Modeling of molecular weight development in atom transfer radical polymerization
โ Scribed by Shiping Zhu
- Publisher
- John Wiley and Sons
- Year
- 1999
- Tongue
- English
- Weight
- 107 KB
- Volume
- 8
- Category
- Article
- ISSN
- 1022-1344
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โฆ Synopsis
A kinetic model has been developed for atom transfer radical polymerization processes using the method of moments. This model predicts monomer conversion, number-average molecular weight and polydispersity of molecular weight distribution. It takes into account the effects of side reactions including bimolecular radical termination and chain transfers. The determining parameters include the ratios of the initiator, catalyst and monomer concentrations, as well as the ratios of the rate constants of propagation, termination, transfer and the equilibrium constant between radicals and their dormant species. The effects of these parameters on polymer chain properties are systematically simulated. The results show that an ideal living radical polymerization exhibiting a linear relationship between number-average molecular weight versus conversion and polydispersity approaching unity is only achievable under the limiting condition of slow monomer propagation and free of radical termination and transfers. Improving polymerization rate usually accompanies a loss of this linearity and small polydispersity. For polymerization systems having a slow initiation, the dormant species exercise a retention effect on chain growing and tend to narrow the molecular weight distribution. Increasing catalyst concentration accelerates the initiation rate and thus decreases the polydispersities. It is also shown that for a slow initiation system, delaying monomer addition helps to reduce the polydispersities. Radical termination and transfers not only slow down the monomer conversion rates but also broaden polymer molecular weight distributions. Under the limiting conditions of fast propagation and termination and slow initiation, the model predicts the conventional free radical polymerization behaviors.
๐ SIMILAR VOLUMES
The attainable ยฎalues of molecular-weight distribution MWD specified by the degree of polymerization and the polydispersity in a batch free-radical polymerization reactor are described. The two-step method based on the quadratic profile of the instantaneous degree of polymerization is used to obtain