Controllable ring‐opening copolymerization of L‐lactide and (3S)‐benzyloxymethyl‐(6S)‐methyl‐morpholine‐2,5‐dione initiated by a biogenic compound creatinine acetate

Abstract

Ring‐opening copolymerization (ROCP) of L‐lactide (L‐LA) and (3S)‐benzyloxymethyl‐(6S)‐methyl‐morpholine‐2,5‐dione [(3S, 6S)‐BMMD] initiated by creatinine acetate, a biogenic organic compound, was performed in the bulk at 130 °C. The copolymerization was well controlled as evidenced by that both the measured values of number‐average molecular weight (Mn,NMR(OH) and Mn,NMR(COOH)) and serine molar fraction (FBz.ser) of synthesized copolymers were close to the corresponding theoretical values; and that the higher isotacticity of synthesized copolymers (85–86%) and lower racemization degree of the ROCP. After removing O‐benzyls of the copolymers with Et3SiH/Et3N/CH2Cl2 under catalysis of PdCl2, functional biodegradable copolymers of L‐lactic acid (L‐Lac) and L‐Ser with designed molar fraction of serine (Fser 1.35%, 3.57%, 5.41%), narrow molecular weight distribution (polydispersity index 1.10–1.36), and improved hydrophilicity (θstat 82.3–89.6°) were finally obtained. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

An Overview of the Synthesis and Synthetic Mechanism of Poly (Lactic acid)

“…This research reviewed the synthetic methods of poly(lactic acid) such as oligomer polycondensation and ring-opening polymerization, and examined methods with organic catalysts that do not include metals to use PLA materials that will apply to biomedical area or microelectronics area [44][45][46][47].…”

Chapter 1. PLA Synthesis. From the Monomer to the Polymer

“…89,90 Living polymerization driven by a carboxylate-activation mechanism is supported by the kinetic studies on the HAG Á OAc-initiated ROP. The proposed mechanisms for the ROP initiated with HAG Á OAc and creatinine are shown in Schemes 1.12 and 1.13, respectively.…”