工业丝用钛系聚酯的结晶动力学研究

doi:10.13475/j.fzxb.20241104401

纺织学报 ›› 2025, Vol. 46 ›› Issue (08): 53-61.doi: 10.13475/j.fzxb.20241104401

工业丝用钛系聚酯的结晶动力学研究

姜庭国¹^,², 况军³, 司虎⁴, 张玉梅¹^,², 陈烨¹^,²(), 王华平¹^,²

1.东华大学材料科学与工程学院, 上海 201620
2.东华大学先进纤维材料全国重点实验室, 上海 201620
3.中石化(上海)石油化工研究院有限公司, 上海 201208
4.中国石化仪征化纤有限责任公司, 江苏仪征 211900

收稿日期:2024-11-19 修回日期:2025-04-07 出版日期:2025-08-15 发布日期:2025-08-15
通讯作者: 陈烨(1982—),男,教授,博士。主要研究方向为纤维功能化及循环再利用。E-mail:chenye@dhu.edu.cn。
作者简介:姜庭国(2000—),男,硕士生。主要研究方向为钛系聚酯工业丝的制备及其性能研究。
基金资助:
中国石油化工股份有限公司技术攻关项目(224168);上海市自然科学基金面上项目(24ZR1400200)

Study on crystallization kinetics of titanium polyester for industrial yarns

JIANG Tingguo¹^,², KUANG Jun³, SI Hu⁴, ZHANG Yumei¹^,², CHEN Ye¹^,²(), WANG Huaping¹^,²

1. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
2. State Key Laboratory of Advanced Fiber Materials, Donghua University, Shanghai 201620, China
3. Sinopec (Shanghai) Petrochemical Research Institute Co., Ltd. Shanghai 201208, China
4. Sinopec Yizheng Chemical Fiber Co., Ltd., Yizheng, Jiangsu 211900, China

Received:2024-11-19 Revised:2025-04-07 Published:2025-08-15 Online:2025-08-15

摘要/Abstract

摘要： 为探究钛、锑2种不同催化体系获得的2种工业丝用聚酯切片的结晶动力学差异,拓宽钛系高黏聚酯在聚酯工业丝领域的应用,借助热重分析仪、差示扫描量热仪、X射线衍射仪等对2种工业丝用聚酯切片进行热性能与结晶性能的表征,并通过Avrami方程对2种工业丝用聚酯切片的非等温结晶动力学与等温结晶动力学进行分析。结果表明:二者均为稳定的一步分解过程,内部可能存在的小分子杂质对结晶行为影响可忽略不计;从切片角度来看,工业丝生产主要与其特性黏度有关;锑系聚酯切片存在冷结晶与正常结晶2部分,推测其结晶温度在185~190 ℃之间;钛系相较于锑系,其结晶速率更快,结晶能力更强,且钛系偏向于二维片晶生长,锑系偏向于三维球晶生长,且钛系的半结晶时间更短,易造成喷丝拉伸不均匀,后续可考虑通过降低牵伸速度等方式来缓解上述问题。

关键词: 工业丝用聚酯切片, 结晶动力学, 球晶, 非等温结晶活化能, 钛系聚酯, 锑系聚酯

Abstract:

Objective In this paper, two crystallization kinetics were used to analyze the crystallization behavior of titanium and antimony series high viscosity polyesters, and the effects of different catalytic systems on the crystallinity of high viscosity polyester chips were discussed. The differences and improvement measures of titanium polyester industrial yarn in production and other aspects compared with antimony polyester industrial yarn were deduced, and the application of titanium polyester industrial yarn in related fields was finally expanded.

Method The thermal stability of polyester chips for industrial yarns was characterized by thermogravimetry and differential scanning, and the crystallization performance of the chips was tested by combining XRD with differential scanning. In addition, the isothermal crystallization and non-isothermal crystallization tests were carried out by differential scanning calorimeter, and the Avrami equation was used to analyze and fit them.ResultsThrough the thermal stability test, it was found that polyester chips catalyzed by titanium and antimony for industrial yarns had only one weight loss step, and the initial decomposition temperatures of the two were very close. The crystallization performance test was characterized by the combination of differential scanning and XRD. Both differential scanning and XRD showed that the crystallinity of the titanium system was higher than that of the antimony system. In addition, in terms of differential scanning, the cooling crystallization peak of the titanium system is narrower and sharper than that of the antimony system, which preliminarily proves that the crystallization rate of the titanium system is faster. In the XRD test, there were four crystal planes (0,-1,1), (0,1,0), (-1,1,0), (1,0,0), which proves that there is no significant difference between the crystal plane structure and the conventional polyester. From the perspective of slicing, the production of industrial yarns was only related to its own intrinsic viscosity. In the isothermal crystallization test, as the temperature continues to increase, the crystallization peak continued to shift to the right and the peak shape gradually became wider. The molecular chain movement appeared more intense, the crystal nucleus was not conducive to formation, and the crystallization time became longer. Through the analysis and fitting of Avrami equation, it was found that ln(-ln(1-X_t)) (X_t means relative crystallinity) has a good linear relationship with lnt. With the continuous increase of temperature, the n value showed a decreasing trend. It is speculated that with the increase of crystallization temperature and the increase of melting time, the structure of microcrystalline nucleus is greatly destroyed, the growth point of crystallization is greatly reduced, and the molecular chain is difficult to achieve large-scale diffusion and adjustment.. In the non-isothermal crystallization test, the peak value was constantly shifted to the left and the peak shape is gradually widened with the increase of the cooling rate, due to the fact that the polyester molecular chain is too late to crystallize. Through the analysis and fitting of the Avrami equation, it is found that the semi-crystallization time of the titanium system was shorter, leading to the upward movement of the curing point in the spinning and cooling process, the increase of the stress gradient and the velocity gradient, which may cause uneven spinning and drawing. Therefore, in the follow-up, the first roller speed would be appropriately reduced to alleviate this problem.

Conclusion Both differential scanning and XRD tests show that the crystallinity of the titanium system is higher than that of the antimony system. Isothermal crystallization and non-isothermal crystallization were used to characterize the crystallization kinetics. It can be found that the crystallization rate of the titanium system is faster, and the crystallization performance is better. The activation energy of non-isothermal crystallization of titanium system is lower, and non-isothermal crystallization activation energy is usually related to the activation energy required for nucleation stability and the activation energy required for segment diffusion into the crystal plane, so the previous relevant conclusions can be verified. Finally, due to the shorter half crystallization time of the titanium system, there may be some problems in the spinning process, so the subsequent drafting process will be adjusted by appropriately reducing the drafting speed of the first roller.

Key words: polyester chips for industrial yarn, crystallization kinetics, spherulites, non-isothermal crystallization activation energy, titanium system polyester, antimony system polyester

中图分类号:

TQ323.41

姜庭国, 况军, 司虎, 张玉梅, 陈烨, 王华平. 工业丝用钛系聚酯的结晶动力学研究[J]. 纺织学报, 2025, 46(08): 53-61.

JIANG Tingguo, KUANG Jun, SI Hu, ZHANG Yumei, CHEN Ye, WANG Huaping. Study on crystallization kinetics of titanium polyester for industrial yarns[J]. Journal of Textile Research, 2025, 46(08): 53-61.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20241104401

http://www.fzxb.org.cn/CN/Y2025/V46/I08/53

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样品	T_c/℃	n	t_1/2/min	lnZ_t	R²
	180	2.590	1.565	-1.495 52	0.989 16
Sb	185	2.348	2.106	-2.051 59	0.986 83
	190	2.262	2.195	-2.079 29	0.988 10
	195	2.080	3.053	-2.647 14	0.984 63
	196	2.279	0.429	1.481 00	0.991 40
Ti	199	2.064	0.626	0.343 96	0.984 36
	202	1.867	0.888	-0.450 81	0.971 05
	205	1.920	1.475	-1.389 77	0.963 83

样品	β/(℃·min^-1)	n	t₁_/₂/min	Z_t	R²
	5	2.675	4.13	0.018	0.983 83
Sb	10	2.604	3.44	0.032	0.979 11
	15	2.597	2.87	0.052	0.975 12
	20	2.837	2.10	0.099	0.991 77
	5	2.302	5.87	0.004	0.948 82
Ti	10	2.343	3.00	0.024	0.950 83
	15	2.663	1.81	0.113	0.950 34
	20	3.154	1.50	0.230	0.968 88

工业丝用钛系聚酯的结晶动力学研究

Study on crystallization kinetics of titanium polyester for industrial yarns

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