Free-radical-initiated chain polymerization unsaturated polyester

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. 

The free radicals first react with the chemical inhibitor which has previously been added to the resin, since the inhibitor material must be chemically dissipated before any reaction between free radicals and the C=C double bonds can proceed [5]. Apparently, the free radicals serve to open the double bonds in the polyester linear chain to set in motion that portion of the polymerization process designated as initiation. Either the opened double bonds react with the vinyl groups of the monomer, or the free radicals serve to also open (add to) these latter unsaturated C=C bonds, permitting them to perform their cross-linking function, uniting the polyester chains into a three-dimensional network. There is further evidence that free radicals may also, to some degree, react with the unsaturated monomer to form various products of decomposition [5]. 

Acrylic esters and unsaturated polyesters are commercially cured with peroxides or peresters. The choice of per compound is determined on the basis of price, the achievable polymerization rate, and the side products formed. The polymerization rate is determined by the decomposition rate of the initiator, when mixed with the material to be cured, as well as on the free radical yield. In addition, attention should be paid to the fact that many per compounds decompose slowly during storage, thus reducing the polymerization activity per unit initiator mass. For this reason, crystalline per compounds are more stable because of the lower diffusion than amorphous or dissolved per compounds. Side products of initiator compounds can have an unfavorable effect on the long-term thermoset properties dibenzoyl peroxide, for example, forms acids dicumyl peroxide forms ketones. Acids can hydrolyze the ester bonds of polyester chains, causing scission, and ketones can... 

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