用生物基 2,5-呋喃二甲酸制造具有高熔点和弹性的热塑性聚醚酯弹性体

Tao Yang, Fei Liu*, Ruixue Gao, Xiaoqin Zhang*, Jiaxi Li, Jinggang Wang* and Jin Zhu, 
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摘要

尽管目前对生物基聚(酯-醚)弹性体(TPEEs)的研究已扩展到各种应用领域,但迄今为止,仅有少数几种具有出色熔融温度的 TPEEs 被报道过。这是因为某些特性,如理想的弹性性能和高熔点,在不使用石油基单体的情况下仍很难获得。为了制备具有高耐热性和弹性恢复能力的生物基 TPEE,本研究合成了呋喃基聚(1,4-环己烷二甲基呋喃二甲酸酯)-聚(四甘醇)多嵌段共聚物(PCFTMG2k)。这些共聚物的软段 PTMG 重量分数(ωPTMG)从 30% 到 80% 不等,同时软段的锰含量保持在 2 kg/mol。结果表明,通过引入结晶能力相对较好的软段并控制软段的含量,可以成功制备出既具有弹性特性又具有较高熔化温度的 TPEE。此外,还研究了共聚物的结晶行为,发现随着软段含量的增加,共聚物会从非结晶态转变为同晶态。更重要的是,含有 80 wt % PTMG 段的 PCFTMG2k-80 在 PTMG 浓度较高的情况下,在 200% 应变和高达 198°C 的温度下进行第一次循环测试时,形状恢复率高达 84.9%,高于几乎所有基于 TPA 的 TPEE。这种 PCFTMG2k 生物基热塑性弹性体将在未来的高熔点热塑性弹性体市场中占据重要地位。
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Fabrication of Thermoplastic Poly(ether-ester) Elastomers with High Melting Temperature and Elasticity from Bio-based 2,5-Furandicarboxylic Acid

Even though current research on bio-based poly(ester-ether) elastomers (TPEEs) has expanded to include applications, only odd TPEEs with outstanding melting temperatures have been reported thus far. This is due to certain features, like desirable elastic properties and high melting temperature, which are still challenging to obtain without the utilization of petroleum-based monomers. In order to prepare bio-based TPEE with both high thermal resistance and elastic recovery, furan-based poly(1,4-cyclohexanedimethylene furandicarboxylate)-poly(tetramethylene glycol) multiblock copolymers (PCFTMG2k) were synthesized in this work. These copolymers had weight fractions of soft segments PTMG (ωPTMG) ranging from 30 to 80% while maintaining Mn of the soft segments at 2 kg/mol. Indeed, while PTMG segments are found to delay substantially the crystallization of the PCF within the copolymers, the results show that TPEEs with both elastic properties and high melting temperatures can be successfully prepared by introducing soft segments with relatively good crystallization ability and controlling the content of soft segments. Moreover, the crystallization behavior of the copolymers was investigated, from which it was found that the copolymers transformed from a non-cocrystallization state to an isodimorphic state as the content of soft segments increased. More importantly, PCFTMG2k-80, containing 80 wt % of the PTMG segment, showed a shape recovery rate as high as 84.9% during the first cyclic test at 200% strain and Tm up to 198°C at a high PTMG concentration, which is higher than those of almost all the TPA-based TPEEs. This PCFTMG2k bio-based TPEE will occupy an important position in the future market of high melting temperature thermoplastic elastomers.

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