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The TFE content dependence of Tm and Tg of ETFE shows unique behavior with the maximal and minimal points. The Tm may be classified into three regions of the different characters as shown in Fig. 1. The existence of the maximal Tm at 50 mol% TFE can be interpreted by presuming the perfectly alternating hypothetical copolymer. The Tm of perfectly alternating copolymer is estimated to be 295 C by performing the extrapolation to the perfectly alternating ratio. This value is supported reasonably by utilizing the modified Flory’s equation as derived by Eby. On the other hand, the existence of minimal Tm at around 70 mol% TFE content is considered to come from the difference in chain conformation between the regions B and C. The copolymer in the region B may be assumed to be a copolymer consisting of hypothetical EeTFE units and TFE units. The copolymer in the region C includes the long TFE segments of helical conformation, as evidenced by the X-ray diffraction data. The Tm increases gradually with an increment of TFE units. Similarly the maximal Tg was reasonably interpreted on the basis of the modified GibbseDimazio’s equation. The Tg extrapolated to the perfectly alternating copolymer was estimated to be 145 C. |
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