纳米结晶纤维素表面修饰聚酰亚胺纤维及其润湿功能性

doi:10.16085/j.issn.1000-6613.2019-0605

摘要/Abstract

摘要：

聚酰亚胺纤维在应用方面存在许多潜在问题，例如聚酰亚胺纤维的低表面活性，使得其界面的润湿性能差，且在水相中易团聚，分散性较差。为此，本文提出在复合路易斯酸及交联剂共同催化作用下，使纳米结晶纤维素（CNC）修饰碱处理后的聚酰亚胺（PI）短切纤维表面，测定了CNC修饰前后PI纤维在水溶液中的分散度及PI纤维成纸的接触角，结果表明PI纤维的浸润功能性得到提高。采用扫描电子显微镜（SEM）观察了纤维的微观形貌，利用傅里叶变换红外光谱（FTIR）和X射线光电子能谱（XPS）表征了纤维表面结构的变化，最后通过多孔材料孔径分析仪测定了纤维成纸的孔径分布变化。结果表明：经CNC处理后的纤维表面发生了酯化反应且存在交联现象，纤维表面氧元素物质分数增加，含氧极性基团和表面粗糙度的增加有助于改善润湿性能，与PI纤维原纸相比，经CNC表面修饰后的纤维所成的纸页与去离子水的接触角降低了14.9°，与乙醇的接触角降低了4.8°，纤维分散度增加了45％，纤维亲水性显著提高，经过表面处理后的纤维在水相体系中的分散性能得到改善。因此，本法可以作为制备高性能纤维和相应复合材料的有效方法。

关键词: 聚酰亚胺纤维, 纤维素, 纳米结构, 接枝, 酯化, 浸润, 分散

Abstract:

Polyimide(PI) fibers have many potential problems in application. The low surface activity of polyimide fibers makes the wettability of the interface poor. It is easy to agglomerate in the aqueous phase, with poor dispersibility. In view of the above problems, this work proposed to modify the surface of polyimide short chopped fibers after alkali treatment with nanocrystalline cellulose (CNC) under the combined catalytic action of Lewis acid and crosslinker. The dispersity of PI fibers in aqueous solution before and after CNC modification and the contact angle of PI fiber paper were measured. The results showed that the wettability of PI fibers was improved. In addition, the structure and properties of PI fibers before and after CNC treatment were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analyzer (TG). The pore size distribution of the PI fiber paper was measured by porous material pore size analyzer. Compared with the original PI fibers, the oxygen content of the fiber surface increased after the CNC treatment for the esterification reaction and cross-linking occurred on the fiber surface. The increase in oxygen-containing polar groups and surface roughness on the PI fibers contributed to improved wetting behavior. The contact angle of PI fiber paper with deionized water was reduced by 14.9o, the contact angle with ethanol was reduced by 4.8°, and the fiber dispersion was increased by 45%. These results indicated that the hydrophilicity of the fiber was remarkably improved, and the dispersion property of the fiber in the aqueous phase system was improved. This investigation showed that the method developed herein was an effective technique to prepare high performance organic fibers and corresponding composite materials.

Key words: polyimide fiber, cellulose, nanostructure, graft, esterification, infiltration, dispersion

中图分类号:

TS772

党洪洋,张国亮,龙柱,王士华,李志强,胡爱林,郭帅,吕文志. 纳米结晶纤维素表面修饰聚酰亚胺纤维及其润湿功能性[J]. 化工进展, 2020, 39(1): 301-310.

Hongyang DANG,Guoliang ZHANG,Zhu LONG,Shihua WANG,Zhiqiang LI,Ailin HU,Shuai GUO,Wenzhi LÜ. Surface modified polyimide fiber with nanocrystalline cellulose andits wettability[J]. Chemical Industry and Engineering Progress, 2020, 39(1): 301-310.

图/表 16

表1 聚酰亚胺短切纤维的主要技术参数

长度/mm	直径/μm	密度/g·cm^-3	断裂强度/GPa	断裂伸长率/%
3	11.28	1.41	4.38	13.98

表2 正交实验因素水平表

水平	A/%	B/%	C/h	D/℃
1	2.12	0.4	5	50
2	3.12	0.6	3	70

表3 测试液的表面能（20℃）

测试液	γ _l/mJ·m^-2	$γ i p$ /mJ·m^-2	$γ i p$ /mJ·m^-2
去离子水	72.80	21.80	51.00
乙醇	48.00	23.00	19.00

表3 测试液的表面能（20℃）

测试液	γ _l/mJ·m^-2	$γ i p$ /mJ·m^-2	$γ i p$ /mJ·m^-2
去离子水	72.80	21.80	51.00
乙醇	48.00	23.00	19.00

表4 正交试验结果

样品	A/%	B/%	C/h	D/℃	CA/(°)
PI	—	—	—	—	79.1
PI-1	2.12	0.4	5	70	65.6
PI-2	2.12	0.4	5	50	68.1
PI-3	2.12	0.6	3	70	68.7
PI-4	2.12	0.6	3	50	69.0
PI-5	3.12	0.4	3	70	64.9
PI-6	3.12	0.4	3	50	67.6
PI-7	3.12	0.6	5	70	64.5
PI-8	3.12	0.6	5	50	67.1
Ⅰ	271.4	266.2	264.0	270.8
Ⅱ	263.8	269.0	270.2	263.4
R	7.6	2.8	6.2	7.4

图1 PI纤维表面接枝CNC机理图

图2 CNC处理前后纤维的红外光谱图

图3 CNC处理前后纤维的XPS全扫描图

图4 CNC处理前后纤维的C1s解析图谱

表5 CNC处理前后纤维表面元素含量的变化

样品	各元素质量分数/%			原子比
样品	C1s	N1s	O1s	N/C	O/C
PI	78.02	6.00	15.98	0.08	0.20
PI-CNC	75.39	4.87	19.74	0.06	0.26

图5 CNC处理前后纤维的SEM图

图6 CNC处理前后纤维的TG和DTG图

图7 纤维在水体中的分散状态图

表6 纤维的分散度及纤维成纸的接触角和表面能（20℃）

	分散度f/%	接触角θ/(°)		$γ f d$ /mJ·m^-2	$γ f p$ /mJ·m^-2	γ _f/mJ·m^-2
	分散度f/%	去离子水	乙醇	$γ f d$ /mJ·m^-2	$γ f p$ /mJ·m^-2	γ _f/mJ·m^-2
PI	30	79.1	63.5	18.38	10.63	29.01
PI-CNC	75	64.2	58.7	5.00	33.20	38.20
变化值	+45	–14.9	–4.8	–13.38	+22.57	+9.10

表6 纤维的分散度及纤维成纸的接触角和表面能（20℃）

	分散度f/%	接触角θ/(°)		$γ f d$ /mJ·m^-2	$γ f p$ /mJ·m^-2	γ _f/mJ·m^-2
	分散度f/%	去离子水	乙醇	$γ f d$ /mJ·m^-2	$γ f p$ /mJ·m^-2	γ _f/mJ·m^-2
PI	30	79.1	63.5	18.38	10.63	29.01
PI-CNC	75	64.2	58.7	5.00	33.20	38.20
变化值	+45	–14.9	–4.8	–13.38	+22.57	+9.10

图8 CNC处理前后纤维原纸的接触角

图9 纤维成纸中纤维分布情况

图10 纤维成纸孔径分布

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