Diallyl phthalate, cyclopolymerization

Figure 2. Relationship between the percentage of hh linkage and the content of uncyclized unit, 100 — fe, obtained for cyclopolymerizations in benzene solutions at 80°C. Key O, diallyl phthalate O, diallyl succinate and , diallyl cis-i 2-cyclo-hexanedicarboxylate. (Reproduced, with permission, from Ref. 21. Copyright 1981, J. Polym. Sci. Polym. Lett. Ed.)...

Cyclopolymerizations also occur with methacrylic anhydride, divinyl formal, o-divinyl benzene, o-diallyl phthalate, and even 1,4-dimethylene cyclohexane ... 

The probability of cyclopolymerization by diallyl o-phthalate by various possible ring closures was calculated by Haward [34]. He predicted that 31% of the monomer units in the soluble polymer were cyclized. Experimentally, Simpson and co-workers [32] found that 41% were involved. This was considered excellent agreement between calculated predictions and empirical observations. 

The most extensive research and development activity has involved diallyl o-phthalate. The studies on the cyclopolymerization of this monomer have already been discussed at length in Section 3 of this chapter. Diallyl isophthalate polymerizes more rapidly than the the ortAo-isomer. It cyclizes less during the early stages of polymerization. Consequently the prepolymer of the isophthalate has more reactive double bonds available for further reaction than the o-phthalate and the final resin produced from it is more highly cross-linked [91]. 

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. 

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