Using kinetics and thermodynamics in the controlled synthesis of low molecular weight polymers in free-radical polymerization

Barner-Kowollik, C. & Davis, T. P. (2001) Using kinetics and thermodynamics in the controlled synthesis of low molecular weight polymers in free-radical polymerization. Macromolecular Theory and Simulations, 10(4).

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Abstract

A simple way of controlling molecular weights in the free-radical copolymerization of styrene and a α-methylstyrene (AMS) is presented and investigated by simulation via the program package PREDICI®. It is shown that the molecular weight of the product copolymers may be varied in a wide range (from ̄w = 500 to 2 · 106) by variation of the comonomer feed ratio and the reaction temperature. The reasons for this simple molecular weight control are associated with the AMS comonomer and are threefold: (i) AMS has a low propagation rate coefficient , due to the increased steric requirements of the monomer, (ii) AMS has a transfer to monomer constant (CM) in comparison with styrene and (iii) AMS has a low ceiling temperature, so that the effective propagation rate coefficient decreases with increasing temperature. In addition to the styrene/AMS system, other comonomer systems showing similar kinetic and thermodynamic features (e. g. the styrene/methyl ethacrylate (MEA) system) may also be used to generate a wide range of molecular weights. The possibilities for controlling molecular weight and end group functionalities by replacing the slowly propagating monomer by a functional monomer are discussed.

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ID Code: 99043
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :14
Export Date: 5 September 2016
CODEN: MTHSE
Correspondence Address: Davis, T.P.; Ctr. for Adv. Macromolecular Design, Sch. of Chemical Engg./Indust. Chem., University of New South Wales, Sydney, NSW 2052, Australia
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Keywords: alpha methylstyrene, copolymer, free radical, polymer, styrene, styrene derivative, unclassified drug, article, chemical reaction, chemical reaction kinetics, computer simulation, molecular model, molecular weight, polymerization, synthesis, thermodynamics
DOI: 10.1002/1521-3919(20010401)10:4<255::AID-MATS255>3.0.CO;2-V
ISSN: 10221344
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 22 Sep 2016 04:50

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