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乙二胺四乙酸对具有低熔点和可控硬度的不饱和聚(己二酸丁二醇酯-共-衣康酸丁二醇酯)共聚酯的影响

Effect of Ethylenediaminetetraacetic Acid on Unsaturated Poly(Butylene Adipate-Co-Butylene Itaconate) Copolyester with Low-Melting Point and Controllable Hardness.

作者信息

Chen Chin-Wen, Hsu Te-Sheng, Rwei Syang-Peng

机构信息

Institute of Organic and Polymeric Materials, National Taipei University of Technology, No. 1, Sec. 3, Chung-Hsiao East Road., Taipei 10608, Taiwan.

Research and Development Center of Smart Textile Technology, National Taipei University of Technology, No. 1, Sec. 3, Chung-Hsiao East Road., Taipei 10608, Taiwan.

出版信息

Polymers (Basel). 2019 Apr 3;11(4):611. doi: 10.3390/polym11040611.

Abstract

A series of copolyesters, poly(butylene adipate-co-butylene itaconate) (PBABI), was synthesized using melt polycondensation from adipic acid (AA), itaconic acid (IA), 1,4-butanediol (1,4-BDO), and ethylenediaminetetraacetic acid (EDTA). ¹H-NMR, FT-IR, GPC, DSC, TGA, DMA, XRD, Shore D, and tensile test were used to systematically characterize the structural and composition/physical properties of the copolyesters. It was found that the melting point (T) and crystallization temperature (T) of the copolyesters were, respectively, between 21.1 to 57.5 °C and -6.7 to 29.5 °C. The glass transition (T) and the initial thermal decomposition (T) temperatures of the PBABI copolyesters were observed to be between -53.6 to -55.8 °C and 313.6 and 342.1 °C at varying ratios of butylene adipate (BA) and butylene itaconate (IA), respectively. The XRD feature peak was identified at the 2θ values of 21.61°, 22.31°, and 23.96° for the crystal lattice of (110), (020), and (021), respectively. Interestingly, Shore D at various IA ratios had high values (between 51.3 to 62), which indicated that the PBABI had soft plastic properties. The Young's modulus and elongation at break, at different IA concentrations, were measured to be at 0.77⁻128.65 MPa and 71.04⁻531.76%, respectively, which could be attributed to a close and compact three-dimensional network structure formed by EDTA as a crosslinking agent. There was a significant bell-shaped trend in a BA/BI ratio of 8/2, at different EDTA concentrations-the ∆H increased while the EDTA concentration increased from 0.001 to 0.05 mole% and then decreased at an EDTA ratio of 0.2 mole%. Since the PBABI copolymers have applications in the textile industry, these polymers have been adopted to reinforce 3D air-permeable polyester-based smart textile. This kind of composite not only possesses the advantage of lower weight and breathable properties for textiles, but also offers customizable, strong levels of hardness, after UV curing of the PBABI copolyesters, making its potential in vitro orthopedic support as the "plaster of the future".

摘要

通过熔融缩聚法,以己二酸(AA)、衣康酸(IA)、1,4 - 丁二醇(1,4 - BDO)和乙二胺四乙酸(EDTA)合成了一系列共聚酯,即聚(己二酸丁二醇酯 - 共 - 衣康酸丁二醇酯)(PBABI)。采用¹H - NMR、FT - IR、GPC、DSC、TGA、DMA、XRD、邵氏D硬度测试和拉伸试验对共聚酯的结构、组成及物理性能进行了系统表征。结果发现,共聚酯的熔点(Tm)和结晶温度(Tc)分别在21.1至57.5℃和 - 6.7至29.5℃之间。在不同的己二酸丁二醇酯(BA)和衣康酸丁二醇酯(BI)比例下,PBABI共聚酯的玻璃化转变温度(Tg)和初始热分解温度(Td)分别在 - 53.6至 - 55.8℃和313.6至342.1℃之间。XRD特征峰在(110)、(020)和(021)晶格的2θ值分别为21.61°、22.31°和23.96°处被识别。有趣的是,在不同IA比例下邵氏D硬度值较高(在51.3至62之间),这表明PBABI具有软质塑料特性。在不同IA浓度下,测得的杨氏模量和断裂伸长率分别为0.77⁻128.65 MPa和71.04⁻531.76%,这可归因于作为交联剂的EDTA形成了紧密且致密的三维网络结构。在不同EDTA浓度下,当BA/BI比例为8/2时存在显著的钟形趋势——随着EDTA浓度从0.001摩尔%增加到0.05摩尔%,∆H增加,然后在EDTA比例为0.2摩尔%时降低。由于PBABI共聚物在纺织工业中有应用,这些聚合物已被用于增强基于3D透气聚酯的智能纺织品。这种复合材料不仅具有纺织品重量轻和透气的优点,而且在PBABI共聚酯紫外线固化后还具有可定制的高强度硬度,使其在体外骨科支撑方面具有作为“未来石膏”的潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bce6/6523200/d31535291d25/polymers-11-00611-sch001.jpg

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