Heterograft copolymers via double click reactions using one‐pot technique

Abstract

The double click reactions (Cu catalyzed Huisgen and Diels-Alder reactions) were used as a new strategy for the preparation of well-defined heterograft copolymers in one-pot technique. The synthetic strategy to the various stages of this work is outlined: (i) preparing random copolymers of styrene (St) and p-chloromethylstyrene (CMS) (which is a functionalizable monomer) via nitroxide mediated radical polymerization (NMP); (ii) attachment of anthracene functionality to the preformed copolymer by the o-etherification procedure and then conversion of the remaining ACH 2 Cl into azide functionality; (iii) by using double click reactions in one-pot technique, maleimide end-functionalized poly(methyl methacrylate) (PMMA-MI) via atom transfer radical polymerization (ATRP) of MMA and alkyne end-functionalized poly (ethylene glycol) (PEG-alkyne) were introduced onto the copolymer bearing pendant anthryl and azide moieties. V V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6969-6977, 2008

Stereoregular poly(methyl methacrylate) with double-clickable ω-end: synthesis and click reaction

“…3,23 The concept inspires polymer chemists to synthesize interesting new classes of topological polymers, such as 'star block polymer', [23][24][25] 'hetero-graft copolymer', 26 H-shaped polymer, 27 P-, Q-, 8-, and α-shaped polymers, 28 and tandem cyclic copolymer. 29 However, the research has still remained fundamental, and facile method to incorporate two different clickable ends is desired.…”

Well-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry

“…Similar behavior was observed in other "grafting onto" cases. 16,20 The success of the "click" reaction to yield the PE-based graft terpolymers was also confirmed by the disappearance of the azide and alkyne peaks at 2104 and 3300 cm -1 in the FTIR spectra ( Figure S6 † ). …”

“…[12][13] Up to now, various well-defined graft copolymers have been synthesized via ''grafting onto'' by combination of CuAAC with ring opening polymerization (ROP), [14][15] atom transfer radical polymerization (ATRP), [16][17][18] reversible addition-fragmentation chain transfer (RAFT) 19 and nitroxide-mediated radical polymerization (NMP). [20][21] Polyethylene-based block copolymers with polystyrene (PSt), polycaprolactone (PCL) and polyacrylate, have attracted significant interest. [22][23] Despite the fact that several well-defined grafts have been synthesized, there are only a very few reports so far dealing with polyethylene-based grafts due to the challenge to control molecular weight and functionality of PE.…”

Synthesis of Terpolymers by Click Reactions

“…[46] Additionally, by using double click reactions (CuAAC and Diels-Alder) in a one-pot technique, an ATRP-generated PMMA-MI (M n,GPC = 3350 g mol ) were efficiently introduced onto the PS backbone bearing pendant anthryl and azide moieties to yield a PSA C H T U N G T R E N N U N G (-g-PMMA)-g-PEG heterograft terpolymer (Scheme 8). [47] More recently, one notable example was shown from a combination of ROMP and a sequential double click reaction strategy, in which poly(ONB-g-PMMA)-b-poly(ONB-g-PCL) and polyA C H T U N G T R E N N U N G (ONB)-g-PtBA)-b-poly(ONB-g-PCL) block brush graft terpolymers were made by sequential CuAAC and Diels-Alder click reactions of PCL-alkyne (M n,NMR = 2800 g mol…”