纺织学报 ›› 2018, Vol. 39 ›› Issue (07): 1-7.doi: 10.13475/j.fzxb.20170901207

• 纤维材料 •    下一篇

有机钛-硅催化剂合成聚酯的动力学研究

  

  • 收稿日期:2017-09-05 修回日期:2018-04-11 出版日期:2018-07-15 发布日期:2018-07-16

Synthesis kinetics of polyester by organic titanium-silicon catalysts

  • Received:2017-09-05 Revised:2018-04-11 Online:2018-07-15 Published:2018-07-16

摘要:

为开发稳定且具有较高活性的钛系催化剂,用制备得到的系列新型钛硅(Ti-Si)复合催化剂催化合成聚对苯二甲酸乙二醇酯,研究了聚合反应动力学及催化剂的用量、缩聚温度对聚合反应和聚酯切片性能的影响,将其与传统锑系催化剂三氧化二锑(Sb2O3 )、钛系催化剂Ti(X)进行对比。结果表明:在研究范围内,Ti-Si 催化剂的最佳用量为19 μg/g,缩聚温度为281 ℃;Ti-Si 催化剂对酯化和缩聚反应均有催化作用,可降低酯化反应的活化能,活化能仅为42.49/mol,提高了酯化反应速度;Ti-Si 催化剂具有较高的催化活性,其缩聚时间比Sb2O3、Ti(X) 均缩短约40 min,缩聚活化能也低于Sb2O3 ,且与 Ti(X) 相近;采用Ti-Si 催化剂制得的聚酯切片在热性能、力学性能方面均与Ti(X)相似,但优于Sb2O3合成的;在色度上,Ti-Si 催化剂合成的聚酯的亮度优于Sb2O3的,b 值与Ti(X)的相似。

关键词: 聚对苯二甲酸乙二醇酯, 钛系催化剂, 酯化反应, 缩聚反应, 反应动力学

Abstract:

In order to prepare stable and highly active titanium catalyst, a series of titanium silicon (Ti-Si) composite catalysts were prepared and the best catalyst was selected. By employing this catalyst in preparation of polyethylene glycol terephthalate (PET), the influence of catalysts dosage and polycondensation temeffect temperature on polymerization reaction and the properties of polyester chips were investigated. In addition, kinetics for polymerization was studied. Polymerization results were also compared with classical antimony catalyst (Sb2O3) and titanium catalyst (Ti(X)). Results show that the optimized dosage of catalyst is 19 μg/g and the suitable polycondensation temperature is 281℃ under the testing condition. Ti-Si catalyst played an effective role both in esterification and polycondensation. Ti-Si catalyst has much lower esterification activation energy which is only 42.49 kJ/mol, and it accelerated the esterification reaction. The polycondensation time by Ti-Si is much shorter (40min) than other catalysts Sb2O3 and Ti(X). The kinetic data for polycondensation demonstrated that the condensation activation energy by Ti-Si is similar to Ti(X), but lower than Sb2O3. The resultant PET chips by Ti-Si catalyst has similar thermal and mechanical properties with those by Ti(X), but better than those by Sb2O3. In addition, the chips by Ti-Si possessed brighter chroma than those by Sb2O3, and have the similar b value with Ti(X).

Key words: polyethylene glycol terehthalate, titanium catalyst, esterification, polycondensation, reaction kinetics

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