Amphiphilic Block‐Graft Copolymers with a Degradable Backbone and Polyethylene Glycol Pendant Chains Prepared via Ring‐Opening Polymerization of a Macromonomer

Abstract

Well-defined amphiphilic block-graft copolymers PCL-b-[DTC-co-(MTC-mPEG)] with polyethylene glycol methyl ether pendant chains were designed and synthesized. First, monohydroxyl-terminated macroinitiators PCL-OH were prepared. Then, ring-opening copolymerization of 2,2-dimethyltrimethylene carbonate (DTC) and cyclic carbonate-terminated PEG (MTC-mPEG) macromonomer was carried out in the presence of the macroinitiator in bulk to give the target copolymers. All the polymers were characterized by (1) H NMR and gel permeation chromatography (GPC). The polymers have unimodal molecular weight distributions and moderate polydispersity indexes. The amphiphilic block-graft copolymers self-assemble in water forming stable micelle solutions with a narrow size distribution.

Synthesis of Amphiphilic Comb-Shape Copolymers Via Ring-Opening Polymerization of a Macromonomer

“…The obtained graft copolymers have nonbiodegradable carbon backbones, limiting their uses for biomedical applications . In the previous work, we reported amphiphilic block‐graft copolymers with a hydrophobic degradable backbone and hydrophilic PEG pendant chains synthesized via ring‐opening polymerization of a cyclic carbonate macromonomer, 2‐methyltrimethylene carbonate‐terminated methoxy poly(ethylene glycol) (MTC‐mPEG 16 ) . Compared with other lactone monomers with a pendant chain, MTC‐mPEG 16 is very easy to be synthesized.…”

“…Compared with other lactone monomers with a pendant chain, MTC‐mPEG 16 is very easy to be synthesized. The polymer from ring‐opening polymerization of MTC‐mPEG 16 is a kind of polycarbonate that is biodegradable and biocompatible …”

Synthesis of degradable molecular brushes via a combination of ring‐opening polymerization and click chemistry

“…It is highly desirable to develop a facile method that can produce backbone‐degradable molecular brushes with high grafting density and a controlled degradation profile. On this aspect, recent progress has produced degradable grafted copolymers containing polyester and polycarbonate backbones with loosely grafted SCs (<1 SC per backbone repeating unit) . For instance, Hedrick and Jérôme have reported the synthesis of degradable grafted copolymers that contain polyester backbone and polymethacrylate SCs with the highest grafting density of 1 SC per backbone repeating unit.…”

Amphiphilic Block‐Graft Copolymers Poly(ethylene glycol)‐b‐(polycarbonates‐g‐palmitate) Prepared via the Combination of Ring‐Opening Polymerization and Click Chemistry

“…Among them, ROP has become the main method because of mild reaction conditions, low thermal effect, fast polymerization rate, and high molecular weight 1. Moreover, the biodegradable materials with different physical, chemical, and biological properties could be synthesized through varying the structure of cyclocarbonate monomers or copolymerizing with other cyclic monomers 6–15…”