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 language | English |
|---|---|
| Pages (from-to) | 928-943 |
| Number of pages | 16 |
| Journal | Journal of Applied Polymer Science |
| Volume | 79 |
| Issue number | 5 |
| DOIs | |
| State | Published - Jan 2001 |
| Externally published | Yes |
Fingerprint
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 journal › Article
}
TY - JOUR
T1 - Broadening of molecular-weight distribution in solid-state polymerization resulting from condensate diffusion
AU - Goodner, Michael D.
AU - Gross, Stephen
AU - Desimone, Joseph M.
AU - Roberts, George W.
AU - Kiserow, Douglas J.
PY - 2001/1
Y1 - 2001/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0035155319&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0035155319&partnerID=8YFLogxK
U2 - 10.1002/1097-4628(20010131)79:5<928::AID-APP170>3.0.CO;2-X
DO - 10.1002/1097-4628(20010131)79:5<928::AID-APP170>3.0.CO;2-X
M3 - Article
AN - SCOPUS:0035155319
VL - 79
SP - 928
EP - 943
JO - Journal of Applied Polymer Science
JF - Journal of Applied Polymer Science
SN - 0021-8995
IS - 5
ER -