KR20030049069A - Preparation of polymer beads - Google Patents
Preparation of polymer beads Download PDFInfo
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- KR20030049069A KR20030049069A KR1020010079163A KR20010079163A KR20030049069A KR 20030049069 A KR20030049069 A KR 20030049069A KR 1020010079163 A KR1020010079163 A KR 1020010079163A KR 20010079163 A KR20010079163 A KR 20010079163A KR 20030049069 A KR20030049069 A KR 20030049069A
- Authority
- KR
- South Korea
- Prior art keywords
- polymer beads
- polymer
- particle size
- solution
- monomer
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 89
- 239000011324 bead Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title description 4
- 239000002245 particle Substances 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 239000004816 latex Substances 0.000 claims abstract description 18
- 229920000126 latex Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008961 swelling Effects 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 12
- 239000003925 fat Substances 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 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 12
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 6
- 238000010557 suspension polymerization reaction Methods 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- -1 methacrylic acid fluoroalkyl ester Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 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
- KFQPRNVTVMCYEH-UHFFFAOYSA-N 1-amino-3-(4-methoxyphenoxy)propan-2-ol Chemical compound COC1=CC=C(OCC(O)CN)C=C1 KFQPRNVTVMCYEH-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
- XAMCLRBWHRRBCN-UHFFFAOYSA-N 5-prop-2-enoyloxypentyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCOC(=O)C=C XAMCLRBWHRRBCN-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 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 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 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
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 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
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000012798 spherical particle Substances 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
Abstract
Description
본 발명은 모노머 팽윤방법에 의한 균일한 폴리머 비드를 제조하는 방법에 관한 것으로서, 더욱 상세하게는 현탁중합에 의해 입자크기가 1∼30㎛인 폴리머 비드를 제조하고, 이 폴리머 비드에 모너머, 가교제 및 개시제를 첨가하여 팽윤시킴으로써 최종적으로 1∼40㎛의 균일한 입자크기를 가진 폴리머 비드의 제조방법에 관한 것이다.The present invention relates to a method for producing uniform polymer beads by the monomer swelling method, and more particularly, to prepare polymer beads having a particle size of 1 to 30 µm by suspension polymerization, and to the polymer beads And finally to a method for producing polymer beads having a uniform particle size of 1 to 40 µm by adding and swelling an initiator.
통상 산업적으로 널리 사용되는 1∼40㎛ 크기의 입자를 가진 폴리머 비드의 제조방법으로는 현탁중합, 분산중합 및 유화중합 등이 있지만, 원하는 입자크기를 가진 균일한 입자분포를 가진 폴리머 비드를 제조하는 것은 용이하지 않다.In general, a method for preparing polymer beads having particles having a size of 1 to 40 μm widely used in industry includes suspension polymerization, dispersion polymerization and emulsion polymerization, but polymer beads having uniform particle distribution having a desired particle size are prepared. Is not easy.
현탁중합은 기계적 힘에 의하여 수용액상에 존재하는 단량체를 분산시켜 폴리머 입자를 제조하는 방법으로서, 이 방법에 의하여 제조된 폴리머 입자는 적어도 100㎛ 이상의 입자크기를 가지며, 기계적 힘에 의하여 입자들이 분산되어 있기 때문에 입자분포가 넓은 경향이 있다.Suspension polymerization is a method for producing polymer particles by dispersing the monomer present in the aqueous solution by mechanical force, the polymer particles produced by this method has a particle size of at least 100㎛ or more, the particles are dispersed by mechanical force As a result, the particle distribution tends to be wide.
따라서, 입자크기 및 입자분포를 조절하기 위해서는 별도의 장치가 요구되어지며, 이러한 장치를 사용하더라도 1∼40㎛ 정도의 입자크기를 가진 폴리머 비드는 얻을 수 있으나, 입자크기 분포가 넓어 균일한 입자를 가진 폴리머 비드를 얻기 힘든 단점이 있었으며, 이와 관련된 종래기술로는 미합중국 특허 제 4,017,670호, 제 4,071,670호, 제 4,085,169호 및 제 4,129,706호 등이 있었다.Therefore, in order to control the particle size and particle distribution, a separate device is required. Even when using such a device, polymer beads having a particle size of about 1 to 40 μm can be obtained, but the particle size distribution is wide so that uniform particles are obtained. There are disadvantages in that it is difficult to obtain the polymer beads having the above, and related arts include US Pat. Nos. 4,017,670, 4,071,670, 4,085,169, and 4,129,706.
또한, 분산중합은 중합되어지는 단량체가 용해되어지는 매질에서 중합이 이루어지기 때문에, 생성된 폴리머는 그 매질에 용해되어지지 않는다. 또한 이 방법은 응집 발생율이 높기 때문에 제조된 폴리머 비드의 가교도는 2% 미만이고, 10㎛ 이상의 입자크기의 폴리머 비드는 제조하기가 어려우며, 입자분포가 넓게 형성되는 단점이 있었다.In addition, since the dispersion polymerization is carried out in a medium in which the monomer to be polymerized is dissolved, the resulting polymer is not dissolved in the medium. In addition, since this method has a high incidence of aggregation, the degree of crosslinking of the prepared polymer beads is less than 2%, polymer beads having a particle size of 10 μm or more are difficult to prepare, and have a wide particle distribution.
그리고, 유화중합은 수용성 개시제와 유화제, 단량체를 사용하여 수용액 상에서 폴리머 비드를 제조하는 방법으로서 이와 관련하여, 미합중국 특허 제 4,522,953호에서는 유화중합에 의한 다공성 폴리스티렌 폴리머 비드를 제조하는 기술을 제시하였지만, 유화제 사용에 의해 입자분포는 매우 좁으나 1㎛ 이상의 입자크기를 가진 폴리머 비드를 제조하기 어렵다는 단점이 있었다.In addition, emulsion polymerization is a method of preparing polymer beads in an aqueous solution using a water-soluble initiator, an emulsifier, and a monomer. In this regard, US Patent No. 4,522,953 discloses a technique for preparing porous polystyrene polymer beads by emulsion polymerization. Particle distribution is very narrow by use, but has a disadvantage in that it is difficult to produce a polymer bead having a particle size of 1㎛ or more.
이에 본 발명자들은 상기와 같은 문제점을 해결하기 위하여 연구 노력하던 중, 현탁중합에 의해 입자크기가 1∼30㎛인 폴리머 비드를 제조하고, 제조된 폴리머 비드에 모너머, 가교제 및 개시제를 첨가하여 팽윤시킴으로써 가교도가 높고 1∼40㎛ 의 균일한 입자크기를 가진 폴리머 비드를 제조할 수 있다는 것을 알게 되어 본 발명을 완성하게 되었다.The inventors of the present invention, while trying to solve the above problems, while producing a polymer beads having a particle size of 1 ~ 30㎛ by suspension polymerization, swelling by adding a monomer, a crosslinking agent and an initiator to the prepared polymer beads The present invention was completed by knowing that polymer beads having a high degree of crosslinking and having a uniform particle size of 1 to 40 μm can be prepared.
따라서, 본 발명의 목적은 좁은 입자크기 분포를 가지는 폴리머 비드를 제조하는 방법을 제공하는 데 있다.Accordingly, it is an object of the present invention to provide a method for producing polymer beads having a narrow particle size distribution.
이와같은 목적을 달성하기 위한 본 발명의 폴리머 비드의 제조방법은 이온교환수, 폴리머 안정제 용액에 단량체, 가교제 및 지용성 개시제 용액을 첨가하여 고속 교반 후 이 용액을 균질기(homogenizer)로 균질화한 다음 60∼90℃에서 중합하여 시드 폴리머 라텍스를 제조하는 단계; 및 상기 시드 폴리머 라텍스를 상온으로 하강시키고, 단량체, 가교제 및 지용성 개시제 용액을 적가하여 팽윤시킨 후 중합하여 입자크기 1∼40㎛의 폴리머 비드를 제조하는 단계로 구성된 것임을 그 특징으로 한다.In order to achieve the above object, the method of preparing the polymer beads of the present invention comprises adding a monomer, a crosslinking agent and a fat-soluble initiator solution to the ion exchange water and the polymer stabilizer solution, and then homogenizing the solution with a homogenizer after high-speed stirring. Polymerizing at ˜90 ° C. to produce seed polymer latex; And lowering the seed polymer latex to room temperature, swelling by dropwise adding a monomer, a crosslinking agent and a fat-soluble initiator solution, and polymerizing the same to prepare polymer beads having a particle size of 1 to 40 μm.
이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
(1) 시드 폴리머 라텍스의 제조(1) Preparation of Seed Polymer Latex
본 발명에 따른 폴리머 비드를 제조하는 방법은 우선 현탁중합을 통해 시드 폴리머 라텍스를 제조하는 단계이다. 즉, 반응기에 이온교환수, 단량체, 가교제, 지용성 개시제 및 안정제를 투입하여 100∼1000 rpm의 고속으로 교반하여 프리혼합 용액을 제조하고, 이 용액을 반응기에서 토출하여 균질기(homogenizer)를 통해 안정한 입자형성 용액을 제조한다. 그 다음 이 용액을 다시 반응기에 투입하여 내부온도를 60∼90℃로 승온시켜 1∼30㎛의 입자크기를 가진 시드 폴리머를 제조한다.The method for producing the polymer beads according to the present invention is a step of first preparing a seed polymer latex through suspension polymerization. That is, ion-exchanged water, monomers, cross-linking agents, fat-soluble initiators and stabilizers are added to the reactor and stirred at a high speed of 100 to 1000 rpm to prepare a premixed solution, and the solution is discharged from the reactor to stabilize through a homogenizer. Prepare a particle forming solution. Then, this solution was added to the reactor again to raise the internal temperature to 60 ~ 90 ℃ to prepare a seed polymer having a particle size of 1 ~ 30㎛.
또한, 상기 프리혼합 용액을 제조함에 있어 충분히 고속으로 교반하지 않으면 균질기를 거친 후 안정하고 원하는 입자형성을 얻을 수 없게 된다.In addition, in the preparation of the premixed solution, if it is not stirred at high speed sufficiently, it is impossible to obtain stable and desired particle formation after passing through a homogenizer.
또한, 상기 균질기를 거치지 않고 프리혼합 용액을 고속 교반후 바로 중합시킬 경우 응집현상이 발생할 뿐만 아니라 100㎛ 이상의 입자분포가 매우 넓은 폴리머 비드가 제조되므로 주의해야 한다.In addition, when the premixed solution is polymerized immediately after high-speed stirring without passing through the homogenizer, not only agglomeration occurs but also polymer beads having a very large particle distribution of 100 μm or more are prepared.
(2) 폴리머 비드의 제조(2) Preparation of Polymer Beads
두 번째 단계로 상기 1단계에서 제조된 시드 폴리머 라텍스를 상온으로 냉각시킨 다음, 단량체, 가교제 및 지용성 개시제 용액을 적하하여 1∼10시간 동안 교반하여 팽윤시킨다. 그 후, 내부온도를 60∼90℃로 다시 승온시켜 최종 크기 1∼40㎛인 폴리머 비드를 제조한다.In the second step, the seed polymer latex prepared in Step 1 is cooled to room temperature, and then the monomer, crosslinking agent and fat soluble initiator solution are added dropwise, and stirred for 1 to 10 hours to swell. Thereafter, the internal temperature is raised to 60 to 90 ° C. to produce polymer beads having a final size of 1 to 40 μm.
2단계에서 사용되는 단량체, 가교제 및 지용성 개시제 용액은 1단계에서 형성된 입자분포가 넓은 가교된 시드 폴리머 비드 입자 사이로 침투하여 그 속에서 팽윤함으로써 입자를 안정하게 만든다. 또한 입자크기가 상이한 시드 폴리머 비드에 불균일 침투함으로써, 폴리머 비드의 입자크기를 균일하게 하는 역할을 한다.The monomer, crosslinking agent, and fat soluble initiator solution used in step 2 penetrates through the wide crosslinked seed polymer bead particles formed in step 1 and makes the particles stable by swelling therein. In addition, the non-uniform penetration of seed polymer beads having different particle sizes serves to make the particle size of the polymer beads uniform.
따라서, 상기 팽윤시간이 1시간 보다 적으면 단량체들이 효과적으로 침투하지 못하여 입자분포가 넓어지게 되고 응집현상이 발생되거나 원하는 구형의 입자를 얻기 힘들며, 또한 10시간을 초과하게 되면 생산성이 저하되는 문제가 있으므로, 팽윤시간은 1∼10시간, 바람직하기로는 3∼8시간이다.Therefore, when the swelling time is less than 1 hour, the monomers do not effectively penetrate and thus the particle distribution becomes wider, and agglomeration phenomenon or a desired spherical particle is difficult to obtain, and when the time exceeds 10 hours, there is a problem that productivity decreases. The swelling time is 1 to 10 hours, preferably 3 to 8 hours.
한편, 상기 각 단계에서 사용되는 이온교환수는 이온교환기를 거쳐 생성된질소기류 하에서의 저항치가 5MΩ이상인 순수로서, 전체 단량체에 대하여 100∼500 중량부로 사용한다.On the other hand, the ion-exchanged water used in each step is pure water having a resistance value of 5 MΩ or more under the nitrogen gas generated through the ion exchanger, and is used in an amount of 100 to 500 parts by weight based on the total monomers.
또한, 단량체로는 방향족 비닐계 단량체, 탄소원자수 1∼20 사이의 아크릴산 또는 메타크릴산 알킬에스터 단량체 및 탄소수 1∼20 사이의 아크릴산 또는 메타크릴산 플루오르알킬에스터 단량체 중에서 선택된 1종 이상의 것을 사용한다.As the monomer, at least one selected from an aromatic vinyl monomer, an acrylic acid or methacrylic acid alkyl ester monomer having 1 to 20 carbon atoms, and an acrylic acid or methacrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms is used.
또한, 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, 알릴아크릴레이트, 1,2-에탄디올디메타크릴레이트, 1,3-프로판디올디메타크릴레이트, 1,3-부탄디올디메타크릴레이트, 1,4-부탄디올디메타크릴레이트, 1,5-펜탄디올디메타크릴레이트, 1,6-헥산디올디메타크릴레이트, 에틸렌글리콜디메타크릴레이트, 프로필렌글리콜디메타크릴레이트, 부틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 폴리에틸렌글리콜디메타크릴레이트, 폴리프로필렌글리콜디메타크릴레이트, 폴리부틸렌글리콜디메타크릴레이트, 알릴메타크릴레이트 및 디알릴말레이트 등에서 선택된 1종 이상의 것으로, 그 함량은 전체 폴리머 비드에 대하여 1∼98 중량부이다.In addition, as a crosslinking agent, 1, 2- ethanediol diacrylate, 1, 3- propanediol diacrylate, 1, 3- butanediol diacrylate, 1, 4- butanediol diacrylate, and 1, 5- pentanediol di Acrylate, 1,6-hexanediol diacrylate, divinylbenzene, ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, poly Propylene glycol diacrylate, polybutylene glycol diacrylate, allyl acrylate, 1,2-ethanediol dimethacrylate, 1,3-propanediol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol di Methacryl At least one selected from latex, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, allyl methacrylate and diallyl maleate, The content is 1 to 98 parts by weight based on the total polymer beads.
또한, 상기 1단계와 2단계에서 사용되는 개시제는 모두 지용성 개시제로서 예를 들면, 벤조일펄옥사이드, 아조비스이소부티로니트릴, 아조비스메틸부티로니트릴, 아조비스시클로헥산카르보니트릴 등에서 선택된 것으로, 그 함량은 전체 폴리머 비드에 대해 0.1∼5.0 중량부이다. 만일 수용성 개시제를 사용할 경우에는 폴리머 비드를 얻기 어렵거나 입자형태가 불균일한 폴리머 비드를 얻게 되는 문제점이 있다.In addition, the initiators used in steps 1 and 2 are all selected from, for example, benzoyl peroxide, azobisisobutyronitrile, azobismethylbutyronitrile, azobiscyclohexanecarbonitrile, etc. as fat-soluble initiators. The content is 0.1 to 5.0 parts by weight based on the total polymer beads. If a water-soluble initiator is used, there is a problem in that it is difficult to obtain polymer beads or to obtain polymer beads having irregular particle shapes.
또한, 본 발명에서 사용되는 안정제는 폴리머 안정제로서, 폴리비닐알콜, 폴리비닐피롤리돈, 메틸 셀룰로즈, 에틸 셀룰로즈, 나트륨 카르복실 메틸 셀룰로즈, 폴리아크릴산, 폴리메타크릴산, 나트륨 폴리아크릴레이트, 나트륨 폴리메타크릴레이트, 젤라틴, 폴리아크릴아미드 및 폴리에틸렌옥시드 등이며, 그 함량은 전체 폴리머 비드에 대해 0.2∼10 중량부이다.In addition, the stabilizer used in the present invention as a polymer stabilizer, polyvinyl alcohol, polyvinylpyrrolidone, methyl cellulose, ethyl cellulose, sodium carboxy methyl cellulose, polyacrylic acid, polymethacrylic acid, sodium polyacrylate, sodium poly Methacrylate, gelatin, polyacrylamide, polyethylene oxide and the like, and the content is 0.2 to 10 parts by weight based on the total polymer beads.
상기 1단계와 2단계를 거쳐 반응종료된 폴리머 비드 용액을 원심분리시킨 후, 이온교환수로 4∼5회 반복 세척한 후, 60℃에서 24시간 진공건조시켜 최종제품을 얻는다.After centrifugation of the polymer bead solution, the reaction was completed through the steps 1 and 2, and then repeatedly washed 4 to 5 times with ion-exchanged water, followed by vacuum drying at 60 ° C. for 24 hours to obtain a final product.
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
이온교환수 1014.29g, 폴리비닐알콜(무게평균 분자량 10,000) 8g을 2L 반응기에 넣고 교반시켰다. 메틸메타크릴레이트 200.65g, 에틸 아크릴레이트 18.71g, 1,6-헥산디올디아크릴레이트 6.64g 및 아조비스이소부티로니트릴 1.5g 용액을 상기 반응기에 넣고 700 rpm 속도로 30분간 교반시켜 프리혼합 용액을 제조하였다.1014.29 g of ion-exchanged water and 8 g of polyvinyl alcohol (weight average molecular weight 10,000) were put into a 2L reactor and stirred. 200.65 g of methyl methacrylate, 18.71 g of ethyl acrylate, 6.64 g of 1,6-hexanediol diacrylate and 1.5 g of azobisisobutyronitrile were added to the reactor and stirred at 700 rpm for 30 minutes to premix the solution. Was prepared.
이렇게 제조된 프리혼합 용액을 반응기에서 토출하여 균질기에서 1000psi 압력으로 두 번 처리하였다. 이 용액을 다시 상기 반응기에 투입하여 질소기류 하에서 250 rpm 속도로 교반하면서 내부온도가 60℃ 가 되도록 가열시킨 다음, 이 온도에서 7시간 동안 반응시켜 입자크기 8.3㎛인 시드 폴리머 라텍스를 제조하였다.The premixed solution thus prepared was discharged from the reactor and treated twice at 1000 psi pressure in a homogenizer. The solution was added to the reactor again and heated at an internal temperature of 60 ° C. while stirring at 250 rpm under a nitrogen stream, and then reacted at this temperature for 7 hours to prepare a seed polymer latex having a particle size of 8.3 μm.
상기에서 제조된 시드 폴리머 라텍스를 상온까지 냉각시켜, 상온에서 메타크릴레이트 187g, 에틸 아크릴레이트 15g, 1,6-헥산디올디아크릴레이트 6g 및 아조비스이소부티로니트릴 1.5g 용액을 분당 5g의 속도로 적하하였다. 적하완료 후 5시간 동안 교반시키고 내부온도를 60℃로 승온시킨 다음, 이 온도에서 다시 7시간 동안 중합하여 평균 입자크기 12.5㎛인 폴리머 비드 라텍스를 제조하였다.The seed polymer latex prepared above was cooled to room temperature, and a solution of 187 g of methacrylate, 15 g of ethyl acrylate, 6 g of 1,6-hexanediol diacrylate, and 1.5 g of azobisisobutyronitrile at a rate of 5 g / min at room temperature was obtained. Was added dropwise. After completion of dropping, the mixture was stirred for 5 hours, the internal temperature was raised to 60 ° C, and then polymerized at this temperature for 7 hours to prepare a polymer bead latex having an average particle size of 12.5 μm.
이렇게 얻어진 폴리머 비드 라텍스를 15,000 rpm 속도로 1시간 동안 원심분리시킨 다음, 원심분리된 폴리비닐알콜이 포함된 상등액을 제거한 후, 이온교환수를 첨가하여 폴리머 입자들을 재분산시키기 위하여 5분간 교반하고 원심분리시켰다. 이러한 세척과정을 5회 반복 실시한 후, 침전된 폴리머 입자들을 60℃에서 24시간 동안 진공건조시켜 폴리머 비드를 제조하였다.The polymer bead latex thus obtained was centrifuged at 15,000 rpm for 1 hour, and then the supernatant containing the centrifuged polyvinyl alcohol was removed, followed by stirring and centrifuging for 5 minutes to re-disperse the polymer particles by adding ion-exchanged water. Separated. After the washing process was repeated five times, the polymer beads were dried by vacuum drying the precipitated polymer particles at 60 ° C. for 24 hours.
실시예 2Example 2
프리혼합 용액 제조시 폴리비닐알콜(무게평균 분자량 10,000)을 12g 사용한것과, 폴리머 비드 라텍스 제조시 단량체, 가교제 및 지용성 개시제 용액을 적하완료 후 4시간 동안 교반하는 것을 제외하고는 상기 실시예 1과 동일한 방법으로 폴리머 비드를 제조하였으며, 최종 제조된 폴리머 비드의 입자크기는 8.3 ㎛였다.12 g of polyvinyl alcohol (weight average molecular weight 10,000) was used to prepare the premixed solution, and the monomer, crosslinking agent and fat soluble initiator solution were prepared in the same manner as in Example 1 except that the solution was stirred for 4 hours after completion of dropping. Polymer beads were prepared by the method, and the particle size of the finally prepared polymer beads was 8.3 μm.
실시예 3Example 3
프리혼합 용액 제조시 폴리비닐알콜(무게평균 분자량 10,000) 8g 대신 폴리비닐피롤리돈 10g 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 폴리머 비드를 제조하였으며, 최종 제조된 폴리머 비드의 입자크기는 10.6 ㎛였다.The polymer beads were prepared in the same manner as in Example 1, except that 10 g of polyvinylpyrrolidone was used instead of 8 g of polyvinyl alcohol (weight average molecular weight 10,000) when preparing the premixed solution. 10.6 μm.
비교예 1Comparative Example 1
이온교환수 1014.29g, 폴리비닐알콜(무게평균 분자량 10,000) 8g을 2L 반응기에 넣고 교반시켰다. 메틸메타크릴레이트 387.65g, 에틸 아크릴레이트 33.71g, 1,6-헥산디올디아크릴레이트 12.64g 및 아조비스이소부티로니트릴 3g 용액을 상기 반응기에 넣고 700 rpm 속도로 30분간 교반시켜 프리혼합 용액을 제조하였다.1014.29 g of ion-exchanged water and 8 g of polyvinyl alcohol (weight average molecular weight 10,000) were put into a 2L reactor and stirred. 387.65 g of methyl methacrylate, 33.71 g of ethyl acrylate, 12.64 g of 1,6-hexanediol diacrylate, and 3 g of azobisisobutyronitrile were added to the reactor and stirred at 700 rpm for 30 minutes to prepare a premixed solution. Prepared.
이렇게 제조된 프리혼합 용액을 반응기에서 토출하여 균질기에서 1000psi 압력으로 두 번 처리하였다. 이 용액을 다시 상기 반응기에 투입하여 질소기류 하에서 250 rpm 속도로 교반하면서 내부온도가 60℃ 가 되도록 가열시킨 다음, 이 온도에서 7시간 동안 반응시켜 입자크기 11.7㎛인 폴리머 라텍스를 제조하였다.The premixed solution thus prepared was discharged from the reactor and treated twice at 1000 psi pressure in a homogenizer. The solution was added to the reactor again and heated at an internal temperature of 60 ° C. while stirring at 250 rpm under a nitrogen stream, and then reacted at this temperature for 7 hours to prepare a polymer latex having a particle size of 11.7 μm.
이렇게 얻어진 폴리머 라텍스를 15,000 rpm 속도로 1시간 동안 원심분리시킨 다음, 원심분리된 폴리비닐알콜이 포함된 상등액을 제거한 후, 이온교환수를 첨가하여 폴리머 입자들을 재분산시키기 위하여 5분간 교반하고 원심분리시켰다. 이러한 세척과정을 5회 반복 실시한 후, 침전된 폴리머 입자들을 60℃에서 24시간 동안 진공건조시켜 폴리머 비드를 제조하였다.The polymer latex thus obtained was centrifuged at 15,000 rpm for 1 hour, and then the supernatant containing the centrifuged polyvinyl alcohol was removed, followed by stirring for 5 minutes to re-disperse the polymer particles by adding ion-exchanged water, and centrifugation. I was. After the washing process was repeated five times, the polymer beads were dried by vacuum drying the precipitated polymer particles at 60 ° C. for 24 hours.
비교예 2Comparative Example 2
프리혼합 용액 제조시 폴리비닐알콜(무게평균 분자량 10,000)을 10g 사용한 것을 제외하고는 상기 비교예 1과 동일한 방법으로 폴리머 비드를 제조하였으며, 최종 제조된 폴리머 비드의 입자크기는 9.6 ㎛였다.Polymer beads were prepared in the same manner as in Comparative Example 1, except that 10 g of polyvinyl alcohol (weight average molecular weight 10,000) was used to prepare the premixed solution, and the particle size of the finally prepared polymer beads was 9.6 μm.
비교예 3Comparative Example 3
이온교환수 1014.29g, 폴리비닐알콜(무게평균 분자량 10,000) 8g을 2L 반응기에 넣고 교반시켰다. 메틸메타크릴레이트 200.65g, 에틸 아크릴레이트 18.71g, 1,6-헥산디올디아크릴레이트 6.64g 및 아조비스이소부티로니트릴 1.5g 용액을 상기 반응기에 넣고 700 rpm 속도로 30분간 교반시켜 프리혼합 용액을 제조하였다.1014.29 g of ion-exchanged water and 8 g of polyvinyl alcohol (weight average molecular weight 10,000) were put into a 2L reactor and stirred. 200.65 g of methyl methacrylate, 18.71 g of ethyl acrylate, 6.64 g of 1,6-hexanediol diacrylate and 1.5 g of azobisisobutyronitrile were added to the reactor and stirred at 700 rpm for 30 minutes to premix the solution. Was prepared.
이렇게 제조된 프리혼합 용액을 반응기에서 토출하여 균질기에서 1000psi 압력으로 두 번 실시하였다. 이 용액을 다시 상기 반응기에 투입하여 질소기류 하에서 250 rpm 속도로 교반하면서 내부온도가 60℃ 가 되도록 가열시킨 다음, 60℃에서 7시간 동안 반응시켜 입자크기 8.5㎛인 시드 폴리머 라텍스를 제조하였다.The premixed solution thus prepared was discharged from the reactor and performed twice at 1000 psi pressure in a homogenizer. The solution was added to the reactor again and heated at an internal temperature of 60 ° C. while stirring at 250 rpm under a nitrogen stream, and then reacted at 60 ° C. for 7 hours to prepare seed polymer latex having a particle size of 8.5 μm.
상기에서 제조된 시드 폴리머 라텍스를 상온까지 냉각시켜, 상온에서 메타크릴레이트 187g, 에틸 아크릴레이트 15g, 1,6-헥산디올디아크릴레이트 6g 및 아조비스이소부티로니트릴 1.5g 용액을 적가하지 않고, 한꺼번에 반응기에 투입하였다. 투입 후 5시간 동안 교반시키고 내부온도를 60℃로 승온시킨 다음, 이 온도에서 다시 7시간 동안 중합하여 평균 입자크기 13.7㎛인 폴리머 라텍스를 제조하였다.The seed polymer latex prepared above was cooled to room temperature, and 187 g of methacrylate, 15 g of ethyl acrylate, 6 g of 1,6-hexanediol diacrylate, and 1.5 g of azobisisobutyronitrile solution were not added dropwise at room temperature. It was put into the reactor all at once. After the addition, the mixture was stirred for 5 hours and the internal temperature was raised to 60 ° C., and then polymerized at this temperature for 7 hours to prepare a polymer latex having an average particle size of 13.7 μm.
이렇게 얻어진 폴리머 라텍스를 15,000 rpm 속도로 1시간 동안 원심분리시킨다음, 원심분리된 폴리비닐알콜이 포함된 상등액을 제거한 후, 이온교환수를 첨가하여 폴리머 입자들을 재분산시키기 위하여 5분간 교반하고 원심분리시켰다. 이러한 세척과정을 5회 반복 실시한 후, 침전된 폴리머 입자들을 60℃에서 24시간 동안 진공건조시켜 폴리머 비드를 제조하였다.The polymer latex thus obtained was centrifuged at 15,000 rpm for 1 hour, the supernatant containing the centrifuged polyvinyl alcohol was removed, and then stirred for 5 minutes and centrifuged to re-disperse the polymer particles by adding ion-exchanged water. I was. After the washing process was repeated five times, the polymer beads were dried by vacuum drying the precipitated polymer particles at 60 ° C. for 24 hours.
상기 실시예 및 비교예에서 제조된 폴리머 비드의 최종 입자크기 및 표준편차를 다음 표 1에 나타내었다.The final particle size and standard deviation of the polymer beads prepared in Examples and Comparative Examples are shown in Table 1 below.
상기 표 1의 결과로부터, 본 발명에 따라 제조된 폴리머 비드의 입자크기는 1∼40㎛이며, 비교예 1∼3에 비하여 표준편차가 적은 것으로 보아 좁은 입자크기 분포를 가진 균일한 폴리머 비드인 것을 확인할 수 있다.From the results of Table 1, the particle size of the polymer beads prepared according to the present invention is 1 to 40㎛, it is a uniform polymer bead having a narrow particle size distribution in view of less standard deviation compared to Comparative Examples 1 to 3 You can check it.
이상에서 상세히 설명한 바와 같이, 본 발명에서는 현탁중합에 의해 시드 폴리머를 제조한 다음, 이 폴리머에 단량체, 가교제 및 지용성 개시제로 된 용액을 팽윤시켜 중합함으로써 1∼40㎛의 입자크기와 입자크기 분포가 작아 균일한 입자크기를 가진 폴리머 비드를 제조할 수 있게 된다.As described in detail above, in the present invention, a seed polymer is prepared by suspension polymerization, and then a polymer of a monomer, a crosslinking agent, and a fat-soluble initiator is swelled and polymerized to obtain a particle size and particle size distribution of 1 to 40 μm. It is possible to produce polymer beads having a small particle size.
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| JPH06136006A (en) * | 1992-09-11 | 1994-05-17 | Japan Synthetic Rubber Co Ltd | Production of polymeric particle |
| US6228925B1 (en) * | 1996-04-23 | 2001-05-08 | Norsk Hydro Asa | Two-stage seed swelling procedure for producing monodisperse PVC particles |
| KR20040016624A (en) * | 2002-08-19 | 2004-02-25 | 제일모직주식회사 | Method of Preparing Monodisperse Functional Polymer Particle |
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| Journal of Polymer Science:Part A:Polymer Chemistry([(3270-3277)쪽] 가교된 폴리스티렌 비드를 한단계 팽윤 중합방법으로 제조하는 것으로, 스티렌과 안정제, 개시제를 포함한 에탄올 용액으로 시드 입자를 제조하고 이에 증류수와 안정제, 계면활성제를 첨가하여 교반한 뒤 스티렌과 가교제, 포로겐 톨루엔, 알콜, 개시제를 포함한 모노머 용액을 적가하고 팽윤시킨 뒤 중합하여 폴리머 비드를 제조함),Vol 38, pp 3270-3277, 2000 * |
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