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用于合成聚(对苯二甲酸乙二酯-异山梨醇酯)的环保型钛-金属双金属配位催化剂与市售单金属锑基或钛基催化剂的比较

Comparison of Eco-friendly Ti-M Bimetallic Coordination Catalysts and Commercial Monometallic Sb- or Ti-Based Catalysts for the Synthesis of Poly(ethylene--isosorbide terephthalate).

作者信息

Xie Shangdong, Qian Sitian, Zhu Kaiyang, Sun Lijiang, Chen Wenxing, Chen Shichang

机构信息

School of Materials and Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China.

Zhejiang Provincial Innovation Center of Advanced Textile Technology, Shaoxing 312000, China.

出版信息

ACS Omega. 2023 May 22;8(22):19237-19248. doi: 10.1021/acsomega.2c07831. eCollection 2023 Jun 6.

Abstract

Sustainable development greatly benefits from the effective synthesis of bio-based copolymers that are environmentally friendly. To enhance the polymerization reactivity for the production of poly(ethylene--isosorbide terephthalate) (PEIT), five highly active Ti-M (M = Mg, Zn, Al, Fe, and Cu) bimetallic coordination catalysts were designed. The catalytic activity of Ti-M bimetallic coordination catalysts and single Sb- or Ti-based catalysts was compared, and the effects of catalysts with a different type of coordination metal (Mg, Zn, Al, Fe, and Cu) on the thermodynamic and crystallization properties of copolyesters were explored. In polymerization, it was found that Ti-M bimetallic catalysts with 5 ppm (Ti) had higher catalytic activity than traditional antimony-based catalysts or Ti-based catalysts with 200 ppm (Sb) or 5 ppm (Ti). The Ti-Al coordination catalyst showed the best-improved reaction rate of isosorbide among the five transition metals used. Utilizing Ti-M bimetallic catalysts, a high-quality PEIT was successfully synthesized with the highest number-average molecular weight of 2.82 × 10 g/mol and the narrowest molecular weight distribution index of 1.43. The glass-transition temperature of PEIT reached 88.3 °C, allowing the copolyesters to be used in applications requiring a higher , like hot filling. The crystallization kinetics of copolyesters prepared by some Ti-M catalysts was faster than that of copolyesters prepared by conventional titanium catalysts.

摘要

可持续发展极大地受益于对环境友好的生物基共聚物的有效合成。为了提高聚(乙烯-异山梨醇对苯二甲酸酯)(PEIT)生产的聚合反应活性,设计了五种高活性的Ti-M(M = Mg、Zn、Al、Fe和Cu)双金属配位催化剂。比较了Ti-M双金属配位催化剂与单一Sb基或Ti基催化剂的催化活性,并探讨了不同配位金属类型(Mg、Zn、Al、Fe和Cu)的催化剂对共聚酯热力学和结晶性能的影响。在聚合过程中,发现含5 ppm(Ti)的Ti-M双金属催化剂比含200 ppm(Sb)或5 ppm(Ti)的传统锑基催化剂或Ti基催化剂具有更高的催化活性。在所使用的五种过渡金属中,Ti-Al配位催化剂对异山梨醇的反应速率提高效果最佳。利用Ti-M双金属催化剂,成功合成了高质量的PEIT,其数均分子量最高可达2.82×10 g/mol,分子量分布指数最窄为1.43。PEIT的玻璃化转变温度达到88.3℃,使得该共聚酯可用于需要更高温度的应用,如热灌装。一些Ti-M催化剂制备的共聚酯的结晶动力学比传统钛催化剂制备的共聚酯更快。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d71/10249036/a661fca4eff3/ao2c07831_0012.jpg

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