Hyperbranched copolymers ofp-(chloromethyl)styrene andN-cyclohexylmaleimide synthesized by atom transfer radical polymerization

Abstract

The hyperbranched copolymers were obtained by the atom transfer radical copolymerization of p‐(chloromethyl)styrene (CMS) with N‐cyclohexylmaleimide (NCMI) catalyzed by CuCl/2,2′‐bipyridine (bpy) in cyclohexanone (C6H10O) or anisole (PhOCH3) with CMS as the inimer. The influences of several factors, such as temperature, solvent, the concentration of CuCl and bpy, and monomer ratio, on the copolymerization were subsequently investigated. The apparent enthalpy of activation for the overall copolymerization was measured to be 37.2 kJ/mol. The fractional orders obtained in the copolymerization were approximately 0.843 and 0.447 for [CuCl]0 and [bpy]0, respectively. The monomer reactivity ratios were evaluated to be rNCMI = 0.107 and rCMS = 0.136. The glass transition temperature of the resultant hyperbranched copolymer increases with increasing fNCMI, which indicates that the heat resistance of the copolymer has been improved by increasing NCMI. The prepared hyperbranched CMS/NCMI copolymers were used as macroinitiators for the solution polymerization of styrene to yield star‐shaped poly(CMS‐co‐NCMI)/polystyrene block copolymers by atom transfer radical polymerization. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1992–1997, 2000

“Green” Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials

“…The successful ATRP of several inimers has been reported. [460][461][462][463][464][465][466] Some of the prepared hyperbranched polymers contained a variety of polar functional groups such as carboxylate, 467 hydroxyl, 468 substituted amine, 469 or disulfide, 430 and they can be particularly useful for coatings applications. Other CRP techniques employing inimers have also been used.…”

Blends of high density polyethylene with branched poly(styrene‐co‐dodecyl acrylate): Rheological, mechanical, and thermal properties

“…It can be noted that all the hyperbranched polymers employed in the aforementioned examples are prepared from condensation method proposed by Flory9 in 1952 and most of them are hyperbranched polyesters. Since Fréchet et al first reported the synthesis of hyperbranched polymers by self‐condensing vinyl polymerization (SCVP) in 1995,10 the species of hyperbranched polymers have been extended greatly and hyperbranched polymers based on styrene and its derivatives,11–13 acrylates and methacrylates,14–17 maleimide,18–19 and isobutylene20 all have been prepared. Our group has reported the use of highly branched polystyrene prepared by ATRP as melt modifier for polycarbonates 21.…”

Copolymerization of 2,2-Diallyl-1,1,3,3-tetraethylquanidinium Chloride with N-(4-Acetylphenyl)maleimide

“…It is known that N-substituted maleimides homopolymerize according to the radical mechanism [2,3] and are involved in copolymerization with styrene [4][5][6][7][8][9], butadiene [4], (meth) acrylic acid and its esters [4,11], vinyl ethers [10][11][12], and vinylketones [13]. In copolymerization with electron-donor monomers, they, being electron acceptors, form copolymers with a high tendency of monomer units toward alternation [4,9,11,12].…”