聚酰胺酸大分子偶联剂乳液的合成及其在回收玻璃纤维增强高温尼龙的界面改性中的应用  

Synthesis of polyamic acid macromolecular coupling agent emulsion and its interface modification of recycled glass fiber-reinforced high-temperature nylon

作　　者：黄博翔 王智玉 沈洋 傅雅琴[1,2] 钱晨 HUANG Boxiang;WANG Zhiyu;SHEN Yang;FU Yaqin;QIAN Chen(School of Materials Science&Engineering,Zhejiang Sci-Tech University,Hangzhou 310018,China;Zhejiang Provincial Innovation Center of Advanced Textile Technology,Shaoxing 312000,China;Zhejiang Sci-Tech University Tongxiang Research Institute,Tongxiang 314500,China)

机构地区：[1]浙江理工大学材料科学与工程学院,杭州310018 [2]浙江省现代纺织技术创新中心(鉴湖实验室),浙江绍兴312000 [3]浙江理工大学桐乡研究院,浙江桐乡314500

出　　处：《浙江理工大学学报（自然科学版）》2024年第4期436-446,共11页Journal of Zhejiang Sci-Tech University(Natural Sciences)

基　　金：国家自然科学基金项目(U20A20264);浙江省自然科学基金项目(LQ22E030012)。

摘　　要：为提升回收玻璃纤维(Recycled glass fiber,rGF)在增强高温尼龙复合材料中的应用价值,制备用于rGF表面处理的耐高温型玻璃纤维浸润剂。以4,4′-联苯醚二酐(ODPA)为二酸酐单体、4,4′-二氨基二苯醚(ODA)为二胺单体,合成聚酰胺酸(PAA),然后与γ-氨丙基三乙氧基硅烷(KH550)反应得到聚酰胺酸大分子偶联剂(PAA-KH550);通过调控ODPA与ODA单体比例,制备得到稳定分散的自乳化PAA-KH550乳液。通过激光粒度分析仪、傅里叶变换红外光谱仪及热失重分析仪对乳液的粒径、化学结构及PAA-KH550乳液固化膜的耐高温性能进行测试;并采用扫描电子显微镜、单纤维强力机、全自动表面张力仪及复合材料界面评价装置对乳液涂覆的GF进行形貌观察、单丝性能测试、浸润性测试及与聚酰胺46(PA46)的界面剪切强度测试。结果表明:乳液平均粒径均为110~125 nm,且粒径分布较小;PAA-KH550乳液固化膜耐高温性能优于PAA乳液固化膜,其5%热分解温度(T_(d5))在350℃以上;制得的乳液能在rGF表面均匀成膜,有效弥补纤维表面缺陷,从而提升rGF的力学性能。此外,乳液涂敷固化后在纤维表面形成的涂层可有效提高纤维表面能,有助于改善GF与PA46的界面结合性能;实验测得经PAA-KH550乳液处理的GF/PA46复合材料的界面剪切强度(IFSS)最高达到(31.29±6.39)MPa,相比未经乳液处理的样品提高了37%。制备的水体系分散稳定的PAA乳液和PAA-KH550乳液,将其应用于rGF表面可有效恢复rGF的综合性能,同时可改善与PA46的界面结合,提高rGF/PA46复合材料的耐高温性能及力学性能,为rGF在高性能复合材料中的应用提供了新方案。To enhance the application value of recycled glass fibers(rGF)in reinforced high-temperature nylon composites,a high-temperature-resistant glass fiber sizing agent for rGF surface treatment was prepared.4,4′-Oxydiphthalic anhydride(ODPA)was used as the dianhydride monomer and 4,4′-Oxydianiline(ODA)as the diamine monomer to synthesize polyamic acid(PAA),which then reacted withγ-Aminopropyltriethoxysilane(KH550)to obtain the polyamic acid macromolecular coupling agent(PAA-KH550).By adjusting the ratio of ODPA to ODA monomers,a self-emulsifying PAA-KH550 emulsion with stable dispersion was prepared.The particle size,chemical structure,and high-temperature resistance of the emulsion and the cured film of PAA-KH550 emulsion were tested by laser particle size analyzer,Fourier transform infrared spectrometer,and thermogravimetric analyzer.The morphology,single filament performance,wettability,and interfacial shear strength with polyamide 46(PA46)of the GF coated with the emulsion were tested by scanning electron microscope,single fiber strength machine,automatic surface tension meter,and composite material interface evaluation device.The results show that the average particle size of the emulsion is 110-125 nm,and the particle size distribution is small;the high-temperature resistance of the cured film of PAA-KH550 emulsion is better than that of the cured film of PAA emulsion,and its 5%thermal decomposition temperature(T_(d5))is above 350℃;the prepared emulsion can form a uniform film on the surface of rGF,and effectively compensate for the surface defects of the fiber,thereby improving the mechanical properties of rGF.In addition,the coating formed on the fiber surface after the emulsion is cured can effectively improve the surface energy of the fiber,which helps to improve the interfacial bonding performance of GF and PA46;the experimental measurement shows that the interfacial shear strength(IFSS)of the GF/PA46 composite material treated with PAA-KH550 emulsion reaches up to(31.29±6.39)MPa,which is 37%higher

关 键 词：回收玻璃纤维 聚酰胺酸 大分子偶联剂 高温尼龙 复合材料 

分 类 号：TB332[一般工业技术—材料科学与工程]