KR100480336B1 - Monodisperse Polymer Particles Having Full Inter-penetrating Polymer Network Structure and Process for Preparing the Same - Google Patents
Monodisperse Polymer Particles Having Full Inter-penetrating Polymer Network Structure and Process for Preparing the Same Download PDFInfo
- Publication number
- KR100480336B1 KR100480336B1 KR10-2001-0086223A KR20010086223A KR100480336B1 KR 100480336 B1 KR100480336 B1 KR 100480336B1 KR 20010086223 A KR20010086223 A KR 20010086223A KR 100480336 B1 KR100480336 B1 KR 100480336B1
- Authority
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- South Korea
- Prior art keywords
- acrylate
- meth
- particles
- polymer particles
- monomer
- Prior art date
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- 239000002245 particle Substances 0.000 title claims abstract description 140
- 229920000642 polymer Polymers 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 38
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 35
- 230000008961 swelling Effects 0.000 claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 239000012071 phase Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 13
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 8
- 239000008346 aqueous phase Substances 0.000 claims abstract description 6
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004793 Polystyrene Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 229920002223 polystyrene Polymers 0.000 claims description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000012674 dispersion polymerization Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 239000000843 powder Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 150000005215 alkyl ethers Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 3
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 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 claims description 2
- 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 claims description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 claims description 2
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 claims description 2
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 2
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 claims description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 claims description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 claims description 2
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 claims description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 2
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 claims description 2
- IBTLFDCPAJLATQ-UHFFFAOYSA-N 1-prop-2-enoxybutane Chemical compound CCCCOCC=C IBTLFDCPAJLATQ-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 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 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000004386 Erythritol Substances 0.000 claims description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch 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
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 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 claims description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 2
- 229940009714 erythritol Drugs 0.000 claims description 2
- 235000019414 erythritol Nutrition 0.000 claims description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 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 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005591 trimellitate group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 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 claims 1
- 240000000662 Anethum graveolens Species 0.000 claims 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 239000004816 latex Substances 0.000 claims 1
- 229920000126 latex Polymers 0.000 claims 1
- 239000011368 organic material Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 18
- 238000004132 cross linking Methods 0.000 description 33
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- 229920006037 cross link polymer Polymers 0.000 description 8
- 238000009826 distribution Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- 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 4
- 125000000129 anionic group Chemical group 0.000 description 4
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- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
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- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
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- SBMYBOVJMOVVQW-UHFFFAOYSA-N 2-[3-[[4-(2,2-difluoroethyl)piperazin-1-yl]methyl]-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCN(CC1)CC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SBMYBOVJMOVVQW-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 125000003010 ionic group Chemical group 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 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
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension 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
- 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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
본 발명의 단분산성 고분자 입자의 제조방법은 (1) 폴리디메틸실록산계(Polydimethylsiloxane-base)의 가교제, 라디칼 중합이 가능한 단량체(a), 개시제, 분산안정제를 알코올상에 용해시켜, 50∼80℃의 온도에서 분산 중합하여 단분산성 가교 시드입자를 제조하는 제1단계; (2) 상기에서 제조된 가교 시드입자를 유화제가 녹아있는 수상에서 재분산시키고, 여기에 개시제가 녹아있는 단량체(b)를 도입하여 팽윤시키는 제2단계; 및 (3) 상기 팽윤된 고분자 입자를 분산안정제를 이용하여 안정화시키고, 중합시키는 제3단계로 이루어진다.The method for producing the monodisperse polymer particles of the present invention comprises (1) dissolving a polydimethylsiloxane-based crosslinking agent, a monomer (a) capable of radical polymerization, an initiator, and a dispersion stabilizer in an alcohol phase, at 50 to 80 ° C. Dispersing polymerization at a temperature of 1 st to produce monodisperse crosslinked seed particles; (2) a second step of dispersing the cross-linked seed particles prepared above in an aqueous phase in which an emulsifier is dissolved, and swelling by introducing a monomer (b) in which an initiator is dissolved therein; And (3) stabilizing the swollen polymer particles using a dispersion stabilizer and polymerizing it.
Description
발명의 분야Field of invention
본 발명은 가교된 입자를 시드(seed)로 하여 이를 팽윤, 중합하여 제조되는 완전 상호침투 가교 구조(full-IPN structure)를 갖는 단분산성 고분자 입자에 관한 것이다. 보다 구체적으로 본 발명은 폴리디메틸실록산 계열의 장쇄형 가교제를 사용하여 단분산성 가교 시드 입자를 제조하고, 여기에 단량체를 도입하여 팽윤, 중합함으로써 제조되는 상호침투 가교 구조를 갖는 단분산성 고분자 입자에 관한 것이다.The present invention relates to a monodisperse polymer particle having a full interpenetrating crosslinked structure (full-IPN structure) prepared by swelling and polymerizing the crosslinked particles as seeds. More specifically, the present invention relates to a monodisperse crosslinked polymer particle having an interpenetrating crosslinked structure prepared by preparing a monodisperse crosslinked seed particle using a long chain crosslinking agent of a polydimethylsiloxane series, and introducing and swelling and polymerizing a monomer therein. will be.
발명의 배경Background of the Invention
단분산성 고분자 입자는 액정 표시 소자용 스페이서, 내열성 입자, 다공질 입자 등에 응용되고 있으며, 최근 고기능, 고부가가치의 재료로 각광을 받고 있다. 그 중의 한 예로서 액정 표시 소자용 고분자 스페이서를 들 수 있는데, 이는 액정 cell의 간격을 일정하게 유지시키기 위한 필수적 재료이다. 이러한 스페이서의 요구조건으로서는 우선 높은 기계적, 열적 특성을 지닌 단분산성의 고분자 입자가 필요한데, 이는 중합을 통한 고분자 입자의 형성시, 가교제를 도입함으로서 해결할 수 있다. Monodisperse polymer particles have been applied to liquid crystal display device spacers, heat resistant particles, porous particles, and the like, and have recently been spotlighted as high-performance and high value-added materials. One example is a polymer spacer for a liquid crystal display device, which is an essential material for maintaining a constant gap between liquid crystal cells. As a requirement of such a spacer, first, monodisperse polymer particles having high mechanical and thermal properties are required, which can be solved by introducing a crosslinking agent in the formation of polymer particles through polymerization.
그러나, 분산중합을 이용하여 1.0 ~ 수 ㎛ 크기의 단분산성 가교 고분자 입자의 제조는 매우 어려운 것으로 알려져 있다. 일반적으로 가교 분산중합시 다분산 혹은 입자의 응집이 관찰된다. 이는 중합반응 초기에 형성되는 핵의 표면이 또한 가교되어 유리상을 형성하기 때문에 분산중합의 독특한 특징 중의 하나인 연속상으로부터의 단량체 흡수에 의한 입자 성장 과정이 효과적이지 못하기 때문이다. However, it is known that the production of monodisperse crosslinked polymer particles having a size of 1.0 to several μm using dispersion polymerization is very difficult. In general, polydispersity or aggregation of particles is observed during crosslinked dispersion polymerization. This is because the particle growth process by monomer absorption from the continuous phase, which is one of the unique features of dispersion polymerization, is not effective because the surface of the nucleus formed at the beginning of the polymerization also crosslinks to form a glass phase.
미국 특허 제5130831호, 제5153068호, 제5486941호, 제5615031호 및 제6190774호에서는 일반적으로 사용되고 있는 스페이서(spacer)의 경우 분산중합이 아닌 서스펜션 중합을 이용하여 고가교 입자를 제조하는 방법을 개시하고 있다. 그러나, 이로부터 단분산의 입자를 얻기 위해서는 메쉬(mesh)등을 이용한 후처리 공정이 필수불가결 하다는 문제점이 있다. U.S. Pat.Nos. 5,130,831,5153068,548,6941,5615031 and 6190774 disclose methods for producing high crosslinked particles using suspension polymerization rather than dispersion polymerization in the case of commonly used spacers. have. However, there is a problem that a post-treatment process using a mesh or the like is indispensable to obtain monodisperse particles therefrom.
또한 미국특허 제5750258호 및 제6117500호에는 메타아크릴로트리메톡시실란(methacryloyltrimethoxysilane)계열의 단량체를 스티렌(styrene) 등의 단량체와 분산중합 한 후, 졸-겔 공정(sol-gel process) 등의 후처리를 이용하여 입자를 가교하는 방법을 개시하고 있다. 그러나, 이 경우 Si-O 결합 이외의 실릴에스테르 결합(silyl ester bond) 형성 등의 부반응으로 인해 결함을 초래하여 최종 입자의 열적, 기계적 안정성이 오히려 저하될 수 있다 (Polymer, vol 41, p.2813, 2000).In addition, US Pat. Nos. 5750258 and 6117500 disclose that after dispersing and polymerizing a monomer of methacrylloyltrimethoxysilane with a monomer such as styrene, a sol-gel process or the like A method of crosslinking particles using a treatment is disclosed. However, in this case, side reactions, such as the formation of silyl ester bonds other than Si-O bonds, may cause defects, which may lower the thermal and mechanical stability of the final particles ( Polymer , vol 41, p.2813). , 2000).
본 발명자는 상기의 문제점을 극복하기 위하여, 폴리디메틸실록산 계열의 장쇄형 가교제(PDMS-type crosslinker, 이하 PTC)를 사용하여 가교구조를 갖는 단분산성 ㎛크기의 고분자 입자를 시드로 하고, 이를 팽윤, 중합함으로써, 완전상호침투 가교(full-IPN) 구조를 갖는 단분산의 고분자 입자를 개발하기에 이른 것이다. 본 발명의 단분산의 고분자 입자의 제조방법은 선택되는 시드 고분자의 가교도에 따라 팽윤도의 결정이 가능하고, 또한 시드 고분자의 가교도와 2차 도입 고분자의 가교도 및 계면 특성에 따라 최종 입자의 형태 예측이 가능하다. 본 발명의 방법으로 제조된 완전상호침투 가교(full-IPN) 구조를 갖는 분산성 고분자 입자는 액정 표시 소자용 스페이서, 내열성 입자, 표면 관능성 입자, 다공질 입자 등에 응용될 수 있다.In order to overcome the above problems, the present inventors use polydimethylsiloxane-based long-chain crosslinking agent (PDMS-type crosslinker, hereinafter PTC) as a seed to form monodisperse μm-sized polymer particles having a crosslinking structure, and swelling, By polymerization, monodisperse polymer particles having a full interpenetrating crosslinked (full-IPN) structure have been developed. In the method for producing monodisperse polymer particles of the present invention, the degree of swelling can be determined according to the degree of crosslinking of the selected seed polymer, and the shape of the final particles can be predicted according to the degree of crosslinking of the seed polymer and the degree of crosslinking and interfacial properties of the secondary introduced polymer. This is possible. Dispersible polymer particles having a full-interpenetrating crosslinked (full-IPN) structure produced by the method of the present invention may be applied to spacers for liquid crystal display devices, heat resistant particles, surface functional particles, porous particles, and the like.
본 발명의 목적은 완전상호침투 가교(full-IPN) 구조를 갖는 단분산성 고분자 입자 및 그 제조방법을 제공하기 위한 것이다.An object of the present invention is to provide a monodisperse polymer particles having a full interpenetrating crosslinked (full-IPN) structure and a method for producing the same.
본 발명의 다른 목적은 시드 입자의 분자량 및 가교도를 조절하여 최종입자의 모폴러지를 제어할 수 있는 단분산성 고분자 입자 및 그 제조방법을 제공하기 위한 것이다. Another object of the present invention is to provide monodisperse polymer particles and a method for preparing the same, which can control the morphology of the final particles by adjusting the molecular weight and degree of crosslinking of the seed particles.
본 발명의 또 다른 목적은 열안정성, 탄성 및 제반물성이 우수한 단분산성 고분자 입자 및 그 제조방법을 제공하기 위한 것이다.Still another object of the present invention is to provide a monodisperse polymer particle having excellent thermal stability, elasticity, and general physical properties, and a method of manufacturing the same.
본 발명의 또 다른 목적은 다양한 관능기가 도입될 수 있는 단분산성 고분자 입자 및 그 제조방법을 제공하기 위한 것이다.Still another object of the present invention is to provide a monodisperse polymer particle and a method for producing the same, into which various functional groups can be introduced.
발명의 상기 목적 및 기타의 목적들은 하기 설명되는 본 발명에 의해 모두 달성될 수 있다. The above and other objects of the invention can be achieved by the present invention described below.
이하 본 발명의 내용을 하기에 상세히 설명한다. Hereinafter, the content of the present invention will be described in detail.
본 발명의 단분산 고분자입자의 제조방법은 (1) 폴리디메틸실록산계(Polydimethylsiloxane-base)의 가교제, 라디칼 중합이 가능한 단량체(a), 개시제, 분산안정제를 알코올상에 용해시켜, 50∼80℃의 온도에서 분산 중합하여 단분산성 가교 시드입자를 제조하는 제1단계; (2) 상기에서 제조된 가교 시드입자를 유화제가 녹아있는 수상에서 재분산시키고, 여기에 개시제가 녹아있는 단량체(b)를 도입하여 팽윤시키는 제2단계; 및 (3) 상기 팽윤된 고분자 입자를 분산안정제를 이용하여 안정화시키고, 중합시키는 제3단계로 이루어진다. The method for producing the monodisperse polymer particles of the present invention comprises (1) dissolving a polydimethylsiloxane-based crosslinking agent, a monomer (a) capable of radical polymerization, an initiator, and a dispersion stabilizer in an alcohol phase, at 50 to 80 ° C. Dispersing polymerization at a temperature of 1 st to produce monodisperse crosslinked seed particles; (2) a second step of dispersing the cross-linked seed particles prepared above in an aqueous phase in which an emulsifier is dissolved, and swelling by introducing a monomer (b) in which an initiator is dissolved therein; And (3) stabilizing the swollen polymer particles using a dispersion stabilizer and polymerizing it.
이하, 본 발명을 상세히 설명하면 다음과 같다. Hereinafter, the present invention will be described in detail.
(1) 제1단계 : 가교 시드 입자의 제조 (1) First step: preparation of crosslinked seed particles
본 발명에서는 시드(seed)입자로 가교된 단분산성 시드입자를 사용한다. 가교되지 않은 선형 시드 고분자를 사용한 일반적인 내열성 고분자의 경우, 팽윤도가 높더라도 선형 고분자가 고온의 환경에서는 입자 밖으로 녹아 나오기 때문에 불순물 역할을 하는 문제점이 있다. 그러나, 본 발명과 같이 시드입자가 가교되어 있을 경우, 2차 중합 고분자와 완전히 상호침투 고분자 가교망 (full-IPN)을 형성하기 때문에 상기와 같은 문제점을 해결할 수 있는 것이다. In the present invention, monodisperse seed particles crosslinked with seed particles are used. In the case of a general heat resistant polymer using a non-crosslinked linear seed polymer, even though the degree of swelling is high, the linear polymer melts out of the particles in a high temperature environment, thereby serving as an impurity. However, when the seed particles are cross-linked as in the present invention, the above problems can be solved because the interpenetrating polymer cross-linking network (full-IPN) is completely formed with the secondary polymer.
본 발명의 가교 시드 입자는 하기 화학식 1 또는 2로 표시되는 폴리디메틸실록산 계열의 장쇄형 가교제(PDMS-type crosslinker, 이하 PTC), 단량체(a), 유용성 개시제 및 분산 안정제를 알콜상에 녹인 후 50∼80℃의 온도에서 40∼100 rpm의 교반 속도로 분산중합하여 제조된다. The crosslinked seed particles of the present invention are prepared by dissolving a polydimethylsiloxane-based long-chain crosslinking agent (PDMS-type crosslinker, hereinafter PTC), a monomer (a), an oil-soluble initiator and a dispersion stabilizer represented by the following Chemical Formula 1 or 2 in an alcohol phase. It is produced by dispersion polymerization at a stirring speed of 40 to 100 rpm at a temperature of ˜80 ° C.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기식에서, R' 는 H 또는 CH3이고, n은 5-600의 정수임.Wherein R 'is H or CH 3 and n is an integer from 5-600.
상기와 같은 폴리디메틸실록산 계열의 장쇄형 가교제를 사용할 경우, 일반적인 단분자 가교제에 비해 분산중합의 중합 초기에 극성 반응 연속상으로부터의 성장 핵 내로의 단량체 흡수과정이 효과적으로 일어나게 된다. 이는 일반적인 단분자 가교제인 디비닐벤젠 또는 디아크릴계열의 가교제에 비하여 가교 밀도가 상대적으로 낮을 뿐 아니라, PTC 자체의 화학적 성질에서 기인하는 소수성(hydrophobicity)에 의해 단량체의 이동(diffusion)이 효과적으로 유도될 수 있기 때문이다. When the long chain crosslinking agent of the polydimethylsiloxane series is used as described above, monomer absorption into the growth nucleus from the polar reaction continuous phase occurs more effectively at the initial stage of the polymerization of the dispersion polymerization than the general monomolecular crosslinking agent. Compared to the divinylbenzene or diacryl crosslinking agent, which is a common monomolecular crosslinking agent, the crosslinking density is relatively low, and the monomer migration can be effectively induced by hydrophobicity due to the chemical properties of PTC itself. Because it can.
결과적으로 PTC를 사용할 경우, 초기 핵 입자의 균일한 성장이 가능할 뿐만 아니라, 빠른 중합 반응 속도를 나타낸다. 아울러, 분산 중합 결과 0.1∼수㎛의 평균 입경을 지니는 단분산성 가교 입자의 제조가 가능한 것이다. As a result, when PTC is used, not only uniform growth of initial nucleus particles is possible, but also a high polymerization reaction rate is exhibited. In addition, it is possible to produce monodisperse crosslinked particles having an average particle diameter of 0.1 to several μm as a result of dispersion polymerization.
특히, 본 발명의 가교 시드 입자의 합성법에서는 PTC의 분자량(Mw)이 약 1,000일 경우 약 1.0 wt% 이상에서 완전 가교망을 형성하게 된다. PTC의 함량이 3∼10%에서는 PTC의 도입량에 비례하여 시드 입자의 가교도가 증가한다. PTC의 함량이 1.0 wt% 미만일 경우, 가교망을 형성하지는 못하지만, 오히려 가교제의 도입량으로부터 시드 입자의 분자량 조절이 가능하다. 따라서, PTC의 도입량에 따라, 다양한 분자량과 가교도를 지니는 시드 고분자 입자가 제조될 수 있으며, 시드 입자의 분자량 및 가교도를 조절함으로써, 최종입자의 모폴러지를 제어할 수 있게 된다.In particular, in the method for synthesizing the crosslinked seed particles of the present invention, when the molecular weight (M w ) of PTC is about 1,000, a fully crosslinked network is formed at about 1.0 wt% or more. When the content of PTC is 3 to 10%, the degree of crosslinking of the seed particles increases in proportion to the amount of PTC introduced. If the content of PTC is less than 1.0 wt%, it does not form a crosslinking network, but rather the molecular weight of the seed particles can be controlled from the amount of crosslinking agent introduced. Therefore, seed polymer particles having various molecular weights and crosslinking degrees can be prepared according to the amount of PTC introduced, and the morphology of the final particles can be controlled by adjusting the molecular weight and the crosslinking degree of the seed particles.
이와 같이 PTC를 사용하여 시드 입자를 가교시키고, 여기에 2차 중합 고분자를 높은 가교도로 다시 가교하였을 경우, 입자의 탄성 및 제반 물성이 매우 우수하게 된다. 특히, 시드 입자가 가교되어 있기 때문에 최종 입자의 열안정성이 매우 우수해진다.When seed particles are crosslinked using PTC as described above, and the secondary polymerized polymer is crosslinked again at a high crosslinking degree, the elasticity and general physical properties of the particles are very excellent. In particular, since the seed particles are crosslinked, the thermal stability of the final particles is very excellent.
본 발명에서 시드 고분자 입자의 제조에 사용되는 연속상은 알콜상으로서, 구체적으로는 메탄올, 에탄올, n-프로판올, 이소프로판올, n-부탄올, t-부탄올 등을 포함한다. 상기 연속상의 용해력을 조절하기 위하여 증류수 또는 벤젠, 톨루엔, 크실렌, 메톡시에탄올과 같은 유기물을 상기 알콜과 혼합하여 사용하기도 한다. The continuous phase used in the preparation of the seed polymer particles in the present invention is an alcohol phase, and specifically includes methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol and the like. In order to control the dissolving power of the continuous phase, distilled water or organic substances such as benzene, toluene, xylene and methoxyethanol may be mixed with the alcohol.
분산중합후 원심분리를 이용하여 다수 세척 건조하여 가교 시드 입자를 분말상태로 얻는다. After dispersion polymerization, a plurality of washing and drying are performed by centrifugation to obtain crosslinked seed particles in powder form.
(2) 제2단계 : 팽윤 공정(2) second step: swelling process
상기로부터 제조된 가교 시드입자를 유화제가 녹아있는 수상에서 초음파를 이용해 재분산시키고, 여기에 개시제가 녹아있는 단량체(b)를 도입하여 팽윤시킨다. 상기 단량체(b)는 유용성 개시제를 용해시켜 0.1∼0.5%의 유화제가 녹아있는 수상에서 기계식 교반기를 이용하여 10∼30분간 유화시킨 후, 가교 시드 분산체에 도입한다. The crosslinked seed particles prepared above are redispersed using ultrasonic waves in an aqueous phase in which an emulsifier is dissolved, and swells by introducing a monomer (b) in which an initiator is dissolved therein. The monomer (b) is dissolved in the oil-soluble initiator, emulsified for 10 to 30 minutes using a mechanical stirrer in an aqueous phase in which 0.1 to 0.5% of an emulsifier is dissolved, and then introduced into the crosslinked seed dispersion.
팽윤 공정은 0∼50℃의 온도에서 수행한다. 이때 도입되는 단량체(b)의 성질에 따라 최종 중합 고분자 입자의 형태가 결정된다. The swelling process is carried out at a temperature of 0 to 50 ° C. At this time, the shape of the final polymerized polymer particles is determined according to the properties of the monomer (b) introduced.
본 발명의 하나의 구체예에서는 팽윤 과정에서 가교 시드 고분자 입자와 동종의 2차 가교 고분자를 형성할 수 있는 단량체를 중합하여 단분산성 고분자 입자를 제조한다. In one embodiment of the present invention, monodisperse polymer particles are prepared by polymerizing a monomer capable of forming a homogeneous secondary crosslinked polymer with a crosslinked seed polymer particle in the swelling process.
본 발명의 또 다른 구체에에서는 가교 시드 고분자 입자와 다른 다양한 단량체를 도입하여 최종 중합 고분자 입자의 형태를 결정할 수 있다. 예컨대, 팽윤단계에서 에폭시 링 혹은 클로로기를 지니는 단량체를 도입하여 중합함으로서 표면에 반응유도기를 지니는 고분자 입자가 제조될 수 있는 것이다. 이 때, 에폭시 링은 개환반응에 의하여 보통 양이온성으로 변환되고 클로로기는 활성화 수소와 반응하여 음이온성으로 변환된다. 이 외에도 상기의 반응 과정을 통하여 다양한 관능기 도입이 가능하다. In another embodiment of the present invention, the cross-linked seed polymer particles and various other monomers may be introduced to determine the shape of the final polymerized polymer particles. For example, polymer particles having a reaction-inducing group on the surface may be prepared by introducing and polymerizing a monomer having an epoxy ring or a chloro group in the swelling step. At this time, the epoxy ring is usually converted to cationic by the ring-opening reaction, and the chloro group is converted to anionic by reacting with activated hydrogen. In addition, various functional groups may be introduced through the reaction process.
또한, 상기 팽윤 단계에서 제2차 가교제로 다가 비닐계 화합물을 2차 단량체 도입량을 기준으로 10-90 중량부, 바람직하게는 30-80 중량부로 첨가하여 가수분해 등의 후처리 없이 완전 상호침투 가교 고분자 입자를 제조할 수 있다. In addition, in the swelling step, the polyvalent vinyl compound as the secondary crosslinking agent is added in an amount of 10-90 parts by weight, preferably 30-80 parts by weight based on the amount of the secondary monomer, thereby completely interpenetrating crosslinking without post-treatment such as hydrolysis. Polymer particles can be produced.
상기 제2차 가교제는 라디칼 중합이 가능한 것으로서 디비닐벤젠, 1,4-디비닐옥시부탄, 디비닐술폰, 디알릴 프탈레이트, 디알릴아크릴아미드, 트리알릴 (이소)시아누레이트, 트리알리 트리멜리테이트 등의 알릴 화합물과, (폴리)에틸렌 글리콜 디(메타)아크릴레이트, (폴리)프로필렌 글리콜 디(메타)아크릴레이트, 펜타에릴트리톨 테트라(메타)아크릴레이트, 펜타에릴트리톨 트리(메타)아크릴레이트, 펜타에릴트리톨 디(데타)아크릴레이트, 트리메틸올프로판 트리(메타)아크릴레이트, 디펜타에릴트리톨 헥사(메타)아크릴레이트, 이펜타에릴트리톨 펜타(메타)아크릴레이트, 글리세롤 트리(메타)아크릴레이트 등의 (폴리)아킬렌 글리콜 디(메타)아크릴레이트계 화합물을 포함한다. The secondary crosslinking agent is capable of radical polymerization, and may be divinylbenzene, 1,4-divinyloxybutane, divinylsulphone, diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanurate, trially trimelli Allyl compounds, such as a tate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, pentaaryl tritol tetra (meth) acrylate, penta erythritol tri ( Meth) acrylate, pentaaryl tritol di (dec) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, inpenta erythritol penta (meth) And (poly) alkylene glycol di (meth) acrylate-based compounds such as acrylate and glycerol tri (meth) acrylate.
상기 (폴리)에틸렌 글리콜 디(메타)아크릴레이트, (폴리)프로필렌 글리콜 디(메타)아크릴레이트등과 같은 2차 가교제는 PTC와 달리 친수성을 가지므로 2차 단량체의 팽윤 과정에서 필수적으로 요구되는 매우 안정한 단량체 에멀젼의 제조가 가능하며, 이에 따라 seed 입자내로의 단량체 팽윤이 용이하게 유도될 수 있다.Secondary crosslinking agents such as (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate and the like have hydrophilicity unlike PTC and therefore are very essential for the swelling process of secondary monomers. It is possible to prepare stable monomer emulsions, which can easily lead to monomer swelling into seed particles.
팽윤과정에서 시드 가교망으로부터 야기되는 탄성력이 최종 입자의 형태에 영향을 미치지 않는 범위에서 가교제 도입량을 적절히 조절한다면 50% 이상의 가교제 함량을 지니는 가교망 형성이 가능하다. In the swelling process, if the amount of crosslinking agent introduced is adjusted in a range such that the elastic force resulting from the seed crosslinking network does not affect the shape of the final particles, it is possible to form a crosslinking network having a crosslinking agent content of 50% or more.
이와 같이 시드 입자가 가교되고 2차 중합 고분자가 높은 가교도로 다시 가교되었을 경우, 입자의 탄성 및 제반 물성이 매우 우수하게 된다. 특히, 시드 입자가 가교되어 있기 때문에 최종 입자의 열안정성이 매우 우수해진다. As such, when the seed particles are crosslinked and the secondary polymerized polymer is crosslinked again with high crosslinking degree, the elasticity and general physical properties of the particles are very excellent. In particular, since the seed particles are crosslinked, the thermal stability of the final particles is very excellent.
(3) 제3단계 : 중합 공정(3) Third step: polymerization process
상기 제2단계에서 팽윤된 고분자 입자를 분산안정제를 이용하여 안정화시키고, 중합시킨다. 제조된 고분자 입자는 상기 시드 고분자 입자 제조와 동일한 과정으로 세척 건조시킨다. The polymer particles swollen in the second step are stabilized using a dispersion stabilizer and polymerized. The prepared polymer particles are washed and dried in the same process as the seed polymer particles.
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.
(A) 폴리디메틸실록산 계열의 가교제(A) Polydimethylsiloxane Crosslinking Agent
본 발명의 폴리디메틸실록산 계열의 장쇄형 가교제는 하기 화학식 1 또는 2로 표시된다. The long chain crosslinking agent of the polydimethylsiloxane series of the present invention is represented by the following formula (1) or (2).
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기식에서, R' 는 H 또는 CH3이고, n은 5-600의 정수임.Wherein R 'is H or CH 3 and n is an integer from 5-600.
상기 PTC의 사슬 길이는 반응 연속상 및 중합 단량체의 선택에 따라 달라질 수 있으며, 분자량(Mw)은 대략 500-50,000 정도의 것을 선택하나, 이에 한정되는 것은 아니다.The chain length of the PTC may vary depending on the reaction continuous phase and the selection of the polymerization monomer, and the molecular weight (M w ) is selected to about 500-50,000, but is not limited thereto.
본 발명에서는 상기 폴리디메틸실록산 계열의 장쇄형 가교제 이외에도 분자량(Mw)이 약 500-10,000 범위이고, 말단 비닐기(vinyl-terminated) 혹은 말단 아크릴레이트(acrylate-terminated)를 갖는 폴리옥시에틸렌글리콜계(polyoxyethyleneglycol-base), 폴리옥시프로필렌글리콜계(polyoxypropylene glycol-base), 폴리테트라메틸렌글리콜계(polytetramethyleneglycol-base) 가교제 및 에폭시아크릴레이트(epoxyacrylate), 우레탄아크릴레이트(urethane acrylate) 등의 반응성 가교제의 도입이 가능하다. 또한 반응 연속상의 선택 및 기타 중합 변수에 따라 분자 구조 설계가 가능하다.In the present invention, in addition to the polydimethylsiloxane-based long chain crosslinking agent, the molecular weight (M w ) is in the range of about 500-10,000 and has a polyvinyl glycol-based terminal having a terminal vinyl group (vinyl-terminated) or terminal acrylate (acrylate-terminated) (polyoxyethyleneglycol-base), polyoxypropylene glycol-base, polytetramethyleneglycol-base crosslinking agent and reactive crosslinking agents such as epoxy acrylate and urethane acrylate This is possible. Molecular structure design is also possible depending on the choice of the reaction continuous phase and other polymerization parameters.
본 발명에서는 적절한 중합 조건에서 상기 PTC를 전체 단량체에 대하여 약 10.0%까지 도입 가능하다.In the present invention, the PTC can be introduced up to about 10.0% of the total monomers under suitable polymerization conditions.
(B) 단량체(B) monomer
상기 제1단계의 시드 고분자 입자의 제조(단량체 a) 및 제2단계의 팽윤 공정(단량체 b)시 첨가되며, 단량체(a) 및 단량체(b)는 서로 같거나 다를 수 있다. It is added during the preparation of the seed polymer particles of the first step (monomer a) and the swelling process of the second step (monomer b), and the monomers (a) and (b) may be the same or different.
본 발명의 단량체는 라디칼 중합이 가능한 단량체로, 구체적으로는 스티렌, p-메틸스티렌, m-메틸스티렌, p-에틸스티렌, m-에틸스티렌, p-클로로스티렌, m-클로로스티렌, p-클로로메틸스티렌, m-클로로메틸스티렌, 스티렌설포닉 에시드, p-t-부톡시스티렌, 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)아크릴 산, 말레 산과 같은 불포화 카복시 산, 알킬(메타) 아크릴아마이드, (메타)아크릴로니트릴로 이루어진 군으로부터 선택된다. Monomers of the present invention are monomers capable of radical polymerization, specifically styrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene, m-ethylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloro Methyl styrene, m-chloromethyl styrene, styrenesulphonic acid, pt-butoxy styrene, mt-butoxy styrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (Meth) acrylate, isobutyl (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 ( Meta) acrylate, di Ethylaminoethyl (meth) acrylate, 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 and (meth) acrylonitrile.
상기 선택되는 단량체의 종류에 따라 제조되는 입자의 형태가 결정된다.The type of the particles to be produced depends on the type of monomer selected.
(C) 개시제(C) initiator
본 발명에서 사용되는 개시제로는 통상의 유용성 개시제가 사용될 수 있다. 구체적으로는 벤조일 퍼록시드, 라우릴 퍼록시드, o-클로로벤조일 퍼록시드, o-메톡시벤조일 퍼록시드, t-부틸퍼록시-2-에틸헥사노에이트, t-부틸 퍼록시이소부티레이트, 1,1,3-3-테트라메틸부틸퍼록시-2-에틸헥사노에이트, 디옥타노일 퍼록시드, 디데카노일 퍼록시드 등과 같은 퍼록시드 계와 2,2'-아조비스이오부티로니트릴, 2,2'-아조비스(2-메틸부티로니트릴), 2,2'-아조비스(2.4-디메틸발레로니트릴) 등과 같은 아조 화합물을 포함한다.As the initiator used in the present invention, conventional oil-soluble initiators can be used. Specifically, benzoyl peroxide, lauryl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, 1, Peroxides such as 1,3-3-tetramethylbutylperoxy-2-ethylhexanoate, dioctanoyl peroxide, didecanoyl peroxide and the like, and 2,2'-azobisiobutyronitrile; Azo compounds such as 2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2.4-dimethylvaleronitrile) and the like.
(D) 분산 안정제(D) dispersion stabilizer
본 발명에서 사용되는 분산 안정제는 알콜상 혹은 수상에 녹을 수 있는 고분자이다. 구체적으로는 젤라틴, 스타치, 히드록시에틸셀룰로오즈, 카복시메틸셀룰로오즈, 폴리비닐피롤리돈, 폴리비닐 알킬 에테르, 폴리비닐 알콜, 폴리디메틸실록산/폴리스티렌 블록공중합체 등이 포함된다. The dispersion stabilizer used in the present invention is a polymer that can be dissolved in an alcohol phase or an aqueous phase. Specific examples include gelatin, starch, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alkyl ether, polyvinyl alcohol, polydimethylsiloxane / polystyrene block copolymer, and the like.
상기 분산안정제의 사용량은 분산 중합 과정에서 생성된 고분자 입자가 중력에 의한 침적이나 입자간 응집을 억제할 수 있을 정도가 바람직하다.구체적으로 전체 반응물에 대하여 제1단계에서는 약 1.5 % 이상이 적절하고, 제3단계에서는 1.0 % 내외가 적절하다.The amount of the dispersion stabilizer is preferably such that the polymer particles produced during the dispersion polymerization can suppress deposition by gravity or agglomeration between particles. Specifically, about 1.5% or more is appropriate in the first step with respect to the total reactants. In the third stage, about 1.0% is appropriate.
(E) 유화제(E) emulsifier
본 발명에서는 상기 유화제가 팽윤공정에서 단량체 에멀젼 제조를 위하여 사용된다. In the present invention, the emulsifier is used for preparing the monomer emulsion in the swelling process.
본 발명의 유화제는 음이온성 유화제가 바람직하다. 구체적으로는, 알킬, 아릴, 알카릴 설페이트, 설포네이트, 포스페이트, 혹은 석시네이트 등과 이들의 에톡시 유도체들이 포함된다. 폴리옥시에틸렌 알킬 에테르, 폴리옥시에틸렌 알킬 페놀 에테르, 폴리에틸렌 글리콜, 등의 비이온성 유화제를 상기의 음이온성 유화제와 혼합하여 사용하기도 한다. 이들 유화제는 또한 중합 중 분산 안정제와 함께 입자의 침적 및 응집을 억제시킨다. 팽윤제 및 단량체 에멀젼 제조시 적절한 함량은 전체 분산체 조성에 대하여 0.1∼0.5%가 적절하다.The emulsifier of the present invention is preferably an anionic emulsifier. Specifically, alkyl, aryl, alkaryl sulfate, sulfonate, phosphate, or succinate and the like and ethoxy derivatives thereof are included. Nonionic emulsifiers such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, polyethylene glycols, and the like may be used in combination with the anionic emulsifiers described above. These emulsifiers also, along with the dispersion stabilizers during polymerization, inhibit the deposition and aggregation of the particles. Suitable amounts for the preparation of swelling agents and monomer emulsions are suitably from 0.1 to 0.5% of the total dispersion composition.
(F) 2차 가교제(F) secondary crosslinking agent
상기 제2차 가교제는 상호 침투 가교 고분자 입자의 제조를 위하여 팽윤단계에서 단량체와 함께 첨가된다. The secondary crosslinking agent is added together with the monomer in the swelling step to prepare the interpenetrating crosslinked polymer particles.
본 발명의 2차 가교제는 라디칼 중합이 가능한 것으로서, 구체적으로는, 디비닐벤젠, 1,4-디비닐옥시부탄, 디비닐술폰, 디알릴 프탈레이트, 디알릴아크릴아미드, 트리알릴 (이소)시아누레이트, 트리알리 트리멜리테이트 등의 알릴 화합물, 헥산디올디아크릴레이트, (폴리)에틸렌 글리콜 디(메타)아크릴레이트, (폴리)프로필렌 글리콜 디(메타)아크릴레이트, 펜타에릴트리톨 테트라(메타)아크릴레이트, 펜타에릴트리톨 트리(메타)아크릴레이트, 펜타에릴트리톨 디(메타)아크릴레이트, 트리메틸올프로판 트리(메타)아크릴레이트, 디펜타에릴트리톨 헥사(메타)아크릴레이트, 이펜타에릴트리톨 펜타(메타)아크릴레이트, 글리세롤 트리(메타)아크릴레이트 등의 (폴리)아킬렌 글리콜 디(메타)아크릴레이트 화합물을 포함한다.The secondary crosslinking agent of the present invention is capable of radical polymerization, specifically, divinylbenzene, 1,4-divinyloxybutane, divinylsulphone, diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanu Allylic compounds such as acrylate and trially trimellitate, hexanediol diacrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, pentaaryl tritol tri (meth) acrylate, pentaaryl tritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate And (poly) alkylene glycol di (meth) acrylate compounds such as inepentaryl tritol penta (meth) acrylate and glycerol tri (meth) acrylate.
본 발명은 하기의 실시예에 의하여 보다 구체화될 것이며, 하기의 실시예는 본 발명의 구체적인 예시에 불과하고 본 발명의 보호범위를 한정하거나 제한하고자 하는 것이 아니다. The present invention will be further illustrated by the following examples, which are only specific examples of the present invention and are not intended to limit or limit the protection scope of the present invention.
실시예 1-5Example 1-5
(a) 가교 시드 입자의 제조(a) Preparation of Crosslinked Seed Particles
반응기에 스티렌 단량체, 지용성 개시제인 아조비스이소부티로니트릴(AIBN) 1.0 g, 분산 안정화제인 폴리비닐피롤리돈 K-30 (분자량 40,000g/mol) 17.9 g, 용매로 에탄올과 메톡시에탄올 (1:1 중량비) 877.7g, 및 가교제로 상기 화학식1의 분자량(Mw) 1,000 전후의 PTC를 스티렌 단량체의 함량에 대하여 0%, 1.0%, 3.0%, 5.0% 및 10.0%로 변화시키며 첨가하였다. 이 때 단량체의 총량은 100.0g이 되도록 조절하였다. 이어서 질소 분위기 하에서, 70 ℃에서 40 rpm의 속도로 교반하면서 중합하였다. 제조된 폴리스티렌 가교 입자는 원심분리기를 이용하여 미반응물과 분산 안정제를 제거한 후 진공 오븐에서 건조시켜 분말 형태로 얻었다.In the reactor, styrene monomer, 1.0 g of azobisisobutyronitrile (AIBN) as a fat-soluble initiator, 17.9 g of polyvinylpyrrolidone K-30 (molecular weight 40,000 g / mol) as a dispersion stabilizer, ethanol and methoxyethanol as a solvent (1 : 1 weight ratio) 877.7g, and the crosslinking agent was added to the PTC before and after the molecular weight (M w ) 1,000 of the formula (1) varying to 0%, 1.0%, 3.0%, 5.0% and 10.0% with respect to the content of the styrene monomer. At this time, the total amount of the monomer was adjusted to 100.0g. Subsequently, polymerization was carried out under a nitrogen atmosphere with stirring at a speed of 40 rpm at 70 ° C. The prepared polystyrene crosslinked particles were obtained in powder form by removing unreacted material and dispersion stabilizer using a centrifuge and drying in a vacuum oven.
상기에서 제조된 폴리스티렌 가교 입자와 그 분산도는 광학 형미경 (Optical Microcsope)과 주사 광학 현미경 (Scanning Electron Microscope) 사진 결과를 이용하여 측정하였다. 시편은 분말 형태의 입자를 유리 위에 단층으로 도포시키고 금으로 코팅하여 제조하였다. 200개 이상 입자를 측정하고 평균 수평균입경, 평균 중량평균입경을 얻었고, 중량평균입경에 대한 수평균입경의 비율로부터 입자 크기분포의 분산지수를 얻었다. 가교되지 않은 시드 입자의 분자량 분포는 겔 투과 크로마토그래피(gel permeation chromatography)로부터 구하였고, 가교도는 팽윤과정에서 단량체의 시드 입자로의 확산률로부터 계산하였다. 그 결과를 표 1에 나타내었다. The polystyrene crosslinked particles prepared as described above and their dispersion degree were measured using optical microcsope and scanning electron micrographs. Specimens were prepared by coating particles in powder form in a single layer on glass and coating with gold. More than 200 particles were measured and the average number average particle diameter and average weight average particle diameter were obtained, and the dispersion index of the particle size distribution was obtained from the ratio of the number average particle diameter to the weight average particle diameter. The molecular weight distribution of the uncrosslinked seed particles was obtained from gel permeation chromatography, and the degree of crosslinking was calculated from the diffusion rate of the monomer into the seed particles during the swelling process. The results are shown in Table 1.
(b) 팽윤 후 중합 반응(b) polymerization after swelling
상기 제1단계에서 제조된 폴리스티렌 선형 혹은 가교 입자를 단량체로 팽윤시킨 후 중합하였다. 구체적으로는 선형 혹은 가교 폴리스티렌 시드 입자 1.0 g을 0.25% SLS(염화 라우릴 설페이트) 수용액 100.0 g에 초음파를 10분간 조사하여 유리 반응기에서 재분산하였다. 이어 동일 SLS 수용액 200.0 g에 벤조일 퍼록시드 개시제가 녹아있는 스티렌 단량체를 초음파 조사와 20000 rpm 이상의 기계식 교반를 동시에 진행하여 10분간 유화시키고 시드 입자 분산액에 적하시켜 상온에서 팽윤시켰다. 단량체의 팽윤비는 시드 입자에 대하여 무게비로 15배로 고정하였다. 스티렌의 팽윤이 종료됨을 확인한 후, 검화도 88% 내외의 폴리비닐알콜 10.0 g이 녹아있는 수용액을 이용하여 전체 함량이 400.0g이 되도록 조절하였다. 이어서, 반응기의 온도를 80℃로 높이고 중합하였다. 상기로부터 제조된 폴리스티렌 입자는 원심분리기를 이용하여 미반응물과 분산 안정제를 반복하여 제거한 후 진공 오븐에서 건조시켜 분말 형태로 얻었다.The polystyrene linear or crosslinked particles prepared in the first step were swelled with a monomer and then polymerized. Specifically, 1.0 g of linear or crosslinked polystyrene seed particles were re-dispersed in a glass reactor by irradiating 100.0 g of an aqueous 0.25% SLS (lauryl chloride sulfate) solution for 10 minutes. Subsequently, the styrene monomer in which the benzoyl peroxide initiator was dissolved in 200.0 g of the same SLS aqueous solution was emulsified for 10 minutes by ultrasonic irradiation and mechanical stirring of at least 20000 rpm, and was added dropwise to the seed particle dispersion to swell at room temperature. The swelling ratio of the monomers was fixed 15 times in weight ratio relative to the seed particles. After confirming that the swelling of the styrene is finished, the total content was adjusted to 400.0g using an aqueous solution in which 10.0 g of polyvinyl alcohol having a saponification degree of about 88% was dissolved. The temperature of the reactor was then raised to 80 ° C. and polymerized. The polystyrene particles prepared above were repeatedly removed by removing the unreacted material and the dispersion stabilizer using a centrifuge and dried in a vacuum oven to obtain a powder form.
실시예 6-7 : 제2차 가교제로 디비닐벤젠을 도입하여 상호침투 가교고분자 입자의 제조Example 6-7 Preparation of Interpenetrating Crosslinked Polymer Particles by Introducing Divinylbenzene as Secondary Crosslinking Agent
제1단계에서 PTC를 5.0 중량% 도입하고, 제2단계의 팽윤과정에서 스티렌과 디비닐벤젠의 중량비를 하기 표2와 같이 변화시키며 도입한 것을 제외하고는 상기 실시예 1-5와 동일하게 수행되었다. 5.0 wt% PTC was introduced in the first step, and the weight ratio of styrene and divinylbenzene was changed in the second step of swelling as shown in Table 2, and the same procedure as in Example 1-5 was performed. It became.
상기 실시예 1-5에서 제조된 폴리스티렌 입자 및 실시예 6-7의 폴리스티렌 입자를 표 2에 정리하였다. The polystyrene particles prepared in Example 1-5 and the polystyrene particles of Example 6-7 are summarized in Table 2.
스티렌 단량체에 의한 완전한 팽윤은 전자현미경 관찰을 통하여 확인하였다. PTC의 함량이 5.0% 이상 도입된, 즉 가교도가 210 molm-3 이상인 폴리스티렌 가교 시드의 경우 스티렌 단량체에 의한 팽윤이 비대칭적으로 일어났다. 낮은 가교도의 시드 입자는 완전한 구형의 semi-IPN을 형성하지만 높은 가교도의 시드 입자는 상분리가 일어남을 확인하였다. 또한 단량체 에멀젼의 완전한 팽윤이 이루어지지 못했는데, 이와 같은 결과는 시드의 가교망으로부터 유도되는 높은 탄성력에 기인한다. 210 molm-3 이하의 낮은 가교도에서도 팽윤 후 중합법으로 도입한 가교제의 량이 50.0% 이상일 경우 다시 가교망 내에서 상분리가 일어났다. 이는 2차 고분자의 가교도가 증가함에 따라 가교 시드와의 상용성이 오히려 감소하기 때문이다. 그러나, 30% 전후의 가교제 함량까지는 full-IPN 구조의 가교망을 형성하였고 매우 균일한 단분산도를 나타냈다.Complete swelling by styrene monomer was confirmed by electron microscopic observation. In the case of polystyrene crosslinked seeds having a content of PTC of 5.0% or more, that is, a crosslinking degree of 210 molm- 3 or more, swelling by styrene monomers occurred asymmetrically. It was confirmed that the seed particles having low degree of crosslinking formed completely spherical semi-IPN, but the seed particles having high degree of crosslinking caused phase separation. In addition, complete swelling of the monomer emulsion was not achieved, which is due to the high elastic force derived from the crosslinking network of the seed. Even at a low crosslinking degree of 210 molm -3 or less, when the amount of crosslinking agent introduced by polymerization after swelling was 50.0% or more, phase separation occurred again in the crosslinking network. This is because the compatibility with the crosslinking seed rather decreases as the degree of crosslinking of the secondary polymer increases. However, up to 30% crosslinker content, the cross-linked network of full-IPN structure was formed and showed very uniform monodispersity.
실시예 8-11 : 제2차 가교제로 헥산디올디아크릴레이트를 도입하여 상호침투 가교고분자 입자의 제조 Example 8-11 Preparation of Interpenetrating Crosslinked Polymer Particles by Introducing Hexanediol Diacrylate as Secondary Crosslinking Agent
가교제로 헥산디올디아크릴레이트를 사용하고, 도입되는 헥산디올디아크릴레이트의 함량을 전체 단량체의 비율에 대해 30 wt%로 고정되도록 도입한 것을 제외하고 상기 실시예 6과 동일하게 수행되었다. It was carried out in the same manner as in Example 6 except that hexanediol diacrylate was used as the crosslinking agent, and the content of hexanediol diacrylate introduced was fixed so as to be fixed at 30 wt% relative to the total monomer ratio.
단량체의 완전한 팽윤은 전자현미경 관찰을 통하여 확인하였다. 상기 실시예 6-7에서 관찰된 상분리 현상을 본 실시예 8-11을 통하여 보다 구체적으로 확인할 수 있었다. Complete swelling of the monomer was confirmed by electron microscope observation. Phase separation observed in Example 6-7 was confirmed in more detail through this Example 8-11.
선형 폴리스티렌 시드를 사용한 실시예 8의 경우 시드 고분자의 다중 상분리가 관찰되었고, 상대적으로 낮은 가교도의 폴리스티렌 시드를 사용하였을 경우 단일상만을 형성하였다가, 높은 가교도의 시드 입자를 팽윤 후 중합했을 경우, 단일상분리 혹은 반구형 상분리 현상이 관찰되었다. In the case of Example 8 using linear polystyrene seeds, multiple phase separation of the seed polymer was observed, and when using a relatively low crosslinking polystyrene seed, only a single phase was formed, and when the high crosslinking seed particles were polymerized after swelling, Phase separation or hemispherical phase separation was observed.
이상의 결과로부터, 시드의 가교 구조 및 가교의 정도, 그리고 팽윤시에 도입되는 가교제의 종류가 입자의 상분리를 유도하는 또 다른 중요한 인자임을 확인하였다. 따라서, 가교 폴리스티렌를 시드 고분자로 이용하고 가교제의 선택 및 그의 상분리 정도를 적절히 조절하면 표 3에 나타낸 바와 같이 여러 형태의 단분산성 고분자 입자를 제조할 수 있음을 알 수 있다. From the above results, it was confirmed that the crosslinking structure of the seed, the degree of crosslinking, and the kind of crosslinking agent introduced at the time of swelling were other important factors inducing phase separation of the particles. Therefore, it can be seen that various types of monodisperse polymer particles can be prepared as shown in Table 3 by using crosslinked polystyrene as a seed polymer and properly controlling the selection of the crosslinking agent and the degree of phase separation thereof.
실시예 12-13 : 단량체로 글리시틸메타크릴레이트를 도입한 상호침투 가교고분자 입자의 제조 Example 12-13 Preparation of Interpenetrating Crosslinked Polymer Particles Incorporating Glycityl Methacrylate as a Monomer
제1단계에서 PTC를 각각 0 및 1.0 중량%를 사용하고, 팽윤 후 중합과정에서 단량체로 글리시틸메타크릴레이트를 스티렌/디비닐벤젠의 비율 70/30 (wt/wt)의 혼합조성에 대하여 10.0% 중량비로 도입한 것을 제외하고는 상기 실시예 6-7과 동일하게 수행되었다. 제조된 입자에 존재하는 관능기는 적절한 적정법을 선택하여 정량적으로 분석하였다. In the first step, 0 and 1.0% by weight of PTC were used, respectively, and the swelling ratio was about 70/30 (wt / wt) of glycidyl methacrylate as a monomer during polymerization. The same procedure as in Example 6-7 was carried out except that 10.0% by weight was introduced. The functional groups present in the prepared particles were analyzed quantitatively by selecting the appropriate titration method.
실시예 14-15 : 단량체로 클로로메틸스티렌를 도입한 상호침투 가교고분자 입자의 제조 Example 14-15 Preparation of Interpenetrating Crosslinked Polymer Particles Incorporating Chloromethylstyrene as a Monomer
제1단계에서 PTC를 각각 0 및 1.0 중량%를 사용하고, 팽윤 후 중합과정에서 단량체로 클로로메틸스티렌을 스티렌/디비닐벤젠의 비율 70/30 (wt/wt)의 혼합조성에 대하여 10.0% 중량비로 도입한 것을 제외하고는 상기 실시예 6-7과 동일하게 수행되었다. 제조된 입자에 존재하는 관능기는 적절한 적정법을 선택하여 정량적으로 분석하였다. In the first step, 0 and 1.0 wt% of PTC were used, respectively, and 10.0% by weight of chloromethylstyrene as a monomer in the polymerization process after swelling, with a styrene / divinylbenzene ratio of 70/30 (wt / wt). The same procedure as in Example 6-7 was carried out except for introducing into. The functional groups present in the prepared particles were analyzed quantitatively by selecting the appropriate titration method.
상기 실시예 12-15에서 제조된 표면 관능성 단분산성 고분자 입자의 특성을 하기 표 4에 정리하였다. The properties of the surface functional monodisperse polymer particles prepared in Example 12-15 are summarized in Table 4 below.
얻어진 고분자 입자는 도입되는 관능성 단량체의 존재 유무에 상관없이 단분산성을 띠고 있는 것으로 나타났다. 수상에서 2차 고분자 중합을 하기 때문에, 수상에서 관능성 단량체의 변형이 일어날 수 있으나, 적절한 pH나 전해질의 첨가를 통하여 방지할 수 있다. 표 4에 나타낸 2종의 표면 관능성 고분자 입자를 통하여 음이온성 혹은 양이온성 이온기를 표면에 치환시킬 수 있다. 예를 들어, 에폭시 링을 함유하는 관능성 입자는 디아민과 개환반응시켜 표면에 양이온성 아민기를 지니게 되고, 글로로기를 지니는 관능성 입자는 활성화 수소를 지니는 디에시드와 치환 반응시켜 음이온기를 도입할 수 있다.The obtained polymer particles were found to have monodispersity regardless of the presence or absence of the functional monomer to be introduced. Since secondary polymer polymerization is carried out in the water phase, deformation of the functional monomer may occur in the water phase, but it can be prevented by adding an appropriate pH or electrolyte. Anionic or cationic ionic groups can be substituted on the surface through the two kinds of surface functional polymer particles shown in Table 4. For example, a functional particle containing an epoxy ring may be ring-opened with diamine to have a cationic amine group on its surface, and a functional particle having a gloro group may be substituted with a dieside having activated hydrogen to introduce an anionic group. have.
본 발명은 폴리디메틸실록산 계열의 장쇄형 가교제를 사용하여 가교구조를 갖는 단분산성 ㎛크기의 고분자 입자를 시드로 하고, 이를 팽윤, 중합함으로써, 완전상호침투 가교(full-IPN) 구조를 갖는 단분산의 고분자 입자 및 그의 제조방법을 제공하는 발명의 효과를 갖는다. The present invention uses a polydimethylsiloxane-based long-chain crosslinking agent as a seed to form monodisperse μm-sized polymer particles having a crosslinking structure, and swells and polymerizes the monodisperse crosslinking (full-IPN) structure. It has the effect of the invention which provides the polymer particle and its manufacturing method.
본 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 changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01315454A (en) * | 1988-03-30 | 1989-12-20 | Japan Synthetic Rubber Co Ltd | Highly crosslinked polymer particle and production thereof |
| JPH02228313A (en) * | 1989-01-12 | 1990-09-11 | Rohm & Haas Co | Manufacture of silicone-containing polymer particle |
| US5077347A (en) * | 1989-10-13 | 1991-12-31 | Kansai Paint Co., Ltd. | Dipsersion of fine particles of a polymer |
| JPH08120005A (en) * | 1994-10-21 | 1996-05-14 | Soken Chem & Eng Co Ltd | Production of polymer particle |
| US5543460A (en) * | 1992-02-06 | 1996-08-06 | Mitsubishi Rayon Co., Ltd. | Graft copolymer particles their production and compositions comprising them |
| KR19990070970A (en) * | 1998-02-26 | 1999-09-15 | 김공수 | Method for producing porous polymer particles |
| JP2000297109A (en) * | 1999-04-14 | 2000-10-24 | Kanegafuchi Chem Ind Co Ltd | Polymer emulsion and manufacture thereof |
| US6248849B1 (en) * | 1994-10-24 | 2001-06-19 | Amcol Corporation | Precipitation polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| KR20010095368A (en) * | 2000-03-23 | 2001-11-07 | 서경도 | Production of monodisperse micron-sized polymer particles |
| US6331578B1 (en) * | 1998-11-18 | 2001-12-18 | Josephine Turner | Process for preparing interpenetrating polymer networks of controlled morphology |
| KR100334401B1 (en) * | 1995-03-30 | 2002-11-30 | 제이에스알 가부시끼가이샤 | Manufacturing method of composite crosslinked polymer particles |
| KR20030020790A (en) * | 2001-09-04 | 2003-03-10 | 서경도 | Preparation of monodisperse amphiphilic polymer particle having hemispheric morphology by dispersion polymerization |
-
2001
- 2001-12-27 KR KR10-2001-0086223A patent/KR100480336B1/en not_active IP Right Cessation
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01315454A (en) * | 1988-03-30 | 1989-12-20 | Japan Synthetic Rubber Co Ltd | Highly crosslinked polymer particle and production thereof |
| JPH02228313A (en) * | 1989-01-12 | 1990-09-11 | Rohm & Haas Co | Manufacture of silicone-containing polymer particle |
| US5077347A (en) * | 1989-10-13 | 1991-12-31 | Kansai Paint Co., Ltd. | Dipsersion of fine particles of a polymer |
| US5543460A (en) * | 1992-02-06 | 1996-08-06 | Mitsubishi Rayon Co., Ltd. | Graft copolymer particles their production and compositions comprising them |
| JPH08120005A (en) * | 1994-10-21 | 1996-05-14 | Soken Chem & Eng Co Ltd | Production of polymer particle |
| US6248849B1 (en) * | 1994-10-24 | 2001-06-19 | Amcol Corporation | Precipitation polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| KR100334401B1 (en) * | 1995-03-30 | 2002-11-30 | 제이에스알 가부시끼가이샤 | Manufacturing method of composite crosslinked polymer particles |
| KR19990070970A (en) * | 1998-02-26 | 1999-09-15 | 김공수 | Method for producing porous polymer particles |
| US6331578B1 (en) * | 1998-11-18 | 2001-12-18 | Josephine Turner | Process for preparing interpenetrating polymer networks of controlled morphology |
| JP2000297109A (en) * | 1999-04-14 | 2000-10-24 | Kanegafuchi Chem Ind Co Ltd | Polymer emulsion and manufacture thereof |
| KR20010095368A (en) * | 2000-03-23 | 2001-11-07 | 서경도 | Production of monodisperse micron-sized polymer particles |
| KR20030020790A (en) * | 2001-09-04 | 2003-03-10 | 서경도 | Preparation of monodisperse amphiphilic polymer particle having hemispheric morphology by dispersion polymerization |
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