Vinyl acetate copolymers, graft polymerization

Graft Polymerization of Vinyl Compounds on Ethylene-Vinyl Acetate Copolymers... 

Ethylene-vinylacetate blends with PVC have been widely used in Europe as permanent polymeric plasticizers for PVC. Low cost and good weatherability of these blends permitted their use in window profiles, cable jacketing and other outdoor applications. Ethylene vinylacetate copolymer with 65-75% vinyl acetate content is quite miscible with PVC exhibiting a single T for the blend [Hammer, 1971 Ranby, 1975 Rellick and Runt, 1985]. Two phases are apparent when the vinylacetate is < 45%. Vinylchloride grafted ethylene-vinyl acetate copolymers have also been used for blending with PVC. 

Emulsion polymerizations of vinyl acetate in the presence of ethylene oxide- or propylene oxide-based surfactants and protective coUoids also are characterized by the formation of graft copolymers of vinyl acetate on these materials. This was also observed in mixed systems of hydroxyethyl cellulose and nonylphenol ethoxylates. The oxyethylene chain groups supply the specific site of transfer (111). The concentration of insoluble (grafted) polymer decreases with increase in surfactant ratio, and (max) is observed at an ethoxylation degree of 8 (112). 

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. 

The selective oxidation of cellulose to dialdehyde by sodium periodate is well known. It has been postulated by Criegee (74) and by Waters (73) that this reaction proceeds by a free radical mechanism. Toda (76) and Morimoto, Okada, Okada, and Nakagawa (77) have concluded that sodium periodate oxidation should initiate graft polymerization. They succeeded in grafting methyl methacrylate and acrylonitrile onto cellulose substrates, such as rayon and paper. A similar procedure is recommended in a patent of Chemische Werke Huels (78) to graft vinyl monomers onto cotton, polyethylene oxide, copolymers of vinyl chloride-vinyl acetate, and others. 

In contrast the polymerization of vinyl acetate in the presence of polymethyl methacrylate gives after selective precipitation appreciable amounts of pure graft copolymer, independently of the nature of the initiator moreover the degree of grafting, evaluated by infrared spectrometry, is about equally important. Similar results were obtained in the system vinyl acetate-polyethyl a-chloroacryl ate. 

Grafting by chain transfer has permitted to combine sequences of two monomers which would not copolymerize directly with each other. Thus Smets and coworkers, by polymerizing vinyl acetate in the presence of polyethyl a-chloroacrylate, obtained, besides some insoluble products, very appreciable amounts of graft copolymers, in which the vinyl acetate content ranged from 40 to 86% (204). 

Similar grafting experiments by the emulsion technique were described (34) in the system vinyl chloride/copolymer butyl methacrylate-methacrylic acid and in the reverse system, and also in the system styrene/polyvinyl chloride. In this last case again as in homogenous medium, the inverse process failed (vinyl chloride on polystyrene). Grafted acrylonitrile copolymers were also prepared in order to improve their dyeability, by polymerizing acrylonitrile in emulsion in the presence of many different polymers as polyvinyl alcohol, polymethacrylamide and polyvinylpyrrolidone (119, 120, 121), polyvinyl acetate and polyacrylic acid (115), wool (224,225), proteins (136), etc. 

The mechanical degradation and production of macroradicals can also be performed by mastication of polymers brought into a rubbery state by admixture with monomer several monomer-polymer systems were examined (10, 11). This technique was for instance studied for the cold mastication of natural rubber or butadiene copolymers in the presence of a vinyl monomer (13, 31, 52). The polymerization of methyl methacrylate or styrene during the mastication of natural rubber has yielded copolymers which remain soluble up to complete polymerization vinyl acetate, which could not produce graft copolymers by the chain transfer technique, failed also in this mastication procedure. Block and graft copolymers were also prepared by cross-addition of the macroradicals generated by the cold milling and mastication of mixtures of various elastomers and polymers, such as natural rubber/polymethyl methacrylate (74), natural rubber/butadiene-styrene rubbers (76) and even phenol-formaldehyde resin/nitrile rubber (125). 

Photolysis of this polymer gives radicals on which side chains can be formed, giving graft polymerization 122, 123, 153). Similarly the polymerization of styrene (152) or vinyl acetate (157) in the presence of bromotrichloromethane gives telomers carrying terminal bromine atoms and trichloromethyl groups. By ultraviolet irradiation (3500 A) in the presence of methyl methacrylate the carbon-bromine links are broken and block copolymers are formed. The telomerization of acrylonitrile and acrylic acid with bromoform is based on the same technique the end groups of both polyacrylonitrile and polyacrylic acid were photolyzed in the presence of acrylamide and afforded polyacrylamide blocks linked to polyacrylonitrile or polyacrylic acid blocks (164, 165). 

Most dispersion polymerizations in C02, including the monomers methyl methacrylate, styrene, and vinyl acetate, have been summarized elsewhere (Canelas and DeSimone, 1997b Kendall et al., 1999) and will not be covered in this chapter. In a dispersion polymerization, the insoluble polymer is sterically stabilized as colloidal polymer particles by the surfactant that is adsorbed or chemically grafted to the particles. Effective surfactants in the dispersion polymerizations include C02-soluble homopolymers, block and random copolymers, and reactive macromonomers. Polymeric surfactants for C02 have been designed by combining C02-soluble (C02-philic) polymers, such as polydimethylsiloxane (PDMS) or PFOA, with C02-insoluble (C02-phobic) polymers, such as hydrophilic or lipophilic polymers (Betts et al., 1996, 1998 Guan and DeSimone, 1994). Several advances in C02-based dispersion polymerizations will be reviewed in the following section. 

These advantages (wet rub and gloss) may be attributed to the fact that during the polymerization process, there are formed grafted copolymers of vinyl acetate and the water soluble colloids present in the polymerizing medium. These graft copolymers possess marked surface activity and contribute to the stabilization of the emulsion in which they are formed.. . . ... 

To survey as completely as possible the grafting behavior of EVA copolymers toward various vinyl compounds, our investigations covered the grafting of vinyl acetate, vinylidene chloride, and acrylic and meth-acrylic esters. As polymerization processes, at first we preferred suspension polymerization to exclude the influence of solvents by terminating or transfer reactions during polymerization. Grafting by emulsion polymerization, in which the EVA copolymer was dissolved in the monomer before polymerization, was difficult because coagulate was formed as polymerization proceeded. 

When grafting acrylonitrile in a swollen condition of the EVA copolymer, only partly soluble or insoluble products are obtained (Table VI). Therefore, we investigated the graft polymerization of acrylonitrile in solution and compared its grafting behavior with that of vinyl chloride and vinyl acetate. The solvent was tert-butyl alcohol, which is known to show a very low transfer tendency (Table VII). 

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