Grafting polyethylenes, rates

On the other hand, the rates of grafting of CTFE onto butadiene- and isoprene-grafted polyethylenes were lower than those onto original ones (Figure 2). As shown in Figure 3, the rate of consumption of the unsaturated groups, as well as the gel fraction, was remarkably accelerated by CTFE. 

In addition to acting as impact modifiers a number of polymeric additives may be considered as processing aids. These have similar chemical constitutions to the impact modifiers and include ABS, MBS, chlorinated polyethylene, acrylate-methacrylate copolymers and EVA-PVC grafts. Such materials are more compatible with the PVC and are primarily included to ensure more uniform flow and hence improve surface finish. They may also increase gelation rates. In the case of the compatible MBS polymers they have the special function already mentioned of balancing the refractive indices of the continuous and disperse phases of impact-modified compound. 

Figure 1. Grafting of styrene in methanol to polyethylene at various dose rates total dose 0.2 X 10 rads. (V) 0.117 X 10s rad/hr, without HsSOk (Y) with 0.1 N H S04 (0)0.196 X 10s rad/hr, without HsSOi (9) with 0.1N H2SOi ( ) 0.279 X 106 rad/hr, without ( ) with 0.1N ffsS04 ( ) 0.546 X 10 rad/hr,...

TABLE VII. Effect of Dose Rate in the Presence of Acid on the Grafting of Styrene in DMF to Polyethylene. 

The parameters which predominantly influence the acid effect in radiation grafting of styrene monomer to polyethylene film are the structure of solvent, the concentration of monomer and the dose rate. Because these three variables are inter-related, it is difficult to predict, a priori, the conditions required to yield an optimum in grafting. In this respect the type of solvent used is particularly important. 

Figure 2. Grafting of styrene in DMF to polyethylene in the presence of HtSOt at various concentrations total dose 0.5 X 10s rad at dose rate 0.080 X 10s rad/hr...

As has been shown in Figure 4, the grafting rate decreased with the increase in the unsaturated groups contained in the polyethylenes. This result may indicate that the rate constants of the re-initiations (8-1)-(8-3) are considerably smaller than that of propagation (6). 

The kinetics of the reaction of solid sodium iodide with 1-bromooctane were studied with a 95 % RS graft of polyethylene oxide) 6-mer methyl ether on 3 % CL polystyrene as catalyst (51)176). The rates were approximately first order in 1-bromooctane and independent of the amount of excess sodium iodide. The rates varied with the amount of the solid catalyst used, but there was not enough data to establish the exact functional dependence. All experiments employed powdered sodium iodide, magnetic stirring, and 75-150 pm catalyst beads. Thus the variables stirring speed and particle size, which normally are affected by mass transfer and intraparticle diffusion, were not studied. Yanagida 177) favors a mechanism of transfer of the sodium iodide by dissolution in the solvent (benzene) and diffusion to the catalyst particle... 

Figure 2. Influence of preirradiation dose of polyethylene films in air on the rate of grafting observed on heating at 135°C. in acrylonitrile (2)...

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-... 

One method is to measure chain-transfer coefficients with low-MW analogues of the polymer. Thus Gilchrist (140) measured the rate at which 14C labelled decane was incorporated into polyethylene in the free-radical polymerization, and hence obtained an estimate of the transfer coefficient with methylene groups this was in fair agreement with another estimate obtained from the effect of the addition of fractions of linear polyethylene on the Mn of the branched polyethylene, which could be separated from linear polymer plus grafted branched polymer by column extraction. Low MW polymer may be used as a transfer agent Schulz and co-workers (189) obtained chain-transfer coefficients in styrene polymerization from the effect of added low MW polymer on Mn. 

Studies in the grafting of mixed monomers to cellulose have also been reported by Sakurada (113). Binary mixtures studied included butadiene with styrene or with acrylonitrile, and styrene with acrylonitrile. Remarkable increases in rate in the case of mixed monomer similar to those found by RAPSON were found in many cases. For example, about 10% of butadiene increased the grafting yield about ten fold. Similar results were found with the addition of acrylonitrile to butadiene and to styrene. Ternary mixtures of monomers were also investigated by both Rapson (109) and Sakurada (113). The large increases in rate with certain mixtures were interpreted by Sakurada as due to a particular balance of gd effects akin in many ways to popcorn polymerization. The effects were found also with polyvinyl alcohol but not with polyethylene where gel effects would perhaps be less prominent. 

The influence of the polymer structure on the irradiation grafting has been examined in the case of styrene to high pressure and low pressure polyethylene films (114). The most important factors which determine the efficiency of grafting are the degree of crystallinity, the thickness of the films and the dose rate. 

Kollicoat IR is a unique polymer for pharmaceutical applications prepared by a graft polymerization process of polyethylene glycol (25%) with polyvinyl alcohol (75%). Kollicoat IR dissolves quickly in water and aqueous solutions of acid and alkali and reduces the surface tension of aqueous solutions to allow the solutions to have high spray rates. The polymer film is very flexible, not tacky, and easily colored. The polymer can be used as instant release coating, pore former, binder, protective colloid, etc. 

The latter effect has not yet been investigated quantitatively. So far, only one interesting paper49 by Odian and Kruse has been reported who performed a mathematical analysis of the grafting of styrene to irradiated polyethylene films for different ratios between the diffusion and the grafting rates. For stationary graft polymerization they derived the following equation ... 

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