甲醛捕获型胶原蛋白基胶黏剂的合成及其构效关系研究

There is given priority to with the solvent-based "three aldehyde-adhesive" , namely, urea-formaldehyde resin, phenolic resin and melamine-formaldehyde resin in wood adhesive industry. There are volatilization of the organic solvent and release of free formaldehyde in their storage and usage, with harming the environment and the human body. Collage, a renewable biomass macromolecule material, can be used as the environment-friendly adhesive because of its non-toxic, bonding performance, gel performance, film-forming performance and so on. There is rich in amino which can react with the free formaldehyde in the collagen’s molecular chain, therefor collagen have certain ability with capturing formaldehyde. While its applications is limited in the adhesive industry because of its poor water-resistance performance. Collagen will be double-modified by the graft polymerization method and the metal coordination method for the specific amino acid to improve its water-resistance performance. A kind of biomass based adhesives with the performance of capturing formaldehyde will be prepared and its structure-activity relationship will be clarified in the project. It will provide the novel ideas for the biomass macromolecule material being applied in the adhesive industry. Contents include: (1) collagen will be grafting-modified using the Methyl acrylic glycidyl ester（GMA）by the soap-free emulsion polymerization and then be coordinating-modified using Al3+. The preparation process and modification mechanism will be studied.（2）Effect law of the chemical structure of collagen matrix adhesives on its application performance such as the bonding performance, water-resistance performance, capturing-formaldehyde ability and so on will be investigated.

木材工业仍以“三醛胶”即脲醛树脂、酚醛树脂、三聚氰胺-甲醛树脂等溶剂型胶黏剂为主，其在贮存和使用过程中不仅存在有机溶剂的挥发，还会释放游离甲醛，对环境和人体造成伤害；胶原蛋白属于可再生的生物质高分子材料，具有无毒性、粘结性、凝胶性、成膜性等，可作为环保型胶黏剂。由于其分子链上富含可与游离甲醛反应的氨基，故具有一定的甲醛捕获能力。但胶原蛋白本身耐水性差，限制了其在胶黏剂行业的应用。本项目拟采用接枝聚合法和特定氨基酸的金属配位法对胶原蛋白进行双重改性，改善其耐水性，制备一种具有甲醛捕获性能的水性胶黏剂，阐明其构效关系，为生物质高分子材料在胶黏剂行业的应用提供新思路。内容包括：（1）拟采用甲基丙烯酸缩水甘油酯通过无皂乳液聚合法对胶原蛋白进行接枝改性，再用Al3+对其进行配位改性，研究其制备工艺和改性机理；（2）研究胶原蛋白基胶黏剂中化学结构对产物黏合性能、耐水性能和甲醛捕获能力等应用性能的影响规律。

胶粘剂通常用于木材工业生产各种木板和复合材料，如胶合板、纤维板和刨花板，用于制造家具、地板、厨柜和墙体材料。全球木材胶粘剂的市场很大，预计到2025 年将达到61.8 亿美元。然而，大多数木材用胶粘剂是以石油基和甲醛基物质为原料，如酚醛树脂、脲醛树脂和三聚氰胺-甲醛树脂。它们会释放有害、致癌的甲醛和其他挥发性有机物，不仅污染环境，对人类健康也构成潜在威胁。因此，研制一种无毒、环保的胶粘剂来替代石油基和甲醛基胶粘剂迫在眉睫。明胶是一种绿色、可再生的动物蛋白质资源，它们来源丰富、生物相容性好、无毒无害，自身具有一定的成膜性和粘性，作为一种可持续的、廉价的生物基材料为传统的含甲醛缩合的石油基胶粘剂提供了更好的替代品。本项目以食品加工和皮革固废中提取的动物蛋白-明胶作为原料，在项目经费资助下，通过多种结构改性设计及优化制备出一系列基于疏水单体/金属离子双重改性策略、纳米纤维素复配改性策略、仿贻贝足丝蛋白策略等的生物基胶黏剂材料，通过条件优化、结构表征及性能测试等手段多角度考察其综合应用性能。研究结果发现金属离子交联改性可以赋予蛋白基胶黏剂优异的耐水性能，CNF改性可大幅度提高其胶合强度，CNC改性可显著提高其耐水性能。所合成的系列动物蛋白基胶黏剂，在木材、塑料、玻璃、橡胶、金属、不锈钢、陶瓷、棉布等基材均表现出良好的粘接性能，特别是仿贻贝丝足蛋白基胶黏剂对于低表面能的基材都表现出优异的粘附作用。该项目的研究拓宽了动物蛋白基胶黏剂的市场应用范围，推进蛋白基胶黏剂取代“三醛胶”和石油基胶黏剂的步伐。在本项目资助下，基于课题研究先后发表SCI 一区论文2篇，二区论文1篇，中文核心5篇，授权发明专利3 件，实用新型专利2件，协助培养硕士研究生2名。