단분산상으로 가교된 고분자 비드의 합성

심상은; 변재만; 전종원; 차윤종; 최순자; Sang Eun Shim; Jae Man Byun; Jongwon Jun; Yoon-Jong Cha; Soonja Choe

Polymer(Korea), Vol.24, No.3, 287-298, May, 2000

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단분산상으로 가교된 고분자 비드의 합성

Preparation of Monodispersed Crosslinked Polymer Beads

심상은, 변재만¹, 전종원¹, 차윤종², 최순자^{1, †}

Akron 대학교 고분자공학과
¹인하대학교 화학공학과
²(주)백산 기술연구소

Sang Eun Shim, Jae Man Byun¹, Jongwon Jun¹, Yoon-Jong Cha², and Soonja Choe^{1, †}

Department of Polymer Engineering, The University of Akron, Akron. OH 44325-0301, U.S.A, Korea
¹Department of Chemical Engineering, Research Institute of Polymer Science and Engineering, Inha Unviersity, Inchon 402-751, Korea
²BAIKSAN CO. LTD., Ansan, Kyunggido, Korea

E-mail:

초록

DVB(divinylbenzene)를 가교제로 하여 마이크로미터 크기의 단분상산 폴리스티렌 입자를 분사 중합법으로 제조하면서, 반응 온도와 단량체, 개시제, 용매 및 공용매의 농도, 안정제 poly(N-divinylpyrrolidone) (PVP)함량과 분자량, 그리고 DVB의 함량이 전환율과 생성 입자의 크기 및 분포도에 미치는 영향을 조사하였다. 분산매로는 에탄올로, 개시제로 AIBN, 공통 분산매로 톨루엔, 그리고 안정제로는 분자량 40000의 PVP를 사용하였다. 반응온도가 높아지고 개시제의 농도가 1%에서 4%로 증가할수록 반응속도와 전환율은 상승하고 모든 반응조건에서 10시간의 반응 결과 전환율과 입자의 크기는 거의 완결 단계에 이르렀으며, 오히려 24시간 동안 반응된 입자의 안정성은 10시간의 것보다 enlEJfdjwuT다. EH한 반응ㅇ온도의상승이 개시제의 농도변화보다 반응속도와 전환율에 더 민감한 영향을 미치는 것으로 관찰되었다. 각각 반응물으이 조성을 변화시키면서 입자크기 및 분산도의 변화를 조사한 결과, 표면 특성이 안정하면 단분산상의 분포도를 갖는 구형의 고분자 입자를 중합할 수 있는 최적의 조건은 0.5% DVB, 25% 스티렌 단량체, 20-25% 톨루엔, PVP 농도는 10∼15%, AIBN의 농도는 2와 4%이었으며, 이 조건에서 10시간의 반응으로 합성된 비드의 평균 입자경은 각각 3.9∼4㎛와 3.4∼9.3㎛이었다.

In preparing micron-sized monodisperse polystyrene beads by dispersion polymerization, the conversion, and the particle size and its distribution were affected by the reaction temperature, concentration of the monomer, solvent and initiator, molecular weight and concentration of the steric stabilizer, amount of oxygen existing in the reactor, and an appropriate combination of these starting materials. Ethanol as a dispersing agent, styrene as a monomer, PVP as a steric stabilizer, AIBN as an initiator, DVB as a cross-linking agent and toluene as a co-solvent were the basic materials for the synthesis. The reaction rate and the conversion were increased with the reaction temperature and the amount of DVB from 1 to 4%, and the conversion was saturated after 10 hours of the reaction time. The optimum reaction recipe for the preparation of the monodisperse PS beads was 25% styrene monomer, 0.5% DVB, 25% toluene, 10-15% PVP, and 2 and 4% AIBN, thereby, 3.9∼4 ㎛ and 3.4∼9.3 ㎛ of polystyrene beads, respectively, were successfully synthesized.

Keywords:Dispersion polymerization;Crosslinked monodisperse particle;Morphology;Polystyrene

[References]

Ugelstad J, Berge A, Ellingsen T, Schmid R, Nilson TN, Mork PC, Stenstad P, Hornes E, Olsvik O, Prog. Polym. Sci., 17, 87 (1992)
Ober CK, Lok KP, U.S. Patent, 4,617,249 (1986)
Hattori M, Sudol ED, El-Aasser MS, J. Polym. Sci. A-Polym. Chem., 30, 2027 (1993)
Almog Y, Levy M, J. Polym. Sci. A-Polym. Chem., 20, 417 (1982)
Kamiyama M, Koyama K, Matsuda H, Sano Y, J. Appl. Polym. Sci., 50, 107 (1993)
Ugelstad J, Mork PC, Kaggerud KH, Ellingsen T, Berge A, Adv. Colloid Interface Sci., 13, 101 (1980)
Okubo M, Konishi Y, Minami H, Colloid Polym. Sci., 275, 797 (1997)
Barrett KE, "Dispersion Polymerization in Organic Media," Wiley, London, 1975 (1975)
Cheng CM, Micale FJ, Vanderhoff JW, El-Aasser MS, J. Polym. Sci. A-Polym. Chem., 30, 235 (1991)
Cheng CM, Vanderhoff JM, El-Aasser MS, J. Polym. Sci. A-Polym. Chem., 30, 245 (1991)
Li K, Stover HDH, "Preparation and Characterization of Highly Crosslinked Polymer Particles from Commercial Divinylbenzene," 75th Canadian Chemical Conference, Edmonton, Alberta, Canada, June 1992 (1992)
Hattori M, Sudol ED, El-Aasser MS, "Highly Crosslinked Polymer Particles by Dispersion Polymerization," 34th IUPAC International Symposium on Macromolecules, Prague, July 13-18, 1992 (1992)
Tseng CM, Lu YY, El-Aasser MS, Vanderhoff JW, J. Polym. Sci. A-Polym. Chem., 24, 2995 (1986)
Margel S, Nov E, Fisher I, J. Polym. Sci. A-Polym. Chem., 29, 347 (1991)
Li K, Stover HDH, J. Polym. Sci. A-Polym. Chem., 31, 2273 (1993)
Ober CK, Lok KP, Hari ML, J. Polym. Sci. C-Polym. Lett., 23, 103 (1985)
Lok KP, Ober CK, Can. J. Chem., 63, 1209 (1985)
Shim SE, Cha YJ, Byun JM, Choe S, J. Appl. Polym. Sci., 71(13), 2259 (1999)
Almog Y, Reich S, Levy M, Brit. Polym. J., 14, 131 (1981)
Corner T, Colloids Surf., 3, 119 (1981)
Ho CH, Chen SA, Amiridis MD, Vanzee JW, J. Polym. Sci. A-Polym. Chem., 35(14), 2907 (1997)
Paine AJ, Macromolecules, 23, 3109 (1990)

[Referenced By]

[1] Ugelstad J, Berge A, Ellingsen T, Schmid R, Nilson TN, Mork PC, Stenstad P, Hornes E, Olsvik O, Prog. Polym. Sci., 17, 87 (1992)

[2] Ober CK, Lok KP, U.S. Patent, 4,617,249 (1986)

[3] Hattori M, Sudol ED, El-Aasser MS, J. Polym. Sci. A-Polym. Chem., 30, 2027 (1993)

[4] Almog Y, Levy M, J. Polym. Sci. A-Polym. Chem., 20, 417 (1982)

[5] Kamiyama M, Koyama K, Matsuda H, Sano Y, J. Appl. Polym. Sci., 50, 107 (1993)

[6] Ugelstad J, Mork PC, Kaggerud KH, Ellingsen T, Berge A, Adv. Colloid Interface Sci., 13, 101 (1980)

[7] Okubo M, Konishi Y, Minami H, Colloid Polym. Sci., 275, 797 (1997)

[8] Barrett KE, "Dispersion Polymerization in Organic Media," Wiley, London, 1975 (1975)

[9] Cheng CM, Micale FJ, Vanderhoff JW, El-Aasser MS, J. Polym. Sci. A-Polym. Chem., 30, 235 (1991)

[10] Cheng CM, Vanderhoff JM, El-Aasser MS, J. Polym. Sci. A-Polym. Chem., 30, 245 (1991)

[11] Li K, Stover HDH, "Preparation and Characterization of Highly Crosslinked Polymer Particles from Commercial Divinylbenzene," 75th Canadian Chemical Conference, Edmonton, Alberta, Canada, June 1992 (1992)

[12] Hattori M, Sudol ED, El-Aasser MS, "Highly Crosslinked Polymer Particles by Dispersion Polymerization," 34th IUPAC International Symposium on Macromolecules, Prague, July 13-18, 1992 (1992)

[13] Tseng CM, Lu YY, El-Aasser MS, Vanderhoff JW, J. Polym. Sci. A-Polym. Chem., 24, 2995 (1986)

[14] Margel S, Nov E, Fisher I, J. Polym. Sci. A-Polym. Chem., 29, 347 (1991)

[15] Li K, Stover HDH, J. Polym. Sci. A-Polym. Chem., 31, 2273 (1993)

[16] Ober CK, Lok KP, Hari ML, J. Polym. Sci. C-Polym. Lett., 23, 103 (1985)

[17] Lok KP, Ober CK, Can. J. Chem., 63, 1209 (1985)

[18] Shim SE, Cha YJ, Byun JM, Choe S, J. Appl. Polym. Sci., 71(13), 2259 (1999)

[19] Almog Y, Reich S, Levy M, Brit. Polym. J., 14, 131 (1981)

[20] Corner T, Colloids Surf., 3, 119 (1981)

[21] Ho CH, Chen SA, Amiridis MD, Vanzee JW, J. Polym. Sci. A-Polym. Chem., 35(14), 2907 (1997)

[22] Paine AJ, Macromolecules, 23, 3109 (1990)