Atom Transfer Radical Polymerization of Glycidyl Methacrylate: A Functional Monomer

Abstract

Summary: A detailed investigation of the polymerization of glycidyl methacrylate (GMA), an epoxy‐functional monomer, by atom transfer radical polymerization (ATRP) was performed. Homopolymers were prepared at relatively low temperatures using ethyl 2‐bromoisobutyrate (EBrIB) as the initiator and copper halide (CuX) with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system. The high polymerization rate in the bulk did not permit polymerization control. However, homopolymerization in solution enabled us to explore the effects of different experimental parameters, such as temperature, solvent (toluene vs. diphenyl ether) and initiator concentration, on the controllability of the ATRP process. SEC analysis of the homopolymers synthesized confirmed the importance of solvent character on molecular weight control, the lowest polydispersity indices ($\overline M _{\rm w} /\overline M _{\rm n} < 1.25$) and the highest efficiencies being found when the polymerizations were performed in diphenyl ether in combination with a mixed halide technique. A novel poly(glycidyl methacrylate)‐block‐poly(butyl acrylate) (PGMA‐b‐PBA) diblock copolymer was prepared through ATRP using PGMA‐Cl as a macro‐initiator. This chain growth experiment demonstrated a good living character under the conditions employed, while simultaneously indicating a facile synthetic route for this type of functional block copolymer. In addition, the isotacticity parameter for the PGMAs obtained was estimated using 1H NMR analysis which gave a value of σGMA = 0.26 in agreement with that estimated in conventional radical polymerization.SEC chromatograms of PGMA‐Cl macroinitiator and PGMA‐b‐PBA diblock copolymer.magnified imageSEC chromatograms of PGMA‐Cl macroinitiator and PGMA‐b‐PBA diblock copolymer.

Synthesis and aggregation properties in water solution of comblike methacrylic polymers with oligo(propylene glycol)‐block‐oligo(ethylene glycol) as side chains

“…29,30 The apparent propagation constant (k app p ) was calculated from the slope of this plot, obtaining a value of k app p ¼ 1.72 Â 10 À4 s À1 , which is a reasonable for the ATRP of a methacrylic monomer as OPGMA. [31][32][33] Coming back to Table 1, it is also observed that the molecular weights determined experimentally by SEC (M n,SEC ) are close to those determined theoretically (M n,theo. ).…”

Multi functionalization of polypropylene with controlled degradation and its structure characterization

“…The aforementioned conclusion can also be indirectly confirmed by M n of PGMA formed during ISCGC (Table IV). M n of PGMA in ISCGC is lower in comparison with that of PGMA formed in tradition synthesis process 38 because the PGMA macroradicals can be quickly terminated by chlorine.…”

“…39 The result indicates that primary protons or secondary protons can also be substituted by chlorine atoms due to its high activity. Resonance at 4.59 ppm is assigned to protons of COOCH 2 group that located at the graft side chains, 38,39 however, chemical shifts of protons in COOCH 2 group shift into lower fields because of electron-withdrawing effect of chlorine atoms on PP backbones. Results from 1 H NMR analysis further confirm that GMA monomers have been successfully grafted onto PP backbone.…”

Controlled Radical Polymerization of 2,3‐Epithiopropyl Methacrylate

“…Zhu et al [18] demonstrated that well-defined poly(GMA) can be prepared using cyanopropyl dithionapthenoate as RAFT agent. Homopolymers of GMA using CuX/PMDETA [19] as catalyst and reverse ATRP conditions (AIBN and N,N, butyldithiocarbamate copper) [20] were also successfully obtained.…”