半芳香尼龙PA12T的微波辅助聚合与表征

doi:10.16085/j.issn.1000-6613.2021-0169

化工进展 ›› 2022, Vol. 41 ›› Issue (1): 336-342.DOI: 10.16085/j.issn.1000-6613.2021-0169

半芳香尼龙PA12T的微波辅助聚合与表征

黄文蕊¹(), 黄正强¹, 付鹏¹^,², 崔喆¹^,², 张晓朦¹, 庞新厂¹^,², 赵清香¹^,²^,³, 刘民英¹^,²^,³()

^1.郑州大学材料科学与工程学院，河南郑州 450001
^2.河南省先进尼龙材料及应用重点实验室(郑州大学)，河南郑州 450001
^3.中国石油和化工行业高性能尼龙工程塑料工程实验室，河南郑州 450052

收稿日期:2021-01-25 修回日期:2021-04-15 出版日期:2022-01-05 发布日期:2022-01-24
通讯作者: 刘民英
作者简介:黄文蕊（1996—），女，硕士研究生，研究方向为半芳香尼龙合成与表征。E-mail：381339196@qq.com。
基金资助:
“十三五”国家重点研发计划(2017YFB0307600);河南省重大科技专项(181100211200)

Microwave-assisted polymerization and characteristic of semi-aromatic nylon PA12T

HUANG Wenrui¹(), HUANG Zhengqiang¹, FU Peng¹^,², CUI Zhe¹^,², ZHANG Xiaomeng¹, PANG Xinchang¹^,², ZHAO Qingxiang¹^,²^,³, LIU Minying¹^,²^,³()

^1.School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
^2.Henan Key Laboratory of Advanced Nylon Materials and Application (Zhengzhou University), Zhengzhou 450001, Henan, China
^3.Engineering Laboratory of High Performance Nylon Engineering Plastics of China Petroleum and Chemical Industry, Zhengzhou 450052, Henan, China

Received:2021-01-25 Revised:2021-04-15 Online:2022-01-05 Published:2022-01-24
Contact: LIU Minying

摘要/Abstract

摘要：

半芳香尼龙具有优异的力学强度、耐热性能和耐溶剂性能，在电子电器、汽车、轨道交通、特种装备中具有重要应用，受到了国内外学者和产业界的广泛关注。然而，传统聚合方法存在的制备周期长、分子量分布宽等技术难题长期得不到有效解决。本文利用微波能够使吸波材料快速、均匀升温的特点，首次在微波辅助条件下制备了耐高温半芳香尼龙PA12T，研究了在密闭条件下，以水作为吸波介质，水的用量、反应温度以及反应时间等条件对聚合产物特性黏数的影响，并对产物结构及热性能进行了表征。结果表明，微波辅助聚合与传统聚合方法相比，反应时间缩短三分之一以上，且产物分子量分布较窄，为解决传统半芳香尼龙聚合方法存在的问题进行了有价值的探索。

关键词: 半芳香尼龙, 微波, 聚合, 热失重

Abstract:

With advanced properties of high-temperature resistant and high strength, semi-aromatic nylon has been widely used in electronic appliances, automobiles, rail transit and special equipments. However, conventional synthesis methods have long-standing technical problems of semi-aromatic nylon with a long preparation cycle and wide molecular weight distribution. In this paper, the rapid and uniform heating under microwave conditions was used for the first time to provide a new solution to these problems though preparing high-temperature resistant semi-aromatic nylon PA12T. The influence of polymerization conditions such as the amount of water used as the wave-absorbing medium, reaction temperature and reaction time on the molecular weight of the polymerized product under a closed system were investigated. The results showed that microwave-assisted polymerization took one third of the time comparing with the traditional method and the product had the narrower molecular weight distribution than conventional polymerization. This method provided a valuable reference for the further study of high efficiency polymerization of semi-aromatic nylon and the design and improvement of microwave reactor.

Key words: semi-aromatic polyamide, microwave, polymerization, degradation

中图分类号:

TQ317

黄文蕊, 黄正强, 付鹏, 崔喆, 张晓朦, 庞新厂, 赵清香, 刘民英. 半芳香尼龙PA12T的微波辅助聚合与表征[J]. 化工进展, 2022, 41(1): 336-342.

HUANG Wenrui, HUANG Zhengqiang, FU Peng, CUI Zhe, ZHANG Xiaomeng, PANG Xinchang, ZHAO Qingxiang, LIU Minying. Microwave-assisted polymerization and characteristic of semi-aromatic nylon PA12T[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 336-342.

图/表 14

图1 微波辅助聚合尼龙示意图

图2 PA12T盐的TG和DTG曲线图

图3 PA12T盐的DSC曲线图

图4 PA12T的黏度与水用量的关系曲线（聚合温度为190℃，时间30min）

图5 PA12T的黏度与聚合温度的关系曲线（反应时间30min）

图6 PA12T的特性黏数与保温时间的关系（聚合温度为210℃）

图7 微波功率与PA12T升温至聚合温度（210℃）所需时间的关系

图8 PA12T的特性黏数与微波功率的关系

图9 PA12T的红外谱图

图10 PA12T核磁谱图

表1 PA12T的核磁氢谱分析

峰代号	δ_H	峰面积
a	7.98	1.01
b	3.69	1.00
c	1.84	1.08
d	1.39	4.40

图11 PA12T的TG和DTG曲线

表2 PA12T的TG分析结果

聚合方式	［η］ /dL · g^-1	M_η/kg · mol^-1	初始分解温度/℃	最大分解速率温度/℃
微波辅助聚合	0.60	5.5	434	474
传统聚合	0.56	5	378	475

图12 PA12T的DSC曲线图

参考文献 17

1	易庆锋, 张勇, 陈健, 等. 耐高温聚酰胺研究进展[J]. 工程塑料应用, 2009(11): 80-82.
	YI Qingfeng, ZHANG Yong, CHEN Jian, et al. Advance on heat-resisting polyamide[J]. Engineering Plastics Application, 2009(11): 80-82.
2	曹民, 章明秋, 黄险波, 等. 聚对苯二甲酰癸二胺的合成与表征[J]. 石油化工, 2008, 37(7): 714-717.
	CAO Min, ZHANG Mingqiu, HUANG Xianbo, et al. Synthesis and characterization of poly(decamethylene terephthalamide)[J]. Petrochemical Technology, 2008, 37(7): 714-717.
3	WANG W, HUANG A, LIU A, et al. Synthesis and characterization of long chain semiaromatic polyamides based on undecanediamine[J]. Journal of Wuhan University of Technology: Mater.‍ Sci. ‍Ed., 2012, 27(4): 689-693.
4	曹民, 黄木军, 张传辉. 半芳香族耐高温尼龙PA12T的合成、表征与性能[J]. 工程塑料应用, 2016, 44(11): 1-6.
	CAO Min, HUANG Mujun, ZHANG Chuanhui. Synthesis, characterization and properties of semi-aromatic heat-resistant nylon PA12T[J]. Engineering Plastics Application, 2016, 44(11): 1-6.
5	胡君, 贺金梅, 黄玉东, 等. 半芳香聚酰胺合成研究现状[J]. 化工新型材料, 2008, 36(10): 23-27.
	HU Jun, HE Jinmei, HUANG Yudong, et al. Present status of synthesis investigation on semi-aromatic polyamides[J]. New Chemical Materials, 2008, 36(10): 23-27.
6	SINGH S K, COLLINS J M. New developments in microwave-assisted solid phase peptide synthesis[J]. Methods in Molecular Biology, 2020, 2103: 95-109.
7	KOMOROWSKA-DURKA M, DIMITRAKIS G, BOGDAL D, et al. A concise review on microwave-assisted polycondensation reactions and curing of polycondensation polymers with focus on the effect of process conditions[J]. Chemical Engineering Journal, 2015, 264: 633-644.
8	NAGAHATA R, TAKEUCHI K. Encouragements for the use of microwaves in industrial chemistry[J]. Chemical Record, 2019, 19: 51-64.
9	TEMUR ERGAN B, BAYRAMOĞLU M. Poly(L-lactic acid) synthesis using continuous microwave irradiation-simultaneous cooling method[J]. Chemical Engineering Communications, 2018, 205(12): 1665-1677.
10	IMAI Y, NEMOTO H, WATANABE S, et al. A new facile and rapid synthesis of aliphatic polyamides by microwave-assisted polycondensation of omega-amino acids and nylon salts[J]. Polymer Journal, 1996, 28: 256-260.
11	PARK K H, WATANABE S, KAKIMOTO M A, et al. Rapid synthesis of aromatic polyamides by microwave-assisted directed polycondensation of aromatic diamines with aromatic dicarboxilic acids[J]. Polymer Journal, 1993, 25(2): 209-213.
12	NAKAMURA T, NAGAHATA R, TAKEUCHI K. Microwave-assisted polyester and polyamide synthesis[J]. Mini-Reviews in Organic Chemistry, 2011(8): 306-314.
13	闫朵. 一步法固相合成聚对苯二甲酰对苯二甲胺[D]. 郑州: 郑州大学, 2018.
	YAN Duo. The synthetic of allyaromatic nylon poly(p-phenylene terephthalamide) by one-step solid-state polycondensation[D]. Zhengzhou: Zhengzhou University, 2018.
14	张力冉. 微波合成聚羧酸超塑化剂性能/热-非热效应研究[D]. 北京: 中国矿业大学, 2015.
	ZHANG Liran. Study on the performance /thermal-athermal effect of microwave synthesis of polycarboxylic ether superplasticizer[D]. Beijing: China University of Mining & Technology, 2015.
15	李召朋, 付鹏, 张俊岭, 等. 粉末状半芳香尼龙PA12T的合成[J]. 高分子通报, 2010(2): 92-96.
	LI Zhaopeng, FU Peng, ZHANG Junling, et al. Synthesis of powderous semi-aromatic nylon PA12T[J]. Chinese Polymer Bulletin, 2010(2): 92-96.
16	WANG W, WANG X, LI R, et al. Environment-friendly synthesis of long chain semiaromatic polyamides with high heat resistance[J]. Journal of Applied Polymer Science, 2009, 114(4): 2036-2042.
17	华幼卿, 金日光. 高分子物理[M]. 4版. 北京: 化学工业出版社. 2013: 161-167.
	HUA Youqing, JIN Riguang. Polymer physics[M]. 4th ed. Beijing: Chemical Industry Press, 2013: 161-167.

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半芳香尼龙PA12T的微波辅助聚合与表征

Microwave-assisted polymerization and characteristic of semi-aromatic nylon PA12T

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