One-pot synthesis of poly(vinyl alcohol)-based biocompatible block copolymers using a dual initiator for ROP and RAFT polymerization

• Published in: Polymer (Guilford) Vol. 54; no. 21; pp. 5595 - 5600
• Main Authors: Yu, Young Chang, Shin, Sang Jin, Ko, Kwang Duk, Yu, Woong-Ryeol, Youk, Ji Ho
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 04.10.2013; Elsevier
• Subjects: alcohols; Applied sciences; biphenyl; composite polymers; Dual initiator; Exact sciences and technology; One-pot synthesis; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; PVA-based biocompatible block copolymers; pyridines; One-pot synthesis; PVA-based biocompatible block copolymers; Dual initiator; Ring opening polymerization; One pot reaction; Organic trithiocarbonate; Lactone copolymer; Vinyl ester copolymer; Vinyl alcohol copolymer; Chlorine containing copolymer; Experimental study; Chemical modification; Free radical polymerization; Chain transfer; Caprolactone copolymer; Aminolysis; Preparation; Diblock copolymer; Living copolymer; Carbonate copolymer; Aliphatic copolymer; Successive reaction
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2013.07.070

Biocompatible poly(ε-caprolactone)-b-poly(vinyl alcohol) (PCL-b-PVA), poly(δ-valerolactone)-b-PVA, and poly(trimethylene carbonate)-b-PVA block copolymers were synthesized at 30 °C using a hydroxyl-functionalized xanthate reversible addition-fragmentation chain transfer (RAFT) agent, 2-hydroxyethyl 2-(ethoxycarbonothioylthio)propanoate, as a dual initiator for ring-opening polymerization (ROP) and RAFT polymerization in a one-pot procedure. The ROP of ε-caprolactone, δ-valerolactone, and trimethylene carbonate was first performed using diphenyl phosphate as the ROP catalyst followed by the RAFT polymerization of vinyl chloroacetate after quenching the ROP with 4-dimethyamino pyridine. The resulting block copolymers were aminolyzed directly to the PVA-based biocompatible block copolymers by adding hexylamine to the reaction mixture. To the best of our knowledge, this is the most convenient method for synthesizing PVA-based biocompatible block copolymers. [Display omitted]