Broadening of molecular-weight distribution in solid-state polymerization resulting from condensate diffusion

Michael D. Goodner, Stephen Gross, Joseph M. Desimone, George W. Roberts, Douglas J. Kiserow

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

A kinetic model for the solid-state polymerization of poly(bisphenol A carbonate) in a single particle has been developed and used to investigate the broadening of molecular-weight distribution as a result of slow condensate diffusion. The model is based on melt-phase transesterification kinetics and Fickian diffusion of phenol, the condensate, in the amorphous regions of the semicrystalline particle. Model predictions compare favorably to experimental data. When diffusion is slow compared to reaction, a condensate concentration gradient is established. This gradient induces a molecular-weight gradient, which results in a broadened overall molecular-weight distribution with an overall polydispersity above the theoretical limit for homogenous step-growth polymerization. As the mass transfer resistance inside the particle is decreased, the average molecular weight increases faster with time, and the overall polydispersity decreases. A stoichiometric imbalance of end groups decreases the obtainable molecular weight but mitigates the deleterious effects of slow condensate diffusion.

Original languageEnglish
Pages (from-to)928-943
Number of pages16
JournalJournal of Applied Polymer Science
Volume79
Issue number5
DOIs
StatePublished - Jan 2001
Externally publishedYes

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Molecular weight distribution
Polymerization
Molecular weight
Polydispersity
Kinetics
Carbonates
Transesterification
Phenol
Phenols
Mass transfer

All Science Journal Classification (ASJC) codes

  • Polymers and Plastics

Cite this

Broadening of molecular-weight distribution in solid-state polymerization resulting from condensate diffusion. / Goodner, Michael D.; Gross, Stephen; Desimone, Joseph M.; Roberts, George W.; Kiserow, Douglas J.

In: Journal of Applied Polymer Science, Vol. 79, No. 5, 01.2001, p. 928-943.

Research output: Contribution to journalArticle

Goodner, Michael D. ; Gross, Stephen ; Desimone, Joseph M. ; Roberts, George W. ; Kiserow, Douglas J. / Broadening of molecular-weight distribution in solid-state polymerization resulting from condensate diffusion. In: Journal of Applied Polymer Science. 2001 ; Vol. 79, No. 5. pp. 928-943.
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