固相聚合对萘环液晶聚芳酯结构与性能的影响

doi:10.13475/j.fzxb.20230702401

纺织学报 ›› 2024, Vol. 45 ›› Issue (09): 50-55.doi: 10.13475/j.fzxb.20230702401

固相聚合对萘环液晶聚芳酯结构与性能的影响

魏朋¹^,²(), 李志强¹, 李娇娇¹, 李俊慧¹, 刘东¹, 耿嘉骏¹

1.中原工学院智能纺织与织物电子学院, 河南郑州 450007
2.先进纺织装备技术省部共建协同创新中心, 河南郑州 450007

收稿日期:2023-07-11 修回日期:2024-01-20 出版日期:2024-09-15 发布日期:2024-09-15
作者简介:魏朋(1987—),男,副教授,博士。主要研究方向为高性能液晶高分子纤维。E-mail: appletree0322@163.com。
基金资助:
国家自然科学基金项目(51803246);河南省高校科技创新人才支持计划资助项目(22HASTIT032);河南省高等学校青年骨干教师培养计划项目(2020GGJS140);中原工学院基本科研业务费专项资金资助项目(K2020YY005)

Influence of solid-state polymerization on structure and properties of naphthalene ring structure aromatic liquid crystal copolyester

WEI Peng¹^,²(), LI Zhiqiang¹, LI Jiaojiao¹, LI Junhui¹, LIU Dong¹, GENG Jiajun¹

1. College of Intelligent Textile and Fabric Electronics, Zhongyuan University of Technology, Zhengzhou, Henan 450007, China
2. Collaborative Innovation Center of Advanced Textile Equipment and Technology by MOE and Henan Provincial Government, Zhengzhou, Henan 450007, China

Received:2023-07-11 Revised:2024-01-20 Published:2024-09-15 Online:2024-09-15

摘要/Abstract

摘要：

为解决液晶聚芳酯熔融缩聚反应后期由于反应温度和熔体黏度过高导致的降解交联副反应以及成形加工困难等问题,以6-羟基-2-萘甲酸(HNA)、2,6-萘二羧酸(NDA)、对苯二甲酸(TA)、4,4'-二羟基联苯(BP)为原料,采用原位一锅熔融聚合法制备了低分子量萘环热致液晶聚芳酯,并对其进行固相聚合。通过差示扫描量热仪、热重分析仪、偏光显微镜、X射线衍射和熔融指数仪对固相聚合后的液晶聚芳酯结构与性能进行了测试。结果表明,液晶聚芳酯的熔融温度和结晶度受聚合时间和温度的影响较大,呈现出先增加后降低的变化趋势,但并不会改变聚芳酯的晶体结构,同样属于正交晶型。此外,固相聚合在温度305 ℃下反应12 h,液晶聚芳酯热学和结晶性能得到明显改善;高于此时间和温度时聚芳酯的熔点开始降低,热降解反应开始进行,热稳定性和结晶性能下降。

关键词: 热致液晶聚芳酯, 熔融聚合, 固相聚合, 热学性能, 晶体结构

Abstract:

Objective Degradation, cross-link side reaction and poor processing ability are caused by high reaction temperature and melt viscosity of liquid crystal copolyesters in the final stage of melt polycondensation. In order to solve such problems, low molecular weight of liquid crystal copolyesters was prepared by one-pot melting transesterification method. The influences of solid-state polymerization time and temperature on thermal properties, crystallization properties and melt index of liquid crystal copolyesters were investigated.

Method In this study, the low molecular weight liquid crystal copolyester derived from 6-hydroxy-2-naphthalene carboxylic acid (HNA), 2, 6-naphthalene dicarboxylic acid (NDA), terephthalic acid, 4,4'-dihydroxy biphenyl (BP) were prepared by in-situ one-pot melt polymerization method. After solid-state polymerization, the structure and properties of liquid crystal polyesters were analyzed by Differential scanning calorimeter, Thermogravimetric analyzer, polarized microscope, X-ray diffraction and melt index.

Results The melting temperature of liquid crystal copolyester (T_m) and the glass transition temperature (T_g) were found to increased and then decreased with the increase of polymerization time. Crystallization enthalpy ΔH_c and melting enthalpy ΔH_m reached the maximum after 12 h of polymerization, and were decreased gradually with the increase of solid-state polymerization time ΔH_c and ΔH_m. Clear marble and textured liquid crystal texture were still observed 8 h after solid-state polymerization, showing nematic liquid crystal behavior, but with the increase of polymerization time, birefringence and texture gradually got blurred. When the polymerization time was increased to 36 h, the crystal structure did not change, remaining in the state of orthogonality. The results showed that the phase transition temperature and crystallization rate of liquid crystal copolyesters were greatly affected by polymerization time and temperature. The crystallization performance of liquid crystal copolyesters was better when the polymerization temperature was 305 ℃ and the polymerization time was about 12 h. The initial degradation temperature of liquid crystal copolyesters after solid state polymerization was generally higher than that of the initial sample, and the temperature corresponding to the maximum mass loss was somewhat lower than that of the sample. The carbon residue of liquid crystal copolyesters at 700 ℃ remained between 42% and 44.5%, indicating that the molecular weight and thermal stability of liquid crystal copolyesters were improved during the polymerization process but the possibility of thermal degradation was increased by long-term high temperature polymerization. With the increase of polymerization time, the melt index at different polymerization temperatures began to decrease rapidly. When the polymerization temperature was 315 ℃, the melt index of copolyesters was decreased the fastest. After 24 h solid-state polymerization, the melt index of copolyesters did not change significantly. Considering that high molecular weight products were obtained under low energy consumption, 8-24 h solid-state polymerization time was appropriate.

Conclusion The structure and properties of liquid crystal copolyester are influenced by the operation parameters of solid-state polymerization, such as temperature, time, nitrogen flow rate and particle size. This research was focused on the influence of temperature and time on the thermal and crystallization properties of liquid crystal copolyester. Owing to the continued reaction of the terminal group, the molecular chain of liquid crystal copolyester after solid-state polymerization increases, the molecular weight increases, and the melting temperature, glass transition temperature and thermal stability are improved. However, after solid-state polymerization for more than 12 h and the temperature is higher than 305 ℃, the concentration of the reactive terminal group inside the particles decreases. When the molecular weight reaches the equilibrium limit, the melting point of the copolyester decreases gradually, and the degradation reaction of the molecular chain gradually dominates, and the thermal stability and crystallinity decrease. The results show that the thermal and crystalline properties of liquid crystal copolyesters are improved significantly after solid state polymerization at 305 ℃ for 12 h, which is conducive to its processing and application.

Key words: thermotropic liquid crystal copolyester, melt polymerization, solid state polymerization, thermal property, crystal structure

中图分类号:

O632

魏朋, 李志强, 李娇娇, 李俊慧, 刘东, 耿嘉骏. 固相聚合对萘环液晶聚芳酯结构与性能的影响[J]. 纺织学报, 2024, 45(09): 50-55.

WEI Peng, LI Zhiqiang, LI Jiaojiao, LI Junhui, LIU Dong, GENG Jiajun. Influence of solid-state polymerization on structure and properties of naphthalene ring structure aromatic liquid crystal copolyester[J]. Journal of Textile Research, 2024, 45(09): 50-55.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20230702401

http://www.fzxb.org.cn/CN/Y2024/V45/I09/50

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固相聚合温度T/℃	聚合时间t/h	T_m/℃	T_g/℃	T_c/℃	ΔT/℃	ΔH_c/(J·g^-1)	ΔH_m/(J·g^-1)
—	0	323.5	124.7	299.2	24.3	2.5	2.4
295	8	326.4	125.6	296.2	30.2	2.7	2.8
	12	328.9	129.8	289.0	39.9	3.0	4.1
	24	325.7	131.6	286.3	39.4	3.0	2.8
	36	313.2	124.6	283.0	30.2	2.1	2.6
305	8	327.8	128.3	285.9	41.9	3.4	3.0
	12	328.2	130.1	288.3	39.9	3.5	3.8
	24	319.2	131.8	278.2	41.0	3.1	3.4
	36	303.6	129.7	269.2	34.4	2.1	2.3
315	8	320.9	132.6	280.1	40.8	3.0	3.0
	12	328.0	133.3	286.4	41.6	3.3	4.7
	24	318.7	135.1	277.0	41.7	2.2	2.6
	36	303.1	133.5	267.2	35.9	2.5	2.5

固相聚合温度 T/℃	聚合时间 t/h	初始降解温度/℃	最大质量损失速率下的温度/℃	700 ℃时残炭量/%
—	0	475.2	505.2	44.5
295	8	475.4	505.4	42.4
	12	474.0	503.1	43.8
	24	476.4	503.4	43.1
	36	477.7	502.7	43.9
305	8	480.8	505.8	43.8
	12	475.5	504.0	43.7
	24	479.2	504.7	44.4
	36	476.9	504.4	43.8
315	8	475.7	501.7	43.9
	12	475.3	503.3	43.5
	24	479.8	503.3	44.4
	36	476.7	504.7	44.3

固相聚合温度 T/℃	聚合时间 t/h	2θ/(°)	d/nm	半峰宽/(°)	X_c/%
—	0	19.34	0.46	0.65	34.10
295	8	19.46	0.45	0.64	39.14
	12	19.33	0.46	0.66	39.33
	24	19.47	0.45	0.65	34.73
	36	19.38	0.46	0.65	34.22
305	8	19.44	0.45	0.64	36.20
	12	19.39	0.46	0.66	38.49
	24	19.46	0.45	0.69	32.87
	36	19.41	0.46	0.64	32.94
315	8	19.38	0.46	0.64	36.82
	12	19.33	0.46	0.68	38.34
	24	19.43	0.46	0.66	34.65
	36	19.25	0.46	0.69	31.27

固相聚合对萘环液晶聚芳酯结构与性能的影响

Influence of solid-state polymerization on structure and properties of naphthalene ring structure aromatic liquid crystal copolyester

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