SynopsisThe high catalytic activity of imidazoles and particularly of 2-ethyl-4-methylimidazole (EMI) for the curing of epoxy resins and the properties of the resulting resins prompted this study concerned with the nature of the curing reaction. Epon 828 epoxy resin and the model compound phenyl glycidyl ether were used BS starting materials with EMI, 2-methylimidazole, and dimethylbenzylamine as catalysts. During the curing of the resin at 50°C., the decrease in the infrared absorption of the epoxy band with time is accompanied by a decrease in the intensity of the imine band of the imidazole moiety, indicating its reaction with the epoxy group and its incorporation into the resin. The measurement of the residual epoxy content after curing for 24 hr. at 50 and 140°C. showed that the imidazoles were not more efficient in completing the epoxy reaction than dimethylbenzylamine. In the experiments with phenyl glycidyl ether the rate of reaction of the epoxy group with EM1 was faster than the rate of polymerization, proving that the imidazole becomes permanently attached to the polymer chain. These results also suggest that the true catalytic species is not EM1 but some addition product thereof. In comparative rate measurements the compound formed from equimolar quantities of EM1 and phenyl glycidyl ether was found to be an excellent catalyst. The NMR analysis of the 1: 1 and 1 : 2 adducts of EM1 and phenyl glycidyl ether has shown that the second mole of phenyl glycidyl ether reacts with the ring nitrogen in the 3 position and not with the hydroxyl group of the mono adduct. By forming the bis adduct in this way the imidazole molecule acts as a crosslinking agent and at the same time introduces an alkoxide ion which can initiate further polymerization. It is very likely that this crosslinking is the process that leads to the superior physical and chemical properties (high heat deflection temperature, resistance to chemicals and oxidation) of the resins prepared with imidazoles as catalysts.

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The synthesis of the following 4-monosubstituted and 4,7-disubstituted 1,10-phenanthrolines is reported: -amyl, cyclohexyl, p-tolyl, p-ethylphenyl, p-i-butylphenyl, p-biphenylyl; also, 4,7-di-n-propyl, -di-n-tridecyl, and di-p-methoxyphenyl.

where anticipated (the shift between «-methyls is 0.31 p.p.m. for isopropyl and 0.26 p.p.m. for sec-butyl; the shift between /3-methyls is ~0.1 p.p.m. for sec-butyl and 0.07 p.p.m. for isobutyl; S-CH3 is a sharp singlet at -2.00 p.p.m. The benzylic CH2 protons are a moderately sharp doublet (8.1 ± 0.2 Hz at -3.92 p.p.m.) for benzyl and broad doublet (7 Hz at -3.90 p.p.m.) for p-hydroxy benzyl. Other CH and CH2 protons in the R groups are not seen well because of interference by the ring protons. The acid OH proton was seen in the range -13 to -15 p.p.m. For the combined OH and COOH proton line was at -13.17 p.p.m.