Grafting chloride

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.]...

MBS polymers are prepared by grafting methyl methacrylate and styrene onto a styrene—butadiene mbber in an emulsion process. The product is a two-phase polymer useful as an impact modifier for rigid poly(vinyl chloride). 

A review covers the preparation and properties of both MABS and MBS polymers (75). Literature is available on the grafting of methacrylates onto a wide variety of other substrates (76,77). Typical examples include the grafting of methyl methacrylate onto mbbers by a variety of methods chemical (78,79), photochemical (80), radiation (80,81), and mastication (82). Methyl methacrylate has been grafted onto such substrates as cellulose (83), poly(vinyl alcohol) (84), polyester fibers (85), polyethylene (86), poly(styrene) (87), poly(vinyl chloride) (88), and other alkyl methacrylates (89). 

Chemical Grafting. Polymer chains which are soluble in the suspending Hquid may be grafted to the particle surface to provide steric stabilization. The most common technique is the reaction of an organic silyl chloride or an organic titanate with surface hydroxyl groups in a nonaqueous solvent. For typical interparticle potentials and a particle diameter of 10 p.m, steric stabilization can be provided by a soluble polymer layer having a thickness of - 10 nm. This can be provided by a polymer tail with a molar mass of 10 kg/mol (25) (see Dispersants). 

Copolymers of diallyl dimethyl ammonium chloride [7398-69-8] with acrylamide have been used in electroconductive coatings (155). Copolymers with acrylamide made in activated aqueous persulfate solution have flocculating activity increasing with molecular weight (156). DADM ammonium chloride can be grafted with cellulose from concentrated aqueous solution catalysis is by ammonium persulfate (157). Diallyl didodecylammonium bromide [96499-24-0] has been used for preparation of polymerized vesicles (158). 

Typical values for mf n are 0.5 to 2.5. Gommercially used bases include sodium hydroxide, potassium hydroxide, calcium hydroxide (lime), magnesium hydroxide, sodium carbonate, sodium alurninate, calcium carbonate, or various mixtures. For certain appHcations, PAG can be made from waste grades of aluminum chloride [7446-70-0] such as spent catalyst solutions from Friedel-Grafts synthesis (see Friedel-Grafts reaction). 

Friedel-Grafts Reaction. Until quite recently, the manufacture of anthraquiaone ia the United States was by the Friedel-Crafts reaction benzene [71-43-2] and phthaUc anhydride [85-44-9] condense ia the preseace of anhydrous aluminum chloride to give o-benzoylbenzoic acid [85-52-9] which, on treatment with concentrated sulfuric acid, is converted iato anthraquiaoae ia high yields and purity (33). 

Not only ate ABS polymers useful engineering plastics, but some of the high mbber compositions are excellent impact modifiers for poly(vinyl chloride) (PVC). Styrene—acrylonitrile-grafted butadiene mbbers have been used as modifiers for PVC since 1957 (87). 

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). 

In the suspension polymerization of PVC, droplets of monomer 30—150 p.m in diameter are dispersed in water by agitation. A thin membrane is formed at the water—monomer interface by dispersants such as poly(vinyl alcohol) or methyl cellulose. This membrane, isolated by dissolving the PVC in tetrahydrofuran and measured at 0.01—0.02-p.m thick, has been found to be a graft copolymer of polyvinyl chloride and poly(vinyl alcohol) (4,5). Early in the polymerization, particles of PVC deposit onto the membrane from both the monomer and the water sides, forming a skin 0.5—5-p.m thick that can be observed on grains sectioned after polymerization (4,6). Primary particles, 1 p.m in diameter, deposit onto the membrane from the monomer side (Pig. 1), whereas water-phase polymer, 0.1 p.m in diameter, deposits onto the skin from the water side of the membrane (Pig. 2) (4). These domain-sized water-phase particles may be one source of the observed domain stmcture (7). 

Another important use of BCl is as a Ftiedel-Crafts catalyst ia various polymerisation, alkylation, and acylation reactions, and ia other organic syntheses (see Friedel-Crafts reaction). Examples include conversion of cyclophosphasenes to polymers (81,82) polymerisation of olefins such as ethylene (75,83—88) graft polymerisation of vinyl chloride and isobutylene (89) stereospecific polymerisation of propylene (90) copolymerisation of isobutylene and styrene (91,92), and other unsaturated aromatics with maleic anhydride (93) polymerisation of norhornene (94), butadiene (95) preparation of electrically conducting epoxy resins (96), and polymers containing B and N (97) and selective demethylation of methoxy groups ortho to OH groups (98). 

Polymers ndResins. / fZ-Butyl peroxyneopentanoate and other peroxyesters of neopentanoic acid can be used as free-radical initiators for the polymeri2ation of vinyl chloride [75-01-4] (38) or of ethylene [74-85-1]. These peresters have also been used in the preparation of ethylene—vinyl acetate copolymers [24937-78-8] (39), modified polyester granules (40), graft polymers of arninoalkyl acrylates with vinyl chloride resins (41), and copolymers of A/-vinyl-pyrrohdinone [88-12-0] and vinyl acetate [108-05-4] (42). They can also be used as curing agents for unsaturated polyesters (43). 

Modifications of epichlorohydrin elastomers by radical-induced graft polymeri2ation have been reported. Incorporated monomers include styrene and acrylonitrile, styrene, maleic anhydride, vinyl acetate, methyl methacrylate, and vinyHdene chloride (81), acryHc acid (82), and vinyl chloride (81,83,84). When the vinyl chloride-modified epichlorohydrin polymers were used as additives to PVC, impact strength was improved (83,84). 

This chapter has so far dealt with the major fields of use of vinyl chloride polymers, namely plasticised PVC homopolymer, unplasticised PVC, including impact-modified grades, and copolymers particular based on vinyl acetate. There are, however, five particular special forms of vinyl chloride polymer which merit separate consideration, namely crystalline PVC, after-chlorinated PVC (often known as CPVC) and certain graft copolymers and two vinyl-chloride-based copolymers. 

The theory of radiation-induced grafting has received extensive treatment. The direct effect of ionizing radiation in material is to produce active radical sites. A material s sensitivity to radiation ionization is reflected in its G value, which represents the number of radicals in a specific type (e.g., peroxy or allyl) produced in the material per 100 eV of energy absorbed. For example, the G value of poly(vinyl chloride) is 10-15, of PE is 6-8, and of polystyrene is 1.5-3. Regarding monomers, the G value of methyl methacrylate is 11.5, of acrylonitrile is 5.6, and of styrene is >0.69. 

Experimental evidence is available to show that at room temperature diperoxides are formed in polyethylene, whereas polypropylene and polyvinyl chloride generate hydroperoxides. The temperature at which the peroxides decompose and initiate grafting depends on the type of polymer used. 

Interfacial polycondensation between a diacid chloride and hexamethylenediamine in the presence of small amounts of ACPC also yield polymeric azoamid, which is a macroazo initiator.[27] In this manner, azodicarbox-ylate-functional polystyrene [28], macroazonitriles from 4,4 -azobis(4-cyano-n-pentanoyl) with diisocyanate of polyalkylene oxide [29], polymeric azo initiators with pendent azo groups [3] and polybutadiene macroazoinitiator [30] are macroazoinitiators that prepare block and graft copolymers. 

It has been found that, for a fixed mineral filler content, the viscosity of PMF-based composites increases when the coat is made of polyethylene [164, 209, 293], poly(vinyl chloride) [316] and polypropylene [326, 327], The picture was different, however, for composites based on the ethylene/vinyl acetate copolymer to which kaolin with grafted poly (vinyl acetate) was added [336]. Addition of PMF with a minimum quantity of grafted polymer results in a sharp drop of flowability (rise of viscosity), in comparison to addition of unmodified filler but with a further increase of the quantity of grafted polymer the flow gradually increases and, depending on the kaolin content and quantity of grafted polymer, may even become higher than in specimens with unmodified filler, for equal concentrations. 

Mixtures of two or more monomers can polymerize to form copolymers. Many copolymers have been developed to combine the best features of each monomer. For example, poly(vinyl chloride) (called a homopolymer because it is made from a single monomers) is brittle. By copolymerizing vinyl chloride with vinyl acetate, a copolymer is obtained that is flexible. Arrangement of the monomer units in a copolymer depends on the rates at which the monomers react with each other. Graft copolymers are formed when a monomer is initiated by free radical sites created on an already-formed polymer chain. 

Lignite can be grafted with synthetic comonomers to obtain lignite fluid loss additives [873]. Comonomers can be AMPS, N,N-dimethylacrylamide, acrylamide, vinylpyrrolidone, vinylacetate, acrylonitrile, dimethylaminoethyl methacrylate, styrene sulfonate, vinyl sulfonate, dimethylaminoethyl methacrylate methyl chloride quaternary, and acrylic acid and its salts. 

---