Cyclopolymerization of diallyl esters

In attempts to copolymerize various diallyl esters with styrene it was found that the reactivity was quite low. Further, the rate and degree of copolymerization was roughly inversely related to the concentration of diallyl ester. With increasing styrene levels, the tendency toward cyclopolymerization decreased [47]. In effect, the diallyl esters act as chain-transfer agents for the polymerization of styrene. Table V gives the chain-transfer constants and the reactivity ratios for the copolymerization with styrene. 

It is noteworthy that the formation of cyclic structures is not confined to diallyl esters. For example, Haward and Simpson found evidence for cyclopolymerizations at low conversion of solutions of divinylbenzene in styrene [48]. Diallyl ammonium halides were among early examples of cyclopolymerizations [49]. Two reviews of interest are Marvel [50] and Butler [51]. 

The diallyl esters of maleic and fumaric acid have found application primarily in copolymer systems. Considering that the distance between the two allyl groups of the maleate ester is similar to those of the o-phthalate, and that of the fumarate is geometrically quite different, it is unfortunate that there seems to have been no study of the cyclopolymerization possibilities of these monomers. In addition there are the problems associated with the copolymerization of an allyl grouping with the double bond of the maleic or fumaric moieties within the same molecule. 

---