Graft polymers, polymer synthesis

A patent (71) describes a combination of anionic and radical techniques to produce a variety of graft polymers. The synthesis proceeds via a capped anionic block polymer, the capping producing a polymerizable vinyl end unit. The capped polymer is then free-radical polymerized with a selected vinyl monomer to produce the graft polymer ... 

Wang, Q.Y., et al. 2003. Grafted conjugated polymers Synthesis and characterization of a polyester side chain substituted poly(p r phenyleneethynylene). Chem Commun 1624. 

Gross-Linking. A variety of PE resins, after their synthesis, can be modified by cross-linking with peroxides, hydrolysis of silane-grafted polymers, ionic bonding of chain carboxyl groups (ionomers), chlorination, graft copolymerization, hydrolysis of vinyl acetate copolymers, and other reactions. 

As shown for the synthesis of PS [291], the monomer may be localized in the vicinity of the filler surface by previously grafting a polymer capable of swelling in the base monomer. Copolymeric latex of polychloroprenemethacrylic acid was added to the aqueous dispersion of chalk. The acid groups reacted with chalk and the latex particles became chemically grafted to chalk. When further portions of styrene were added they were completely absorbed by modified chalk. 

There are additional factors that may reduce functionality which are specific to the various polymerization processes and the particular chemistries used for end group transformation. These are mentioned in the following sections. This section also details methods for removing dormant chain ends from polymers formed by NMP, ATRP and RAFT. This is sometimes necessary since the dormant chain-end often constitutes a weak link that can lead to impaired thermal or photochemical stability (Sections 8.2.1 and 8.2.2). Block copolymers, which may be considered as a form of end-functional polymer, and the use of end-functional polymers in the synthesis of block copolymers are considered in Section 9.8. The use of end functional polymers in forming star and graft polymers is dealt with in Sections 9.9.2 and 9.10.3 respectively. 

The chain architecture and chemical structure could be modified by SCVCP leading to a facile, one-pot synthesis of surface-grafted branched polymers. The copolymerization gave an intermediate surface topography and film thickness between the polymer protrusions obtained from SCVP of an AB inimer and the polymer brushes obtained by ATRP of a conventional monomer. The difference in the Br content at the surface between hyperbranched, branched, and linear polymers was confirmed by XPS, suggesting the feasibility to control the surface chemical functionality. The principal result of the works is a demonstration of utility of the surface-initiated SCVP via ATRP to prepare surface-grafted hyperbranched and branched polymers with characteristic architecture and topography. 

Fig. 15. Schematic representation of the synthesis of hyperbranched, branched, and linear polymers grafted from functionalized silicon wafers SFM images and XPS spectra of the surface-grafted polymers. (Reproduced with permission from [48],Copyright 2001 American Chemical Society.)...

FIGURE 5.10 Synthesis of a polyethyleneglycol-polystyrene graft polymer by etherification of Merrifield resin using potassium tetra(oxyethylene) oxide, followed by extension of the chain by reaction of the potassium salt, which is present as the crown ether.21 In several TentaGel resins, the connecting bond is an ethyl ether that is more acid-stable than the benzyl ether. 

Ding, J. F, Chuy, C. and Holdcroft, S. 2002. Enhanced conductivity in morphologically controlled proton exchange membranes Synthesis of macromonomers by SFRP and their incorporation into graft polymers. Macromolecules 35 1348-1355. 

The grafting of polymers to substrates has been studied for over fifty years and remains an important goal in polymer science. Recent work has focused on the synthesis of so-called polymer brushes whereby the polymer chains stretch out away from the substrate or interface [1-5]. This contemporary topic is a direct descendent of earlier work on organic graft copolymers in industry and academia. Research in this area is driven by the need to control the interfacial properties of films and the compatibility of blends. 

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