PMMA의 입체특성에 따른 r<sup>2</sup>과 s<sup>2</sup> 사이의 상관계수의 영향

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Polymer(Korea), Vol.17, No.5, 492-497, September, 1993

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PMMA의 입체특성에 따른 r²과 s² 사이의 상관계수의 영향

Stereospecific Effects of PMMA on Correlation Coefficient between r₂ and s₂

서길수

초록

폴리(메틸 메타크릴레이트)의 상관계수 ρ를 구하기 위하여 중합도, 온도 그리고 입체형태(conformation)를 변화시키면서 다음의 3가지 무차원비 즉, 4>₀/2>₀², 4>₀/2>₀², 그리고 2s²>₀를 각각 계산하였다. 여기서 2>₀과 2>₀은 2승 평균 말단간 거리와 2승 평균 회전반경을 의미한다. 이들의 무차원비로부터 r²과 s²사이의 상관계수 ρ와 ρ의 온도계수를 계산하였으며, 이소탁틱 PMMA 경우 중합도가 증가함에 다라 상관계수 ρ가 최대치를 나타내다가 일정한 값으로 수렴하는데 반해, 신디오탁틱 PMMA의 경우는 상관계수 ρ가 첫번째 극대치, 극소치, 두번째 극대치를 나타낸 후 일정한 값으로 수렴하는 진동현상을 보였다.

The dimensionless ratios 4>₀,/2>₀²,4>₀,/2>₀², and 2>s²₀/2>₀2>₀ have been computed for poly(methyl methacrylate) as functions of chain length and stereochemical constitution. The squared end-to-end distance and radius of gyration for a Particular conformation are denoted by r² s², respectively, and angular brackets denote the average of the enclosed property. The correlation coefficient ρ between r² and s² and the temperature coefficient of ρ were calculated from these dimernsionless ratios. Local maxima and minima can be seen in ρ as a function of degree of polymerlzation in syndiotactic PMMA chains, but only local maxima are appeared in isotactic PMMA chains.

[References]

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[1] Flory PJ, "Statistical Mechanics of Chain Molecules, Wiley, New York (1969)

[2] Flory PJ, Crescenzi V, Mark JE, J. Am. Chem. Soc., 86, 146 (1964)

[3] Abe A, Jernigan RL, Flory PJ, J. Am. Chem. Soc., 88, 631 (1966)

[4] Tonelli AE, Macromolecules, 9, 547 (1976)

[5] Abe A, Mark JE, J. Am. Chem. Soc., 98, 6468 (1976)

[6] Welsh WJ, DeBolt L, Mark JE, Macromolecules, 19, 2978 (1986)

[7] Mattice WL, Sienicki K, J. Chem. Phys., 90, 1956 (1989)

[8] Galiatsatos V, Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem., 33(1), 572 (1992)

[9] Neuberger NA, Mattice W, Computer Simulation of Polymers, R.J. Roe, Ed., Prentice Hall, New Jersey (1991)

[10] Mattice WL, J. Chem. Phys., 87, 5512 (1988)

[11] Flory PJ, Suter UW, Mutter M, J. Am. Chem. Soc., 98, 5733 (1976)

[12] Jernigan RL, Flory PJ, J. Chem. Phys., 50, 4185 (1969)

[13] Pannikottu A, Mattice WL, Macromolecules, 24, 2644 (1990)

[14] Flory PJ, Macromolecules, 7, 381 (1974)

[15] Flory PJ, Abe A, J. Chem. Phys., 54, 135 (1971)

[16] Bowen HJM, Sutton LE, Tables of Interatomic Distances and Configurations in Molecules and Ions, Chemical Society, London (1958)

[17] Sundararajan PR, Flory PJ, J. Am. Chem. Soc., 96, 5025 (1974)

[18] Sakurada I, Nakajima A, Yoshizaki O, Nakamae K, Kolloid Z., 186, 41 (1962)

[19] Flory PJ, Fisk S, J. Chem. Phys., 44, 2243 (1966)

[20] Bovey FA, Tiers GVD, J. Polym. Sci., 44, 173 (1960)

[21] Fox TG, Polymer, 3, 111 (1962)

[22] Vasudevan P, Santappa M, J. Polym. Sci. A: Polym. Chem., 9, 483 (1971)

[23] Schulz GV, Wunderlich W, Kirste R, Makromol. Chem., 75, 22 (1964)

[24] Moore WR, Fort RF, J. Polym. Sci. A: Polym. Chem., 1, 929 (1963)