Glass transition temperature-composition relationship of oxyethylene copolymers with chloromethyl/(ethylthio)methyl, chloromethyl/(ethylsulfinyl)methyl, or chloromethyl/(ethylsulfonyl)methyl side groups

Abstract

The glass transition temperature (Tg)/composition relationships of three series of copolymers, poly[oxy(chloromethyl)ethylene-co-oxy(ethylthiomethyl) ethylene](CE-ETE), poly[oxy(chloromethyl) ethylene-co-oxy(ethylsulfinylmethyl)ethylene] (CE-ESXE), and poly(oxy(chloromethyl)ethylene-co-oxy(ethylsulfonylmethyl)ethylene) (CE-ESE) were studied. The Fox equation fit the Tg/composition data only for the CE-ETEs. The densities of CE-ESXE and CE-ESE copolymers were calculated assuming that the densities of the homopolymers were additive at the Tg (reference temperature) and the thermal expansion coefficients were used to calculate densities at room temperature. Those were compared with the experimental values and showed good agreement. The reason for the Tg deviation of the copolymers from the linear additivity was not clear. However it is probably related to the high polarity of the sulfone and sulfoxide groups in the copolymers, and their very strong dipolar interactions.