桐油基环氧固化剂的制备、性能和固化反应研究.doc

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○一二年五月十五号南京林业大学 毕业论文第 2 页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，C 21 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; C 21 二元酸; 环氧固化剂南京林业大学 毕业论文第 3 页AbstractTung 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 acid); The product characterization(TMAA) was tested by gc-ms combination (GC-MS) analysis, elemental analysis, ir, 1 HNMR and 13 CNMR,the result is that TMAA is the mixture of six oil with points,and that Futong acid methyl ester and acrylic happened [4 + 2] Diels-Alder into ring reaction.Then three kinds of novel C21 diacid polyamide curing agents with various amine values were synthesized from tung oil. Besides the various mechanical properties and kinetic temperature of the curing which is the mixture of the three kinds of curing agent and bisphenol A epoxy resin.The results showed that in comparison to the cured product of polyamide prepared from C36 dimer acid, the cured product of polyamides made from TMAA and bisphenol A epoxy resin (DGEBA) had higher strength ,modulus, Tg and heat distortion temperature. Keywords：Methyl eleostearate; Diels-Alder reaction; C21 dicarboxylic acid; Epoxy firming agent 南京林业大学 毕业论文第 4 页目 录摘 要 ...............................................................................................................................................2Abstract............................................................................................................................................3目 录 ...............................................................................................................................................4第一章 绪论 ...................................................................................................................................51.1 桐油及其衍生物的介绍 ...........................................................................................................51.1.1 桐油 Diels-Alder 反应 ...................................................................................................51.2 环氧树脂 ...................................................................................................................................61.3 环氧树脂固化剂 .......................................................................................................................61.3.1 环氧树脂固化剂的分类 .................................................................................................71.3.2 环氧树脂固化剂的发展趋势 .........................................................................................71.4 聚酰胺环氧树脂固化剂的研究现状………………………………………………………………………. 91.4.1 C36 二聚酸聚酰胺环氧树脂固化剂的缺点 ............................................................................91.4.2 桐油制备 C21 聚酰胺环氧固化剂 ................................................................................10第二章 桐酸甲酯与丙烯酸的 Diels-Alder 加成反应 ................................................................122.1 实验原理 ......................................................................................................................................................122.2 实验部分 ................................................................................................................................132.2.1 试剂与仪器 ......................................................................................................。