유화중합의 모델연구 1. Pseudo-homopolymerization

박상보; 서차수

Journal of the Korean Industrial and Engineering Chemistry, Vol.9, No.2, 294-299, April, 1998

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유화중합의 모델연구 1. Pseudo-homopolymerization

Study on Model of Emulsion Polymeration 1. Pseudo-homopolymerization

박상보, 서차수

초록

입자당 한 개 이상의 성장라디칼리 있는 일반계에서 근사적인 psedo-homopolymerization (PHP)방법의 신뢰성을 간접적으로 증명하기 위하여, 벌크중합의 Mayo-Lewis식이 Interval Ⅱ 동안 유화중합의 순간공중합조성식으로부터 확률적으로 유도됨을 보였다. Ballard등에 의하여 제안된 유화공중합의 확장된 Smith-Ewart식으로부터 0-1계(입자당 1개 이하의 성장라디칼이 있는 계)에 대하여 완전해를 얻었다. 이 해를 사용하여 입자당 평균라디칼수와 순간공중합조성이 몇 분 이내에 정상상태에 도달함을 예측할 수 있었다. 따라서 0-1계에 국한하여 PHP근사방법의 신뢰성을 직접 증명 할 수 있었다. 모델계산의 목적으로 Styrene-butadiene(St-Bu)과 Styrene-methyl methacrylate(St-MMA)계를 예로 들었다.

To prove pseudo-homopolymerization(PHP) method indirectly for general system which includes more than one growing radicals per particle, Mayo-Lewis equation of bulk copolymer system was derived form probability equation about instantaneous copolymer composition of emulsion copolymer system during intervalⅡ. From Extended Smith-Ewart equation proposed by Ballard et al. in emulsion copolymerization, exact solution, average number of radicals per particle and instantaneous copolymer composition were predected to reach the steady state which a few minutes. So the reliability of this approximation method could by proved directly for 0-1 system. Styrene-butadiene(St-Bu) and Styrene-methyl methacrylate(St-MMA) system were used for model calculations.

[References]

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[1] Harkins WD, J. Am. Chem. Soc., 69, 1428 (1947)

[2] Smith WV, Ewart RH, J. Chem. Phys., 16, 592 (1948)

[3] Lichti G, Gillbert RG, Napper DH, "Emulsion Polymerization," ed. I. Piirma, Academic Press, New York (1982)

[4] Gilbert RG, "Emulsion Polymerization, Academic Press, New York (1995)

[5] Ballard MJ, Napper DH, Gilbert RG, J. Polym. Sci. A: Polym. Chem., 19, 939 (1981)

[6] Chen SA, Wu KW, J. Polym. Sci. A: Polym. Chem., 26, 1487 (1988)

[7] Nomura M, J. Appl. Polym. Sci., 26, 17 (1981)

[8] Park SB, Kim BK, Shin YJ, Polymer, 9, 746 (1989)

[9] Park SB, Chang HS, Shin YJ, Polymer, 14, 227 (1990)

[10] Penboss IA, Gilbert RG, Napper DH, J. Chem. Soc.-Faraday Trans., 82, 2247 (1986)

[11] Mayo FD, Lewis FM, J. Am. Chem. Soc., 68, 1594 (1944)

[12] Flory PJ, "Principles of Polymer Chemistry," Conrnell University Press, Ithaca (1953)