纺织学报 ›› 2023, Vol. 44 ›› Issue (06): 21-27.doi: 10.13475/j.fzxb.20230100402

• 纺织科技新见解学术沙龙专栏: 高品质芳纶生产关键技术及其产品应用 • 上一篇    下一篇

基于直接氟化技术的芳纶表/界面结构设计与制备研究进展

吕钧炜1,2, 罗龙波1,2, 刘向阳1,2()   

  1. 1.四川大学 高分子科学与工程学院, 四川 成都 610065
    2.四川大学 高分子材料工程国家重点实验室,四川 成都 610065
  • 收稿日期:2023-01-03 修回日期:2023-03-20 出版日期:2023-06-15 发布日期:2023-07-20
  • 通讯作者: 刘向阳
  • 作者简介:吕钧炜(1996—),男,博士生。主要研究方向为高性能高分子材料及其表/界面可控设计。
  • 基金资助:
    国家重点研发计划项目(2022YFB3707900);国家自然科学基金项目(51633004);国家自然科学基金项目(52173008)

Advances in design and fabrication of aramid fiber's surface and interface structure based on direct fluorination

LÜ Junwei1,2, LUO Longbo1,2, LIU Xiangyang1,2()   

  1. 1. College of Polymer Science and Engineering, Sichuan University, Chengdu, Sichuan 610065, China
    2. State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu, Sichuan 610065, China
  • Received:2023-01-03 Revised:2023-03-20 Published:2023-06-15 Online:2023-07-20
  • Contact: LIU Xiangyang

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摘要：

直接氟化技术作为一种高效、低成本以及可规模化应用的表面处理手段,已广泛应用于材料表面及其复合材料界面的结构设计与调控,以改善复合材料界面的应力传递及其制件的宏观力学性质。从直接氟化技术的原理出发,首先介绍了直接氟化的反应机制、应用领域及当前研究进展,并重点关注了直接氟化技术在纤维表面及复合材料界面的结构设计领域中的应用。同时,根据直接氟化在纤维表面引入的不同活性中心的差异,将直接氟化对纤维表面结构设计的发展历程归纳为3个主要研究阶段:直接氟化调控纤维表面的结构及极性、在纤维表面引入C—F键作为活性中心的衍生接枝反应和在纤维表面引入自由基作为活性中心的衍生接枝反应。最后,针对直接氟化技术的优势和工艺特点,展望了直接氟化技术在复合材料结构设计领域的应用潜力、存在的问题和发展趋势。

关键词: 芳纶, 表面处理, 界面结构设计, 直接氟化技术, 纤维复合材料

Abstract:

Significance Due to the advantages of low density, high strength, excellent environmental stability and wave-transparent of aramid fiber, it is gradually becoming the most important representative fiber in the high-performance organic fiber family. Among the wide range of applications of aramid fiber, the use as reinforcements in advanced composites might be the most important. However, poor interfacial interaction between aramid fiber and composite matrix has been a key issue to limit further mechanical improvements in composite design. Herein, direct fluorination using elemental fluorine or F2/N2 mixture to direct treat aramid fiber surface is efficient strategy to enhance composite interface. Utilizing the ultra-strong oxidation of F2, direct fluorination could easily dope fluorine content groups with high polarity in a large scale to improve wettability between fiber and matrix, while post-purification is needed due to the characteristic of vapor-solid reaction. Besides, direct fluorination induced C—F bonds also have significant designability in derived grafting reactions for further well-performed composite interface. Therefore, direct fluorination exhibits huge potential in the future composite design and manufacturing.
Progress Advances of direct fluorination in enhancing composite interface could be divided into three stages: ① Direct fluorination induced high-polar fluorine-contained groups and extra oxygen species significantly improves the interfacial wettability between fiber and polymer matrix, where the optimized interfacial wettability would enhance the interfacial combination of the composite; ② C—F bonds not only have high polarity, but also exhibit flexible feasibility in deriving reactions like nucleophilic substitution and atom transfer radical polymerization, thus further grafting reaction could be realized on fluorinated aramid fiber surface to obtain better composite interfacial properties; ③ Direct fluorination with typical radical characteristic induces significant radical species in fluorinated aramid fiber, then the relevant polymerization with high grafting density could be restricted on fluorinated aramid surface and got much better composite interface. Therefore, direct fluorination exhibited flexible ability in designing numerous high-performance interfacial structures of composite product servicing in different environments.
Conclusion and Prospect In previous research work, it has been demonstrated that direct fluorination is a low-cost and industrially applicable fiber surface treatment technique that can significantly improve the surface properties of fibers and their interfacial bonding with the polymer matrix while maintaining the intrinsic excellent mechanical properties of the fibers, thus improving the mechanical properties of the interfacial phase in the composite. In fact, further development and application of direct fluorination technology in the design and construction of interfacial structures for fiber surface modification and its reinforced composites is still needed, which is expected to better solve potential scientific and technical problems in the development of the mechanics of fiber-reinforced composites and provide new methods for the modulation of fiber surface modification and its interfacial properties of composites. Three problems and trends in the research of direct fluorinated aramid surface modification and its composite interface are listed as follows: ① Due to the high chemical reaction activity of fluorine gas, the current principles and methods of its regulation are insufficient, how to more effectively regulate the fluorination reaction rate and the selectivity of fluorination reaction sites, as well as how to more effectively avoid the chain-breaking behavior of macromolecular chains are the focus of further research and development of direct fluorination technology; ② It is necessary to construct continuous gradient changing polar structures and their interfacial properties on the fiber surface through direct fluorination reactions and their derivative grafting reactions, so as to more accurately describe and establish the quantitative constitutive relationship between the physicochemical structure of the fiber surface and the fine mechanics of the composite interface; ③ More efficient methods and corresponding engineering equipment are in high demand for regulating the homogeneity of direct fluorinated fibers.

Key words: aramid fiber, surface treatment, interface structure design, direct fluorination, fiber composite material

中图分类号: 

  • TS195.6

图1

直接氟化处理芳纶纤维和PBO纤维的反应机制"

图2

金属离子催化选择性氟化芳纶纤维的机制示意图"

图3

氟化芳纶表面引发羟乙基甲基丙烯酸酯接枝聚合的原理及其表面形貌 注:Ph和Bpy分别代表苯环和2,2'-联吡啶。"

图4

直接氟化引入自由基引发的芳纶表面自由基聚合反应过程和机制"

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