Block Graft Copolymerization

Many block and graft copolymer syntheses involve radical polymerization at some stage of the overall preparation. This section deals with direct syntheses of 

In the standard nomenclature [poly(MA)- m/i-poly Mn)] the first named monomer(s) form the backbone while those named second are the grafts or arms. Thus, PMMA-g/ cj//-PS indicates a backbone of PMMA and grafts of PS. 

Graft copolymerizations are categorized according to their method of formation into three main types.  

Four types of grafting from processes are distinguished by the mechanism of radical foiTnation. 

Specific forms of graft copolymers may go under different names. 

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Fig. 6 Transmission electron micrograph (TEM) of the cross-section of a PDMAAm(poly-dimethylacrylamide)-b-PST(polystyrene) block-graft-copolymerized surface stained in iodine vapor, a Spurr s resin, b PST layer, c PDMAm layer, d dithiocarbamate (DC)-derivatized PST film...

Surface block-graft-copolymerization, based on the photochemistry of N, AT-diethyldithiocarbamate has been applied to precisely design biocompatible and functional surfaces (patterns of immobilized heparin or proteins), as well as block-grafted surfaces on polystyrene [83]. Polystyrene surfaces have also been patterned by immobilization of poly(Af-isopropylacrylamide) by photolithography, and subsequently used for regiospecific cell attachment [84]. Surface modification of polydimethylsiloxane microfluidic devices by UV induced polymer grafting improved the stability of the electroosmotic mobility and improved electrophoretic resolution of peptides [85]. 

Ceresa, J. A. Block Graft Copolymerization. New York Wiley, 1973. 

Thermoplastic elastomers are often multiphase compositions in which the phases are intimately dispersed. In many cases, the phases are chemically bonded by block or graft copolymerization. In others, a fine dispersion is apparentiy sufficient. In these multiphase systems, at least one phase consists of a material that is hard at room temperature but becomes fluid upon heating. Another phase consists of a softer material that is mbberlike at RT. A simple stmcture is an A—B—A block copolymer, where A is a hard phase and B an elastomer, eg, poly(styrene- -elastomer- -styrene). 

Thermoplastic elastomers are multiphase composites, in which the phases are intimately depressed. In many cases, the phases are chemically bonded by block or graft copolymerization. At least one of the phases consists of a material that is hard at room temperature. ... 

Bamford, Eastmond and coworkers have employed metal complexpolymeric halide redox systems to initiate block and graft copolymerization. The polymeric halides can be synthesized by a variety of techniques, including radical polymerization,281 anionic polymerization (Scheme 7.28),"so... 

Anionic polymerization of pivalolactone with the polystyrene anion produced only homopolymer mixtures, but the polystyrene carboxylate anion was able to give a block copolymer336. The block efficiency depends on catalyst ratio and conversion because the initiation step is slow compared with propagation337. Tough and elastic films were obtained by graft copolymerization or block copolymerization of pivalolactone onto elastomers containing tetrabutylammonium carboxylate groups338,339. ... 

Ceresa, R. J., ed., Block and Graft Copolymerization, Vols. 1 and 2, Wiley-Interscience, New York, 1973, 1976. 

Chemical processes are far more varied and may involve either the formation of radicals or ions along a polymeric backbone. Both cationic processes3 as well as radical processes have been widely used for graft copolymerization of vinyl monomers onto various polymers. Radical graft copolymerization has been reported for many polymers including styrene-butadiene block copolymers, and acrylonitrile-butadiene-styrene terpolymer, ABS.3 7 9... 

In this paper graft copolymerization onto both polystyrene and styrene-butadiene block copolymer will be discussed. It will be shown that radical processes do not permit the addition of monomers onto polystyrene and that one must use anionic initiation in order... 

Chemical Initiation of Graft Copolymerization onto Styrene-Butadiene Block Copolymer... 

Contrarily to the carbonium ion graft copolymerization, carbanion initiation has been attempted for the synthesis of block copolymers. 

In our first chapter, we summarize the synthesis of aliphatic polyesters. This includes homopolyesters, random, block, graft, and star- and hyper-branched polyesters. Mainly materials such as PLA and PCL homopolymers have so far been used in most applications. There are, however, many others monomers which one can use as homopolymers or in copolymerization with lactide and caprolactone. Different molecular stuctures give a wider range of physical properties as well as the possibility of regulating the degradation rate. 

Poly( ethylene oxide)-block-poly (propylene oxide)-hZock-poly(ethylene oxide)-g-poly(acrylic acid) (PEO-fc-PPO-fc-PEO-g-PAA, Pluronic-PAA) graft copolymers were synthesized by free radical grafting copolymerization of acrylic acid monomers onto PEO-h-PPO-h-PEO (Pluronic F127) and the aqueous solution properties were characterized by Bromberg [133, 134]. Chiu et al. [135] reported on the micellization of (non-ionic) poly(stearyl methacrylate)-gra/f-poly(ethylene glycol) graft copolymers. 

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