多酚改性纤维增强聚合物基复合材料研究进展

方策; 宋立健; 丁玉梅; 谭晶; 杨卫民; 程礼盛

多酚改性纤维增强聚合物基复合材料研究进展

方策¹,
宋立健^{1, 3},
丁玉梅¹,
谭晶¹,
杨卫民^{1, 2},
程礼盛^{1, 2, ,}

1.
北京化工大学　机电工程学院, 北京 100029
2.
有机无机复合材料国家重点实验室, 北京 100029
3.
中国石化　北京化工研究院, 北京 100013

基金项目: 国家自然科学基金 (52073012)

详细信息

通讯作者:
程礼盛，博士，副教授，硕士生导师，研究方向为高分子材料先进制造　E-mail: chengls@mail.buct.edu.cn

中图分类号: (TB331)
计量
- 文章访问数: 67
- HTML全文浏览量: 54
- 被引次数: 0
出版历程
- 收稿日期: 2023-02-22
- 修回日期: 2023-03-23
- 录用日期: 2023-04-05
- 网络出版日期: 2023-04-19

Research progress on polyphenols modified fiber reinforced polymer composites

Ce FANG¹,
Lijian SONG^{1, 3},
Yumei DING¹,
Jing TAN¹,
Weimin YANG^{1, 2},
Lisheng CHENG^{1, 2
, ,}

1.
College of Mechanical and Electrical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
2.
State Key Laboratory of Organic-Inorganic Composites, Beijing 100029, China
3.
Beijing Research Institute of Chemical Industry, Sinopec Corporation, Beijing 100013, China

Funds: National Natural Science Foundation of China(No. 52073012)

摘要

摘要: 目的纤维增强聚合物基复合材料已被广泛应用于航空航天、汽车制造、特种设备生产等领域，复合材料的整体性能由多种因素决定，其中纤维和基体的结合强度至关重要，较低的界面结合将导致复合材料的整体力学性能降低。多酚是常见的植物次生代谢物，作为纤维与基体间的粘合剂能够有效改善纤维增强聚合物基复合材料力学性能并丰富其功能特性，避免改性过程中的高污染、高耗能、使人体暴露在危险化学环境下等问题，研究并使用生态友好的多酚对复合材料进行改性符合当下绿色、可持续化应用的发展要求。方法本文对目前纤维增强聚合物基复合材料改性所使用的多酚结构和特性进行了总结，同时介绍了多酚在纤维表面制备改性涂层的方法及改性纤维增强聚合物基复合材料的应用，最后对多酚改性的未来研究方向和重点进行了展望。结果多酚中含有大量疏水芳香环和酚羟基，目前研究并运用在纤维增强聚合物基复合材料改性方面的多酚化学物质，主要包括邻苯二酚、多巴胺、没食子酸和单宁酸。多酚在纤维表面制备改性涂层的方法包括：① 自聚合：指不依赖其余化学物质，仅通过自身被氧化的方式在纤维表面发生聚合形成涂层，并能通过二次修饰将其他改性材料结合在涂层上。② 共沉积：指在多酚自聚合过程中添加其他组分，使其他组分也能进入并富集在自聚合后的涂层中。共沉积改性方法可以通过改变共沉积组分的含量和分子结构来容易地调节涂层表面性质，为纤维表面快速稳定的制备多酚涂层提供了思路。多酚改性纤维增强聚合物基复合材料的应用主要分为四个方面：(1)改善力学性能：多酚聚合后良好的黏附性能，其改性能够增加纤维的表面粗糙度和提升基体的浸润性，极大的提升了纤维与基体间的结合强度，改善复合材料的力学性能。(2)抗紫外：多酚结构中含有的大量苯羟基和醌基团能够清除自由基及活性氧，可以降低紫外光对复合材料的光氧化作用，提高材料抗紫外稳定性。(3)阻燃：多酚可以清除燃烧过程中产生的自由基，并通过热解反应产生碳烟、碳及炭黑，隔绝气体和热源的接触，从而提高材料的阻燃性能。(4)抗水热老化：多酚改性改善了纤维与基体之间的机械互锁和界面相互作用，提升了其耐水热老化性能。结论多酚作为一种具有绿色发展前景的改性材料，其改性具有方法简单、反应条件温和、不损伤纤维表面且环境友好等特性。多酚改性能够赋予纤维增强聚合物基复合材料更多元化的功能，进一步拓展其应用范围。多酚改性仍有很大的发展空间，主要包括：(1)增强对多酚聚合沉积机制的探讨。(2)对多酚改性过程进行改良与优化。(3)进一步开发多酚改性的功能型复合材料。
- 纤维增强聚合物基复合材料 /
- 改性方法 /
- 多巴胺 /
- 邻苯二酚 /
- 没食子酸 /
- 单宁酸
Abstract: Polyphenols are compounds with abundant phenolic hydroxyl groups which can be widely found in natural plants. Polyphenols can interact with the various materials to form hydrogen bonds, metal coordination and π-π interactions. Over the past few years, polyphenols have been widely applied in material functional modifications. In this paper, the structures and properties of polyphenols, including dopamine, catechol, gallic acid and tannic acid were reviewed. Meanwhile, the modification methods of fiber surface and the applications of fiber reinforced polymer composites were introduced. Finally, a prospective analysis on the future research direction and focus of polyphenol modification studies were provided.
- fiber reinforced polymer composites /
- method of modification /
- dopamine /
- catechol /
- gallic acid /
- tannic acid

HTML全文

图 1 不同多酚结构：(a) 邻苯二酚(CL)；(b) 多巴胺(DA)；(c) 没食子酸(GA)；(d) 单宁酸(TA)

Figure 1. Structure of polyphenols: (a) Catechol(CL); (b) Dopamine(DA); (c) Gallic acid(GA); (d)Tannic acid(TA) `

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图 2 多酚与其它材料之间的相互作用^[33]

Figure 2. Various interactions between polyphenols with different materials^[33]

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图 3 在碳纤维(CF)上制作“砖混”结构示意图^[34]

Figure 3. Schematic illustration of fabrication of brick-and-mortar wall on the carbon fiber(CF)^[34]

CF—Carbon fiber; PDA—Polydopamine; PNi—Polydopamine-Ni(OH)₂

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图 4 (a) CF共沉积处理工艺示意图; (b) 不同复合材料的 IFSS ；(c) CF复合材料的界面增强机制 ^[48]

Figure 4. (a) Schematic illustration of co-deposition treatment procedure of CF; (b) IFSS of different composites; (c) Interfacial enhancement mechanism of CF composites^[48]

APTES—Aminopropyltriethoxysilane

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图 5 超高分子量聚乙烯(UHMWPE)纤维的TA表面改性工艺图^[49]

Figure 5. Scheme diagram of TA surface modification to Ultra high molecular weight polyethylene(UHMWPE) fiber^[49]

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图 6 碳纤维增强复合材料(CFRP)断口表面的SEM图像: (a) 原始 CF/RPU 复合材料: (b) (CF-Ni)/RPU 复合材料; (c), (d) (CF-TA-Ni)/RPU 复合材料^[67]

Figure 6. SEM images of the Carbon Fibre Reinforced Polymer (CFRP) fractured surface: (a) pristine CF/RPU composites; (b) (CF-Ni)/RPU composites; (c), (d) (CF-TA-Ni)/RPU composites^[67]

RPU—Rigid polyurethane

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图 7 TA混合物2 h内颜色变化(a)及紫外吸收光谱(b) ^[75]

Figure 7. (a) The color change of TA mixed solution before and after 2 hours; (b) The UV absorption spectra for the mixtures^[75]

DPPH—(2,2-diphenyl-1-picrylhydrazyl); BA—Boric acid; MEL—Melamine

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图 8 垂直燃烧试验中CFRP在不同时间的代表性图像^[78]

Figure 8. Images during vertical burning test at different times. Flame was applied for 10 s to CFRP samples for ignition ^[78]

DGEBA—Diglycidyl ether bisphenol A

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表 1 多酚对纤维改性处理

Table 1. Fiber modification by polyphenols

Fiber	Matrix	Main compositions of coating	Performances	References
Carbon fiber	Epoxy	GAGelatin	IFSS：85.6 MPaSurface energy of $ {\gamma }^{P} $:75.41 $ {\rm{mN}}\cdot {{\rm{m}}}^{-1} $	^[59]
Polyester fiber	None	GAEthylenediamine (EDA)	Water contact angle reduced by $ 57.2° $The tensile strength of the modified fiber paper (2.022 kN/m) were increased by 35.2%	^[60]
Carbon fiber	Polyimide (PI)	PDAFe³⁺ mineralization (β-FeOOH)	Tensile strength:202.5 MPaTensile modulus:7.445 GPaLow wear rates under different sliding speed (5 N, 200-500 r/min, 60 min)	^[61]
Carbon fiber	Nanosilica Epoxy	PDA	After the 3-week salt spray test, the ILSS value of the PDA-SiO₂CFRP laminate is still 11% higher than that of the unmodified CFRP.	^[62]
Glass fiber	None	PDAAg nanoparticles	Conductivity：$ 2.49\times {10}^{6}\;{\rm{S}}{\cdot {\rm{m}}}^{-1} $Great flexibility (could easily operate as a conductive wire for a LED light even under various bending angles)	^[52]
UHMWPE fiber	Rubber	CLTEPANano zinc oxide (ZnO NPs)	Water contact angle：$ 36.2° $Surface energy：$ 37.8\; {\rm{mJ}}/{{\rm{m}}}^{2} $Pull-out force：32.3 N	^[63]
PET fiber	Epoxy	CLPEI	Water contact angle：$ 58.9° $The fabric melting temperature and decomposition temperature increased from 253.78℃ and 394.08℃ to 255.01℃ and 398.21℃, respectively.	^[64]
Polyamides fiber	None	TAThiophene	Conductivity：$ 45 {\rm{k}}\Omega \cdot {\rm{c}}{{\rm{m}}}^{-1} $Electrothermal Performance (within 75 s, the temperature rises from 26.8 to 29.1℃ and basically reaches a robust level)	^[51]
Wood fiber	None	TAFe (II) ions	Surface area is increased 66.8% by TAThe complexes promote the pyrolysis of wood fibers at lower temperature (162℃) and generate more residual char (110%)	^[65]

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