超临界流体回收碳纤维树脂复合材料

碳纤维树脂复合材料回收再利用是碳纤维产业可持续发展的重要一环,因此受到学术界及产业界的广泛关注。 超临界流体回收碳纤维方法是一种高效、清洁,并且对碳纤维性能损伤较小的回收方法。 本文回顾了超临界流体回收碳纤维树脂复合材料研究进展,系统讨论超临界体系、反应条件、催化剂等对树脂降解率、回收碳纤维性能的影响,并对超临界流体回收碳纤维树脂复合材料的未来发展进行了展望。     

以2-苯基-4,4'-二氨基二苯醚为基础的热固性聚酰亚胺树脂及其复合材料

以2-苯基-4,4'-二氨基二苯醚(p-ODA)、异构二苯醚二酐(ODPA)和苯乙炔基苯酐(PEPA)为原料,通过两步法合成了聚合度分别为1,2和3的酰亚胺树脂低聚物,并通过模压成型法制备了单向碳纤维增强的聚酰亚胺复合材料.表征了酰亚胺树脂低聚物的溶解性、熔体黏度及其固化物聚酰亚胺树脂的热性能,结果表明,聚酰亚胺树脂具有良好的溶解性,在N,N-二甲基乙酰胺(DMAc)、四氢呋喃(THF)及1,4-二氧六环等溶剂中的溶解度大于30%;所有酰亚胺树脂低聚物的最低熔体黏度均在10 Pa·s以下,具有良好的成型工艺性;聚酰亚胺树脂具有良好的热性能,玻璃化转变温度(Tg)最高可达300℃,5%热失重温度(T5%)最高可达545℃,碳纤维增强聚酰亚胺复合材料PIC-4,4'-ODPA-2具有最佳的高低温力学性能.     

耐高温可溶性聚酰亚胺树脂及其复合材料

制备了2种耐高温可溶型聚酰亚胺树脂(PI-1, PI-2)及其复合材料, 系统研究了树脂的工艺性, 纯树脂固化物的热性能及其复合材料的界面形貌、 介电性能和力学性能. 研究结果表明, 树脂低聚物在极性非质子溶剂中具有良好的溶解性, 且熔体黏度较低, 表明其具有优异的加工性能. 两种树脂固化物在空气中的5%热失重温度均高于550 ℃, PI-1树脂的玻璃化转变温度(T_g)为430 ℃, PI-2树脂的T_g为380 ℃. 石英纤维/PI-1和石英纤维/PI-2复合材料具有较低的介电常数和介电损耗. 碳纤维/PI-1复合材料在420 ℃下的弯曲强度保持率可达62%, 层间剪切强度保持率可达48%, 具有较优异的高温力学性能. 采用普通模压工艺制备了厚度高达45 mm的复合材料制件, 进一步证明这2种树脂具有优异的工艺性.     

耐高温端乙炔基聚醚酰亚胺改性含硅芳炔树脂

采用预共聚法,以含硅芳炔树脂(PSA)和端乙炔基聚醚酰亚胺(PEI)为原料,制备了端乙炔基聚醚酰亚胺改性的含硅芳炔(PEI-PSA)树脂及其与T300碳纤维平纹布的复合材料T300/PEI-PSA。通过动态热机械分析(DMA)和X射线能谱仪(EDS)研究了溶剂、溶液浓度、反应温度对预共聚反应的影响,确定了预共聚反应的最佳条件,得到了均匀分散的PEI-PSA树脂。通过红外光谱(FT-IR)、核磁共振氢谱(1 H-NMR)、差示扫描量热(DSC)、热失重(TG)、DMA和EDS等表征了PEI、PEI-PSA树脂及T300/PEI-PSA复合材料的结构和性能。结果表明,当PEI质量分数为20%时,PEI-PSA树脂浇铸体的弯曲强度达44.5 MPa,较PSA树脂浇铸体提高了90.2%;T300/PEI-PSA复合材料的弯曲强度达602.7 MPa,较T300/PSA复合材料的弯曲强度提高了124%。     

邻苯二甲腈基联苯酚醛树脂中空微球的制备与性能研究

以苯酚及4,4′-二氯甲基联苯为单体,盐酸作催化剂经Friedel-Crafts烷基化反应,合成了联苯酚醛(BN)树脂,并在此基础上通过BN树脂和4-硝基邻苯二甲腈发生亲核反应合成了邻苯二甲腈基联苯酚醛(PBN)树脂,采用高温发泡法制备了邻苯二甲腈基联苯树脂中空微球.利用红外吸收光谱(FTIR)、核磁氢谱(~1H-NMR)、凝胶渗透色谱(GPC)、热失重(TG)以及扫描电子显微镜(SEM)等对制备的PBN树脂以及PBN中空微球进行了结构与性能表征.研究结果表明,采用自固化和固化剂固化的PBN树脂中空微球均已完全固化,2种固化产物中都形成了异吲哚啉和酞菁环结构,固化剂固化产物中还有三嗪环结构的形成.PBN树脂的自固化产物和固化剂固化产物固化物在1000°C氩气氛围残炭率分别为67%和70%,在600°C空气氛围残炭率分别为70%和47%.PBN树脂中空微球粒径分布范围为350~800μm,数均粒径和体积平均粒径分别为562和583μm,单分散指数为1.04.     

氨基硅油改性碳纤维/环氧树脂复合材料的耐老化性能

通过在复合树脂基体中引入氨基硅油进行改性,制备了不同氨基硅油含量的碳纤维/环氧树脂复合材料,在湿热环境下进行老化实验后,通过动态热机械分析(DMA)、热重分析(TGA)、拉伸性能测试、扫描电镜(SEM)及接触角测定等方法研究氨基硅油对于碳纤维/环氧树脂复合材料热力学性能、力学强度保持率和耐水性能的改善效果。实验结果表明,经老化实验后含氨基硅油材料的抗拉强度保持率最高提升了13.23%。当氨基硅油含量为8 wt%时,复合材料表面接触角均值大于90~o。氨基硅油对环氧树脂基体的改性可改善碳纤维/环氧树脂复合材料的耐湿热老化性能。     

超临界正丁醇对回收碳纤维复合材料的降解及表征

采用响应面分析方法设计超临界正丁醇降解废弃的碳纤维/环氧树脂(CF/EP)复合材料降解实验,用以回收碳纤维.通过Design-Expert V8.0建立环氧树脂降解率和工艺参数之间的数学模型,获得了最优工艺参数;通过图形优化研究了工艺参数对环氧树脂基体降解率的影响规律;通过场发射电子扫描显微镜、原子力显微镜、X射线光电子能谱仪、显微共焦激光拉曼光谱仪及单丝拉伸等分析最优工艺参数下回收的碳纤维的表面形貌、表面化学、石墨化程度及力学性能.结果表明,建立的数学模型拟合误差范围为±5.5%,实现了回收工艺参数的预估;单因素对环氧树脂基体降解率的影响程度为:反应温度保温时间添加剂浓度正丁醇含量;最优工艺参数为:反应温度330℃,保温时间60 min,添加剂浓度0.0538 mol/L,投料比0.024g/mL.回收的碳纤维表面无残留树脂,没有发生明显的石墨化,且表面平均粗糙度与原碳纤维相近;与原始碳纤维相比,回收的碳纤维的拉伸强度约为原碳纤维的93.58%,杨氏模量约为原碳纤维的94.87%.     

苯并噁嗪改性液体成型环氧树脂的研究

采用具有低固化收缩特性的苯并噁嗪树脂(benzoxazine,BOZ)对液体成型环氧树脂进行改性,以期在不改变液体成型树脂耐热性、工艺性及力学性能的前提下,大幅度降低树脂的固化收缩率.对比研究了不同BOZ含量改性树脂的固化收缩特性、固化反应特性、液体成型工艺性及力学性能.并采用真空辅助树脂浸渗(vacuum assisted resin infusion,VARI)工艺制备了单向碳纤维织物增强复合材料,研究了复合材料的力学性能.结果表明,加入BOZ对液体成型树脂的反应性、工艺性及耐热性影响不大,改性树脂的固化收缩随BOZ含量的提高逐渐减小,其中BOZ质量分数为15 wt%的改性树脂,较未改性树脂的固化收缩减小约80%,拉伸强度提高约19%,冲击强度提高约148%.以此改性树脂作为基体的复合材料相对于未改性树脂复合材料的拉伸强度提高约23%,层间剪切强度提高约9%,具有良好的力学性能和界面结合性能.     

镍/碳纳米纤维复合物的制备及其吸波性能

以乙二胺为碳源,自制的镍纤维为催化剂,利用原位复合的方法制备得到一系列不同比例的镍/碳纤维复合物,并研究了其吸波性能.由于镍纤维和碳纤维均具有一定的电磁波耗散能力,因此得到的产物无需任何处理,可以直接作为吸波材料使用.结果表明,通过改变镍纤维的加入量,可以改变产物的镍碳比,进而实现对复合材料吸波性能的调控.在合适比例条件下制备得到的纤维复合物具有较好的吸波性能,当纤维复合物含量为25%时,其反射率的最小值可达-14.3dB.该材料在轻质吸波材料领域具有很好的应用价值.     

可循环回收利用的本征导热聚六氢三嗪树脂研究

采用多聚甲醛(PFA)和含有芳香酰胺特殊结构的4,4'-二氨基苯酰替苯胺(DABA)为原料,通过利用分子链间氢键强相互作用向树脂固化网络中引入局域微观有序结构增大声子传播自由程,合成一种新型本征导热聚六氢三嗪热固性树脂(DABA-PHT).通过对树脂预聚过程和机理、固化工艺、导热性能、降解性能及循环回收利用性能的研究表明:水能够作为催化剂有效加速预聚反应、大幅缩短预聚时间,且酰胺N-H键未参与交联反应;DABA-PHT树脂易于合成和加工,且具有良好的力学、耐热、降解和循环回收利用性能,热导率达到0.38 W·m~(-1)·K~(-1),接近普通环氧树脂的2倍,有望用来制备可循环回收利用的高热导率热固性树脂基复合材料.     

Reprocessible Epoxy Networks with Tunable Physical Properties: Synthesis,Stress Relaxation and Recyclability

In order to extend the application of epoxy vitrimer,1,4-cyclohexanedicarboxylic acid (CHDA) was used as a co-curing agent and structure modifier for sebacic acid (SA) cured diglycidyl ether of bisphenol A (DGEBA) epoxy vitrimer to tailor the mechanical properties of epoxy vitrimers with 1,5,7-triazabicylo[4.4.0]dec-5-ene (TBD) as a transesterification catalyst.The glass transition temperature (Tg) ofvitrimer increased gradually with the increase in CHDA content.Vitrimers behaved from elastomer to tough and hard plastics were successfully achieved by varying the feed ratio of CHDA to SA.Both the Young's modulus and storage modulus increased apparently with the increase in CHDA content.Stress relaxation measurement indicated that more prominent stress relaxation occurred at elevated temperatures and the stress relaxation decreased with the increase of CHDA content due to the reduced mobility of the vitrimer backbone.The vitrimers showed excellent recyclability as evidenced by the unchanged gel fraction and mechanical properties after compression molded for several times.With tunable mechanical properties,the epoxy vitrimers may find extensive potential applications.     

基于多重动态共价键的环氧类玻璃网络的制备与性能

以三羟甲基丙烷三缩水甘油醚(TTE)为基体, 2,2′-(1,4-亚苯基)-双[4-硫醇1,3,2-二氧杂戊烷](BDB)和3,3-二硫代二丙酸(DTDPA)为交联剂, 通过环氧-巯基“点击”反应和环氧-羧酸酯化反应, 制备了基于多重动态共价键(硼酸酯键、 二硫键和酯键)的环氧类玻璃网络. 利用红外光谱和拉曼光谱对其结构进行了表征, 结果表明, 环氧类玻璃中不仅存在硼酸酯键、 二硫键和酯键, 还存在可逆氢键, 并且大量氢键的存在能提高环氧类玻璃的交联度. 对所得环氧网络的热稳定性、 热机械性能和力学性能进行了测试, 并对基于多重动态共价键环氧网络进行了自修复、 焊接、 形状记忆和再加工能力测试. 结果表明, 在80 ℃下可实现网络的完全自修复、 再加工与焊接, 且焊接后样品的力学性能(拉伸强度)恢复率在80%以上, 具有优异的功能性.     

An Interfacial Dynamic Crosslinking Approach toward Catalyst-free and Mechanically Robust Elastomeric Vitrimer with a Segregated Structure

Elastomeric vitrimers with covalent adaptable networks are promising candidates to overcome the intrinsic drawbacks of conventional covalently-crosslinked elastomers; however, most elastomeric vitrimers show poor mechanical properties and require the addition of exogenous catalysts. Herein, we fabricate a catalyst-free and mechanically robust elastomeric vitrimer by constructing a segregated structure of sodium alginate (SA) in the continuous matrix of epoxidized natural rubber (ENR), and further crosslinking the composite by exchangeable hydroxyl ester bonds at the ENR-SA interfaces. The manufacturing process of the elastomeric vitrimer is facile and environmentally friendly without hazardous solvents or exogenous catalysts, as the abundant hydroxyl groups of the segregated SA phase can act as catalyst to activate the crosslinking reaction and promote the dynamic transesterification reaction. Interestingly, the segregated SA structure bears most of the load owing to its high modulus and small deformability, and thus ruptures preferentially upon deformation, leading to efficient energy dissipation.Moreover, the periodic stiffness fluctuation between rigid segregated SA phase and soft ENR matrix is beneficial to the crack-resisting. As a result,the elastomeric vitrimer manifests exceptional combination of catalyst-free, defect-tolerance, high tensile strength and toughness. In addition,the elastomeric vitrimer also exhibits multi-shape memory behavior which may further broaden its applications.     

环氧树脂类玻璃高分子研究进展

类玻璃高分子(Vitrimer)是一类具有可逆共价交联网络的高分子,其能够在维持交联结构的同时实现交联网络的重构,兼具热固性高分子和热塑性高分子的双重优势。基于通用热固性树脂形成的Vitrimer材料不仅能具有良好的力学性能和耐溶剂性等,还能表现出类似热塑性树脂的流动性和重复加工性能,为从源头上实现交联树脂的回收和再利用提供了有效的途径。近年来,围绕Vitrimer材料的研究已取得了蓬勃的发展,其中数环氧树脂Vitrimer的研究最为广泛,本文将系统介绍环氧树脂Vitrimer的设计理念及其性能特点,梳理该领域的典型研究体系,并指出可能的发展方向,为传统热固性树脂的可再生和高性能化发展提供参考。     

Bio‐based epoxy vitrimers: Reprocessibility,controllable shape memory,and degradability

The research activities in the development of recyclable and reprocessable covalently crosslinked networks, and the construction of polymers from renewable resources are both stemmed from the economical and environmental problems associated with traditional thermosets. However, there is little effort in combination of these two attractive strategies in material designs. This article reported a bio‐based vitrimer constructed from isosorbide‐derived epoxy and aromatic diamines containing disulfide bonds. The resulted dynamic epoxy resins showed comparable thermomechanical properties as compared to similar epoxy networks cured by traditional curing agent. Rheological tests demonstrated the fast stress relaxation of the dynamic network due to the rapid metathesis of disulfide bonds at temperature higher than glass transition temperature. This feature permitted the recycling and reprocessing of the fragmented samples for several times by hot press. The dynamic epoxy resins also exhibited shape‐memory effect, and it is demonstrated that the shape recovery ratio could be readily adjusted by controlling the stress relaxation in the temporary state at programming temperature. Moreover, the degradability of the dynamic epoxy resins in alkaline aqueous solution was also demonstrated. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1790–1799     

Thermal properties enhancement of epoxy resins by incorporating polybenzimidazole nanofibers filled with graphene and carbon nanotubes as reinforcing material

Enhancement of thermal properties of epoxy resins was achieved by incorporation of polybenzimidazole (PBI) fibermats filled with carbon nanomaterials, prepared by the solution electrospinning technique. Different type of carbon nanostructures (carbon nanotubes, graphite flakes, graphene nanoplatelets and carbon black) were compared as fillers in polybenzimidazole fibers. The carbon-PBI-fibermats showed remarkable thermal transport properties and therefore, they were studied as thermal reinforcement material for epoxy composites. Mechanical and thermal properties of produced composites were evaluated and the effectiveness of different types of carbon fillers examined. Results showed that the produced carbon filled fibermats can be used effectively as a thermal reinforcing material in epoxy resins, offering several advantages.     

环氧氯丙烷修饰的对位和间位芳纶涂覆剂研究

制备了具有环氧丙基侧链的对位芳纶(PPTA-ECH)和间位芳纶(PMIA-ECH),并将其用做对位芳纶(PPTA)织物/环氧树脂复合材料中PPTA织物的涂覆剂。采用场发射扫描电子显微镜(FE-SEM)及XPS等方法对PPTA织物表面的PPTA-ECH涂层结构进行了表征。考察了PPTA-ECH和PMIA-ECH涂覆的PPTA织物/环氧树脂复合材料的层间剪切强度和面内剪切强度,并与未经涂覆的PPTA织物复合材料的性能作比较。结果表明,PPTA-ECH和PMIA-ECH可显著改善PPTA织物和环氧树脂之间的界面性能。涂覆了PPTA-ECH及PMIA-ECH的PPTA织物/环氧树脂复合材料的层间剪切强度(ILSS)比未经涂覆的复合材料分别提高了26.20%和14.76%,面内剪切强度(ISS)分别提高了26.98%和11.86%。由于PPTA-ECH对PPTA纤维具有更强的亲和能力,因此PPTA-ECH在层间剪切强度和面内剪切强度方面的增强效果均优于PMIA-ECH。对PPTA-ECH在PPTA纤维表面铺展与吸附及对复合材料的增强机理也进行了初步探讨。作为新型涂覆剂,PPTA-ECH在对位芳纶复合材料的开发应用方面具有潜在的应用前景。     

“Solid-Liquid” Vitrimers Based on Dynamic Boronic Ester Networks

The "solid-liquid" behavior of vitrimers have not been systematically investigated. Herein, a series of "solid-liquid" vitrimers bearing varying contents of dynamic boronic ester bonds were synthesized via thiol-ene click reactions. These vitrimers allow for flexibile modulation of their network structures and thus show a range of intriguing properties including high stretchability, flexible transition from elasticity to plasticity, strong strain rate dependence, and solid-liquid performance. The dynamic association rate of boronic ester bonds within these vitrimers could be apparently accelerated via increasing the content of boronic ester, which could be used to shape-program the flat vitrimer films into various complex 3 D structures just with external force. Materials with such versatile dynamic behavior may open up a range of new applications.     

Understanding the Reshaping of Fluorinated Polyester Vitrimers by Kinetic and DFT Studies of the Transesterification Reaction

Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Following up on a recent report on catalyst-free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in α- or β-position, parallel DFT calculations and an experimental kinetic study on model molecules are presented in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate.     

Interacting blends of Styrenated unsaturated poly (ester–amide)s with commercial unsaturated polyester resin (o-phthalic anhydride based)

Unsaturated poly (ester–amide)s resins (UPEAs) were prepared by the reaction between an epoxy resin, namely diglycidyl ether of bisphenol-A (DGEBA) and unsaturated aliphatic bisamic acids (B_1–4) using a base catalyst. These UPEAs were then diluted by styrene and blended with commercial unsaturated polyester resin (o-phthalic anhydride based) to produce a homogeneous resin. The curing of these Styrenated UPEAs–UPR blends was carried out using Benzoyl peroxide (BPO) as a catalyst and N,N′-Dimethyl aniline (DMA) as a promoter. The glass fiber reinforced composites (i.e. laminates) of these Styrenated UPEAs–UPR (o-phthalic anhydride based) blends were fabricated. The mechanical and chemical resistance properties of the glass fiber composites have also been evaluated. The unreinforced cured samples of the Styrenated UPEAs–UPR (o-phthalic anhydride based) blends were also analyzed by thermogravimetry (TGA).