Equilibrium polymerization of cyclic carbonate oligomers

被引:14
作者
Ballone, P
Jones, RO
机构
[1] Forschungszentrum Julich, Inst Festkorperforsch, D-52425 Julich, Germany
[2] Univ Messina, Dipartimento Fis, I-98166 Messina, Italy
关键词
D O I
10.1063/1.1389294
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A model of the polymerization of ring oligomers of bisphenol A polycarbonate (BPA-PC) is used to investigate the influence of dimensionality (2D or 3D), density and temperature on the size distribution of the polymer chains. The polymerization step is catalyzed by a single active particle, conserves the number and type of the chemical bonds, and occurs without a significant gain in either potential energy or configurational entropy. Monte Carlo and molecular dynamics simulations show that polymerization of cyclic oligomers occurs readily at high density and is driven by the entropy associated with the distribution of interparticle bonds. Polymerization competes at lower densities with long range diffusion, which favors small molecular species, and is prevented if the system is sufficiently dilute. Polymerization occurs in 2D via a weakly first order transition as a function of density and is characterized by low hysteresis and large fluctuations in the size of polymer chains. Polymerization occurs more readily in 3D than in 2D, and is favored by increasing temperature, as expected for an entropy-driven process. (C) 2001 American Institute of Physics.
引用
收藏
页码:3895 / 3905
页数:11
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