Organic Curing Agents for Polysulfide Sealants. II. Additions of Thiols to Nitrile Oxides: Scope, Relative Reactivities and Application to the Cure of Polysulfide Sealants

Abstract

Efficient addition between various nitrile oxides and both short (C2) and long chain (C16) alkyl thiols , aliphatic dithiols and aryl thiols occurred rapidly at ambient temperature with the formation of thiohydroximic acid derivatives. Competitive experiments with bis( nitrile oxides) showed that for terephthalonitrile oxide the second addition proceeded more readily than the first whereas with anthracene-9,l0-bis(carbonitrile oxide) elevated temperatures were needed to obtain the diadduct. Relative reactivities of a number of thiols with nitrile oxides were also determined spectroscopically . Reaction between prop-2-ene-1-thiol and p-nitrobenzonitrile oxide afforded products resulting from both cycloaddition and 1,3-addition with the latter predominating. The polysulfide prepolymer LP-2 was cured effectively at ambient temperatures by both terephthalonitrile oxide and 4,4'-sulfonylbisbenzonitrile dioxide at CNO to SH ratios of 1.5 and higher giving tack-free products within 0.5 h and 90% cure in under 4 h. For the less highly cross-linked LP-32-based sealants, curing was a little slower. Unreinforced sealants produced in this manner were firm elastomers with hardness of 35-40 (Rex A). The naphthalenebis (carbonitrile oxides) afforded softer products while anthracene-9,10- bis(carbonitrile oxide) was ineffective. One-part formulations involving in situ generation of nitrile oxide from hydroximoyl chlorides and barium hydroxide (formed by action of water vapour on barium oxide) were also produced.