Synthesis of Brush Copolymers Based on a Poly(1,4-butadiene) Backbone via the “Grafting From” Approach by ROMP and ATRP

Abstract

The synthesis of brush copolymers based on a strictly 1,4-polybutadiene (PB) backbone is reported via the “grafting from” strategy by combining two highly controlled polymerization methods: ring-opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP). ROMP of a cis-3,4-disubstituted cyclobutene derivative (inimer) containing two initiating sites for ATRP was first investigated with Grubb’s first-generation catalyst ((Cy3P)2RuCl2(CHPh)), leading to well-controlled polymerization for up to 75. The well-defined 1,4-polybutadiene backbones obtained ( ranging from 3600 to 25 200 g·mol−1, PDI ≤ 1.16) were then used as macroinitiators in ATRP with styrene, methyl methacrylate, and tert-butyl acrylate. While styrene polymerization led to nonnegligible side reactions, well-defined PB-g-poly(methyl methacrylate) ( = 19 900−98 200 g mol−1, PDI ≤ 1.20) and PB-g-poly(tert-butyl acrylate) ( = 36 600−140 000 g mol−1, PDI ≤ 1.21) were obtained through this synthetic approach. In addition, the morphology of a PB-g-poly(tert-butyl acrylate) was studied through AFM measurements.

Synthesis and characterization of graft copolymers PnBA-g-PS by miniemulsion polymerization

“…[1][2][3][4][5][6] Especially, can be tuned by molecular design, graft copolymers have potential applications as compatibilizers, thermoplastic elastomers, impactresistant plastics, adhesive and renewable materials. Aided by broad evolution of living/controlled polymerization such as anionic polymerization, ring-opening polymerization (ROP), atom transfer radical polymerization (ATRP), single electron transfer radical polymerization (SET-LRP), nitroxide-mediated polymerization (NMP), reversible addition-fragmentation transfer (RAFT), ring-opening metathesis polymerization (ROMP), there are many opportunities in the synthesis of well-defined graft polymers with flexibility, diversity and functionality.…”

Efficient synthesis of narrowly dispersed amphiphilic double-brush copolymers through the polymerization reaction of macromonomer micelle emulsifiers at the oil–water interface

“…The enhanced steric repulsion between the densely grafted side chains forces the main chains to elongate. They were successfully synthesized via several grafting strategies, including "graft-through" [6][7][8][9][10][17][18][19][20] , "graft-from" 4,5,12,13,21,22 , "graft-to" [23][24][25] , as well as their varied combinations 26 , which have been summarized in recent reviews 2,3 . During the past decades, polymer molecular brushes have received progressively growing attention.…”

Core-Clickable PEG-Branch-Azide Bivalent-Bottle-Brush Polymers by ROMP: Grafting-Through and Clicking-To

“…The graft-to strategy requires an efficient coupling reaction to attach a functional molecule to every monomer unit of a linear polymer; “click”64 reactions such as the copper-catalyzed azide-alkyne cycloaddition65,66 (CuAAC) and thiol-ene coupling have proven useful in this regard 43,46,67–70. Graft-from and graft-through methodologies require highly efficient polymerization reactions capable of initiation and propagation in sterically-demanding environments 48,51–53,71. Recent developments in efficient, controlled polymerization coupled with new click reactions provide materials chemists with the tools to generate novel functional nanoscopic materials 72–77…”