Versatile Synthesis of Functional Biodegradable Polymers by Combining Ring-Opening Polymerization and Postpolymerization Modification via Michael-Type Addition Reaction
作者：5. W. Chen, H.C. Yang, R. Wang, R. Cheng, F.H. Meng*, W.X. Wei, and Z.Y. Zhong*
關鍵字：biodegradable polymers
論文來源：期刊
具體來源：Macromolecules 2010, 43, 201–207
發表時間：2010年
Various functional biodegradable polymers were readily prepared based on novel cyclic carbonate monomers, acryloyl carbonate (AC) and methacryloyl carbonate (MAC), by combining ringopening polymerization (ROP) and Michael-type conjugate addition. AC and MAC monomers were synthesized in four straightforward steps from 1,1,1-tris(hydroxymethyl)ethane with good overall yields (ca. 40%). AC and MAC were able to copolymerize with ε-caprolactone (ε-CL) and D,L-lactide (LA) in
toluene at 110 C using stannous octoate as a catalyst, yielding biodegradable copolymers with controlled (meth)acryloyl functional groups and molecular weights. The acryloyl groups were amenable to the Michaeltype conjugate addition with varying thiol-containing molecules such as 2-mercaptoethanol, 3-mercaptopropanoic acid, cysteamine, cysteine, and arginine-glycine-aspartic acid-cysteine (RGDC) peptide under mild conditions, to provide biodegradable materials with vastly different functionalities (e.g., hydroxyl, carboxyl, amine, amino acid, and peptides) and properties (e.g., hydrophilicity, cell adhesion). Notably, 100% functionalization was achieved with 2-mercaptoethanol, cysteamine and cysteine. Initial cell culture studies demonstrated enhanced cell adhesion and growth on films containing functional RGDC peptides as compared to those of the parent copolymer. Therefore, combination of ROP and Michael-type conjugate addition provides a versatile access to diverse types of functional biodegradable materials.