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Chain polymerization of ester functionalized monomers

Tao Xie, University of Massachusetts Amherst


The overall purpose of this dissertation is to develop new polymer materials containing ester functionalities. This document will be separated into two sections covering two synthetic research projects that I have worked on for my Ph.D. dissertation. Both projects involved chain polymerizations of ester-functionalized monomers. A key feature of this thesis was to gain an in-depth understanding of the individual chain polymerizations employed, namely, anionic ring-opening polymerization of dialkyl cyclopropane-1,1-dicarboxylates and radical polymerization of multifunctional captodative monomers. Part I focuses on developing a new synthetic methodology based on anionic ring-opening polymerizations of cyclopropanes geminally substituted on the cycle. The goal was to obtain carbon-chain polymers with ester substituents located on every third-carbon atom of the backbone, a substitution pattern that cannot be achieved by any other synthetic method. Ester groups are chosen not only because of their electron-withdrawing nature that ensures enough activation but also because the structural versatility offered by ester groups allows to tailor polymer properties in a very easy way. Conditions allowing this ring-opening polymerization to proceed in a living way are identified. By taking advantage of the living character of the anionic polymerization, a control over the polymer end-groups, molecular weight and molecular weight distribution of the polymers can be achieved. Tailoring the polymer properties is also possible by varying the ester groups. Chemical modification of the polymer offers another way to obtain new polymers such as polyelectrolyte having the same substitution pattern. In part II, a possible answer is proposed to the environmental issues the coating industry is currently facing which include the toxicity of acrylic monomers used and generation of volatile organic compounds during the process. New functionalized bis(α substituted acrylate)s were developed that can be assumed non/less toxic based on previous literature. The new functionalities introduced in the monomers are crucial in affecting not only their reactivity toward the photopolymerization involved in the coating production but also some properties of the final coatings. Both of these aspects are covered in the research.

Subject Area


Recommended Citation

Xie, Tao, "Chain polymerization of ester functionalized monomers" (2001). Doctoral Dissertations Available from Proquest. AAI3027275.