Graft copolymerization of methylmethacrylate with N‐substituted maleimide‐styrene copolymer by ATRP

Abstract

Atom transfer radical polymerization (ATRP) was employed to prepare graft copolymers having poly(MBr)-alt-poly(St) copolymer as backbone and poly(methyl methacrylate) (PMMA) as branches to obtain heat resistant graft copolymers. The macroinitiator was prepared by copolymerization of bromine functionalized maleimide (MBr) with styrene (St). The polymerization of MMA was initiated by poly(MBr)-alt-poly(St) carrying bromine groups as macroinitiator in the presence of copper bromide (CuBr) and bipyridine (bpy) at 110°C. Both macroinitiator and graft copolymers were characterized by 1 H NMR, GPC, DSC, and TGA. The ATRP graft copolymerization was supported by an increase in the molecular weight (MW) of the graft copolymers as compared to that of the macroinitiator and also by their monomodal MW distribution.

Synthesis of amphiphilic copolymer brushes possessing alternating poly(methyl methacrylate) and poly(N‐isopropylacrylamide) grafts via a combination of ATRP and click chemistry

“…In general, comb‐shaped polymer brushes can be categorized into homopolymer brushes and copolymer brushes. Since the pioneering work reported by Tsukahara et al3, 4 in 1989, extensive investigations have been devoted to the synthesis of homopolymer brushes mainly via three approaches including grafting‐through,5–20 grafting‐from,21–39 and grafting‐onto 40–46. In the past decade, the advent of controlled polymerization techniques, such as ring‐opening polymerization (ROP),5, 24, 25, 30, 37, 43 nitroxide‐mediated polymerization (NMP),47–49 atom transfer radical polymerization (ATRP),16, 31–33, 35, 39 and reversible addition‐fragmentation chain transfer (RAFT) polymerization,50, 51 have rendered the grafting‐from approach more appealing, starting with macroinitiators with the initiating sites distributed on every repeating unit.…”

Synthesis and properties of sulfonated poly(phosphazene)‐graft‐poly(styrene‐co‐N‐benzylmaleimide) copolymers via atom transfer radical polymerization for proton exchange membrane

“…The copolymers 3 and 4 were characterized by the FTIR spectroscopy (Figure ). The characteristic absorption of carbonyl groups in MI was observed at 1704 cm −1 , indicating the polymerization of styrene‐co‐ N ‐benzylmaleimide [Figure (a)] . Upon sulfonation of copolymer 3 , we obtained copolymer 4 and measured the FTIR [Figure (b)] which showed a broad absorption band at 3452.1 cm −1 , corresponding to the O–H in the sulfonic acid group (HO–SO 2 –) or absorbed moisture (HO–H).…”

Functional Polymers with Controlled Microstructure Based on Styrene and N ‐Substituted Maleimides

“…Other N-substituted maleimides copolymerized with styrene included N-n-hexyl maleimide [31], N-cyclohexyl maleimide [31], N-benzyl maleimide [31], N-phenyl maleimide [32][33][34][35], N-(alkyl-substituted phenyl) maleimides [33], N-(substituted phenyl) maleimides [36], N-(1-naphtyl) maleimide [37], N-(2-chlorophenyl) maleimide [38], N-pentafluorophenyl maleimide [39], N- [3,5-bis(trifluoromethyl)phenyl] maleimide [39], N-(3-trifluoromethylphenyl) maleimide [39], N-(4-trifluoromethylphenyl) maleimide [39], and N-maleoyl amino acids prepared from maleic anhydride and an amino acid, either L-alanine or L-phenylalanine [40]. Alternating copolymers prepared from styrene and N-substituted maleimides bearing an initiator allowing the introduction of grafts from the copolymer backbone by atom-transfer radical polymerization (ATRP) have been described first by Ç akir et al using (2,5-dioxo-2,5-dihydro-1h-pyrrole-1-yl)methyl 2-bromopropanoate as the N-substituted maleimide followed by polymerization of methyl methacrylate by ATRP to create the grafts [41]. Deng and Chen [42] employed N- [2-(2-bromoisobutyryloxy)ethyl] maleimide as comonomer of styrene and polymerized tert-butyl acrylate from the ATRP initiator to prepare brushes.…”