桐油基环氧固化剂的制备、性能和固化反应研究.docVIP

南京林业大学 本科毕业设计（论文） 题 目：桐油基环氧固化剂的制备与研究 学 院： 化学工程学院 专 业：高分子材料与工程 学 号： 080207113 学生姓名： 李波波 指导教师： 方明锋 职 称： 讲 师 二○一二年五月十五号 摘要 桐油是我国一种重要的工业原料和出口商品，但其利用率低有待于进一步深加工。桐油的改性衍生物用作环氧固化剂时可使环氧树脂具有极好的粘结性、挠曲性、韧性、抗化学品性、抗湿性及表面光洁性，可广泛应用于各领域。目前已合成的C36二酸聚酰胺环氧固化剂热变形温度低、刚性较差，为此合成具有相对短的21个碳原子的碳链，能够提高固化物的耐热温度和模量。 本实验通过正交实验探讨出桐油的甲醇酯交换产物桐酸甲酯与丙烯酸Diels-Alder加成合成C21二元酸单甲酯（TMAA）的最佳工艺条件是：桐甲酯和丙烯酸物料比为1：0.247，反应温度180℃，反应时间3h，阻聚剂加入量为丙烯酸质量的1%，产率为85%；通过气质联用(GC-MS)分析、元素分析、红外光谱、1HNMR和13CNMR测试表征出产物（TMAA）是六种同分异构体的混合物以及桐酸甲酯和丙烯酸发生了[4+2]的Diels-Alder成环反应。然后将TMAA和不同多元胺进行胺酰胺化制备了三种不同胺值的C21二酸聚酰胺环氧固化剂，并研究了三种固化剂和双酚A环氧树脂（DGEBA）的固化物的各项机械性能及热力学温度。 结果表明相比较于C36二聚酸聚酰胺固化物，C21二酸聚酰胺固化物具有较高的模量和强度，其Tg和热变形温度也较高。 关键词：桐酸甲酯; Diels-Alder反应; C21二元酸; 环氧固化剂 Abstract Tung oil is a kind of important industrial raw material and export goods in our country,but the low utilization ratio needs to be further processing. When the modified derivatives of tung oil was used as epoxy firming agent ,it can make epoxy resin have a good bonding, bend, toughness, chemical resistance, resistance to wet sex and bright surface .Then it can be widely used in various fields. The C36 diacid polyamide curing agents which has been synthesized has the low heat distortion and poor rigid.So the synthesis of short period of 21 carbon atoms to carbon chain can improve the heat temperature and modulus of the cured products. This experiment is that Monomethyl ester of C21 dicarboxylic acid(TMAA), a new derivative of C21 dicarboxylic acid, was prepared by Diels-Alder reaction with methyl eleostearate and acrylic acid, the optimal reaction conditions indicated by orthogonal experiment were as follows: with 1% p-benzenediol by weight of acrylic acid used as polymerization inhibitor, the reaction temperature was maintained at 180℃ for 3h at a feed ratio of 1：0.247 (the ratio of Methyl eleostearate to acrylic acidgc-ms combination (GC-MS) analysis, elemental analysis, ir, 1 HNMR and 13 CNMR,the result is that TMAA is the