高亲水性环氧树脂的制备及对碳纤维的表面处理

doi:10.7503/cjcu20160459

摘要/Abstract

摘要：

在三乙胺催化下, 以己二酸和环氧树脂制备了己二酸改性环氧树脂(AAEP), 通过考察反应温度等因素对己二酸转化率和AAEP环氧值的影响, 得到了AAEP合成的最佳条件. 用傅里叶变换红外光谱和核磁共振对AAEP进行了表征. 用KOH中和AAEP得到己二酸改性环氧树脂钾盐(AAEPK), 测试了AAEPK乳液的性质和AAEPK处理后碳纤维的分散性, 并通过场发射扫描电子显微镜和X射线光电子能谱对碳纤维的表面形貌和基团进行了研究. 结果表明, AAEPK具有高亲水性, 适用于碳纤维处理剂, 当AAEPK的浓度和吸附量分别为1.0%(质量分数)和3.0 mg/g时, 处理剂可在纤维表面均匀分布, 使得碳纤维在树脂基体中的分散性得到改善. 研究了处理剂对碳纤维/环氧树脂复合材料弯曲和剪切性能的影响, 发现处理后碳纤维短丝/环氧树脂复合材料的弯曲强度和碳纤维布/环氧树脂复合材料的层间剪切强度较未处理的试样分别增加了168%和113%, 说明AAEPK处理后碳纤维在基体中分散性和黏结性的提高是碳纤维/环氧树脂复合材料力学性能提高的主要原因.

关键词: 己二酸, 环氧树脂, 亲水性, 碳纤维, 处理剂

Abstract:

Adipic acid modified epoxy resin(AAEP) was elaborated with adipic acid and epoxy resin using triethylamine as the catalyst. To optimize the reaction conditions, the effects of synthetic parameters were investigated on the conversion rate of adipic acid and the epoxy value of AAEP. Fourier transform infrared(FTIR) and nuclear magnetic resonance(¹H NMR) were used to characterize the chemical structures of AAEP. Then, the AAEP was neutralized with KOH to obtain the hydrophilic potassium adipic acid modified epoxy resin(AAEPK), which can be employed as a treating agent for carbon fiber(CF) in order to improve the dispersion and adhesive effect of CFs in the resin matrix. The selected concentration and adsorption amount were 1.0% and 3.0 mg/g according to the evaluation of the AAEPK emulsion properties and the CFs dispersion. In addition, the surface morphology and groups of treated CFs were assessed by Field emission scanning electron microscope(FE-SEM) and X-ray photoelectron spectroscopy(XPS). The results indicate that AAEPK is evenly distributed on the CF surface, and the dispersion of CFs in the resin matrix is improved dramatically. Furthermore, the flexural strength of treated chopped CF composite and interlaminar shear strength(ILSS) of treated CF cloth composite were proved to increase by 168% and 113%, which evaluates that the primary actions of AAEPK improving the mechanical properties of CF/epoxy resin composite was the improvement of dispersion and interface adhesive effect between CFs and the matrix.

Key words: Adipic acid, Epoxy resin, Hydrophilicity, Carbon fiber, Treating agent

中图分类号:

O631
TQ342

TrendMD:

吴波, 郑帼, 刘旭钊, 孙玉, 刘会兵, 朱佳文. 高亲水性环氧树脂的制备及对碳纤维的表面处理. 高等学校化学学报, 2016, 37(10): 1891.

WU Bo, ZHENG Guo, LIU Xuzhao, SUN Yu, LIU Huibing, ZHU Jiawen. Preparation of High Hydrophilic Epoxy Resin and Its Treatment on Carbon Fiber Surface^†. Chem. J. Chinese Universities, 2016, 37(10): 1891.

图/表 13

Scheme 1 Preparation of AAEPK

Fig.1 Effect of molar ratio(A), reaction temperature(B), reaction time(C) and content of catalyst(D) on conversion of adipic acid and epoxy value of AAEP

Fig.2 FTIR spectra of E44 epoxy resin(a) and AAEPK(b)

Fig.3 1H NMR spectra of E44 epoxy resin(A) and AAEPK(B)The peaks are corresponding to the positions of chemical structures in Scheme 1.

Table 1 Influence of epoxy value of AAEPK on the emulsion centrifugal stability

Epoxy value/(mmol·g^-1)	0.2	0.3	0.4	0.5	0.6	0.7	0.8	0.9	1.0
Precipitation mass/g	0	0	0	0.001	0.002	0.056	0.093	0.125	0.180

Fig.4 Influence of concentration and epoxy value of AAEPK on the emulsion surface properties(A) Surface tension; (B) contact angle.

Fig.5 Influence of epoxy value of AAEPK on the emulsion size distributionEpoxy value/(mmol·g-1): (A) 0.4; (B) 0.6; (C) 0.8; (D) 1.0. The peak values are corresponding to the peak areas.

Fig.6 Influence of adsorption amount of AAEPK on the CFs dispersion

Table 2 Element compositions of the surfaces of CF and CF-AAEPK

Sample	Element content(%)
Sample	C	O	N
CF	82.95	10.99	1.92
CF-AAEPK	72.73	22.74	1.35

Fig.7 FE-SEM images of CFs treated by AAEPKAdsorption amount of AAEPK/(mg·g-1): (A) 0; (B) 1.0; (C) 2.0; (D) 3.0; (E) 4.0; (F) 5.0.

Fig.8 C1s XPS spectra of untreated CF(A) and CF-AAEPK(B)

Fig.9 Mechanical property of CF/epoxy resin composites(A) Flexural strength of chopped CF/epoxy resin composites; (B) ILSS of CF cloth/epoxy resin composites. ILSS: interlaminar shear strength.

Fig.10 FE-SEM images of the fractured surfaces of the CF cloth/epoxy resin composites(A) CF composite; (B) AAEPK-CF composite. Insets are the partial enlangement to the FE-SM images.

参考文献 24

[1]	Vishkaei M. S., Salleh M. A. M., Yunus R., Biak D. R. A., Danafar F., Mirjalili F., J. Compos. Mater., 2011, 45(18), 1885—1891
[2]	Ren F.Z., Fabrication and Performance of Short Carbon Fiber Reinforced Magnesium-based Composite, Chongqing University, Chongqing, 2011
	(任富忠. 短碳纤维增强镁基复合材料的制备及其性能的研究, 重庆: 重庆大学, 2011)
[3]	Tiedje E. W., Guo P., J. Mater. Civil. Eng., 2014, 26(7), 06014013-1—06014013-4
[4]	Giraud I., Franceschi-Messant S., Perez E., Lacabanne C., Dantras E., Appl. Surf. Sci., 2013, 266, 94—99
[5]	Wen J., Xia Z., Choy F., Compos. Part B: Eng., 2011, 42(1), 77—86
[6]	Vogt-Birnbrich B., Awokola M. G., Beyers H., Aqueous Dispersions of Epoxy Resins, US 6258875 B1, 2001-07-10
[7]	Li J., Li P., Cai Q., Yang X. P., New Chemical Materials, 2015, 43(1), 178—181
	(李晋, 李鹏, 蔡晴, 杨小平. 化工新型材料 2015, 43(1), 178—181)
[8]	Su Y. Q., Tang B. J., Dong A. Q., Zhao Y., Zhang Z. G., Acta Materiae Compositae Sinica, 2011, 28(6), 80—85
	(苏玉芹, 汤冰洁, 董安琪, 肇研, 张佐光.复合材料学报, 2011,28(6), 80—85)
[9]	Yuan C. D., Duan C. H., Xu Y. S., Cao T. Y., Thermosetting Resin, 2007, 22(2), 19—22
	(袁才登, 段春华, 许涌深, 曹同玉.热固性树脂, 2007,22(2), 19—22)
[10]	Zhang Z. Y., Huang Y. H., Liao B., Cong G. M., Chem. J. Chinese Universities, 2002, 23(5), 974—978
	(张肇英, 黄玉惠, 廖兵, 丛广民.高等学校化学学报, 2002,23(5), 974—978)
[11]	Huang X.X., Preparation of Hydrophobic and Oleophilic Waterborne Epoxy Emulsion and Its Application to Water/Oil Separation Filter Paper, South China University of Technology, Guangzhou, 2012
	(黄相璇. 超疏水/超亲油水性环氧树脂乳液涂层的制备及在油水分离滤纸中的应用研究, 广州: 华南理工大学, 2012)
[12]	Li C., Guo L. M., Technical Textiles, 2011, 29(6), 40—42
	(李超, 郭腊梅.产业用纺织品, 2011,29(6), 40—42)
[13]	GB/T2895-2008, Plastics-polyester Resin-determination of Partial Acid Value and Total Acid Value, Standard Press of China, Beijing, 2008
	(GB/T2895-2008GB/T2895-2008. 塑料聚酯树脂部分酸值和总酸值的测定, 北京: 中国标准出版社, 2008)
[14]	GB/T1677-2008, Determinating the Epoxy Value of Plasticizers, Standard Press of China, Beijing, 2008
	(GB/T1677-2008.增塑剂环氧值的测定, 北京: 中国标准出版社, 2008)
[15]	GB/T22237-2008, Surface Active Agents-determination of Surface Tension, Standard Press of China, Beijing, 2008
	(GB/T22237-2008GB/T22237-2008. 表面活性剂表面张力的测定, 北京: 中国标准出版社, 2008)
[16]	GB/T24368-2009, Test Method for Hydrophobic Contamination on Glass by Contact Angle Measurement, Standard Press of China, Beijing, 2009
	(GB/T24368-2009GB/T24368-2009. 玻璃表面疏水污染物检测接触角测量法, 北京: 中国标准出版社, 2009)
[17]	Jung M. J., Ju W. K., Ji S. I., Park S. J., Lee Y. S., J. Ind. Eng. Chem., 2009, 15(3), 410—414
[18]	Yang Y., Cement. Concrete. Res., 2002, 32(5), 747—750
[19]	GB/T1449-2005, Fiber-reinforced Plastic Composites-determination of Flexural Properties, Standard Press of China, Beijing, 2005
	(GB/T1449-2005. 纤维增强塑料弯曲性能试验方法, 北京: 中国标准出版社, 2005)
[20]	JC/T773-2010, Fibre-reinforced Plastics Composites-Determination of Apparent Interlaminar Shear Strength by Short-beam Method, Standard Press of China, Beijing, 2010
	(JC/T773-2010. 纤维增强塑料短梁法测定层间剪切强度, 北京: 中国标准出版社, 2010)
[21]	Deng X., Mammen L., Butt H. J., Vollmer D., Science, 2012, 335(6064), 67—70
[22]	Cheng Q., Tang J., Zhang H., Qin L. C., Chem. Phys. Lett., 2014, 616/617, 35—39
[23]	Sun H., Guo G., Memon S. A., Xu W., Zhang Q., Zhu J. H., Compos. Part A: Appl. S., 2015, 78, 10—17
[24]	Song H. H., Oh H. J., Lee H. C., Kim S. S., Compos. Part. B: Eng., 2013, 45(1), 172—177