Synthesis and Characterization of Backbone Degradable Azlactone-Functionalized Polymers

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• 作者：Matthew C. D. Carter ; James Jennings ; Visham Appadoo ; David M. Lynn
• 刊名：Macromolecules
• 出版年：2016
• 出版时间：August 9, 2016
• 年：2016
• 卷：49
• 期：15
• 页码：5514-5526
• 全文大小：576K
• 年卷期：0
• ISSN：1520-5835

文摘

We report the design of reactive and degradable copolymers that contain both azlactone side chain functionality and hydrolyzable backbone ester groups. Copolymerization of the vinyl monomer 2-vinyl-4,4-dimethylazlactone (VDMA) and the cyclic ketene acetal 2-methylene-1,3-dioxepane (MDO) using conventional or reversible-deactivation radical polymerization techniques yielded copolymers and block copolymers that exhibit amine reactivity associated with poly(vinyl azlactone)s but also hydrolytic degradability associated with conventional polyesters. Our results demonstrate that control over monomer feed ratios and other parameters can be used to tune both copolymer composition (e.g., the number/ratio of azlactone and ester repeat units) and the physical properties of the resulting materials (e.g., glass transition temperatures and ability to self-assemble into nanoscale structures). Post-fabrication functionalization of reactive azlactone groups in MDO-co-VDMA copolymers by treatment with primary amines proceeds rapidly and quantitatively, and can be achieved without disruption or degradation of backbone ester groups. These azlactone-functionalized copolymers are thus well suited for use as templates for the design of new degradable polymers and as building blocks for the design of covalently and ionically cross-linked macromolecular thin films, capsules, and gels that degrade in aqueous environments.