马来酸酐接枝氧化石墨烯并改性双马树脂复合材料的微观结构及力学性能

陈宇飞; 田麒源; 董磊; 刘祯达; 吕思呈; 朱莉; 聂鹏

doi:10.13801/j.cnki.fhclxb.20200605.001

马来酸酐接枝氧化石墨烯并改性双马树脂复合材料的微观结构及力学性能

doi: 10.13801/j.cnki.fhclxb.20200605.001

陈宇飞^{1, 2, ,},
田麒源¹,
董磊¹,
刘祯达¹,
吕思呈¹,
朱莉¹,
聂鹏¹

1.
哈尔滨理工大学　材料科学与工程学院，哈尔滨 150040
2.
哈尔滨理工大学　工程电介质及应用技术教育部重点实验室，哈尔滨 150080

基金项目: 国家自然科学基金(51177030)；哈尔滨创新人才专项(2015RAXXJ029)；哈尔滨理工大学创新项目(201910214126)

详细信息

通讯作者:
陈宇飞，博士，教授，研究方向为介电复合材料、高性能航空材料结构与性能　E-mail：chenyufei@hrbust.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2020-03-23
- 录用日期: 2020-05-25
- 网络出版日期: 2020-06-05
- 刊出日期: 2021-01-15

Microstructure and mechanical properties of bismaleimide composite modified by graphene oxide grafting with maleic anhydride

1.
College of Materials Science and Engineering, Harbin University of Science and Technology, Harbin 150040, China
2.
Key Laboratory of Engineering Dielectrics and its Application, Ministry of Education, Harbin University of Science and Technology, Harbin 150080, China

摘要

摘要: 采用改进的Hummers法制备了氧化石墨烯(GO)，并用马来酸酐(MAH)接枝改性制得MAH接枝氧化石墨烯(MAH-GO)。以二烯丙基双酚A (BBA)和双酚A双烯丙基醚(BBE)为活性稀释剂，4,4’-二氨基二苯甲烷型双马来酰亚胺(MBMI)为反应单体合成MBMI-BBA-BBE (MBAE)树脂基体；并以MAH-GO为增强体通过原位聚合制得MAH-GO/MBAE复合材料，表征MAH-GO的微观结构及其对复合材料力学性能的影响。结果表明：MAH成功接枝在GO表面，片层结构清晰，且表面出现褶皱，采用化学滴定法测定接枝率约为11.32%。MAH-GO/MBAE复合材料的微观形貌结果表明，当适量的MAH-GO加入体系中后，MAH-GO/MBAE复合材料断裂纹呈“树枝状”无规则发散，为典型的韧性断裂。当MAH-GO添加量为0.5wt%时，MAH-GO在基体中分散均匀，MAH-GO/MBAE复合材料的冲击强度和弯曲强度分别为15.88 kJ/m²和142.13 MPa，比基体树脂分别提高了67.68%和43.61%，力学性能得到明显改善。
- 双马来酰亚胺 /
- 氧化石墨烯 /
- 马来酸酐 /
- 微观结构 /
- 力学性能
Abstract: Graphene oxide (GO) was prepared by improved Hummers method and to obtain maleic anhydride (MAH)-GO by graft modification with MAH. 4,4’-diamino diphenyl methane bismaleimide (MBMI) resin as the reactive monomer, diallyl bisphenol A (BBA) and bisphenol A bisallyl ether (BBE) as reactive diluents, MBMI-BBA-BBE (MBAE) resin matrix was synthesized. The MAH-GO/MBAE composites were prepared by in-situ polymerization, the microstructure of MAH-GO was characterized and the effect of the reinforcement on mechanical properties of the MAH-GO/MBAE composites was studied. The results show that MAH is successfully grafted on the surface of GO, with clear lamellar structure and folds on the surface, and the graft rate is determined by chemical titration to be about 11.32%. The micromorphology of MAH-GO/MBAE composites shows that the fracture cracks are irregularly divergent and are typical ductile fracture, when MAH-GO is an appropriate amount and uniformly dispersed in the matrix resin. The impact strength and the bending strength of the MAH-GO/MBAE composite are 15.88 kJ/m² and 142.13 MPa, which are 67.68% and 43.61% higher than that of the matrix resin, respectively, when the content of MAH-GO is 0.5wt%. The mechanical properties have been improved obviously.
- bismaleimide /
- graphene oxide /
- maleic anhydride /
- microstructure /
- mechanical properties

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图 1 马来酸酐接枝氧化石墨烯(MAH-GO)的反应机制

Figure 1. Reaction mechanism of graphene oxide grafted by maleic anhydride (MAH-GO)

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图 2 石墨、GO和MAH-GO的FTIR图谱

Figure 2. FTIR spectra of graphite, GO and MAH-GO

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图 3 石墨粉、GO和MAH-GO的XRD图谱

Figure 3. XRD patterns of graphite powder, GO and MAH-GO

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图 4 GO和MAH-GO的SEM图像

Figure 4. SEM images of GO and MAH-GO

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图 5 1天和30天后MAH-GO在溶剂中的分散情况的照片

Figure 5. Photos of MAH-GO dispersing in solvents after 1 day and 30 days

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图 6 MAH-GO/MBAE复合材料的SEM图像

Figure 6. SEM images of MAH-GO/MBAE composites

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图 7 GO/MBAE和MAH-GO/MBAE复合材料的冲击强度和弯曲强度

Figure 7. Impact strength and bending strength of GO/MBAE and MAH-GO/MBAE composites

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表 1 MAH-GO/(MBMI-BBA-BBE) (MBAE)复合材料的配方

Table 1. Formulation of MAH-GO/(MBMI-BBA-BBE) (MBAE) composites

Composite	MAH-GO mass fraction/wt%
MBAE	0
MAH-GO/MBAE1	0.1
MAH-GO/MBAE2	0.3
MAH-GO/MBAE3	0.5
MAH-GO/MBAE4	0.7
MAH-GO/MBAE5	0.9
Notes: MBMI—4,4'-diamino diphenyl methane bismaleimide resin; BBA—Diallyl bisphenol A; BBE—Bisphenol A bisallyl ether.

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