Adduct Rubbers: A Versatile New Family of Elastomers

Abstract

A versatile family of elastomers has been prepared by free radical addition of aliphatic mercaptans to the double bonds of diene polymers. High saturation levels were readily achieved without degradation of the basic polymer chain. The technology is similar to ordinary emulsion polymerization. By varying the nature of the base polymer, the mercaptan used, and the extent of saturation, a wide range of compositions and of physical properties were attained in the adducts. In general, resistance to aging, ozone attack, heat, solvent swelling, and to permeation by gases increased with increasing extent of saturation. Outstanding performance in these qualities was achieved by adducts of polymers whose double bonds had been over 90 per cent saturated. A highly saturated methyl mercaptan adduct of polybutadiene showed (1) stress-strain and air aging properties at 400° and 500° F better than commercially available ethylacrylate copolymers and various semicommercial heat resistant elastomers; (2) permeability resistance equivalent to butyl; (3) solvent swell intermediate between neoprene and medium nitrile content butadiene-acrylonitrile rubbers, with a Tg below −30° C; (4) ozone resistance comparable to the better commercially available saturated rubbers. Increased solvent resistance was obtained by preparing adducts of the appropriate butadiene-acrylonitrile copolymers. Adducts with saturation levels up to about 85 per cent could be cured by the same procedures used for the base polymers. Activated or butyl-type curing systems were required for higher saturation levels. The relative rates at which aliphatic mercaptans add to the several types of double bonds present in emulsion diene polymers have been examined in a preliminary way.

New horizons in elastic polymers

“…Mercaptan adducts of polybutadiene mentioned earlier have exceptional resistance to high temperatures, ozone and 7-radiation (11).…”