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J Chem Phys. 2005 Oct 8;123(14):144901.

Simulation and theory of self-assembly and network formation in reversibly cross-linked equilibrium polymers.

Author information

1
Department of Chemistry, Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA. jkindt@emory.edu

Abstract

A simulation model of hard spheres capable of reversible assembly into chains, which then may reversibly cross-link into networks, has been studied through grand canonical Monte Carlo simulation. Effects of varying intra- and interchain bond strengths, chain flexibilities, and restrictions on cross-linking angle were investigated. Observations including chain-length distributions and phase separation could be captured in most cases using a simple model theory. The coupling of chain growth to cross-linking was shown to be highly sensitive to the treatment of cross-linking by chain ends. In some systems, ladderlike domains of several cross-links joining two chains were common, resulting from cooperativity in the cross-linking. Extended to account for this phenomenon, the model theory predicts that such cooperativity will suppress phase separation in weakly polymerizing chains and at high cross-link concentration. In the present model, cross-linking stabilizes the isotropic phase with respect to the nematic phase, causing a shift in the isotropic-nematic transition to higher monomer concentration than in simple equilibrium polymers.

PMID:
16238418
DOI:
10.1063/1.2046629
[Indexed for MEDLINE]

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