耐水性大豆蛋白木材胶黏剂用功能改性剂的制备与表征

发布时间：2018-05-15 08:06

  本文选题：大豆蛋白胶黏剂 + PAE树脂　； 参考：《东北林业大学》2016年硕士论文

【摘要】：随着人们对居住环境的要求不断提高,对于室内建筑装修和家具制造所使用人造材的安全性越来越重视,开发环境友好型生物质基木材胶黏剂已成为必然趋势。大豆蛋白作为生物质材料的代表,来源广泛、可再生,可以为制备新型木材胶黏剂提供新方向。由于大豆蛋白的复杂四级结构以及分子量巨大,所制备的大豆蛋白胶黏剂存在固含量低、粘度大、耐水性能及胶合性能差的不足,使实际应用受到很大限制。本文提出以碱降解液化蛋白(D-SPI)、酸热处理蛋白粉(A-SPI)和聚酰胺多胺环氧氯丙烷(PAE,作为交联改性剂)复配,制备一种固含量较高、粘度较低、胶合性能、耐水性和工艺使用性能优良的大豆蛋白胶黏剂,重点就交联改性剂的制备与性能优化进行研究。本文首先就PAE的合成工艺进行优化,采用两步合成法,先后探究了多胺种类、多胺/己二酸摩尔比、反应温度、反应时间、环氧氯丙烷/多胺摩尔比、烷基化工艺以及终止酸的种类和用量(pH值)对所制备PAE性能影响,最终优化出了最佳制备工艺：PA中间体合成时,己二酸/二乙烯三胺摩尔比为1：1.05,聚酰胺多胺(PA)中间体制备时先在125℃充分盐化溶解后,再逐步升温至185℃下保持2h；烷基化反应时,环氧氯丙烷与二乙烯三胺的摩尔比为1：1,在35℃保持0.5h后再于50℃C下反应至目标粘度；反应终点时,使用甲酸与硫酸调节产品pH值至3.5。此工艺下制备的PAE树脂性能最优,在保证体系交联程度的同时,尽可能提高环氧氯丙烷支化程度和阳离子含量,且产品固含量高、储存期长。将所优化的PAE树脂用于对大豆蛋白胶黏剂的改性,并与其他三种常见改性剂(乙二醛、环氧树脂及异氰酸酯)进行对比,结果证明：PAE树脂可以很好的提高胶黏剂性能,在胶合强度及耐水性能方面优于脲醛树脂,压制的胶合板湿强度达到1.12MPa,满足GB/T17657-1999《人造板及饰面人造板理化性能试验方法》中对于Ⅰ类胶合板的性能要求,为大豆蛋白胶黏剂在木材加工领域取代醛基类合成胶黏剂提供技术支持。同时,本文还利用傅立叶红外光谱(FT-IR)、核磁共振分析仪(NMR)、热重分析仪(TG)、扫描电子显微镜(SEM)结合压板实验,对PAE改性大豆蛋白胶黏剂的配方进行了优化,并对相关的改性机理进行了探究,结果证明：PAE中氮杂环丁烷等活性基团可以与大豆蛋白及木材中的胺基、羟基、羧基发生反应,使三者固化后形成稳定的耐水耐热性能良好的空间结构；最佳的PAE改性大豆蛋白胶黏剂的配方为D-SPI/A-SPI质量比为1：3,PAE添加比例为胶黏剂蛋白含量的30%,以此配方制备的PAE改性大豆蛋白基木材胶黏剂具有最优的胶合强度、耐水性和工艺使用性,有望推广应用。
[Abstract]:With the increasing demand for living environment, more and more attention has been paid to the safety of artificial wood used in indoor building decoration and furniture manufacturing, and the development of environment-friendly biomass-based wood adhesive has become an inevitable trend. Soybean protein, as a representative of biomass materials, can be regenerated from a wide range of sources, which can provide a new direction for the preparation of new wood adhesives. Because of the complex quaternary structure and the huge molecular weight of soybean protein, the prepared soybean protein adhesive has the disadvantages of low solid content, high viscosity, poor water resistance and poor adhesion, so its practical application is greatly limited. In this paper, a high solid content, low viscosity and adhesive properties were prepared by alkali degradation of liquefaction protein (D-SPI), acid-heat treatment protein powder (A-SPI) and polyamide polyamine epichlorohydrin (PAE) as crosslinking modifiers. The preparation and optimization of crosslinking modifier were studied in this paper. In this paper, the synthesis process of PAE was optimized, and the kinds of polyamines, the molar ratio of polyamine to adipic acid, the reaction temperature, the reaction time, the molar ratio of epichlorohydrin and polyamine were investigated. The effects of alkylation process and the type and dosage of the terminated acids on the properties of the PAE were studied. Finally, the optimum preparation process was optimized for the synthesis of the intermediate: PA. The molar ratio of adipic acid to diethylenetriamine is 1: 1.05.The intermediate of polyamide polyamine (PAA) is prepared by fully salinizing and dissolving at 125 鈩，

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