Exploiting Sodium Coordination in Alternating Monomer Sequences to Toughen Degradable Block Polyester Thermoplastic Elastomers.
Exploiting Sodium Coordination in Alternating Monomer Sequences to Toughen Degradable Block Polyester Thermoplastic Elastomers.
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在交替的单体序列中利用钠配位，以强化可降解的块聚酯热塑性弹性体。
DOI：
10.1021/acs.macromol.2c00068
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发表时间：
2022-03-22
期刊：
影响因子：
5.5
通讯作者：
Williams, Charlotte K.
中科院分区：
文献类型：
--
作者：
Gregory, Georgina L.;Williams, Charlotte K.
循环材料经济需要闭环可回收的热塑性弹性体（TPE），但目前许多材料在回收过程中会降解，几乎所有材料都是普遍存在的碳氢化合物。这里描述了具有规则放置的羧酸钠/锂侧链的良好控制的嵌段聚酯TPE。它们显示出比未官能化的类似物显著更高的拉伸强度，具有高弹性和弹性恢复。这些材料是使用受控聚合制备的，利用在不同聚合循环之间切换的单一催化剂。高摩尔质量的阿坝嵌段聚酯（60-100 kg mol-1; 21重量%A-嵌段）使用ε-癸内酯（衍生自蓖麻油; B-嵌段）的开环聚合，随后邻苯二甲酸酐与4-乙烯基-环氧环己烷（A-嵌段）的交替开环共聚来构建。聚酯经历有效的官能化以将规则放置的羧酸安装到A嵌段上。聚合物与氢氧化钠或氢氧化锂的反应控制电离程度（0-100%）;电离的聚合物显示出更高的拉伸强度（20 MPa）、弹性（>2000%）和弹性恢复（>80%）。在一种情况下，钠官能化导致比羧酸聚合物高35倍的断裂应力;在所有情况下，改变钠的量调节性能。领先的样品2-COONa 75（Mn 100 kg mol-1，75%钠）显示出较宽的工作温度范围（−52至129 °C），并通过在200 °C下热压回收（×3），而不会损失机械性能。阿坝嵌段聚合物的有效合成和在完全交替的单体序列中的精确电离都是可以推广到许多其他单体、官能团和金属的概念。这些材料部分是生物衍生的，具有可降解的酯骨架化学性质，提供有用的特性，并允许热再加工;这些特性作为未来的可持续TPE具有吸引力。
Thermoplastic elastomers (TPEs) that are closed-loop recyclable are needed in a circular material economy, but many current materials degrade during recycling, and almost all are pervasive hydrocarbons. Here, well-controlled block polyester TPEs featuring regularly placed sodium/lithium carboxylate side chains are described. They show significantly higher tensile strengths than unfunctionalized analogues, with high elasticity and elastic recovery. The materials are prepared using controlled polymerizations, exploiting a single catalyst that switches between different polymerization cycles. ABA block polyesters of high molar mass (60–100 kg mol–1; 21 wt % A-block) are constructed using the ring-opening polymerization of ε-decalactone (derived from castor oil; B-block), followed by the alternating ring-opening copolymerization of phthalic anhydride with 4-vinyl-cyclohexene oxide (A-blocks). The polyesters undergo efficient functionalization to install regularly placed carboxylic acids onto the A blocks. Reacting the polymers with sodium or lithium hydroxide controls the extent of ionization (0–100%); ionized polymers show a higher tensile strength (20 MPa), elasticity (>2000%), and elastic recovery (>80%). In one case, sodium functionalization results in 35× higher stress at break than the carboxylic acid polymer; in all cases, changing the quantity of sodium tunes the properties. A leading sample, 2-COONa75 (Mn 100 kg mol–1, 75% sodium), shows a wide operating temperature range (−52 to 129 °C) and is recycled (×3) by hot-pressing at 200 °C, without the loss of mechanical properties. Both the efficient synthesis of ABA block polymers and precision ionization in perfectly alternating monomer sequences are concepts that can be generalized to many other monomers, functional groups, and metals. These materials are partly bioderived and have degradable ester backbone chemistries, deliver useful properties, and allow for thermal reprocessing; these features are attractive as future sustainable TPEs.
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