水性环氧上浆剂的制备及其在碳纤维增强PA6复合材料中的应用研究
发布时间：2019-04-15 22:47
【摘要】：由于碳纤维的脆性,在碳纤维的生产和加工过程中往往会经历反复摩擦过程而发生断裂,降低了纤维本体强度,且易产生大量毛丝,不利于后续应用。通过上浆工艺,碳纤维表面包覆一层聚合物上浆剂,在保护碳纤维本体性能同时可减少毛丝量,改善纤维集束性,使得碳纤维加工性能和生产环境得到显著改善。另外,碳纤维表面包覆的上浆树脂还可增加基体树脂对碳纤维的浸润性,减少界面缺陷,从而能提高纤维与树脂基体间的界面结合强度。由此可见上浆剂在碳纤维生产加工过程中扮演十分重要的角色。本论文首先以环氧树脂E-44、E-51及双酚F型环氧树脂BPF为上浆树脂主体,外加多种复配乳化剂,制备了一类外加乳化型环氧上浆剂(EX-SA)；其次,以二乙醇胺(DEA)和对氨基苯甲酸(PABA)分别对环氧树脂E-44进行改性,合成了DEA改性E-44和PABA改性E-44两种新型的环氧树脂,并采用自乳化的方法,成功制备了阳离子型上浆剂(CA-SA)和阴离子型上浆剂(AN-SA)；再次,以聚乙二醇(PEG)对环氧树脂E-51进行改性,合成了PEG改性E-51的环氧树脂,自乳化制备了非离子型上浆剂(NO-SA).探讨研究了上述四类环氧树脂乳液的最佳制备工艺。采用商购的日本上浆剂(JP-SA)和自制的四类环氧乳液上浆剂对碳纤维进行上浆处理,对碳纤维的上浆率、毛丝量、上浆碳纤维的表面形貌和性质,以及上浆碳纤维单丝力学性能等进行了评价。此外,对上浆碳纤维-聚酰胺复合材料的机械性能进行了研究。主要研究结果如下：1、EX-SA的最佳制备条件为环氧树脂E-44、离子型乳化剂十二烷基硫酸钠(SDS)加入量2%、非离子型乳化剂聚氧乙烯脱水山梨醇单油酸酯(T-80)加入量2%、非离子型乳化剂烷基酚聚氧乙烯醚(OP-10)加入量4%、乳化温度80℃、乳化时间30 min、加水速率3mL/min。CA-SA的最佳制备条件为E-44与DEA摩尔比为1：1.1、反应温度70℃、反应时间60 min、加冰乙酸成盐温度60℃、加水温度80℃、加水速率5mL/min。AN-SA的最佳制备条件为PABA与E-44摩尔比1：1、反应温度80℃、反应时间2h、成盐时加入三乙醇胺(TEA)与PABA摩尔比1：0.8、成盐温度65℃,加水温度60℃。NO-SA的最佳制备条件为E-51与PEG 1000的摩尔比1：1、催化剂三苯基膦(TPP)添加量0.5%、反应温度180℃、反应时间3h、加水温度80℃。2、EX-SA和JP-SA处理碳纤维的上浆率略高于自乳化上浆剂(CA-SA、AN-SA、 NO-SA)处理碳纤维的上浆率。碳纤维经上浆处理后,纤维毛丝量有较大幅度的减少。未上浆碳纤维表面有较为明显凹凸不平的沟槽,上浆后纤维表面沟槽变浅。上浆处理后碳纤维表面O有较大幅度提高,此外,CA-SA和AN-SA处理碳纤维的表面还含有少量N元素。上浆后碳纤维在300-450℃范围内出现上浆剂的失重现象。碳纤维单丝拉伸强度在上浆前后变化不大,但上浆后纤维拉伸强度的离散性减小。3、碳纤维复合材料的密度随碳纤维含量的增加而增大,流动性随着碳纤维含量的增加而减小。碳纤维复合材料的拉伸强度和弯曲强度随碳纤维含量的增加而增大,与未上浆碳纤维相比,上浆碳纤维制备复合材料的拉伸强度与弯曲强度增加,未上浆碳纤维制备复合材料的悬臂梁缺口(Izod)冲击强度随碳纤维含量的增加而减小,而经上浆处理后制备复合材料的Izod冲击强度随碳纤维含量的增加先增加后减小。未上浆碳纤维制备复合材料的断面,纤维与树脂基体结合面光滑,而经过上浆处理碳纤维制备复合材料的断面,碳纤维与树脂基体结合面粗糙,基体树脂与碳纤维结合紧密。随着碳纤维含量的增加,复合材料的储能模量逐渐增大,损耗角正切值减小且向高温方向偏移。
[Abstract]:Due to the brittleness of the carbon fiber, the fracture is often experienced during the production and processing of the carbon fiber, so that the strength of the fiber body is reduced, and a large number of filaments are easily generated, and the subsequent application is not favorable. The surface of the carbon fiber is coated with a layer of polymer sizing agent through a sizing process, so that the performance of the carbon fiber body can be protected, the yarn amount can be reduced, the fiber bundling property is improved, and the processing performance and the production environment of the carbon fiber are greatly improved. In addition, the sizing resin coated on the surface of the carbon fiber can increase the wettability of the matrix resin to the carbon fiber and reduce the interface defect, so that the interface bonding strength between the fiber and the resin matrix can be improved. It can be seen that the sizing agent plays a very important role in the process of carbon fiber production. In this paper, epoxy resin E-44, E-51 and bisphenol F epoxy resin BPF are used as the main body of sizing resin, and a variety of compound emulsifiers are applied to prepare a kind of additive emulsion type epoxy sizing agent (EX-SA). Two new types of epoxy resins modified E-44 and PA-modified E-44 were synthesized with diethanolamine (DEA) and p-aminobenzoic acid (PABA), and the self-emulsifying method was used to successfully prepare cationic sizing agent (CA-SA) and anionic sizing agent (AN-SA). The epoxy resin E-51 was modified with polyethylene glycol (PEG), and the epoxy resin of PEG-modified E-51 was synthesized and the non-ionic sizing agent (NO-SA) was prepared by self-emulsification. The optimum preparation technology of the above four kinds of epoxy resin emulsion was discussed. A commercial Japanese sizing agent (JP-SA) and a self-made four-class epoxy emulsion sizing agent are used for sizing the carbon fiber, and the sizing rate of the carbon fiber, the filament amount, the surface appearance and the property of the sizing carbon fiber, and the mechanical property of the sizing carbon fiber monofilament are evaluated. In addition, the mechanical properties of the sizing carbon fiber-polycarbodiimide composite were studied. The main results are as follows:1. The best preparation conditions for EX-SA are epoxy resin E-44, ionic emulsifier sodium dodecyl sulfate (SDS) adding amount of 2%, non-ionic emulsifier polyoxyethylene sorbitan monooleate (T-80) is added in an amount of 2%, the non-ionic emulsifier alkylphenol polyoxyethylene ether (OP-10) is added with an amount of 4 percent, the emulsifying temperature is 80 DEG C, the emulsification time is 30 minutes, the water adding rate is 3 mL/ min, the optimal preparation condition of the CA-SA is that the molar ratio of the E-44 to the DEA is 1: 1.1, the reaction temperature is 70 DEG C, the reaction time is 60 minutes, the glacial acetic acid is added to the salt temperature of 60 DEG C, The optimum preparation conditions for AN-SA were: the molar ratio of PABA to E-44 was 1:1, the reaction temperature was 80 鈩，
本文编号：2458556
[Abstract]:Due to the brittleness of the carbon fiber, the fracture is often experienced during the production and processing of the carbon fiber, so that the strength of the fiber body is reduced, and a large number of filaments are easily generated, and the subsequent application is not favorable. The surface of the carbon fiber is coated with a layer of polymer sizing agent through a sizing process, so that the performance of the carbon fiber body can be protected, the yarn amount can be reduced, the fiber bundling property is improved, and the processing performance and the production environment of the carbon fiber are greatly improved. In addition, the sizing resin coated on the surface of the carbon fiber can increase the wettability of the matrix resin to the carbon fiber and reduce the interface defect, so that the interface bonding strength between the fiber and the resin matrix can be improved. It can be seen that the sizing agent plays a very important role in the process of carbon fiber production. In this paper, epoxy resin E-44, E-51 and bisphenol F epoxy resin BPF are used as the main body of sizing resin, and a variety of compound emulsifiers are applied to prepare a kind of additive emulsion type epoxy sizing agent (EX-SA). Two new types of epoxy resins modified E-44 and PA-modified E-44 were synthesized with diethanolamine (DEA) and p-aminobenzoic acid (PABA), and the self-emulsifying method was used to successfully prepare cationic sizing agent (CA-SA) and anionic sizing agent (AN-SA). The epoxy resin E-51 was modified with polyethylene glycol (PEG), and the epoxy resin of PEG-modified E-51 was synthesized and the non-ionic sizing agent (NO-SA) was prepared by self-emulsification. The optimum preparation technology of the above four kinds of epoxy resin emulsion was discussed. A commercial Japanese sizing agent (JP-SA) and a self-made four-class epoxy emulsion sizing agent are used for sizing the carbon fiber, and the sizing rate of the carbon fiber, the filament amount, the surface appearance and the property of the sizing carbon fiber, and the mechanical property of the sizing carbon fiber monofilament are evaluated. In addition, the mechanical properties of the sizing carbon fiber-polycarbodiimide composite were studied. The main results are as follows:1. The best preparation conditions for EX-SA are epoxy resin E-44, ionic emulsifier sodium dodecyl sulfate (SDS) adding amount of 2%, non-ionic emulsifier polyoxyethylene sorbitan monooleate (T-80) is added in an amount of 2%, the non-ionic emulsifier alkylphenol polyoxyethylene ether (OP-10) is added with an amount of 4 percent, the emulsifying temperature is 80 DEG C, the emulsification time is 30 minutes, the water adding rate is 3 mL/ min, the optimal preparation condition of the CA-SA is that the molar ratio of the E-44 to the DEA is 1: 1.1, the reaction temperature is 70 DEG C, the reaction time is 60 minutes, the glacial acetic acid is added to the salt temperature of 60 DEG C, The optimum preparation conditions for AN-SA were: the molar ratio of PABA to E-44 was 1:1, the reaction temperature was 80 鈩，
本文编号：2458556
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