邻苯二酚基多糖交联剂合成与表征及其对豆胶性能影响  

Synthesis and characterization of catechol-based polysaccharide crosslinking agent and its effect on the properties of soybean protein adhesive

作　　者：唐望明 徐艳涛 赵涵 王瑜瑶 李建章[1] 高强[1] TANG Wangming;XU Yantao;ZHAO Han;WANG Yuyao;LI Jianzhang;GAO Qiang(College of Materials Science and Technology,Beijing Forestry University,Beijing 100083,China)

机构地区：[1]北京林业大学材料科学与技术学院,北京100083

出　　处：《林业工程学报》2022年第3期136-143,共8页Journal of Forestry Engineering

基　　金：国家自然科学基金(32071702);北京林业大学大学生创新创业训练计划项目(X201910022109);北京林业大学杰出青年人才培养项目(2019JQ03004)。

摘　　要：仿照贻贝蛋白高黏附结构,合成邻苯二酚基多糖交联剂(CP)用以增强大豆蛋白胶黏剂的耐水胶接性能,研究CP原料中玉米淀粉与叔丁基二甲基氯硅烷保护的3,4-二羟基苯甲酸(DHBAT)质量比、CP加入量、胶合板热压工艺(涂胶量、热压温度和热压时间)对大豆蛋白胶黏剂制备胶合板耐水胶接性能的影响规律,表征CP和改性大豆蛋白胶黏剂(SPI-CP)的功能性基团以及胶黏剂热稳定性、结晶区间、断面形貌等解析CP对大豆蛋白胶黏剂的增强机制。试验结果表明:通过4-二甲基氨基-吡啶和N,N-二环己基碳二亚胺催化的酯化反应将邻苯二酚结构成功接枝到玉米淀粉制成CP;CP的最佳配方为m(多糖)∶m(DHBAT)=1∶2,加入量为6%。SPI-CP胶黏剂制备胶合板耐水胶合强度较未改性时提高了64.62%,达1.07 MPa,干状胶合强度提高了154.44%,达2.29 MPa,满足国家标准中的Ⅱ类胶合板要求。这归因于CP中的邻苯二酚结构氧化形成醌类结构与蛋白氨基发生席夫碱反应,形成化学键交联,增强胶黏剂的耐水胶接性能;SCI-CP胶黏剂制备胶合板的优化热压工艺参数为热压温度130℃,热压时间4.5 min(板坯厚4.5 mm),双面涂胶量250 g/m^(2)。Catechol based polysaccharide(CP) crosslinking agent was synthesized to enhance the water resistance of soybean protein adhesive through imitating the high adhesion structure of mussel protein.The effects of the mass ratio of corn starch to tert-butyldimethylchlorosilane protected 3,4-dihydroxybenzoic acid(DHBAT) in CP,the amount of added CP,and the hot-pressing process(glue amount,hot-pressing temperature,and hot-pressing time) on the water resistance of soybean protein adhesive were studied.The functional groups of CP and modified soybean protein adhesive(SPI-CP),thermal stability,crystallization and fracture surface of the adhesive were tested to analyze the strengthening mechanism of CP affecting soybean protein adhesive.The test results showed that the catechol structure was successfully grafted onto corn starch to produce CP by esterification catalyzed by 4-dimethylamino-pyridine and N,N-dicyclohexylcarbon-diimine.The optimized formula of CP was m(polysaccharide)∶m(DHBAT)=1∶2 and 6% CP addition.The water-resistant strength of the plywood prepared by the SPI-CP adhesive was increased to 1.07 MPa,counting an increase of 64.62%,and the dry adhesive strength was increased to 2.29 MPa,counting an increase of 154.44%,which met type Ⅱ plywood requirements of Chinese standards.This was attributed to the oxidation of catechol structure in CP to form quinone structure and the Schiff-base reaction of amino in soybean to form covalent bond based cross-linking structure,which enhanced the bonding performance of soybean adhesive.The optimal parameters of the hot-pressing process for the preparation of the SCI-CP adhesive for plywood were as follows:the amount of applied adhesive on both sides of veneer was 250 g/m~2,the hot-pressing temperature was 130 ℃,and the hot-pressing time was 4.5 min when the slab thickness was 4.5 mm.

关 键 词：大豆蛋白胶黏剂 邻苯二酚基多糖交联剂 胶合板 耐水胶合强度 热压工艺 

分 类 号：S781.4[农业科学—木材科学与技术]