Thermoplastic elastomers benefit from high elasticity and straightforward (re)processability; they are widely used across a multitude of sectors. Currently, the majority derive from oil, do not degrade or undergo chemical recycling. Here a new series of ABA triblock polyesters are synthesized and show high-performances as degradable thermoplastic elastomers; their composition is poly(cyclohexene-alt-phthalate)-b-poly(ε-decalactone)-b-poly(cyclohexene-alt-phthalate) {PE–PDL–PE}. The synthesis is accomplished using a zinc(II)/magnesium(II) catalyst, in a one-pot procedure where ε-decalactone ring-opening polymerization yielding dihydroxyl telechelic poly(ε-decalatone) (PDL, soft-block) occurs first and, then, addition of phthalic anhydride/cyclohexene oxide ring-opening copolymerization delivers semi-aromatic polyester (PE, hard-block) end-blocks. The block compositions are straightforward to control, from the initial monomer stoichiometry, and conversions are high (85–98%). Two series of polyesters are prepared: (1) TBPE-1 to TBPE-5 feature an equivalent hard-block volume fraction (f_hard = 0.4) and variable molar masses 40–100 kg mol⁻¹; (2) TBPE-5 to TBPE-9 feature equivalent molar masses (∼100 kg mol⁻¹) and variable hard-block volume fractions (0.12 < f_hard < 0.4). Polymers are characterized using spectroscopies, size-exclusion chromatography (SEC), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). They are amorphous, with two glass transition temperatures (∼−51 °C for PDL; +138 °C for PE), and block phase separation is confirmed using small angle X-ray scattering (SAXS). Tensile mechanical performances reveal thermoplastic elastomers (f_hard < 0.4 and N > 1300) with linear stress–strain relationships, high ultimate tensile strengths (σ_b = 1–5 MPa), very high elongations at break (ε_b = 1000–1900%) and excellent elastic recoveries (98%). There is a wide operating temperature range (−51 to +138 °C), an operable processing temperature range (+100 to +200 °C) and excellent thermal stability (T_d,5% ∼ 300 °C). The polymers are stable in aqueous environments, at room temperature, but are hydrolyzed upon gentle heating (60 °C) and treatment with an organic acid (para-toluene sulfonic acid) or a common lipase (Novozyme® 51032). The new block polyesters show significant potential as sustainable thermoplastic elastomers with better properties than well-known styrenic block copolymers or polylactide-derived elastomers. The straightforward synthesis allows for other commercially available and/or bio-derived lactones, epoxides and anhydrides to be developed in the future.

中文翻译：

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具有半芳族聚合物端嵌段的三嵌段聚酯热塑性弹性体，通过开环共聚

热塑性弹性体得益于高弹性和直接（再）加工性；它们被广泛应用于众多领域。当前，大多数来自石油，不降解或不进行化学回收。此处合成了一系列新的ABA三嵌段聚酯，它们具有可降解的热塑性弹性体的高性能。它们的成分是聚（环己烯ALT -邻苯二甲酸酯） - b -聚（ε癸内酯） - b -聚（环己烯ALT -邻苯二甲酸酯）{PE-PDL-PE}。使用锌（II）/镁（II）完成合成）催化剂，在一个一锅法中，首先发生ε-十内酯开环聚合反应，生成二羟基远螯聚（ε-癸烯酮）（PDL，软嵌段），然后加入邻苯二甲酸酐/环己烯氧化物开环共聚反应提供半芳香族聚酯（PE，硬嵌段）端嵌段。从最初的单体化学计量开始，嵌段的组成很容易控制，转化率很高（85-98％）。制备了两个系列的聚酯：（1）TBPE-1至TBPE-5具有等效的硬嵌段体积分数（f _hard = 0.4）和40-100 kg mol ^-1的可变摩尔质量；（2）TBPE-5至TBPE-9具有当量摩尔质量（〜100 kg mol ^-1）和可变硬块体积分数（0.12 < f_硬<0.4）。使用光谱学，尺寸排阻色谱（SEC），热重分析（TGA），差示扫描量热法（DSC）和动态机械热分析（DMTA）对聚合物进行表征。它们是无定形的，具有两个玻璃化转变温度（PDL为-51°C； PE为+138°C），并且通过小角度X射线散射（SAXS）确认了嵌段相分离。拉伸机械性能揭示了热塑性弹性体（ ˚F_硬<0.4和Ñ > 1300）与线性应力-应变关系，高的极限拉伸强度（ σ _b = 1-5兆帕），非常高的断裂伸长率（ ε _b= 1000–1900％）和优异的弹性回复率（98％）。有宽的工作温度范围（-51至+138°C），可操作的加工温度范围（+100至+200°C）和出色的热稳定性（T _d，5％〜300°C）。的聚合物在含水环境中稳定，在室温下，但在温和加热（60℃）处理和用有机酸（水解段-甲苯磺酸）或普通脂肪酶（Novozyme®51032）。与众所周知的苯乙烯嵌段共聚物或聚丙交酯衍生的弹性体相比，这种新型的嵌段聚酯具有更好的性能，具有可持续发展的热塑性弹性体的巨大潜力。简单的合成方法允许将来开发其他可商购的和/或生物衍生的内酯，环氧化物和酸酐。