Microstructure and Thermal Properties of Ethylene/Vinyl Chloride Copolymers

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Abstract
The microstructure of ethylene/vinyl chloride (E/VC) copolymers, prepared by partial reduction of PVC with a variety of reagents, was analyzed using carbon-13 NMR spectroscopy. The effect of the reduction mechanism on the microstructure and stereochemistry of the copolymers was studied. The reduction with tri-n-butyltin hydride (TBTH) produced copolymers with higher degrees of alternating monomer units than copolymers obtained by reduction with lithium aluminum hydride (LAH). Reduction with lithium triethylborohydride (SH) produced blockier copolymers. The correlation of monomer sequence and distribution with thermal stability and dehydrochlorination rate in these copolymers was investigated. Partial reduction of PVC by all reagents was shown to produce E/VC copolymers with improved thermal stability compared to PVC. In the series of copolymers produced by TBTH reduction, improvement in thermal stability increased with an increase in E content and reached a maximum at 40% E content but dropped steadily thereafter. All copolymers from SH reduction showed a considerable drop in their dehydrochlorination rate compared to PVC. The stabilization effect reached a maximum at ∼7 mol% E content and stayed constant throughout.