废弃芳纶粉末环氧化改性及其固化物性能

doi:10.16085/j.issn.1000-6613.2020-2224

化工进展 ›› 2021, Vol. 40 ›› Issue (10): 5692-5698.DOI: 10.16085/j.issn.1000-6613.2020-2224

废弃芳纶粉末环氧化改性及其固化物性能

于鹏达¹(), 张晓娴², 张金峰³, 谈继淮¹, 王芳³, 王芳³, 付博¹, 朱新宝¹^,⁴()

^1.南京林业大学化学工程学院，江苏南京 210037
^2.南京市产品质量监督检验院，江苏南京 210019
^3.中国石化仪征化纤有限责任公司，江苏仪征 211900
^4.安徽省环氧树脂及其助剂工程研究中心，安徽黄山 245900

收稿日期:2020-11-06 修回日期:2021-01-06 出版日期:2021-10-10 发布日期:2021-10-25
通讯作者: 朱新宝
作者简介:于鹏达（1995—），男，硕士研究生，研究方向为精细有机合成。E-mail：2649469348@qq.com。
基金资助:
江苏省重点研发计划(164030040)

Epoxidation modification of waste aramid fiber powder and properties of curing products

YU Pengda¹(), ZHANG Xiaoxian², ZHANG Jinfeng³, TAN Jihuai¹, WANG Fang³, WANG Fang³, FU Bo¹, ZHU Xinbao¹^,⁴()

^1.College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, Jiangsu, China
^2.Nanjing Institute of Product Quality Inspection, Nanjing 210019, Jiangsu, China
^3.Yizheng Chemical Fibre Company Limited, Sinopec, Yizheng 211900, Jiangsu, China
^4.Anhui Engineering Research Center of Epoxy Resin and Additives, Huangshan 245900, Anhui, China

Received:2020-11-06 Revised:2021-01-06 Online:2021-10-10 Published:2021-10-25
Contact: ZHU Xinbao

摘要/Abstract

摘要：

针对国内对位芳纶（PPTA）在实际生产中产生的低分子量PPTA粉末，探讨了一种有效回收再利用的方法。本文以低分子量PPTA为原料、环氧氯丙烷为改性剂，采用金属化/取代反应，制备了环氧氯丙烷（ECH）修饰的PPTA（PPTAGE），并通过单因素实验优化了PPTAGE合成条件。结果表明：合成条件为m(ECH）∶m(PPTA)=3∶1、NaH用量（与总投料量质量之比）0.4%、反应温度80℃、反应时间4.5h时，PPTAGE接触角最小，纤维表面能最佳。将改性前后的芳纶分别作为环氧树脂的填料，得到固化物样条，研究了PPTAGE对环氧树脂复合材料力学性能的影响。固化物力学性能研究表明，PPTAGE可以在一定程度上提高与环氧树脂基体的黏合，在添加量为1%时，复合材料的力学性能达到最佳；热重（TGA）分析表明，固化物热稳定性较PPTA/E-51有所提高；扫描电镜（SEM）测试表明，PPTAGE/E-51冲击断裂面为韧性断裂。

关键词: 对位芳纶, 环氧氯丙烷, 氢化钠, 环氧化, 固化性能

Abstract:

Aiming at the high-value low-molecular-weight para-aramid (PPTA) produced from the waste material of para-aramid fiber production, an effective recycling method was discussed. Epoxy group modified PPTA(PPTAGE) was prepared with PPTA as the raw material and epichlorohydrin as the modifier using an adopting metalized/substitution reaction. The synthesis conditions of PPTAGE were optimized through single factor experiments. The results showed that the suitable synthesis conditions of PPTAGE were m(ECH)∶m(PPTA)=3∶1, the amount of NaH (the mass percentage of the materials input) was 0.4%, the reaction temperature was 80℃ and the reaction for 4.5h. The modified aramid fiber was used as the filler of the epoxy resin to obtain the cured products, and the effect of PPTAGE on the mechanical properties of the cured product was studied. The properties of the cured product indicated that the modified PPTA can improve the adhesion of PPTA to the epoxy resin matrix. When the addition amount was 1%, the mechanical properties of the cured product was the best. After adding PPTAGE, the cured product was thermal stalely. Compared with PPTA/E-51, its performance was improved. SEM test showed that the impact fracture surface of PPTAGE/E-51 was ductile fracture.

Key words: para-aramid, epichlorohydrin, sodium hydride, epoxidation, curing product

中图分类号:

TQ323.5

于鹏达, 张晓娴, 张金峰, 谈继淮, 王芳, 王芳, 付博, 朱新宝. 废弃芳纶粉末环氧化改性及其固化物性能[J]. 化工进展, 2021, 40(10): 5692-5698.

YU Pengda, ZHANG Xiaoxian, ZHANG Jinfeng, TAN Jihuai, WANG Fang, WANG Fang, FU Bo, ZHU Xinbao. Epoxidation modification of waste aramid fiber powder and properties of curing products[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5692-5698.

图/表 7

图1 PPTA环氧化改性的单因素实验结果

图2 PPTA和PPTAGE的红外光谱

表1 环氧化改性前后PPTA的BET表征

物质	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/nm
原料	7.28	0.0186	102.42
PPTAGE	9.46	0.0209	92.38

图3 两种填充物质量分数对复合材料力学性能的影响

图4 PPTA/E-51、PPTAGE/E-51和E-51的TG分析

表2 固化物的热重数据

材料	T_10%/℃	T_50%/℃	T_{最大失重速率%}/℃	最大残留量/%
PPTA/E-51	354	382	370	12
PPTAGE/E-51	354	386	372	17
E-51	352	383	369	15

图5 1%PPTA/E-51复合材料和1%PPTAGE/E-51复合材料冲击断面的SEM谱图

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废弃芳纶粉末环氧化改性及其固化物性能

Epoxidation modification of waste aramid fiber powder and properties of curing products

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