Copolymers peroxidation chain mechanism

Hexafluoiopiopylene and tetiafluoioethylene aie copolymerized, with trichloiacetyl peroxide as the catalyst, at low temperature (43). Newer catalytic methods, including irradiation, achieve copolymerization at different temperatures (44,45). Aqueous and nonaqueous dispersion polymerizations appear to be the most convenient routes to commercial production (1,46—50). The polymerization conditions are similar to those of TFE homopolymer dispersion polymerization. The copolymer of HFP—TFE is a random copolymer that is, HFP units add to the growing chains at random intervals. The optimal composition of the copolymer requires that the mechanical properties are retained in the usable range and that the melt viscosity is low enough for easy melt processing. 

Solomon (3, h, 5.) reported that various clays inhibited or retarded free radical reactions such as thermal and peroxide-initiated polymerization of methyl methacrylate and styrene, peroxide-initiated styrene-unsaturated polyester copolymerization, as well as sulfur vulcanization of styrene-butadiene copolymer rubber. The proposed mechanism for inhibition involved deactivation of free radicals by a one-electron transfer to octahedral aluminum sites on the clay, resulting in a conversion of the free radical, i.e. catalyst radical or chain radical, to a cation which is inactive in these radical initiated and/or propagated reactions. 

We shall consider here graft copolymerization only by free-radical processes. There are three main techniques for preparing graft copolymers via a free-radical mechanism. All of them involve the generation of active sites along the backbone of the polymer chain. These include (i) chain transfer to both saturated and unsaturated backbone or pendant groups (ii)radiative or photochemical activation and (iii) activation of pendant peroxide groups. 

Graft epoxy-acrylic copolymer prepared with a free radical initiator is an example of the "grafting from" process. In the case where benzoyl peroxide was used as the free radical initiator, it is determined that about 77% of the free radical initiator instead of causing initiation of monomers, chain transfers with the epoxy resin backbone, followed by the "grafting from" of22onomers onto the epoxy resin. Benzoyl peroxide is known to decompose mostly (90 ) to the benzoyloxy radical and the (10 ) phenyl radical. Mechanisms of grafting can be demonstrated in the following two schemes. (Schemes A and B). 

The synthesis of ABA blocks from a glassy thermoplastic A and an elastomeric B produces other elastoplastics with attractive properties. Polyester chains can be extended with di-isoeyanate, which is then treated with cumene hydroperoxide to leave a peroxide group at both ends of the chain. By heating this in the presence of styrene, a vinyl polymerization is initiated and an ABA block created. The modulus-temperature curves show how the mechanical properties can be modified in this way (Figure 15.7). These block copolymers are known as thermoplastic elastomers. 

To produce block copolymers by free-radical polymerization, a radical center must be produced at the end of the chain from where fresh chain growth may take place. Two of the ways by which such terminal radicals can be produced are (a) decomposition of peroxide groups introduced as an internal part of a polymer chain backbone or as an end group and (b) breaking of C-C bonds in the polymer chain by mechanical means. More recently, the advent of hving or controlled free radical polymerization has opened up a more versatile route to block copolymers by the free radical process. 

Aqueous dispersions of charged copolymer latexes are active supports of cobalt catalysts for autoxidations of tetralin by cobalt-pyridine complexes and of 2,6-di-rm-butylphenol and 1-decanethiol by CoPcTs. Since these reactants are insoluble in water, a simple explanation of the catalytic activity is that the organic polymer serves to solubilize the reactants in the phase that contains the cobalt catalyst. All three reactions have initial rates that are independent of substrate concentration, as determined by absorption of dioxygen from a gas buret. All three reactions appear to proceed by different mechanisms. Tetralin autoxidation is a free radical chain process promoted by the CoPy complex, whereas the CoPcTs reactions are not free radical chain processes. The thiol autoxidation is reported to involve hydrogen peroxide, whereas the 2,6-di-re/t-butylphenol autoxidation apparently does not. 

The stabilization of poly(vinyl chloride) against light has been reviewed by Wirth and Andreas. Detailed mechanistic studies have indicated the importance of peroxides in the process of photo-oxidation. It was suggested that protection could be successfully achieved by exclusion of radiation of A < 380 nm. E.s.r. examination of irradiated samples demonstrated the intervention of peroxides in the mechanisms with the ultimate formation of carbonyl groups which caused chain scission by Norrish cleavage. Photo-oxidation of samples of poly(vinyl chloride) modified by incorporation of acrylonitrile-butadiene-styrene, methyl methacrylate-butadiene-styrene, and methyl methacrylate-acrylonitrile-butadiene-styrene copolymers has been investigated. Discolouration was accelerated by the presence of the modifiers. Thermal pre-treatment accelerated photo-induced decomposition. Mechanical properties were also examined, and scanning electron microscopy showed surface defects due to decomposition of the modifier. ... 

---