Diallyl carbonate polymerization

There are several interesting polymerization schemes intermediate between a sequential IPN and an SIN. For example, in in situ prepared sequential IPNs, both monomers are polymerized via free radical reaction [He et ai, 1993 Rouf et ai, 1994]. The two monomers must have quite different reactivities towards the free radicals. This situation arises with vinyl or acrylic double bonds and aUylic double bonds. The allylic double bonds react about 100 times slower than acrylic or methacrylic bonds. Often, two initiators are used, one reacting at a lower temperature, and the other at a higher temperature. In one of the systems studied, based on methyl methacrylate and diallyl carbonate of bisphenol-A (DACBA), first, crosslinked PMMA was formed at moderate temperatures. Then, by just increasing the temperature after completion of the first polymerization, the synthesis of the allylic network followed. 

In this chapter, procedures for the polymerization of allyl acetate and related monocarboxylates of diallyl carbonate types, of diallyl phthalates, and of diallyl esters of other dicarboxylic acids are discussed. 

These discussions have been extended to the bulk polymerizations of diallyl adipate (DAA), diethylene glycol bis (allyl carbonate) (DEGBAC), and diallyl diphenate (DAD) accompanied by a greatly delayed gelation The monomer type, actual gel point (%), theoretical gel point (%) are, respectively, as follows DAA, 25.6, 3.6 DEGBAC, 23.0, 3.7 DAD, 29.2, 3.4. 

Network polymers were produced by in situ free radical-initiated polymerization of dlethylene bis(allyl carbonate) during World War II and unfilled clear castings of this resin are still available under the trade name of CR-39 (16). This monomer was also copolymerized with diallyl phthalate and prepolymers of the latter called DAP to produce polyesters,... 

As allyl components for IPN synthesis the following compounds were used diethylene glycol bis(allyl carbonate) (DEGAC), diallyl phthalate (DAP), dial-lyl adipate (DAA), and the commercial product of condensation of monoallyl maleinate and epoxy oligomer ED-20. Polymerization of diallyl compoimds by formation of IPNs had been performed in the presence of 5 mass % of dibenzoyl peroxide for DEGAC and diciunyl peroxide. As a hardener of epoxy oligomer, complexes of boron trilluoride with an aniline and benzylamine have been used. 

A combination of carbon chain and ester bonds results from the free-radical polymerization of diallyl diglycol carbonate ester. Polymerization proceeds more slowly than with corresponding divinyl monomers. 

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