The effect of the mass ratio of hard and soft segments on some properties of thermoplastic poly(ester-siloxane)s

Abstract

A series of thermoplastic elastomers based on soft polydimethylsiloxane (PDMS) and hard poly(butylene terephthalate) (PBT) segments was synthesized using a two-step transesterification reaction in the melt. The molar mass of the soft PDMS component was constant (M̄ n P DMS = 1056 g mol -1 ) while the starting reaction mixture compositions were varied to obtained copolymers with a mass ratio of hard to soft segments in the range from 70/30 to 40/60. The structure and composition of the copolymers was verified by 1 H NMR spectroscopy. It appeared that there was a pronounced molar mass maximum when the PBT content of the copolymers was approximately 60 mass%, whereas all samples were considerably inhomogeneous with respect to the distribution of the lengths of the hard segments. Differential scanning calorimetry-(DSC) thermograms showed that the melting and crystallization temperature increased with increasing PBT content, as did the total degree of crystallinity, which was confirmed by wide-angle X-ray scattering (WAXS) analysis. Thermogravimetric analysis (TGA) performed in nitrogen gave subtle differences for samples of different composition, including that of the PBT homopolymer, whereas in oxygen these differences were more pronounced in the way the thermo-oxidative stability of the obtained copolymers decreased with decreasing PBT content. Finally, it was shown that the hardness depended directly on the PBT content, ie the higher the PBT content, the greater the hardness of the corresponding copolymer.