KR100658446B1 - Method of producing polymer beads by emulsion polymerization - Google Patents
Method of producing polymer beads by emulsion polymerization Download PDFInfo
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- KR100658446B1 KR100658446B1 KR1020000056980A KR20000056980A KR100658446B1 KR 100658446 B1 KR100658446 B1 KR 100658446B1 KR 1020000056980 A KR1020000056980 A KR 1020000056980A KR 20000056980 A KR20000056980 A KR 20000056980A KR 100658446 B1 KR100658446 B1 KR 100658446B1
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- Prior art keywords
- polymer
- ion
- soluble initiator
- particle size
- exchanged water
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- 229920000642 polymer Polymers 0.000 title claims abstract description 113
- 239000011324 bead Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 83
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 49
- 239000003999 initiator Substances 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 239000000839 emulsion Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000004816 latex Substances 0.000 claims description 32
- 229920000126 latex Polymers 0.000 claims description 32
- 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 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 17
- 239000003431 cross linking reagent Substances 0.000 claims description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000193 polymethacrylate Polymers 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical class CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 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 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- ZDWZXBJFITXZBL-UHFFFAOYSA-N S(=O)(=O)(O)C=CC1=CC=CC=C1.[Na] Chemical compound S(=O)(=O)(O)C=CC1=CC=CC=C1.[Na] ZDWZXBJFITXZBL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 9
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 238000012674 dispersion polymerization Methods 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- -1 methacrylic acid fluoroalkyl ester Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- HTWRFCRQSLVESJ-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOC(=O)C(C)=C HTWRFCRQSLVESJ-UHFFFAOYSA-N 0.000 description 1
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 1
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- QSBXBPKFRZJKTN-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate 5-prop-2-enoyloxypentyl prop-2-enoate Chemical compound C(C=C)(=O)OCCCCCCOC(C=C)=O.C(C=C)(=O)OCCCCCOC(C=C)=O QSBXBPKFRZJKTN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- ZBTGXRBMYGTQHK-UHFFFAOYSA-N azanium;2-nonylphenolate Chemical compound N.CCCCCCCCCC1=CC=CC=C1O ZBTGXRBMYGTQHK-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C08J3/16—Powdering or granulating by coagulating dispersions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
Abstract
본 발명은 유화중합에 의해 폴리머 비드를 제조하는 방법에 관한 것으로서, 유화중합에 의해 시드 폴리머를 제조한 후, 그 시드 폴리머 상에 단량체, 반응성 유화제 및 지용성 개시제를 포함하는 프리에멀젼을 반복적으로 중합시키는 것으로, 이는 좁은 입자크기분포를 나타내면서도 입자의 크기는 1∼30㎛ 범위로 커지며 반응성 유화제를 사용함으로 인해 입자를 개개로 나누는 후처리 공정이 용이하다.The present invention relates to a method for producing polymer beads by emulsion polymerization, wherein after the seed polymer is prepared by emulsion polymerization, a pre-emulsion comprising a monomer, a reactive emulsifier and a fat-soluble initiator on the seed polymer is repeatedly polymerized. This shows a narrow particle size distribution, but the size of the particles increases in the range of 1 to 30 μm and facilitates the post-treatment process of dividing the particles into individual pieces by using a reactive emulsifier.
폴리머비드*유화중합*반응성유화제*지용성개시제*입자크기 Polymer Beads * Emulsion Polymerization * Reactive Emulsifier * Fat-Soluble Initiator * Particle Size
Description
본 발명은 유화중합에 의한 폴리머 비드의 제조방법에 관한 것으로서, 더욱 상세하게는 유화중합에 의해 시드(seed) 폴리머를 제조한 후 그 폴리머 상에 단량체, 반응성 유화제 및 지용성 개시제를 사용하여 점차적으로 중합시켜 최종적으로 1∼30㎛의 입자크기를 가지는 폴리머 비드를 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing polymer beads by emulsion polymerization, and more particularly, to prepare a seed polymer by emulsion polymerization, and then polymerizing the polymer gradually using monomers, reactive emulsifiers and fat-soluble initiators on the polymer. To finally produce a polymer bead having a particle size of 1 ~ 30㎛.
일반적으로 10㎛ 정도의 입자크기를 가지는 폴리머 비드는 많은 산업분야에서 널리 사용되고 있지만, 이것을 제조하기는 그리 쉽지 않다. Generally, polymer beads having a particle size of about 10 μm are widely used in many industries, but they are not easy to manufacture.
폴리머 비드를 제조하는 방법으로는 크게 현탁중합(suspension polymerization), 분산중합(dispersion polymerization) 및 유화중합(emulsion polymerization) 등의 방법이 사용되고 있다.As a method of preparing the polymer beads, methods such as suspension polymerization, dispersion polymerization, and emulsion polymerization are widely used.
현탁중합에 있어서, 폴리머 입자는 기계적 힘에 의하여 수용액상에 존재하는 단량체를 분산시켜 제조한다. 이 방법에 의하여 제조된 폴리머 입자는 적어도 100㎛ 이상의 입자크기를 가지며, 기계적 힘에 의하여 입자분포를 조절하기 위해서는 별도의 장치가 필요하다. 이와 관련하여, 미합중국 특허 제4,017,670호, 제4,071,670호, 제4,085,169호 및 제4,129,706호 등에서는 현탁중합에 의하여 폴리스티렌 폴리머 비드를 제조하는 기술이 개시되어 있다.In suspension polymerization, polymer particles are prepared by dispersing monomers present in an aqueous solution by mechanical force. The polymer particles produced by this method have a particle size of at least 100 μm or more, and a separate device is required to control the particle distribution by mechanical force. In this regard, US Pat. Nos. 4,017,670, 4,071,670, 4,085,169, 4,129,706, and the like disclose techniques for producing polystyrene polymer beads by suspension polymerization.
그런데, 현탁중합을 통해 폴리머 비드를 제조하는 방법은 입자분포가 넓어 균일한 입자의 폴리머 비드를 얻기 어려운 문제가 있다.However, the method for producing polymer beads through suspension polymerization has a problem that it is difficult to obtain polymer beads of uniform particles due to wide particle distribution.
분산중합은 중합되는 단량체가 용해되어질 수 있는 매질에서 중합이 이루어지며, 생성된 폴리머는 그 매질에 용해되어지지 않는다. 또한, 이 제조법은 응집발생율이 높기 때문에 제조된 폴리머 비드의 가교도는 2% 미만이며, 10㎛ 또는 그 이상의 입자크기의 폴리머 비드를 제조할 때에는 입자분포가 넓게 형성되어진다.Dispersion polymerization is carried out in a medium in which the monomer to be polymerized can be dissolved, and the resulting polymer is not dissolved in the medium. In addition, because of the high agglomeration incidence in this production method, the degree of crosslinking of the produced polymer beads is less than 2%, and when the polymer beads having a particle size of 10 µm or larger are produced, a wide particle distribution is formed.
다시말해, 분산중합을 통해 폴리머 비드를 제조할 경우 높은 가교도를 가진 폴리머 비드를 얻는 것이 어렵다.In other words, when preparing polymer beads through dispersion polymerization, it is difficult to obtain polymer beads having a high degree of crosslinking.
한편, 유화중합은 수용성 개시제와 유화제, 단량체를 사용하여 수용액상에서 폴리머 비드를 제조하는 방법이다. 유화제를 사용함으로 인해 입자분포는 좁으며, 1㎛ 이하의 입자크기를 가지는 폴리머 비드가 제조된다. 이와 관련되어 미합중국 특허 제4,522,953호에서는 유화중합에 의하여 다공성 폴리스티렌 폴리머 비드를 제조하는 기술이 개시되어 있다.On the other hand, emulsion polymerization is a method of producing polymer beads in an aqueous solution using a water-soluble initiator, an emulsifier, and a monomer. By using an emulsifier, the particle distribution is narrow, and polymer beads having a particle size of 1 μm or less are produced. In this regard, US Pat. No. 4,522,953 discloses a technique for producing porous polystyrene polymer beads by emulsion polymerization.
상기한 바와 같이, 유화중합은 1㎛ 이상의 입자크기를 가지는 폴리머 비드를 얻는 것이 어렵다.As described above, it is difficult for the emulsion polymerization to obtain polymer beads having a particle size of 1 µm or more.
결과적으로, 현탁중합, 분산중합 및 유화중합은 각각의 단점이 존재하고 있으며, 따라서 각각의 장점을 살리되 단점을 극복하는 방법이 모색되어지고 있다.As a result, suspension polymerization, dispersion polymerization and emulsion polymerization have their respective disadvantages, and thus, methods for overcoming the disadvantages have been sought, while utilizing the advantages.
이에, 본 발명자들은 유화중합에 의해 폴리머 비드를 제조하되 넓은 범위의 가교도를 가지고 입자크기의 범위는 넓되 입자크기 분포는 좁은 폴리머 비드를 제조하기 위해 연구노력하던 중, 유화중합에 의해 시드(seed) 폴리머를 제조한 후 이 폴리머 상에 단량체, 반응성 유화제 및 지용성 개시제를 중합시킨 결과 1∼30㎛의 입자크기를 갖는 폴리머 비드를 제조할 수 있음을 알게되어 본 발명을 완성하게 되었다.Thus, the present inventors are preparing polymer beads by emulsion polymerization, but have a wide range of crosslinking degree, and have a wide range of particle sizes, but have been researched to prepare polymer beads having a narrow particle size distribution, and seeded by emulsion polymerization. After preparing a polymer and polymerizing a monomer, a reactive emulsifier, and a fat-soluble initiator on the polymer, it was found that a polymer bead having a particle size of 1 to 30 μm can be prepared.
따라서, 본 발명의 목적은 넓은 범위의 가교도와 입자크기를 갖되, 좁은 입자분포를 갖도록 폴리머 비드를 제조하는 방법을 제공하는 데 있다.Accordingly, it is an object of the present invention to provide a method for producing polymer beads to have a wide range of crosslinking degree and particle size, but to have a narrow particle distribution.
이와같은 목적을 달성하기 위한 본 발명의 폴리머 비드의 제조방법은 이온교환수를 투입하여 내부온도가 60∼90℃에 도달될 때 이온교환수, 단량체, 가교제 및 반응성 유화제의 프리에멀젼(pre-emulsion) 용액과 수용성 개시제를 투입한 후 중합하여 입자크기가 0.1∼0.2㎛ 되도록 시드 폴리머 라텍스를 제조하는 제 1단계; 상기 시드 폴리머 라텍스에 이온교환수, 단량체, 가교제, 반응성 유화제 및 지용성 개시제의 프리에멀젼 용액을 적가한 후 중합하여 입자크기 0.2∼0.4㎛ 되도록 폴리머 비드를 제조하는 제 2단계; 제 2단계의 폴리머 비드에 이온교환수, 단량체, 가교제, 반응성 유화제 및 지용성 개시제의 프리에멀젼 용액을 적가한 후 중합하여 입자크기 0.8∼1.0㎛ 되도록 폴리머 비드를 제조하는 제 3단계; 및 계속적으로 전단계의 폴리머 비드에 이온교환수, 단량체, 가교제, 반응성 유화제 및 지용성 개시제의 프리에멀젼 용액을 적가한 후 중합하는 과정을 1∼3회 반복하되, 마지막 단계 에서는 반응성 유화제 대신에 폴리머 안정제를 사용하여 중합하여 입자크기 1.0∼30㎛ 되도록 폴리머 비드를 제조하는 단계를 포함하는 것을 그 특징으로 한다.
The method for producing the polymer beads of the present invention for achieving the above object is a pre-emulsion of ion-exchanged water, monomers, cross-linking agents and reactive emulsifiers when the internal temperature reaches 60 ~ 90 ℃ by adding ion-exchanged water A first step of preparing a seed polymer latex so as to add a solution and a water-soluble initiator and then polymerize to have a particle size of 0.1 to 0.2 μm; A second step of preparing polymer beads to have a particle size of 0.2 to 0.4 μm by dropwise addition of pre-emulsion solution of ion-exchanged water, monomer, crosslinking agent, reactive emulsifier and fat-soluble initiator to the seed polymer latex; A third step of preparing a polymer bead having a particle size of 0.8-1.0 μm by adding a dropwise addition of ion-exchanged water, a monomer, a crosslinking agent, a reactive emulsifier and a preemulsion solution of a fat-soluble initiator to the polymer beads of the second step; And continuously adding the pre-emulsion solution of ion-exchanged water, monomers, crosslinking agents, reactive emulsifiers and fat-soluble initiators to the polymer beads in the previous step, and then repeating the polymerization one to three times. It characterized by comprising the step of polymerizing using to prepare the polymer beads to a particle size of 1.0 to 30㎛.
본 발명에 따른 폴리머 비드의 제조방법을 단계별로 살펴보면 다음과 같다.Looking at the step of producing a polymer bead according to the present invention step by step.
우선 제 1단계에서는 이온교환수를 투입하여 내부온도가 60∼90℃에 도달될 때 이온교환수, 단량체, 가교제 및 반응성 유화제의 프리에멀젼(pre-emulsion) 용액과 수용성 개시제를 점차로 투입한 후 중합하여 입자크기가 0.1∼0.2㎛ 되도록 시드 폴리머 라텍스를 제조한다.In the first step, ion-exchanged water is added and the pre-emulsion solution and water-soluble initiator of ion-exchanged water, monomers, crosslinking agents and reactive emulsifiers are gradually added when the internal temperature reaches 60-90 ° C, and then polymerization is performed. To produce a seed polymer latex so as to have a particle size of 0.1 to 0.2 μm.
그 다음 제 2단계에서는, 상기 시드 폴리머 라텍스에 이온교환수, 단량체, 가교제, 반응성 유화제 및 지용성 개시제의 프리에멀젼 용액을 적가한 후 중합하여 입자크기 0.2∼0.4㎛ 되도록 폴리머 비드를 제조한다.In the second step, a pre-emulsion solution of ion-exchanged water, a monomer, a crosslinking agent, a reactive emulsifier and a fat-soluble initiator is added dropwise to the seed polymer latex, followed by polymerization to prepare polymer beads having a particle size of 0.2-0.4 μm.
그리고 나서, 상기 제 2단계의 폴리머 비드에 이온교환수, 단량체, 가교제, 반응성 유화제 및 지용성 개시제의 프리에멀젼 용액을 적가한 후 중합하여 입자크기 0.8∼1.0㎛ 되도록 폴리머 비드를 제조한다.Then, a pre-emulsion solution of ion-exchanged water, a monomer, a crosslinking agent, a reactive emulsifier, and a fat-soluble initiator is added dropwise to the polymer beads of the second step, followed by polymerization to prepare polymer beads to have a particle size of 0.8 to 1.0 μm.
그 다음, 계속하여 전단계를 통해 얻어진 폴리머 비드에 이온교환수, 단량체, 가교제, 반응성 유화제 및 지용성 개시제의 프리에멀젼 용액을 적가한 후 중합하는 과정을 1∼3회 반복하여 입자크기 1.0∼30㎛ 되도록 폴리머 비드를 제조한다.Subsequently, the pre-emulsion solution of ion-exchanged water, monomer, crosslinking agent, reactive emulsifier and fat-soluble initiator was added dropwise to the polymer beads obtained through the previous step, and the polymerization process was repeated one to three times to obtain a particle size of 1.0 to 30 μm. Polymer beads are prepared.
각 단계에서 유화제로는 반응성 유화제를 사용하되 다만, 마지막 단계에서는 중합후 제품의 후처리 공정을 용이하게 하기 위하여 반응성 유화제 대신에 폴리머 안정제를 사용한다.In each step, a reactive emulsifier is used as an emulsifier. In the final step, a polymer stabilizer is used instead of a reactive emulsifier to facilitate the post-treatment process of the product after polymerization.
반응성 유화제를 사용함으로써 모든 단량체에 적용할 수 있으며, 중합 후 안정성, 내수성 및 후처리 등의 특성을 개선시킬 수 있고, 유화제로 인한 발포특성도 저하시킬 수 있다. 특히, 모든 단계 중합후 개개의 입자들로 나누어지기 위해서 수행되는 후처리 과정에서는 사용된 유화제를 제거해야 하는데, 종래의 유화제는 제품에 유화제 형태로 잔존하기 때문에 제거하기가 용이하지 않고 제거하더라도 입자들이 서로 응집되어 개개의 입자들로 분리하기 어려운 단점이 있다. 그러나, 반응성 유화제는 단량체와 함께 중합되어지기 때문에 마지막 단계에서 폴리머 안정제를 사용하면 쉽게 개개의 입자들로 분리할 수 있는 장점이 있다.By using a reactive emulsifier can be applied to all monomers, it is possible to improve the properties such as stability after polymerization, water resistance and post-treatment, and to lower the foaming characteristics due to the emulsifier. In particular, the post-treatment process, which is carried out in order to be divided into individual particles after every stage of polymerization, needs to remove the used emulsifier. Conventional emulsifiers remain in the form of emulsifiers in the product, so they are not easy to remove, There is a disadvantage that it is difficult to separate into individual particles due to aggregation with each other. However, since the reactive emulsifier is polymerized together with the monomer, the use of a polymer stabilizer in the last step has the advantage of being easily separated into individual particles.
이와같은 반응성 유화제의 예로는 중합성 노닐페놀 에톡실레이트(polymerizable nonylphenol ethoxylate) 유도체, 메타크실레이트 유도체 및 나트륨 스티렌술폰산 등을 들 수 있으며, 그 함량은 각 단계의 모노머 100중량부에 대하여 0.2∼4.0중량부인 것이 바람직하다.Examples of such reactive emulsifiers include polymerizable nonylphenol ethoxylate derivatives, methacrylate derivatives and sodium styrenesulfonic acid, and the content thereof is 0.2 to 4.0 with respect to 100 parts by weight of the monomer in each step. It is preferable that it is a weight part.
개시제의 경우는 시드 폴리머를 제조하는 제 1단계에서는 수용성 개시제를 사용하여 입자크기를 조절한다. 만일, 시드 폴리머 라텍스를 제조하는 1단계에서 지용성 개시제를 사용할 경우에는 입자크기를 조절하기가 쉽지 않고, 재현성 있는 입자크기를 얻을 수 없다. In the case of the initiator, in the first step of preparing the seed polymer, the particle size is controlled by using a water-soluble initiator. If the fat-soluble initiator is used in the first step of preparing the seed polymer latex, it is not easy to control the particle size and a reproducible particle size cannot be obtained.
제 2단계부터 마지막 단계까지는 지용성 개시제를 사용하여 입자크기를 증가시킨다. 만일, 이 단계에서 수용성 개시제를 사용하면 입자크기를 증가시키기에 용 이하지 않다.From the second stage to the last stage, the fat-soluble initiator is used to increase the particle size. If a water-soluble initiator is used at this stage, it is not easy to increase the particle size.
그리고, 1단계에서는 에멀젼의 크기를 조절하기 위해 고형분의 함량을 낮추고, 반응성 유화제의 함량을 조절하면서 단량체 및 가교제 혼합용액과 수용성 개시제를 가하여 가교된 시드 폴리머를 제조한다. 이때, 가교제의 함량을 조절하여 가교도를 조절한다.In the first step, the crosslinked seed polymer is prepared by adding a monomer and a crosslinking agent mixed solution and a water-soluble initiator while lowering the content of solids to adjust the size of the emulsion, and adjusting the content of the reactive emulsifier. At this time, the degree of crosslinking is controlled by adjusting the content of the crosslinking agent.
제 2단계에서부터 마지막 전단계까지는 앞 단계의 폴리머 라텍스를 사용하여 이온교환수, 단량체, 가교제, 반응성 유화제 및 지용성 개시제의 프리에멀젼 용액을 서서히 적가하여 반응시킨다. 이때, 적가시간과 중합시간이 충분하지 못하거나 반응성 유화제를 사용하지 않는 경우 응집현상이 발생되므로 유의하여야 한다.From the second step to the last step, the polymer latex of the previous step is reacted by gradually dropping the preemulsion solution of ion-exchanged water, monomer, crosslinking agent, reactive emulsifier and fat-soluble initiator. At this time, the dropping time and the polymerization time is not enough, or if the reactive emulsifier is not used, it should be noted that the aggregation occurs.
마지막 단계에서는 앞단계의 폴리머 라텍스를 사용하여 이온교환수, 단량체, 가교제, 폴리머 안정제 및 지용성 개시제의 프리에멀젼 용액을 서서히 적가하여 반응시킨다. 반응종료후 후처리 공정을 용이하기 위해서는 반응성 유화제 대신에 폴리머 안정제를 사용해야 한다는 점에 유의해야 한다.In the last step, the polymer latex of the previous step is reacted by slowly dropwise adding a preemulsion solution of ion-exchanged water, monomer, crosslinking agent, polymer stabilizer and fat-soluble initiator. Note that a polymer stabilizer should be used in place of the reactive emulsifier to facilitate the post-treatment process after completion of the reaction.
반응종료된 라텍스 제품을 원심분리시킨 후 이온교환수로 4∼5회 반복 세척한 후, 60℃에서 24시간 진공건조시켜 최종제품을 얻는다.After completion of the reaction, the latex product was centrifuged and washed repeatedly with ion exchange water for 4 to 5 times, followed by vacuum drying at 60 ° C for 24 hours to obtain a final product.
본 발명의 각 단계에서 사용되는 단량체는 방향족 비닐계 단량체, 탄소원자수 1∼20의 아크릴산 또는 메타크릴산 알킬에스테르 단량체, 탄소원자수 1∼20의 아크릴산 또는 메타크릴산 플루오로알킬에스테르 단량체 중에서 선택된 1종 이상의 것이다.The monomer used in each step of the present invention is one selected from an aromatic vinyl monomer, acrylic acid or methacrylic acid alkyl ester monomer having 1 to 20 carbon atoms, acrylic acid or methacrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms. It is more than that.
가교제로는 1,2-에탄디올디아크릴레이트, 1,3-프로판디올디아크릴레이트, 1,3-부탄디올디아크릴레이트, 1,4-부탄디올디아크릴레이트, 1,5-펜탄디올디아크릴레이트, 1,6-헥산디올디아크릴레이트, 디비닐벤젠, 에틸렌글리콜디아크릴레이트, 프로필렌글리콜디아크릴레이트, 부틸렌글리콜디아크릴레이트, 트리에틸렌글리콜디아크릴레이트, 폴리에틸렌글리콜디아크릴레이트, 폴리프로필렌글리콜디아크릴레이트, 폴리부틸렌글리콜디아크릴레이트, 알킬아크릴레이트, 1,2-에탄디올디메타크릴레이트, 1,3-프로판디올디메타크릴레이트, 1,3-부탄디올디메타크릴레이트, 에틸렌글리콜디메타크릴레이트, 프로필렌글리콜디메타크릴레이트, 부틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 폴리에틸렌글리콜디메타크릴레이트, 폴리프로필렌글리콜디메타크릴레이트, 폴리부틸렌글리콜디메타크릴레이트, 알릴메타크릴레이트 및 디알릴말레이트 중에서 선택된 1종 이상의 것이며, 그 함량은 전체 폴리머 비드에 대해 1∼98중량부이다.As crosslinking agent, 1, 2- ethanediol diacrylate, 1, 3- propanediol diacrylate, 1, 3- butanediol diacrylate, 1, 4- butanediol diacrylate, 1, 5- pentanediol diacrylate 1,6-hexanediol diacrylate, divinylbenzene, ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol Diacrylate, polybutylene glycol diacrylate, alkyl acrylate, 1,2-ethanediol dimethacrylate, 1,3-propanediol dimethacrylate, 1,3-butanediol dimethacrylate, ethylene glycol Dimethacrylate, Propylene Glycol Dimethacrylate, Butylene Glycol Dimethacrylate, Triethylene Glycol Dimethacrylate, Polyethylene Glycol Dimethacrylate, Polypropylene Glycol Koldi dimethacrylate, polybutylene glycol dimethacrylate, allyl methacrylate and diallyl will end at least one selected from acrylate, the content is 1-98 parts by weight based on the total polymer beads.
마지막 단계에서 첨가되는 폴리머 안정제의 구체적인 예로는, 폴리비닐알콜, 메틸 셀룰로스, 에틸 셀룰로스, 나트륨 카르복실 메틸 셀룰로스, 폴리아크릴산, 폴리메타크릴산, 나트륨 폴리아크릴레이트, 나트륨 폴리메타크릴레이트, 젤라틴, 폴리아크릴아미드 및 폴리에틸렌옥사이드 등이며, 그 함량은 마지막 단계 조성에서 사용된 모노머 100중량부에 대하여 0.2∼2.0중량부인 것이 바람직하다.Specific examples of the polymer stabilizer added in the last step include polyvinyl alcohol, methyl cellulose, ethyl cellulose, sodium carboxy methyl cellulose, polyacrylic acid, polymethacrylic acid, sodium polyacrylate, sodium polymethacrylate, gelatin, poly Acrylamide and polyethylene oxide, and the content thereof is preferably 0.2 to 2.0 parts by weight based on 100 parts by weight of the monomer used in the last step composition.
한편, 개시제 중 제 1단계에서 사용되는 수용성 개시제의 구체적인 예로는 칼륨퍼설페이트, 나트륨퍼설페이트, 암모늄퍼설페이트, 아조계 수용성 개시제를 들 수 있으며, 그 함량은 1단계에서 사용된 모노머 100중량부에 대해 0.1∼2.0중량부이다.Meanwhile, specific examples of the water-soluble initiator used in the first step among the initiators include potassium persulfate, sodium persulfate, ammonium persulfate, and azo water-soluble initiators, and the content thereof is 100 parts by weight of the monomer used in the first step. 0.1 to 2.0 parts by weight.
제 2단계에서부터 마지막 단계까지 사용되는 지용성 개시제의 구체적인 예로는 벤조일퍼옥사이드, 아조비스이소부티로니트릴, 아조비스메틸부티로니트릴, 아조비스시클로헥산카르보니트릴 등을 들 수 있으며, 그 함량은 제 2단계에서부터 마지막 단계의 조성에서 사용된 모노머 100중량부에 대하여 0.1∼2.0중량부인 것이 바람직하다.Specific examples of the fat-soluble initiator used from the second stage to the last stage include benzoyl peroxide, azobisisobutyronitrile, azobismethylbutyronitrile, azobiscyclohexanecarbonitrile, and the like. It is preferable that it is 0.1-2.0 weight part with respect to 100 weight part of monomers used by the composition from the last step to the last step.
한편, 폴리머 비드 제조시에 사용되는 이온교환수는 이온교환기를 거쳐 생성된 질소기류 하에서 저항치가 5MΩ 이상인 순수로서, 전체 단량체에 대하여 100∼500중량부 되도록 사용한다.On the other hand, the ion-exchanged water used in the production of the polymer beads is pure water having a resistance value of 5 MΩ or more under the nitrogen stream generated through the ion exchange group, and is used so as to be 100 to 500 parts by weight based on the total monomers.
이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.
실시예 1Example 1
1)제 1 단계1) First step
이온교환수 180g을 1ℓ반응기에 투입하여 질소기류 하에서 내부온도가 80℃ 되도록 가열한 후, 이온교환수 50g, 스티렌 97g, 디비닐벤젠 3g 및 SE-10N(ASAHI DENKA KOGYO K.K 제품, 암모늄 노닐페놀 에톡실레이트 설페이트) 1g의 프리에멀젼 용액을 가한 후 15분간 교반하였다. 그후 2% 칼륨퍼설페이트 용액 100g을 가한 후 6시간 동안 중합하였다. 이때, 제조된 시드 폴리머 라텍스의 평균입자크기는 0.15㎛이었다.180 g of ion-exchanged water was added to a 1 liter reactor and heated to an internal temperature of 80 ° C. under a nitrogen stream. Toxyl sulfate) 1 g of a preemulsion solution was added and stirred for 15 minutes. Thereafter, 100 g of a 2% potassium persulfate solution was added thereto, followed by polymerization for 6 hours. At this time, the average particle size of the prepared seed polymer latex was 0.15㎛.
2)제 2 단계2) the second stage
제 1 단계에서 제조된 시드 폴리머 라텍스 20g에 이온교환수 130g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 150g, 스티렌 116.4g, 디비닐벤젠 3.6g, SE-10N(ASAHI DENKA KOGYO K.K 제품) 1.2g 및 아조비스 이소부티로니트릴 1.2g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 중합을 행하였다. 이때의 평균입자크기는 0.26㎛이었다.130 g of ion-exchanged water was added to 20 g of the seed polymer latex prepared in the first step, and heated to 70 ° C. under nitrogen stream, and 150 g of ion-exchanged water, 116.4 g of styrene, 3.6 g of divinylbenzene, and SE-10N ( A preemulsion solution of 1.2 g of ASAHI DENKA KOGYO KK and 1.2 g of azobis isobutyronitrile was added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, polymerization was carried out for 6 hours. At this time, the average particle size was 0.26 탆.
3)제 3 단계3) the third step
제 2 단계에서 제조된 폴리머 라텍스 40g에 이온교환수 60g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 150g, 스티렌 97g, 디비닐벤젠 3g, SE-10N(ASAHI DENKA KOGYO K.K 제품) 1g 및 아조비스이소부티로니트릴 1g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 동안 중합을 행하였다. 이때의 평균입자크기는 0.85㎛이었다.60 g of ion-exchanged water was added to 40 g of the polymer latex prepared in the second step, and heated to 70 ° C. under nitrogen stream, and 150 g of ion-exchanged water, 97 g of styrene, 3 g of divinylbenzene, and SE-10N (ASAHI DENKA KOGYO) A preemulsion solution of 1 g of KK) and 1 g of azobisisobutyronitrile was added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, polymerization was carried out for 6 hours. At this time, the average particle size was 0.85 mu m.
4)제 4 단계4) fourth step
제 3 단계에서 제조된 폴리머 라텍스 60g에 이온교환수 40g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 120g, 스티렌 97g, 디비닐벤젠 3g, SE-10N(ASAHI DENKA KOGYO K.K 제품) 1g 및 아조비스이소부티로니트릴 1g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 동안 중합하였다. 이때의 평균입자크기는 2.0㎛이었다.40 g of ion-exchanged water was added to 60 g of the polymer latex prepared in the third step, and heated to 70 ° C. under nitrogen stream, and then 120 g of ion-exchanged water, 97 g of styrene, 3 g of divinylbenzene, and SE-10N (ASAHI DENKA KOGYO). A preemulsion solution of 1 g of KK) and 1 g of azobisisobutyronitrile was added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, the polymerization was carried out for 6 hours. At this time, the average particle size was 2.0 µm.
5)제 5 단계5) 5th step
제 4 단계에서 제조된 폴리머 라텍스 120g에 이온교환수 20g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 120g, 스티렌 106.7g, 디비닐벤젠 3.3g, SE-10N(ASAHI DENKA KOGYO K.K 제품) 1.1g 및 아조비스이소부티로니트릴 1.1g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 동안 중합하였다. 이때의 평균입자크기는 6.5㎛이었다.20 g of ion-exchanged water was added to 120 g of the polymer latex prepared in the fourth step, and heated to 70 ° C. under nitrogen stream, followed by 120 g of ion-exchanged water, 106.7 g of styrene, 3.3 g of divinylbenzene, and SE-10N (ASAHI A preemulsion solution of 1.1 g of DENKA KOGYO KK) and 1.1 g of azobisisobutyronitrile was added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, the polymerization was carried out for 6 hours. The average particle size at this time was 6.5 µm.
6)제 6 단계6) the sixth step
제 5 단계에서 제조된 폴리머 라텍스 200g에 이온교환수 200g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 180g, 스티렌 116.4g, 디비닐벤젠 3.6g, 폴리비닐알콜 1.2g 및 아조비스이소부티로니트릴 1.2g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 동안 중합하였다. 이때의 평균입자크기는 9.6㎛이었다.200 g of ion-exchanged water was added to 200 g of the polymer latex prepared in the fifth step and heated to 70 ° C. under nitrogen stream, followed by 180 g of ion-exchanged water, 116.4 g of styrene, 3.6 g of divinylbenzene, and 1.2 g of polyvinyl alcohol. And a pre-emulsion solution of 1.2 g of azobisisobutyronitrile were added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, the polymerization was carried out for 6 hours. At this time, the average particle size was 9.6 mu m.
최종적으로 얻어진 폴리머 라텍스를 15,000rpm속도로 1시간 동안 원심분리시켰다. 원심분리된 폴리비닐알콜이 포함된 상등액을 제거한 후, 이온교환수를 첨가하여 폴리머 입자들을 재분산시키기 위하여 5분간 교반하여 원심분리시켰다. 이러한 세척과정을 5회 반복하였다. 세척 후 침전된 폴리머 입자들을 60℃에서 24시간 동안 진공건조하였다.The finally obtained polymer latex was centrifuged at 15,000 rpm for 1 hour. After removing the supernatant containing the centrifuged polyvinyl alcohol, it was centrifuged by stirring for 5 minutes to re-disperse the polymer particles by the addition of ion-exchange water. This washing procedure was repeated five times. After washing, the precipitated polymer particles were vacuum dried at 60 ° C. for 24 hours.
실시예 2Example 2
상기 실시예 1과 동일한 방법으로 폴리머 비드를 제조하되, 다만 제 4단계까지만 수행하고, 제 4단계에서 SE-10N 대신에 폴리비닐알콜 1g을 사용하였다. 최종 입자크기는 2.2㎛이었다.In the same manner as in Example 1, polymer beads were prepared, but only up to the fourth step, and in the fourth step, 1 g of polyvinyl alcohol was used instead of SE-10N. The final particle size was 2.2 μm.
실시예 3Example 3
상기 실시예 1과 동일한 방법으로 폴리머 비드를 제조하되, 다만 제 5단계까지만 수행하고, 제 5단계에서 SE-10N 대신에 폴리비닐알콜 1.1g을 사용하였다. 최종 입자크기는 6.8㎛이었다.Polymer beads were prepared in the same manner as in Example 1, but were performed only up to the fifth step, and 1.1 g of polyvinyl alcohol was used instead of SE-10N in the fifth step. The final particle size was 6.8 mu m.
실시예 4Example 4
상기 실시예 1과 동일한 방법으로 폴리머 비드를 제조하되, 다만 제 6단계까지만 수행하고, 제 6단계에서 폴리비닐알콜 대신에 나트륨폴리메타크릴레이트 1.2g을 사용하였다. 최종 입자크기는 9.3㎛이었다.To prepare a polymer bead in the same manner as in Example 1, but only up to the sixth step, 1.2 g of sodium polymethacrylate was used in place of the polyvinyl alcohol in the sixth step. The final particle size was 9.3 μm.
비교예 1Comparative Example 1
1)제 1단계1) First step
이온교환수 180g을 1ℓ 반응기에 투입하여 질소기류 하에서 내부온도가 80℃ 되도록 가열한 후, 이온교환수 50g, 스티렌 97g, 디비닐벤젠 3g 및 나트륨 도데실설페이트 1g의 프리에멀젼 용액을 가한 후 15분간 교반하였다. 그후 2% 칼륨퍼설페이트 용액 100g을 가한 후 6시간 중합하였다. 이때, 제조된 시드 폴리머 라텍스의 평균입자크기는 0.15㎛이었다.180 g of ion-exchanged water was added to a 1 liter reactor and heated to an internal temperature of 80 ° C. under a nitrogen stream. Then, 50 g of ion-exchanged water, 97 g of styrene, 3 g of divinylbenzene, and 1 g of sodium dodecyl sulfate were added, followed by 15 minutes. Stirred. Thereafter, 100 g of a 2% potassium persulfate solution was added thereto, followed by polymerization for 6 hours. At this time, the average particle size of the prepared seed polymer latex was 0.15㎛.
2)제 2단계2) second stage
제 1 단계에서 제조된 시드 폴리머 라텍스 20g에 이온교환수 130g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 150g, 스티렌 116.4g, 디비닐벤젠 3.6g, 나트륨 도데실설페이트 1.2g 및 아조비스이소부티로니트릴 1.2g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 동안 중합하였다. 이때의 평균입자크기는 0.24㎛이었다.130 g of ion-exchanged water was added to 20 g of the seed polymer latex prepared in the first step, and heated to 70 ° C. under nitrogen stream, and then 150 g of ion-exchanged water, 116.4 g of styrene, 3.6 g of divinylbenzene, and sodium dodecyl sulfate. A preemulsion solution of 1.2 g and 1.2 g of azobisisobutyronitrile was added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, the polymerization was carried out for 6 hours. At this time, the average particle size was 0.24 mu m.
3)제 3단계3) Third step
제 2 단계에서 제조된 폴리머 라텍스 40g에 이온교환수 60g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 150g, 스티렌 97g, 디비닐벤젠 3g, 나트륨 도데실설페이트 1g 및 아조비스이소부티로니트릴 1g의 프리에 멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 동안 중합하였다. 이때의 평균입자크기는 1.9㎛이었다.60 g of ion-exchanged water was added to 40 g of the polymer latex prepared in the second step, and heated to 70 ° C. under nitrogen stream, followed by 150 g of ion-exchanged water, 97 g of styrene, 3 g of divinylbenzene, 1 g of sodium dodecyl sulfate, and azo. A premersion solution of 1 g of bisisobutyronitrile was added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, the polymerization was carried out for 6 hours. The average particle size at this time was 1.9 µm.
4)제 4 단계4) fourth step
제 3 단계에서 제조된 폴리머 라텍스 60g에 이온교환수 40g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 120g, 스티렌 97g, 디비닐벤젠 3g, 나트륨 도데실설페이트 1g 및 아조비스이소부티로니트릴 1g의 프리에멸젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간동안 중합하였다. 이때의 평균입자크기는 1.9㎛이었다.40 g of ion-exchanged water was added to 60 g of the polymer latex prepared in the third step, and heated to 70 ° C. under nitrogen stream, followed by 120 g of ion-exchanged water, 97 g of styrene, 3 g of divinylbenzene, 1 g of sodium dodecyl sulfate, and azo. A preemulation solution of 1 g of bisisobutyronitrile was added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, the polymerization was carried out for 6 hours. The average particle size at this time was 1.9 µm.
5)제 5 단계5) 5th step
제 4 단계에서 제조된 폴리머 라텍스 120g에 이온교환수 20g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 120g, 스티렌 106.7g, 디비닐벤젠 3.3g, 나트륨 도데실설페이트 1.1g 및 아조비스이소부티로니트릴 1.1g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간동안 중합을 행하였다. 이때의 평균입자크기는 6.3㎛이었다.20 g of ion-exchanged water was added to 120 g of the polymer latex prepared in the fourth step, and heated to 70 ° C. under nitrogen stream, followed by 120 g of ion-exchanged water, 106.7 g of styrene, 3.3 g of divinylbenzene, and sodium dodecyl sulfate 1.1. A preemulsion solution of g and 1.1 g of azobisisobutyronitrile was added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, polymerization was carried out for 6 hours. At this time, the average particle size was 6.3 mu m.
6)제 6 단계6) the sixth step
제 5 단계에서 제조된 폴리머 라텍스 200g에 이온교환수 200g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 180g, 스티렌 116.4g, 디비닐벤젠 3.6g, 폴리비닐알콜 1.2g 및 아조비스이소부티로니트릴 1.2g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 동안 중합하였다. 이때의 평균입자크기는 9.8㎛이었다.200 g of ion-exchanged water was added to 200 g of the polymer latex prepared in the fifth step and heated to 70 ° C. under nitrogen stream, followed by 180 g of ion-exchanged water, 116.4 g of styrene, 3.6 g of divinylbenzene, and 1.2 g of polyvinyl alcohol. And a pre-emulsion solution of 1.2 g of azobisisobutyronitrile were added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, the polymerization was carried out for 6 hours. At this time, the average particle size was 9.8 μm.
이와같이 얻어진 폴리머 라텍스를 15,000rpm 속도로 1시간 원심분리시켰다. 원심분리된 폴리비닐알콜이 포함된 상등액을 제거한 후, 이온교환수를 첨가하여 폴리머 입자들을 재분산시키기 위하여 5분간 교반하고 원심분리시켰다. 이러한 세척과정을 5회 반복하였다. 세척후 침전된 폴리머 입자들은 60℃에서 24시간 동안 진공건조하였다.The polymer latex thus obtained was centrifuged at 15,000 rpm for 1 hour. After removing the supernatant containing the centrifuged polyvinyl alcohol, the mixture was stirred for 5 minutes and centrifuged to add redispersed polymer particles. This washing procedure was repeated five times. The precipitated polymer particles were vacuum dried at 60 ° C. for 24 hours.
비교예 2Comparative Example 2
상기 비교예 1과 동일한 방법으로 폴리머 비드를 제조하되, 다만 제 6 단계에서 폴리비닐알콜 대신에 나트륨 도데실설페이트 1.2g을 사용하였다. 최종 입자크기는 9.0㎛이었다.Polymer beads were prepared in the same manner as in Comparative Example 1, except that 1.2 g of sodium dodecyl sulfate was used instead of polyvinyl alcohol in the sixth step. The final particle size was 9.0 μm.
비교예 3Comparative Example 3
1)제 1 단계1) First step
이온교환수 180g을 1ℓ반응기에 투입하여 질소기류 하에서 내부온도가 80℃ 되도록 가열한 후, 이온교환수 50g, 스티렌 97g, 디비닐벤젠 3g 및 SE-10N(ASAHI DENKA KOGYO K.K 제품) 1g의 프리에멀젼 용액을 가한 후 15분간 교반하였다. 그후 2% 칼륨퍼설페이트 용액 100g을 가한 후 6시간 동안 중합하였다. 이때, 제조된 시드 폴리머 라텍스의 평균입자크기는 0.15㎛이었다.180 g of ion-exchanged water was added to a 1 liter reactor and heated to an internal temperature of 80 ° C. under a nitrogen stream, followed by 50 g of ion-exchanged water, 97 g of styrene, 3 g of divinylbenzene, and 1 g of SE-10N (ASAHI DENKA KOGYO KK) The solution was added and stirred for 15 minutes. Thereafter, 100 g of a 2% potassium persulfate solution was added thereto, followed by polymerization for 6 hours. At this time, the average particle size of the prepared seed polymer latex was 0.15㎛.
2)제 2 단계2) the second stage
제 1 단계에서 제조된 시드 폴리머 라텍스 20g에 이온교환수 130g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 150g, 스티렌 116.4g, 디비닐벤젠 3.6g, SE-10N(ASAHI DENKA KOGYO K.K 제품) 1.2g 및 칼륨퍼설 페이트 1.2g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 동안 중합하였다. 이때의 평균입자크기는 0.23㎛이었다.130 g of ion-exchanged water was added to 20 g of the seed polymer latex prepared in the first step, and heated to 70 ° C. under nitrogen stream, and 150 g of ion-exchanged water, 116.4 g of styrene, 3.6 g of divinylbenzene, and SE-10N ( 1.2 g of ASAHI DENKA KOGYO KK) and 1.2 g of potassium persulfate were added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, the polymerization was carried out for 6 hours. At this time, the average particle size was 0.23 mu m.
3)제 3 단계3) the third step
제 2 단계에서 제조된 폴리머 라텍스 40g에 이온교환수 60g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 150g, 스티렌 97g, 디비닐벤젠 3g, SE-10N(ASAHI DENKA KOGYO K.K 제품) 1G 및 칼륨퍼설페이트 1g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 동안 중합하였다. 이때의 평균입자크기는 0.35㎛이었다.60 g of ion-exchanged water was added to 40 g of the polymer latex prepared in the second step, and heated to 70 ° C. under nitrogen stream, and 150 g of ion-exchanged water, 97 g of styrene, 3 g of divinylbenzene, and SE-10N (ASAHI DENKA KOGYO) KK) 1G and 1 g of potassium persulfate were added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, the polymerization was carried out for 6 hours. At this time, the average particle size was 0.35 탆.
4)제 4 단계4) fourth step
제 3 단계에서 제조된 폴리머 라텍스 60g에 이온교환수 40g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 120g, 스티렌 97g, 디비닐벤젠 3g, SE-10N(ASAHI DENKA KOGYO K.K 제품) 1g 및 칼륨퍼설페이트 1g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 동안 중합하였다. 이때의 평균입자크기는 0.43㎛이었다.40 g of ion-exchanged water was added to 60 g of the polymer latex prepared in the third step, and heated to 70 ° C. under nitrogen stream, and then 120 g of ion-exchanged water, 97 g of styrene, 3 g of divinylbenzene, and SE-10N (ASAHI DENKA KOGYO). 1 g of KK) and 1 g of potassium persulfate were added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, the polymerization was carried out for 6 hours. At this time, the average particle size was 0.43 µm.
5)제 5 단계5) 5th step
제 4 단계에서 제조된 폴리머 라텍스 120g에 이온교환수 20g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 120g, 스티렌 106.7g, 디비닐벤젠 3.3g, SE-10N(ASAHI DENKA KOGYO K.K 제품) 1.1g 및 칼륨퍼설페이트 1.1g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간동안 중합하였다. 이때의 평균입자크기는 0.56㎛이었다.20 g of ion-exchanged water was added to 120 g of the polymer latex prepared in the fourth step, and heated to 70 ° C. under nitrogen stream, followed by 120 g of ion-exchanged water, 106.7 g of styrene, 3.3 g of divinylbenzene, and SE-10N (ASAHI 1.1 g of DENKA KOGYO KK) and 1.1 g of potassium persulfate were added dropwise at a rate of 5 g per minute. After completion of the dropwise addition, the polymerization was carried out for 6 hours. At this time, the average particle size was 0.56 탆.
6)제 6 단계6) the sixth step
제 5 단계에서 제조된 폴리머 라텍스 200g에 이온교환수 200g을 투입하여 질소기류 하에서 내부온도가 70℃ 되도록 가열한 후, 이온교환수 180g, 스티렌 116.4g, 디비닐벤젠 3.6g, 폴리비닐알콜 1.2g 및 칼륨퍼설페이트 1.2g의 프리에멀젼 용액을 분당 5g의 속도로 적가하였다. 적가완료후 6시간 동안 수행하였다. 이때의 평균입자크기는 0.68㎛이었다.200 g of ion-exchanged water was added to 200 g of the polymer latex prepared in the fifth step and heated to 70 ° C. under nitrogen stream, followed by 180 g of ion-exchanged water, 116.4 g of styrene, 3.6 g of divinylbenzene, and 1.2 g of polyvinyl alcohol. And 1.2 g of potassium persulfate preemulsion solution were added dropwise at a rate of 5 g per minute. 6 hours after completion of the dropwise addition. At this time, the average particle size was 0.68 mu m.
이와같이 얻어진 폴리머 라텍스를 15,000rpm 속도로 1시간 원심분리시켰다. 원심분리된 폴리비닐알콜이 포함된 상등액을 제거한 후, 이온교환수를 첨가하여 폴리머 입자들을 재분산시키기시 위하여 5분간 교반하고 원심분리시켰다. 이러한 세척과정은 5회 반복하여 실행하였다. 세척후 침전된 폴리머 입자들은 60℃에서 24시간 진공건조하였다.The polymer latex thus obtained was centrifuged at 15,000 rpm for 1 hour. After removing the supernatant containing the centrifuged polyvinyl alcohol, the mixture was stirred for 5 minutes and centrifuged in order to re-disperse the polymer particles by adding ion-exchanged water. This washing process was repeated five times. The precipitated polymer particles were vacuum dried at 60 ° C. for 24 hours.
상기 표 1의 결과로부터, 본 발명에서와 같이 제 1단계에서 유화중합을 통해 시드 폴리머 라텍스를 제조하고, 반응성 유화제와 지용성 개시제를 사용하여 점차적으로 중합시킨 것은 후처리 공정에서 개개입자로 분리가 용이하고 최종입자크기의 조절범위도 넓은 반면, 비교예 1과 2에서와 같이 유화제로서 비반응성 유화제를 사용하면 입자의 뭉침이 발생되고 비교예 3에서와 같이 개시제로서 시드 폴리머 제조에서와 같이 수용성 개시제를 사용할 경우에는 입자크기가 작은 문제점이 있었다. From the results of Table 1, the seed polymer latex was prepared by emulsion polymerization in the first step as in the present invention, and then gradually polymerized using a reactive emulsifier and a fat-soluble initiator, and easily separated into individual particles in a post-treatment process. While the final particle size can be controlled in a wide range, the use of a non-reactive emulsifier as an emulsifier as in Comparative Examples 1 and 2 results in agglomeration of particles and the use of a water-soluble initiator as in the preparation of the seed polymer as an initiator as in Comparative Example 3. When used, there was a problem of small particle size.
이상에서 상세히 설명한 바와 같이, 본 발명에 따라 유화중합에 의해 시드 폴리머를 제조한 후, 그 시드 폴리머 상에 단량체, 반응성 유화제 및 지용성 개시제를 포함하는 프리에멀젼을 반복적으로 중합시킨 결과, 좁은 입자크기분포를 나타내면서도 입자의 크기는 1㎛ 이상으로 커지며 후처리 공정이 용이하게 폴리머 비드를 제조할 수 있게 되었다.
As described in detail above, after the seed polymer was prepared by emulsion polymerization according to the present invention, a narrow particle size distribution was obtained by repeatedly polymerizing a preemulsion including a monomer, a reactive emulsifier and a fat-soluble initiator on the seed polymer. Although the particle size is larger than 1㎛ and the post-treatment process can be easily produced polymer beads.
Claims (9)
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| US5292814A (en) * | 1987-04-29 | 1994-03-08 | Ernst Bayer | Process for the preparation of monodispersed polymer beads |
| KR20020060317A (en) * | 2001-01-10 | 2002-07-18 | 구광시 | Manufacturing method of polymer bead |
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| US5292814A (en) * | 1987-04-29 | 1994-03-08 | Ernst Bayer | Process for the preparation of monodispersed polymer beads |
| US5130343A (en) * | 1991-03-13 | 1992-07-14 | Cornell Research Foundation, Inc. | Process for producing uniform macroporous polymer beads |
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