Grafting graft copolymers

In graft copolymers the chain backbone is composed of one kind of monomer and the branches are made up of another kind of monomer. 

Remember from Sec. 1.3 that graft copolymers have polymeric side chains which differ in the nature of the repeat unit from the backbone. These can be prepared by introducing a prepolymerized sample of the backbone polymer into a reactive mixture—i.e., one containing a source of free radicals—of the side-chain monomer. As an example, consider introducing polybutadiene into a reactive mixture of styrene ... 

Figure 9.17 Plot of log [i ]M versus retention volume for various polymers, showing how different systems are represented by a single calibration curve when data are represented in this manner. The polymers used include linear and branched polystyrene, poly(methyl methacrylate), poly(vinyl chloride), poly(phenyl siloxane), polybutadiene, and branched, block, and graft copolymers of styrene and methyl methacrylate. [From Z. Grubisec, P. Rempp, and H. Benoit, Polym. Lett. 5 753 (1967), used with permission of Wiley.]...

Solution polymers are the second most important use for acryflc monomers, accounting for about 12% of the monomer consumption. The major end use for these polymers is in coatings, primarily industrial finishes. Other uses of acryflc monomers include graft copolymers, suspension polymers, and radiation curable inks and coatings. 

Monomer compositional drifts may also occur due to preferential solution of the styrene in the mbber phase or solution of the acrylonitrile in the aqueous phase (72). In emulsion systems, mbber particle size may also influence graft stmcture so that the number of graft chains per unit of mbber particle surface area tends to remain constant (73). Factors affecting the distribution (eg, core-sheU vs "wart-like" morphologies) of the grafted copolymer on the mbber particle surface have been studied in emulsion systems (74). Effects due to preferential solvation of the initiator by the polybutadiene have been described (75,76). 

In addition to graft copolymer attached to the mbber particle surface, the formation of styrene—acrylonitrile copolymer occluded within the mbber particle may occur. The mechanism and extent of occluded polymer formation depends on the manufacturing process. The factors affecting occlusion formation in bulk (77) and emulsion processes (78) have been described. The use of block copolymers of styrene and butadiene in bulk systems can control particle size and give rise to unusual particle morphologies (eg, coil, rod, capsule, cellular) (77). 

M. G. Huguet andT. R. Paxton, Colloidal andMorphological Behavior of Block and Graft Copolymers Plenum, New York, 1971,pp. 183—192. 

Material Protection. The graft copolymers of ethylene sulfide on polyethyleneimine can be used as an antifouHng anticorrosion substrate for iron (439). PEIs or their derivatives are also used in electrolysis baths as brighteners in the electrochemical deposition of metals (440,441). 

In addition to providing fully alkyl/aryl-substituted polyphosphasenes, the versatility of the process in Figure 2 has allowed the preparation of various functionalized polymers and copolymers. Thus the monomer (10) can be derivatized via deprotonation—substitution, when a P-methyl (or P—CH2—) group is present, to provide new phosphoranimines some of which, in turn, serve as precursors to new polymers (64). In the same vein, polymers containing a P—CH group, for example, poly(methylphenylphosphazene), can also be derivatized by deprotonation—substitution reactions without chain scission. This has produced a number of functionalized polymers (64,71—73), including water-soluble carboxylate salts (11), as well as graft copolymers with styrene (74) and with dimethylsiloxane (12) (75). 

H. A. J. Battaerd and G. W. Tregear, Polymer Reriem, Graft Copolymers, Vol. 16, Wiley-Interscience, New York, 1967. 

A hydrolyzed cereal soHd, predominately a hexasaccharide, is used in high pH lime muds for reducing the yield point and gel strength (67). This additive has been used in systems treated with both sodium hydroxide and potassium hydroxide in addition to other additives common to lime muds (68). A second viscosity-reducing additive used in lime muds is a graft copolymer of acryflc acid and calcium flgnosulfonate (69). Both of these materials are used at levels of 6—17 kg/m (2—6 lb /bbl). 

Acrylamide graft copolymers such as those with starch (qv)(131), dextran (132), and lignin (qv) (133), have been studied to try to reduce copolymer costs. A general disadvantage of acrylamide copolymers is greater cost compared to partially hydroly2ed polyacrylamides. 

Grafting can also occur in the amide nitrogen, either through an anionic-type mechanism which is beheved to operate when ethylene oxide [75-21 -8] and similar copolymers are grafted to polyamides, or through a polycondensation mechanism when secondary amides are formed as graft copolymers (70). 

Fig. 6. Illustration of (a) compatibiLization of immiscible blends of polymers and B by block or graft copolymers and (b) the subsequent modification of...

The additive approach to compatibilization is limited by the fact that there is a lack of economically viable routes for the synthesis of suitable block and graft copolymers for each system of interest. The compatihilizer market is often too specific and too small to justify a special synthetic effort. 

Moreover, commercially available triblock copolymers designed to be thermoplastic elastomers, not compatihilizers, are often used in Heu of the more appealing diblock materials. Since the mid-1980s, the generation of block or graft copolymers in situ during blend preparation (158,168—176), called reactive compatibilization, has emerged as an alternative approach and has received considerable commercial attention. 

Etherification and esterification of hydroxyl groups produce derivatives, some of which are produced commercially. Derivatives may also be obtained by graft polymerization wherein free radicals, initiated on the starch backbone by ceric ion or irradiation, react with monomers such as vinyl or acrylyl derivatives. A number of such copolymers have been prepared and evaluated in extmsion processing (49). A starch—acrylonitrile graft copolymer has been patented (50) which rapidly absorbs many hundred times its weight in water and has potential appHcations in disposable diapers and medical suppHes. 

Copolymers of VDC can also be prepared by methods other than conventional free-radical polymerization. Copolymers have been formed by irradiation and with various organometaHic and coordination complex catalysts (28,44,50—53). Graft copolymers have also been described (54—58). 

Although they lack commercial importance, many other poly(vinyl acetal)s have been synthesized. These include acetals made from vinyl acetate copolymerized with ethylene (43—46), propjiene (47), isobutjiene (47), acrylonitrile (48), acrolein (49), acrylates (50,47), aHyl ether (51), divinyl ether (52), maleates (53,54), vinyl chloride (55), diaHyl phthalate (56), and starch (graft copolymer) (47). 

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