Syntheses and Polymerization of p-(Substituted phenyl)1, 3, 5-triazine Monomers Using Imidates

Abstract

A variety of 2-amino-4-(p-substituted phenyl) - and 2, 4-dipheny1-6-(vinyl or isopropeny1)1, 3, 5-triazines were readily synthesized in high yields by the reaction of benzimidoylguanidines and N-benzimidoylbenzamidine with unsaturated carboxylic acid chlorides.
The hompolymerization of these triazine monomers and the copolymerization with methyl naethacrylate were investigated in dioxane at 60°C using a, c'-azobisisobutyronitrile or a t 30°C using N, N-dimethylaniline-benzoyl peroxide as an initiator. Q values obtained were very large and negative e values were decreasedw ith increasing electron-releasinge ffect of p- (substituted phenyl) group. This could be related to a negative inductive effect and a conjugation of phenyl group with a double bond through the triazine nucleus.
On the other hand, the introduction of 2-am ino-4-phenyl- and 2, 4 -diphenyl-1, 3, 5-triazines to a polymer as pendants decreased the flexibility of the polymer chain, and softening point rised considerably with increasing triazine ring content. And copolymers containing 2, 4diphenyltriazine rings became readily soluble in nonpolar solvents such as benzene, carbon tetrachloride and chloroform, whereas copolymers containing 2-amino-1-phenyltriazine rings were soluble in polar solvents such as dioxane, N, N-dimethylformamide and acetic acid. From the above results, it was found that the interaction between aminotriazines of these polymers was less than that of the polymers containing guanamine structure (2, 4-diaminotriazine rings), and the rigidity and the hydrophobicity of aromatic rings attached to triazine rings reasonably affected the physical and thermal properties of the polymers.