를 혼합하고, 상기 혼합물 및 연속상 용매에 분산 안정제를 첨가하여 반응시켜, 질소 분위기에서 안정화시키고, 그리고 상기 안정화된 반응물에 물을 첨가하여 교반함으로써, 졸-겔 반응을 유도하여 고분자를 가교화시키는 단계를 포함하는 것을 특징으로 한다. 본 발명에 따른 실란기 및 불포화 탄소를 포함하는 단량체는 하기 화학식 1이나 화학식 2로 표시된다:In the method for producing the monodisperse polymer crosslinked fine particles according to the present invention, a monomer containing an silane group and an unsaturated carbon, an initiator, and a monomer to be polymerized are mixed, and a dispersion stabilizer is added to the mixture and the continuous phase solvent to react with nitrogen. Stabilizing in an atmosphere, and adding water to the stabilized reactant to stir to induce a sol-gel reaction to crosslink the polymer. Monomers comprising a silane group and an unsaturated carbon according to the present invention are represented by the following formula (1) or (2):
[화학식 1] [화학식 2][Formula 1] [Formula 2]
R―R'―Si(OR")3 R―R'―SiR'(OR")2 R-R'-Si (OR ") 3 R-R'-SiR '(OR") 2
상기 식에서, R은 비닐계, 아크릴계, 또는 메타아크릴계를 포함하는 라디칼 중합이 가능한 불포화 탄화수소, R′은 C1∼C5의 알킬기, 및 R″은 C1∼C 5의 알킬기이다.In the above formula, R is an unsaturated hydrocarbon capable of radical polymerization including vinyl, acrylic or methacrylic, R 'is an alkyl group of C 1 to C 5 , and R ″ is an alkyl group of C 1 to C 5 .
단분산성 고분자 가교 미립자, 실란기, 분산중합, 졸-겔 반응.Monodisperse polymer crosslinked fine particles, silane group, dispersion polymerization, sol-gel reaction.
Description
발명의 분야Field of invention
본 발명은 분산중합을 이용한 단분산성 고분자 가교 미립자의 제조 방법에 관한 것이다. 보다 구체적으로 본 발명은 분산중합 중에 새로운 방법을 적용함으로써, 극도의 단분산성, 높은 가교 함량, 및 균일한 미크론 크기의 입경을 갖는 단분산성 고분자 가교 미립자를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing monodisperse polymer crosslinked fine particles using dispersion polymerization. More specifically, the present invention relates to a method for producing monodisperse polymer crosslinked fine particles having extremely monodispersibility, high crosslinking content, and uniform micron size particle diameter by applying a new method during dispersion polymerization.
발명의 배경Background of the Invention
분산중합은 일반적으로 극성을 띠는 용매(주로 알콜계 용매) 및 분산 안정제를 사용하는데, 분산중합을 할 때 성장하던 올리고머는 임계 분자량에서 그 용해력을 잃기 때문에 침적 및 응집되고, 이 응집체는 분산 안정제에 의하여 안정화되어 핵을 형성한다. 이어서, 잔여 단량체가 연속상으로부터 핵으로 흡수되며, 잔여 단량체가 모두 소비될 때까지 핵이 성장하여 최종 고분자 입자를 형성한다.Dispersion polymerization generally uses a polar solvent (mainly an alcohol solvent) and a dispersion stabilizer. The oligomers grown during dispersion polymerization are deposited and aggregated because they lose their solubility at the critical molecular weight, and the aggregate is a dispersion stabilizer. Is stabilized to form a nucleus. The residual monomer is then absorbed from the continuous phase into the nucleus and the nucleus grows until the remaining monomer is consumed to form the final polymer particles.
일반적인 선형 고분자의 분산중합과는 달리, 분산중합에서 가교제를 이용하여 공중합시킬 경우, 형성된 핵의 표면이 높은 가교도를 지니는 유리상이기 때문에 연속상으로부터 단량체의 흡수를 방해하고, 결과적으로 단량체 흡수가 효과적으로 일어나지 못한다. 따라서, 분산 가교 중합 메커니즘에서는 단분산성 고분자 입자를 제조하는 것이 어렵다. 설사, 제조된 고분자 입자가 단분산성을 갖는다고 하더라도, 그 표면이 매우 거칠다.Unlike dispersion polymerization of general linear polymers, when copolymerizing with a crosslinking agent in dispersion polymerization, since the surface of the formed nucleus is a glass phase having a high degree of crosslinking, it prevents the absorption of monomer from the continuous phase and consequently monomer absorption does not occur effectively. can not do it. Therefore, it is difficult to produce monodisperse polymer particles in the dispersion crosslinking polymerization mechanism. Even if the produced polymer particle has monodispersity, the surface is very rough.
종래의 분산 가교 중합 메카니즘의 단점을 보완하기 위하여, 미국특허 제4,952,651호 및 미국특허 제4,617,249호는 단량체의 흡수에 의한 핵의 성장보다는 연속상에서 생성된 2차 핵이 기존 핵 표면으로 연속 침적됨으로써 입자가 성장되는 분산 중합법을 개시한다.In order to compensate for the shortcomings of the conventional dispersed crosslinking polymerization mechanism, U.S. Pat. Disclosed is a dispersion polymerization method in which is grown.
또한, 미국특허 제5,216,096호는 단일 분산 중합을 이용하여, 0.5 %의 가교제 함량에서도 다분산이나 응집을 보인 분산 중합법을 개시한다.U.S. Patent No. 5,216,096 also discloses a dispersion polymerization method that exhibits polydispersion or aggregation even at a crosslinking agent content of 0.5% using a single dispersion polymerization.
또한, 유기 가교제나 우레탄 아크릴레이트를 이용한 중합 방법도 보고되었다.Moreover, the polymerization method using the organic crosslinking agent and urethane acrylate was also reported.
그러나, 상기 방법들에 의하여 단분산성 고분자 입자를 제조하기 위해서는 가교제의 농도가 5 % 이내로 제한되는 등의 문제점이 있다.However, in order to produce monodisperse polymer particles by the above methods, there is a problem such that the concentration of the crosslinking agent is limited to within 5%.
따라서, 본 발명자들은 상기 종래기술의 문제점들을 해결하기 위하여, 분산중합 중에 새로운 방법인 실란기 및 불포화 탄소를 포함하는 단량체를 이용한 졸- 겔 반응법을 적용하고, 분산 안정제의 함량을 조절함으로써, 극도의 단분산성, 높은 가교 함량, 및 균일한 미크론 크기의 입경을 갖는 단분산성 고분자 가교 미립자를 제조하는 방법을 완성하였다.Therefore, in order to solve the problems of the prior art, the present inventors apply a sol-gel reaction method using a monomer containing a silane group and an unsaturated carbon, which is a new method, during dispersion polymerization, and by controlling the content of the dispersion stabilizer, A method for producing monodisperse polymer crosslinked fine particles having a monodispersity, a high crosslinking content, and a particle size of uniform micron size was completed.
본 발명의 목적은 분산중합 중에 새로운 방법인 실란기 및 불포화 탄소를 포함하는 단량체를 이용한 졸-겔 반응법을 적용하여 단분산성 고분자 가교 미립자를 제조하는 방법을 제공하기 위한 것이다.An object of the present invention is to provide a method for producing monodisperse polymer cross-linked fine particles by applying a sol-gel reaction method using a monomer containing a new silane group and unsaturated carbon during the dispersion polymerization.
본 발명의 다른 목적은 극도의 단분산성을 갖는 단분산성 고분자 가교 미립자를 제조하는 방법을 제공하기 위한 것이다.Another object of the present invention is to provide a method for producing monodisperse polymer crosslinked fine particles having extremely monodispersity.
본 발명의 또 다른 목적은 높은 가교 함량을 갖는 단분산성 고분자 가교 미립자를 제조하는 방법을 제공하기 위한 것이다.Another object of the present invention is to provide a method for producing monodisperse polymer crosslinked fine particles having a high crosslinking content.
본 발명의 또 다른 목적은 입자의 엉김 현상이 없고 단량체의 흡수력이 저해되지 않는 단분산성 고분자 가교 미립자를 제조하는 방법을 제공하기 위한 것이다.Still another object of the present invention is to provide a method for producing monodisperse polymer crosslinked fine particles, in which particles are not entangled and the absorption of monomers is not impaired.
본 발명의 또 다른 목적은 균일하고 표면이 매끄러운 미크론 크기의 입경을 갖는 단분산성 고분자 가교 미립자를 제조하는 방법을 제공하기 위한 것이다.It is another object of the present invention to provide a method for producing monodisperse polymer crosslinked fine particles having a particle size of micron size uniform and smooth surface.
본 발명의 상기 및 기타의 목적들은 상세히 설명되는 본 발명에 의하여 모두 달성될 수 있다.
The above and other objects of the present invention can be achieved by the present invention described in detail.
발명의 요약Summary of the Invention
본 발명에 따른 단분산성 고분자 가교 미립자의 제조 방법은 실란기 및 불포화 탄소를 포함하는 단량체, 개시제, 및 중합을 원하는 단량체를 혼합하고, 상기 혼합물 및 연속상 용매에 분산 안정제를 첨가하여 반응시켜, 질소 분위기에서 안정화시키고, 그리고 상기 안정화된 반응물에 물을 첨가하여 교반함으로써, 졸-겔 반응을 유도하여 고분자를 가교화시키는 단계를 포함하는 것을 특징으로 한다.In the method for producing the monodisperse polymer crosslinked fine particles according to the present invention, a monomer containing an silane group and an unsaturated carbon, an initiator, and a monomer to be polymerized are mixed, and a dispersion stabilizer is added to the mixture and the continuous phase solvent to react with nitrogen. Stabilizing in an atmosphere, and adding water to the stabilized reactant to stir to induce a sol-gel reaction to crosslink the polymer.
본 발명에 따른 실란기 및 불포화 탄소를 포함하는 단량체는 하기 화학식 1이나 화학식 2로 표시된다:Monomers comprising a silane group and an unsaturated carbon according to the present invention are represented by the following formula (1) or (2):
[화학식 1] [화학식 2][Formula 1] [Formula 2]
R―R'―Si(OR")3 R―R'―SiR'(OR")2 R-R'-Si (OR ") 3 R-R'-SiR '(OR") 2
상기 식에서, R은 비닐계, 아크릴계, 또는 메타아크릴계를 포함하는 라디칼 중합이 가능한 불포화 탄화수소, R′은 C1∼C5의 알킬기, 및 R″은 C1∼C 5의 알킬기이다.In the above formula, R is an unsaturated hydrocarbon capable of radical polymerization including vinyl, acrylic or methacrylic, R 'is an alkyl group of C 1 to C 5 , and R ″ is an alkyl group of C 1 to C 5 .
이하 본 발명의 내용을 하기에 상세히 설명한다.Hereinafter, the content of the present invention will be described in detail.
발명의 구체예에 대한 상세한 설명Detailed Description of the Invention
본 발명에 따른 단분산성 고분자 가교 미립자를 제조하는 방법은 실란기를 가지면서도 유기물과 반응이 가능한 실란기 및 불포화 탄소를 포함하는 단량체를 이용하여 분산중합이 진행됨과 동시에 졸-겔 반응을 통하여 입자를 가교시키는 방법이다. 분산중합 과정 중 실란기 및 불포화 탄소를 포함하는 단량체를 전체 반응물에 대하여 0.6∼5 중량%(사용되는 전체 단량체에 대하여 5∼40 중량%)를 사용하고, 반응 초기에 1∼7 중량%의 물을 첨가함으로 졸-겔 반응을 유도하여 제조되는 입자를 가교시키는 공정 및 입자의 가교 과정에서 발생할 수 있는 입자들간의 엉김현상과 분산중합 반응 메커니즘상 가교제의 효과에 의하여 발생할 수 있는 성장 입자의 단량체 흡수력 저해를 줄이기 위하여 분산 안정제를 5∼15 중량% 가하는 공정을 특징으로 한다. In the method for preparing the monodisperse polymer cross-linked fine particles according to the present invention, the dispersion polymerization is carried out using a monomer containing a silane group and an unsaturated carbon that can react with an organic substance while having a silane group and at the same time crosslink the particles through a sol-gel reaction. It is a way to. In the dispersion polymerization process, the monomer containing the silane group and the unsaturated carbon is used in an amount of 0.6 to 5% by weight (5 to 40% by weight based on the total monomers used) based on the total reactants, and 1 to 7% by weight of water at the beginning of the reaction Incorporation of monomer into the sol-gel reaction by adding a monomer and the ability of monomers to grow due to the effect of crosslinking agent on the entanglement between the particles that can occur during the crosslinking process and the dispersion polymerization reaction mechanism It is characterized by the addition of 5 to 15% by weight of the dispersion stabilizer to reduce the inhibition.
본 발명에 따른 단분산성 복합 가교 고분자 입자의 제조는 다음과 같은 과정을 거쳐 제조한다. 먼저 가교제의 역할을 하게 되는 화학식 1 및 화학식 2와 같은 가교제 역할을 하는 실란기와 라디칼 중합이 가능한 불포화 탄소를 포함한 단량체를 개시제와 함께 중합을 원하는 단량체에 완전히 녹인다. 이어서, 이 단량체 혼합물을 고분자 분산 안정제와 함께 알코올용액을 함유하는 밀폐 반응기에 첨가하고 질소 분위기에서 수 시간 동안 안정화시킨다. 안정화된 반응물에 소량의 물을 첨가하고 수분 교반한 후 50∼80 ℃의 온도에서 24 시간 동안 40∼100 rpm의 교반 속도로 교반하며 중합한다. 제조된 고분자 입자는 원심분리법에 의하여 알콜로 수 차례 세척하고 상온 감압 조건에서 건조하여 미세 분말 형태로 얻는다.The monodisperse composite crosslinked polymer particles according to the present invention are prepared through the following process. First, a monomer including a silane group acting as a crosslinking agent such as Formula 1 and Formula 2, which acts as a crosslinking agent, and an unsaturated carbon capable of radical polymerization are completely dissolved together with the initiator in the desired monomer. This monomer mixture is then added to the closed reactor containing the alcohol solution together with the polymer dispersion stabilizer and stabilized for several hours in a nitrogen atmosphere. A small amount of water is added to the stabilized reaction and stirred for several minutes, followed by polymerization at a stirring speed of 40 to 100 rpm at a temperature of 50 to 80 ° C. for 24 hours. The prepared polymer particles are washed several times with alcohol by centrifugation and dried under reduced pressure at room temperature to obtain fine powder.
본 발명에 따른 실란기 및 불포화 탄소를 포함하는 단량체는 하기 화학식 1이나 화학식 2로 표시된다:Monomers comprising a silane group and an unsaturated carbon according to the present invention are represented by the following formula (1) or (2):
[화학식 1] [화학식 2][Formula 1] [Formula 2]
R―R'―Si(OR")3 R―R'―SiR'(OR")2 R-R'-Si (OR ") 3 R-R'-SiR '(OR") 2
상기 식에서, R은 비닐계, 아크릴계, 또는 메타아크릴계를 포함하는 라디칼 중합이 가능한 불포화 탄화수소, R′은 C1∼C5의 알킬기, 및 R″은 C1∼C 5의 알킬기이다.In the above formula, R is an unsaturated hydrocarbon capable of radical polymerization including vinyl, acrylic or methacrylic, R 'is an alkyl group of C 1 to C 5 , and R ″ is an alkyl group of C 1 to C 5 .
본 발명에서 사용되는 실란기와 불포화 탄소를 포함한 단량체로는 실란계 반응기를 가지고 있으면서도 라디칼 중합이 가능한 단량체로 화학식 1 및 화학식 2와 같은 구조의 단랑체로 한정하며, 그 양이 전체 반응물에 대하여 0.6 중량%(사용되는 전체 단량체에 대하여 5 중량%) 이하일 때는 실란 그룹의 용액 내 밀도가 졸-겔 반응을 일으킬 만큼 충분하지 못하여 가교제의 역할을 하지 못함으로 바람직하지 않고 5 중량%(사용되는 전체 단량체에 대하여 40 중량%)이상일 때는 높아진 가교 밀도로 인하여 성장하는 입자가 연속상으로부터의 효과적으로 단량체의 흡수를 하지 못함으로 균일한 크기의 단분산성 입자의 제조가 거의 불가능하기 때문에, 사용되는 양은 전체 반응물에 대하여 5∼40 중량% 정도가 바람직하다.The monomer containing the silane group and the unsaturated carbon used in the present invention is a monomer capable of radical polymerization while having a silane-based reactor, and is limited to monolayers having the structures shown in Chemical Formulas 1 and 2, the amount of which is 0.6% by weight based on the total reactants. (Less than 5% by weight relative to the total monomers used), the density in the solution of the silane group is not sufficient to cause a sol-gel reaction and thus does not serve as a crosslinking agent. More than 40% by weight), since the increased crosslinking density prevents the growth of particles from effectively absorbing monomers from the continuous phase, it is almost impossible to produce monodisperse particles of uniform size. About 40 weight% is preferable.
따라서, 이러한 방법을 통한 단분산성 가교입자의 제조는 기존의 단분산성을 유지하기 위한 가교제의 농도가 5 중량% 이하로 제한되었던 것에 반하여, 40 중량%이하의 가교제 농도에서 단분산성의 가교입자를 제조할 수 있다는 장점이 있다.Therefore, the production of monodisperse crosslinked particles through this method produced monodisperse crosslinked particles at a crosslinking agent concentration of 40 wt% or less, whereas the concentration of the crosslinking agent for maintaining monodispersity was limited to 5 wt% or less. The advantage is that you can.
본 발명에서 사용되는 중합 단량체로는 라디칼 중합이 가능한 단량체로, 구체적으로는 스티렌, p- 혹은 m-메틸스티렌, p- 혹은 m-에틸스티렌, p- 혹은 m-클로 로스티렌, p- 혹은 m-클로로메틸스티렌, 스티렌설포닉 에시드, p- 혹은 m-t-부톡시스티렌, 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, 프로필 (메타)아크릴레이트, n-부틸 (메타)아크릴레이트, 이소부틸 (메타)아크릴레이트, t-부틸 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, n-옥틸 (메타)아크릴레이트, 라우릴 (메타)아크릴레이트, 스테아릴 (메타)아크릴레이트, 2-히드록시에틸 (메타)아크릴레이트, 폴리에틸렌 글리콜 (메타)아크릴레이트, 메톡시폴리에틸렌 글리콜 (메타)아크릴레이트, 글리시딜 (메타)아크릴레이트, 디메틸아미노에틸 (메타)아크릴레이트, 디에틸아미노에틸 (메타)아크릴레이트, 비닐 아세테이트, 비닐 프로피오네이트, 비닐 부티레이트, 비닐 에테르, 알릴 부틸 에테르, 알릴 글리시틸 에테르, (메타)아크릴산, 말레산과 같은 불포화 카복시산, 알킬(메타)아크릴아마이드, (메타)아크릴로니트릴 등을 들 수 있는데 그 양으로는 전체 반응물에 대하여 10∼30 중량%가 바람직하다.The polymerization monomer used in the present invention is a monomer capable of radical polymerization, specifically, styrene, p- or m-methylstyrene, p- or m-ethylstyrene, p- or m-chlorostyrene, p- or m -Chloromethylstyrene, styrenesulfonic acid, p- or mt-butoxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethyl Aminoethyl (meth) a Relate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ether, allyl butyl ether, allyl glycidyl ether, (meth) acrylic acid, unsaturated carboxylic acids such as maleic acid, alkyl (meth) acrylamide, (meth) acrylic Ronitrile and the like, although the amount is preferably 10 to 30% by weight based on the total reactants.
본 발명에 사용되는 개시제로는 일반적으로 사용되는 기존의 유용성 개시제로서, 구체적으로는 벤조일 퍼옥시드, 라우릴 퍼옥시드, o-클로로벤조일 퍼옥시드, o-메톡시벤조일 퍼옥시드, t-부틸퍼옥시-2-에틸헥사노에이트, t-부틸 퍼옥시이소부티레이트, 1,1,3-3-테트라메틸부틸퍼옥시-2-에틸헥사노에이트, 디옥타노일 퍼옥시드, 디데카노일 퍼옥시드 등과 같은 퍼옥시드계의 화합물과 2,2'-아조비스이오부티로니트릴, 2,2'-아조비스(2-메틸부티로니트릴), 2,2'-아조비스(2.4-디메틸발레로니트릴) 등과 같은 아조 화합물을 포함한다. 사용에 적절한 양은 전체 단량체에 대하여 1 중량% 내외이다.The initiators used in the present invention are conventional oil-soluble initiators that are generally used, specifically benzoyl peroxide, lauryl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, t-butylperoxy Such as 2-ethylhexanoate, t-butyl peroxyisobutyrate, 1,1,3-3-tetramethylbutylperoxy-2-ethylhexanoate, dioctanoyl peroxide, didecanoyl peroxide and the like Peroxide compounds, 2,2'-azobisiobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2.4-dimethylvaleronitrile) and the like Same azo compounds. Suitable amounts for use are around 1% by weight relative to the total monomers.
본 발명에서 사용되는 분산 안정제는 알콜상 혹은 수상에 녹을 수 있는 고분자로서 실란기와 반응하지 않으면서 안정효과를 보일 수 있는 고분자로 한정한다. 구체적으로는 폴리비닐피롤리돈, 폴리비닐 알킬 에테르, 폴리디메틸실록산/폴리스티렌 블록공중합체 등이 포함된다. 분산중합 과정 중에 졸-겔 반응이 일어남으로 인하여 발생할 수 있는 입자의 불균일성과 입자의 엉김현상을 해결하기 위하여 안정제의 함량은 전체 반응물에 대하여 2∼15 중량% 정도가 바람직하다.The dispersion stabilizer used in the present invention is limited to a polymer which can dissolve in an alcohol phase or an aqueous phase and exhibit a stabilizing effect without reacting with a silane group. Specific examples include polyvinylpyrrolidone, polyvinyl alkyl ethers, polydimethylsiloxane / polystyrene block copolymers, and the like. In order to solve particle nonuniformity and particle entanglement that may occur due to the sol-gel reaction during the dispersion polymerization process, the amount of stabilizer is preferably about 2 to 15% by weight based on the total reactants.
본 발명에 연속상은 알콜상으로서, 구체적으로는 메탄올, 에탄올, n-프로판올, 이소프로판올, n-부탄올, t-부탄올 등을 포함하며, 연속상의 용해력을 조절하기 위하여 벤젠 또는 톨루엔, 자일렌, 메톡시에탄올과 같은 유기물을 상기 알콜과 혼합하여 사용하기도 한다.In the present invention, the continuous phase is an alcohol phase, specifically methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and the like, and benzene or toluene, xylene, methoxy Organics such as ethanol may also be used in combination with the alcohol.
본 발명에서 실란과 졸-겔 반응을 유도하기 위하여 첨가되는 물의 양은 전체 반응물에 대하여 1 중량% 이하일 경우 충분한 졸-겔 반응을 일으킬 수 없기 때문에 바람직하지 않고, 7 중량% 이상일 때는 입자의 성장이 불안정해지기 때문에 단분산성의 입자를 얻기 힘들다. 따라서 사용되는 물의 양은 전체 반응물에 대하여 1∼7 중량%가 바람직하다.In the present invention, the amount of water added to induce the silane and sol-gel reaction is not preferable because it may not cause sufficient sol-gel reaction when it is 1 wt% or less with respect to the total reactant, and when it is 7 wt% or more, the growth of particles is unstable. It is difficult to obtain monodisperse particles because it becomes. Therefore, the amount of water used is preferably 1 to 7% by weight based on the total reactants.
본 발명에 따라 새로운 방법으로 제조된 단분산성 고분자 가교 미립자는 극도의 단분산성을 가지며, 균일하고 표면이 매끄러운 미크론 크기의 입경을 갖는다.The monodisperse polymer crosslinked fine particles produced by the new method according to the present invention have extremely monodispersibility, and have a particle size of uniform and smooth surface micron size.
본 발명은 기존 분산 중합방법으로 제조하기 어려운 단분산성 가교 고분자 입자를 졸-겔방법을 응용한 새로운 방법의 분산중합 시스템을 이용하여 해결하였고, 또한 이와 같은 방법은 높은 가교함량을 가지는 입자를 성공적으로 제조 할 수 있는 방법으로써, 최종 제조된 고분자 입자의 구조 안정성을 향상시킬 수 있을 뿐만 아니라 유무기의 복합 물질로 화학적 안정성 및 내열성이 필요한 기존 고분자 유기 입자의 접근이 어려운 여러 분야에 응용이 가능하다.The present invention solved the monodisperse crosslinked polymer particles, which are difficult to be produced by the existing dispersion polymerization method, using a new dispersion polymerization system using a sol-gel method. As a method of manufacturing, it is possible to improve the structural stability of the finally prepared polymer particles, as well as to be applied to various fields in which the existing polymer organic particles that require chemical stability and heat resistance as an organic-inorganic composite material are difficult to access.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
실란기 및 불포화 탄소를 포함하는 단량체의 함량 변화:Change in content of monomers containing silane groups and unsaturated carbons:
실시예 1A∼1BExamples 1A-1B
반응기에 스티렌 단량체, 지용성 개시제인 아조비스 이소부티로니트릴 0.125 g, 폴리비닐피롤리돈 K-30 (분자량 40,000 g/mol) 분산 안정제 8.0 g, 용매로 메탄올 76.375 g. 그리고 가교제로 메타크릴록시 프로필트리메톡시실란을 선택하여 스티렌 단량체에 대한 중량분율로 변화시키며 첨가하였다. 이때 단량체의 총량은 12.5 g이 되도록 조절하였고 메타크릴록시 프로필트리메톡시실란은 중량분율 20 및 30 %씩 첨가하였다. 상온에서 수 시간 동안 교반한 후 전체 중량에 대하여 3 중량%의 물을 첨가한 후 다시 수분 교반한 후 70 ℃에서 24 시간 동안 40 rpm의 교반 속도로 교반하면서 중합하였다. 제조된 폴리스티렌 가교 입자는 원심분리기를 이용하여 미반응물과 분산 안정제를 제거한 후 진공 오븐에서 24시간 건조시켜 분 말 형태로 얻었다. 평균입경, 분산지수, 중합도 등의 물성 결과는 하기 표 1에 나타내었다.Styrene monomer, 0.125 g of azobis isobutyronitrile as a fat-soluble initiator, 8.0 g of polyvinylpyrrolidone K-30 (molecular weight 40,000 g / mol) dispersion stabilizer, 76.375 g of methanol as a solvent. And methacryloxy propyltrimethoxysilane was selected as a crosslinking agent, and it added to the weight fraction with respect to the styrene monomer. At this time, the total amount of the monomer was adjusted to 12.5 g and methacryloxy propyltrimethoxysilane was added in 20 and 30% by weight. After stirring at room temperature for several hours, 3% by weight of water was added to the total weight, followed by water stirring, followed by polymerization at a stirring speed of 40 rpm for 24 hours at 70 ° C. The prepared polystyrene crosslinked particles were removed in an unreacted substance and dispersion stabilizer using a centrifuge and dried in a vacuum oven for 24 hours to obtain a powder form. Physical properties such as average particle diameter, dispersion index, and degree of polymerization are shown in Table 1 below.
비교실시예 1Comparative Example 1
메타크릴록시 프로필트리메톡시실란을 중량분율 50 %로 첨가한 것을 제외하고는, 상기 실시예 1과 동일하게 폴리스티렌 가교 입자를 제조하였다.Polystyrene crosslinked particles were prepared in the same manner as in Example 1, except that methacryloxy propyltrimethoxysilane was added in a weight ratio of 50%.
상기 표에 나타난 바와 같이, 본 발명에 따라 제조된 단분산성 고분자 가교 미립자는 높은 가교 함량을 유지하면서도 매우 뛰어난 단분산성을 가지며, 미크론 크기의 입경을 균일하게 갖는다는 것을 알 수 있다.As shown in the table, it can be seen that the monodisperse polymer crosslinked fine particles prepared according to the present invention have very excellent monodispersity while maintaining a high crosslinking content, and have a uniform particle size of micron size.
분산 안정제의 함량 변화:Change in content of dispersion stabilizers:
실시예 2A∼2BExamples 2A-2B
분산 안정제로 사용되는 폴리비닐피롤리돈 K-30의 함량을 전체 반응물에 대하여 8 및 10 중량%로 변화시키고, 메타크릴톡시 프로필트리메톡시실란을 전체 단 량체에 대하여 20 중량% 사용한 것을 제외하고는, 상기 실시예 1과 동일하게 폴리스티렌 가교 입자를 제조하였다.The content of polyvinylpyrrolidone K-30 used as a dispersion stabilizer was changed to 8 and 10% by weight based on the total reactants, and 20% by weight of methacryloxy propyltrimethoxysilane was used based on the total monomers. Was prepared in the same manner as in Example 1 polystyrene cross-linked particles.
비교실시예 2Comparative Example 2
폴리비닐피롤리돈 K-30의 함량을 전체 반응물에 대하여 2 중량% 사용한 것을 제외하고는, 상기 실시예 2와 동일하게 폴리스티렌 가교 입자를 제조하였다.Polystyrene crosslinked particles were prepared in the same manner as in Example 2, except that 2 wt% of polyvinylpyrrolidone K-30 was used based on the total reactants.
상기 표에 나타난 바와 같이, 본 발명에 따라 제조된 단분산성 고분자 가교 미립자는 특정한 분산 안정제의 함량에 따라, 입자의 엉김 현상이 없고 단량체의 흡수력이 저해되지 않으므로, 균일한 미크론 크기의 입경을 가질 뿐만 아니라, 뛰어난 단분산성을 갖는다는 것을 알 수 있다.As shown in the table, the monodisperse polymer cross-linked fine particles prepared according to the present invention, according to the content of a specific dispersion stabilizer, there is no particle entanglement and the absorption of the monomer is not impaired, it has a uniform micron size Instead, it can be seen that it has excellent monodispersity.
본 발명은 분산중합 중에 새로운 방법인 실란기 및 불포화 탄소를 포함하는 단량체를 이용한 졸-겔 반응법을 적용함으로써, 극도의 단분산성 및 높은 가교 함 량을 갖고, 입자의 엉김 현상이 없고 단량체의 흡수력이 저해되지 않고, 균일하고 표면이 매끄러운 미크론 크기의 입경을 갖는 단분산성 고분자 가교 미립자를 제조하는 방법을 제공하는 효과가 있다.
The present invention has an extremely monodispersible and high crosslinking content by applying a sol-gel reaction method using a monomer containing a silane group and an unsaturated carbon, a new method during dispersion polymerization, has no particle entanglement phenomenon and absorbency of the monomer There is an effect of providing a method of producing monodisperse polymer crosslinked fine particles having a particle size of a micron size that is uniform and smooth without being inhibited.
발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다. Simple modifications or variations of the invention may be readily made by those skilled in the art, and all such modifications or changes may be considered to be included within the scope of the present invention.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020030070006A KR100615346B1 (en) | 2003-10-08 | 2003-10-08 | Process for Preparing of Monodisperse Cross-linked Polymer Particles Using Monomers Comprising Silan Group and Unsaturated Carbon |
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| KR1020030070006A KR100615346B1 (en) | 2003-10-08 | 2003-10-08 | Process for Preparing of Monodisperse Cross-linked Polymer Particles Using Monomers Comprising Silan Group and Unsaturated Carbon |
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