Phenylglycidyl ether, copolymerization

Table 3. Hammett reaction constants q for the copolymerization of p-N02, p-C02CH3, p-Cl, p-H, p-CHj, and p-OCH3 substituted phenylglycidyl ethers with hexahydrophthalic anhydride initiated with tri-n-butylamine ...

Another reactivity order is reported for the copolymerization of anhydrides with phenylglycidyl ether and with 3,3-bis-chloromethyloxacyclobutane 41) glutaric > phthalic > succinic anhydrides. 

Tanaka and Kakiuchi52 > analyzed the conversion curves for the copolymerization of substituted phenylglycidyl ethers with hexahydrophthalic anhydride and found a first-order dependence with respect to the initiator at the maximum reaction rate (Eq. (80)), and second-order kinetics for the region of initiation (Eq. (81)). 

Second-order kinetics with respect to the amine and epoxide was also found by Antipova et al. 65) for the curing of epoxy resins with hexahydrophthalic anhydride, by Sorokin et al.321 for the reaction of phenylglycidyl ether with phthalic anhydride in the presence of butanol, Luston and Manasek 45 74) for the copolymerization of 2-hydroxy-4-(2,3-epoxypropoxy)benzophenone with phthalic anhydride in the absence or in the presence of proton donors, and Kudyakov et al. 98) for the curing of epoxy resins with maleic anhydride. 

Boos and Flauschildt90) obtained for the model copolymerization of phenylglycidyl ether with hexahydrophthalic anhydride activation energies of 96 kJ/mol up to 75% conversion and 27 kJ/mol for higher conversions. Frequency factors are also very different (log A = 13.7 and 5.5, respectively). The frequency factors as well as the temperature coefficients of the solution viscosities depended on the initiator concentration. The activation energy determined by the same authors 90) for the curing of epoxy resins at conversions lower than 75% was 86.4 kJ/mol and the frequency factor log A = 11.8 whereas at higher conversions these values were not obtained. 

MALDI-TOF analysis showed that imidazoles used as initiators in the strictly alternating copolymerization of phenylglycidyl ether (PGE) and phthalic anhydride (PA) remain chemically bound to the polyester chains during the whole reaction. °... 

Various copolymers were reported from trioxane with dioxolane or with glycidyl ethers. Fcff instance, a copolymer of trioxane and dioxolane forms with SnCU, BF3, or Ha04 catalysts. The products from each reaction differ in molecular weights and in molecular weight distributions. Copolymerizations of trioxane with phenylglycidyl ether yield random copolymers. 

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