Chapter 21
Synthesis of Cyclic Carbonate Functional Polymers Dean C. Webster and Allen L. Crain
Downloaded by UNIV LAVAL on June 18, 2013 | http://pubs.acs.org Publication Date: May 8, 1998 | doi: 10.1021/bk-1998-0704.ch021
Research Laboratories, Eastman Chemical Company, P.O. Box 1972, Kingsport, TN 37662-5150
Polymers with pendant cyclic carbonate functionality were synthesized via the free radical copolymerization of vinyl ethylene carbonate (4-ethenyl-1,3-dioxolane-2-one, VEC) with other unsaturated monomers. Both solution and emulsion free radical processes were used. In solution copolymerizations, it was found that VEC copolymerizes completely with vinyl ester monomers over a wide compositional range. Conversions of monomer to polymer are quantitative with complete incorporation of VEC into the copolymers. Cyclic carbonate functional latex polymers were prepared by the emulsion copolymerization of VEC with vinyl acetate and butyl acrylate. VEC incorporation was quantitative and did not affect the stability of the latex. When copolymerized with acrylic monomers, however, VEC is not completely incorporated into the copolymer. Sufficient levels can be incorporated to provide adequate cyclic carbonate functionality for subsequent reaction and crosslinking. The unincorporated VEC can be removed using a thin film evaporator. The Tg of VEC copolymers can be modeled over the compositional range studied using either linear or Fox models with extrapolated values of the Tg of VEC homopolymer.
Cyclic carbonate functional polymers have been explored on a limited basis over a number of years. The cyclic carbonate group is an attractive functional group due to its reactivity with primary amines at ambient or slightly elevated temperatures to form crosslinked networks [7]. Cyclic carbonate functional polymers will also react with carboxylic acid functional polymers [2] at higher temperatures to form crosslinked coatings. Cyclic carbonate functional polymers have been prepared using several different routes. Bisphenol-A epoxy resins have been transformed into cyclic
©1998 American Chemical Society In Functional Polymers; Patil, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
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304 carbonate functional resins by reaction of the oxirane with C 0 [3,4,5], Similarly, trimethylolpropane triglycidyl ether has been converted to the corresponding Afunctional cyclic carbonate by reaction with C 0 [
