Free‐radical copolymerization of ethyl α‐hydroxymethylacrylate with methyl methacrylate by reversible addition–fragmentation chain transfer

Abstract

The controlled free‐radical homopolymerization of ethyl α‐hydroxymethylacrylate and copolymerization with methyl methacrylate were performed in chlorobenzene at 70 °C by the reversible addition–fragmentation chain transfer polymerization technique with 2,2′‐azobisisobutyronitrile as the initiator. 2‐Phenylprop‐2‐yl dithiobenzoate and 2‐cyanoprop‐2‐yl dithiobenzoate were used as chain‐transfer agents in the homopolymerization, whereas only the former was used in the copolymerization. All reactions presented pseudolinear kinetics. The effect of the monomer feed ratio on the copolymerization kinetics was examined. The conversion level decreased when the proportion of ethyl α‐hydroxymethylacrylate in the monomer feed was larger. Kinetic studies indicated that the radical polymerizations proceeded with apparent living character according to experiments, demonstrating an increase in the molar mass with the monomer conversion and a relatively narrow molar mass distribution. All copolymers were statistical in chain structure, as confirmed by determinations of the monomer reactivity ratios. The monomer reactivity ratios were determined, and the Mayo–Lewis terminal model provided excellent predictions for the variations of the intermolecular structure over the entire conversion range. Additionally, the chemical modification of poly(ethyl α‐hydroxymethylacrylate) was carried out to introduce glucose pendant groups into the structure. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5618–5629, 2006

Chemical modification of block copolymers based on 2-hydroxyethyl acrylate to obtain amphiphilic glycopolymers

“…Our lab has an extensive experience on the incorporation of different carbohydrates onto hydroxylated polymers, i.e., poly(vinyl alcohol), [46] ethylene-vinyl alcohol [47][48][49][50][51][52][53], poly(2-hydroxyethyl methacrylate) [54] and poly(ethyl α-hydroxymethylacrylate). [55] The present research describes a satisfactory combination of those two aforementioned approaches. First, the polymerization by ATRP of well-controlled di and triblock copolymers, based on HEA and butyl acrylate (BA), and their further characterization were addressed.…”

Stereospecific Anionic Polymerization of α‐(Hydroxymethyl)acrylate with Protective Group

“…The polymer [ poly(2) ] has hydrophilicity, biocompatibility, and hydroxyl functionality, so that its applications to composites with wood, adhesives, coatings, curing agents, and photoresists have been investigated. Recently, reversible addition‐fragmentation chain transfer (RAFT) polymerization of 2 has been reported, which achieved the control of molecular weight with high conversion …”

Glycopolymers obtained by chemical modification of well‐defined block copolymers

“…There are mainly two approaches to prepare glycopolymers;20 by either polymerization of carbohydrate‐containing monomers25–36 or by the postpolymerization chemical modification of synthetic polymers 37–51. The first one includes the synthesis of glycomonomers protected or unprotected by using standard chemical modification15, 16, 19, 52 or click chemistry approaches20, 53–56 and posterior polymerization using different methodologies; that is, conventional and controlled radical polymerization, living anionic polymerization, cyanoxyl mediated polymerization, ring opening polymerization or combination of different techniques 25–36.…”