Vinyl chloride radiation effect

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. 

For low radiation doses, peroxides accumulate almost linearly with dose. However, after a certain dose has been reached, their concentration tends to level off. This conclusion can be derived from the observed change in the rate of graft copolymerization initiated by polymers subjected to increasing doses of preirradiation in air. Figure 2 illustrates this effect in the case of grafting acrylonitrile onto polyethylene (2). The drop in the yield of peroxide production presumably results from the efficient radiation-induced decomposition of these peroxides. Peroxides are known to decompose under free radical attack, and selective destruction of peroxides under irradiation has been established experimentally (8). This decomposition can become autocatalytic, and sometimes the concentration of peroxides may reach a maximum at a certain dose and decrease on further irradiation. Such an effect was observed in the case of poly (vinyl chloride). Figure 3 shows the influence of preirradiation dose on the grafting ratio obtained with poly (vinyl chlo-... 

The Russian workers (12) also noted a significant effect of time of exposure to the radiation field before stress application on the resultant creep rate of poly (vinyl chloride) samples (Figure 8). 

Armstrong et al. have extensively studied the effect of this radiation on grafting butadiene, styrene, vinyl chloride, vinyl esters, acrylic, and methacrylic esters, acrylonitrile and other less common monomers on Nylon 66 fibers. They observed the influence of oxygen, water, methanol, acetic acid, dose of irradiation as well as temperature (160-163). 

The butadiene and butadiene-acrylic monomer systems polymerize when irradiated on PVC or vinyl chloride copolymer latex. The structure of the polymer obtained may be grafted if it can be proved that the copolymer properties are different from the blend properties. To elucidate the structure we studied a copolymer obtained by polymerizing butadiene-acrylonitrile on a PVC homopolymer lattice. Owing to practical reasons and to exclude the secondary effect of catalytic residues we used y radiation. However, we shall observe in a particular case the properties of peroxide-initiated graft copolymer. 

Radiation-induced Degradation.—There have been several reports on radiation effects in polymers,288 including single crystals,287 fluoropolymers,288 polyamides,289 polysiloxanes,270 polyethylene and its copolymers,271 polypropylene,272 polyolefins,273 polystyrene and its copolymers,274 poly(vinyl chloride) and related polymers,275 rubbers,278 polysulphones and other sulphur-containing polymers,277 polycarbonate,278 nylon,279 poly(vinylpyridines),280 and wool.281... 

Measurements of the frequency and temperature dependence of the H T, in poly(dimethyl siloxane) revealed relaxations due to methyl rotation and segmental motions and also an oxygen impurity effect The experimental data could not be fitted using thermally activated Arrhenius behaviour, as was also true of backbone motions in poly(vinyl chloride). " Multiple side-group motions have also been observed in poly (diethyl siloxane) and poly(L-histidine). Backbone motions have been observed in poiy(diethyl siloxane), poly(oxymethylene), poly(ethylene terephthalate), poly(p-phenylene sulphide), aromatic polyamides, and PTFE. A close similarity between the effects of entanglements and radiation cross-linking on the of cis-polyisoprene has been found. ... 

While one would expect that polymerizations of a monomer in a heterogeneous system with ultraviolet radiation would be difficult because of the blocking effect of the continuous phase, emulsion polymerizations of vinyl chloride have been carried out. The design of a small-scale pilot plant has even been reported upon [180]. With anionic emulsifers, the process is actually mechanistically similar to chemically initiated latex polymerization of VCM [181]. At high conversions, inversion of the latex and the formation of a free-flowing powder containing 35-70< /b PVC may take place [182]. Stable latexes were also formed in the presence of cationic surfactants [183]. 

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