Abstract

A series of poly(trimethylene terephthalate)-block-poly(ethylene oxide) (PTT-b-PEOT) copolymers with different compositions of rigid PTT and flexible PEOT segments were synthesized via condensation in the melt. The influence of the block length and the block ratio on the micro-separated phase structure and elastic properties of the synthesized multiblock copolymers was studied. The PEOT segments in these copolymers were kept constant at 1130, 2130 or 3130 g/mol, whereas the PTT content varied from 30 up to 50 wt %. The phase separation was assessed using differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The crystal structure of the synthesised block copolymers and their microstructure on the manometer scale was evaluated by using WAXS and SAXS analysis. Depending on the PTT/PEOT ratio, but also on the rigid and flexible segment length in PTT-b-PEO copolymers, four different domains were observed i.e.,: a crystalline PTT phase, a crystalline PEO phase (which exists for the whole series based on three types of PEOT segments), an amorphous PTT phase (only at 50 wt % content of PTT rigid segments) and an amorphous PEO phase. Moreover, the elastic deformability and reversibility of PTT-b-PEOT block copolymers were studied during a cyclic tensile test. Determined values of permanent set resultant from maximum attained stain (100% and 200%) for copolymers were used to evaluate their elastic properties.

Highlights

  • Polyester thermoplastic elastomers (TPE) have been known since the 1970s by the trade nameHytrel

  • The semicrystalline microphase created by segregation of rigid segments act as physical crosslinks, playing a role similar to chemical crosslinks in vulcanizates and imparting the material’s elastomeric behaviour. It was confirmed [7] that, in PTT-b-PEOT, copolymer separates into a semicrystalline PTT hard phase and a poly(ethylene oxide) (PEO)-rich amorphous soft phase

  • The effect of the flexible polyether (PEOT) segment length (1130 (P1), 2130 (P2), 3130 (P3) g/mol) on the microseparated phase structure of the synthesized PTT-b-PEOT block copolymers was investigated by using the differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA)

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Summary

Introduction

Polyester thermoplastic elastomers (TPE) have been known since the 1970s by the trade nameHytrel. The majority of these commercially available poly(ether-ester) block copolymers with elastic properties consisting of crystallisable butylene terephthalate sequences (rigid polyester segments) and poly(alkylene oxide) sequences (flexible polyether segments) were produced based on the petrochemical monomers [1]. The growing interest in eco-friendly products creates an increased demand for production of TPEs which will be partially or fully based on monomers from renewable sources. After the development of production of bio-based 1,3-propanediol (PDO), lactic acid from starch-derived glucose, and 1,4-butanediol (BDO) using Genomatica’s technology, growing production of polyesters and thermoplastic elastomers [2,3,4] based on these renewable source monomers has Polymers 2016, 8, 237; doi:10.3390/polym8070237 www.mdpi.com/journal/polymers. Several types of bio-based TPEs based on poly(butylene terephthalate)

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