Synthesis of poly(allyl 2-ylidene-acetate) and subsequent post-polymerization modification via thiol–ene reaction

Abstract

Poly(allyl 2-ylidene-acetate) (M_w = 125 300 g mol⁻¹) was synthesized via rhodium mediated catalysis of allyl 2-diazoacetate and its polymerization kinetics and polymer characteristics are presented and discussed. This polymer represents the first functional polymethylene accessible by a thiol–ene click-chemistry post-polymerization modification. Thiol–ene reactions were conducted under UV-irradiation utilizing 2,2-dimethoxy-2-phenylacetophenone as a photo-initiator. Differences to other polymethylenes, such as the inherent ability of poly(allyl 2-ylidene-acetate) to self-crosslink, and polymer characteristics are discussed. The inherent ability to self-crosslink is further utilized to form stable thin films. Subsequent modification of the surface leads to different surface properties as proven by contact angle measurement.