Graft copolymers grafting onto

Three methods exist for synthesizing graft copolymers. Grafting onto involves the reaction between functional groups on two different polymers ... 

Acrylonitrile has been grafted onto many polymeric systems. In particular, acrylonitrile grafting has been used to impart hydrophilic behavior to starch (143—145) and polymer fibers (146). Exceptional water absorption capabiUty results from the grafting of acrylonitrile to starch, and the use of 2-acrylamido-2-methylpropanesulfonic acid [15214-89-8] along with acrylonitrile for grafting results in copolymers that can absorb over 5000 times their weight of deionized water (147). 

A waterborne system for container coatings was developed based on a graft copolymerization of an advanced epoxy resin and an acryHc (52). The acryhc-vinyl monomers are grafted onto preformed epoxy resins in the presence of a free-radical initiator grafting occurs mainly at the methylene group of the aHphatic backbone on the epoxy resin. The polymeric product is a mixture of methacrylic acid—styrene copolymer, soHd epoxy resin, and graft copolymer of the unsaturated monomers onto the epoxy resin backbone. It is dispersible in water upon neutralization with an amine before cure with an amino—formaldehyde resin. 

In 1975 Wacker-Chemie introduced silicones under the name of m-polymers. These are also room temperature curing liquid polymers which give rubbery materials on cross-linking and are available both as one- and two-component systems. Their particular feature is that they contain dispersions of copolymers such as those of styrene and n-butyl acrylate in the shape of rods or rice grains in the fluid silicone polymer. A small amount of the organic copolymer is also grafted onto the silicone backbone. 

Polymers are classified according to their chemical structures into homopolymers, copolymers, block copolymers, and graft copolymers. In a graft copolymer, sequences of one monomer are grafted onto a backbone of the other monomer and can be represented as follows ... 

Chitosan, having a similar chemical backbone as cellulose, is a linear polymer composed of a partially deacety-lated material of chitin [(l-4)-2-acetamide-2-deoxy-/3-D-glucan]. Grafting copolymer chains onto chitosan can improve some properties of the resulting copolymers [48-50]. Yang et al. [16] reported the grafting reaction of chitosan using the Ce(IV) ion as an initiator, but no detailed mechanism of this initiation has been published so far. 

Two other forms of copolymers that can be prepared under certain conditions are called block copolymers and graft copolymers. Block copolymers are those in which different blocks of identical monomer units alternate with each other graft copolymers are those in which homopolymer branches of one monomer unit are "grafted" onto a homopolymer chain of another monomer unit. 

Graft copolymer (Section 31.3) A copolymer in which homopolymer branches of one monomer unit are grafted onto a homopolymer chain of another monomer unit. 

Another consequence of the absence of sponataneous transfer and termination reactions is that the polymer chains formed remain living 3), i.e. they carry at the chain end a metal-organic site able to give further reactions. Block copolymer synthesis is probably the major application 12 14), but the preparation of co-functional polymers, some chain extension processes, and the grafting onto reactions arise also directly from the long life time of the active sites. 

The electrophilic functions most commonly used in grafting onto processes are ester 141 144), benzylic halide 145,146) and oxirane, 47). Other functions such as nitrile or anhydride could be used as well. The backbone is a homopolymer (such as PMMA) or a copolymer containing both functionalized and unfunctionalized units. Such species can be obtained either by free radical copolymerization (e.g. styrene-acrylonitrile copolymer) or by partial chemical modification of a homopolymer (e.g. 

The same procedure can be employed to make well defined comb-like polymers Living polystyrene can be grafted onto a partially chloromethylated polystyrene89 146), or onto a random copolymer of styrene and methyl methacrylate containing less than 10% of the latter monomer I48). 

Ti-SBA-15 Grafting method. SBA-15 prepared first using the amphiphilic triblock copolymer poly(ethyleneox-ide) -poly (propyleneoxide) -poly (ethyleneoxide) (EO-PO-EO) as template and TEOS as Si source. The composition was 2 g copolymer 0.021 mol TEOS 0.12 mol HC1 3.33 mol H20. The solid was calcined at 600 K for 4 h to remove the copolymer. Ti in the form of titanium isopropoxide was grafted onto the dehydrated surface of SBA-15 Pore diameter = 6.3 nm, surface area = 518 m2/g, pore volume = 0.68 (25)... 

Scheme 3. Synthetic routes leading to various rod-coil block copolymers via grafting onto" (16a, 16b, 20) or grafting from" (18) reactions.

Many vinyl monomers were reported to have been grafted onto fluoropolymers, such as (meth)acrylic acid and (meth)acrylates, acrylamide, acrylonitryl, styrene, 4-vinyl pyridine, N-vinyl pyrrolidone, and vinyl acetate. Many fluoropolymers have been used as supports, such as PTFE, copolymers of TFE with HFP, PFAVE, VDF and ethylene, PCTFE, PVDF, polyvinyl fluoride, copolymers ofVDF with HFP, vinyl fluoride and chlorotrifluoroethylene (CTFE). The source of irradiation has been primarily y-rays and electron beams. The grafting can be carried out under either direct irradiation or through the use of preliminary irradiated fluoropolymers. Ordinary radical inhibitors can be added to the reaction mixture to avoid homopolymerization of functional monomers. 

Graft copolymers are also used as compatibilizers to tie together different phases. HIPS contains PS grafted onto polybutadiene backbones. This allows stress or strain to be transferred from the PS to the polybutadiene phase transferring energy that might break the brittle PS to the more flexible polybutadiene phase. That is why HIPS is stronger than PS itself. 

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