Study on synthesis of the fabric polyester-amide hot-melting adhesive has been carried on the copolycondensation reaction, which taking the PET resin after the alcoholysis, dimer acid and the 1, 6-hexamethylenediamine as the raw materials. Inspected the PET amount used and the glycol amount used ratio, the response the acid composition, the temperature and the time to the resultant performance influence. The optimized reaction conditions are that the reaction temperature is 235℃, the condensation reaction time is 2 h, and the mass ratio of PET and glycol is equal to 1.8: 1. The softening point of obtained product is 122℃. The intensity maintenance rate is 87% after the laundering strips, and the intensity maintenance rate is 83% after dry cleans strips.
研究了以二聚酸、己二酸、己二胺、哌嗪为原料，通过缩聚反应，制得用于 热熔胶的含哌嗪二聚酸型聚酰胺树脂。考察了合成组成与产物软化点、剪切强度 的关系，以及反应温度和时间对产物软化点和粘度的影响。得到的优化反应条件 为：反应温度为 230℃，反应时间 4h，二聚酸与共聚酸摩尔比在 4～6 之间，己 二胺与哌嗪摩尔比在 1/1 以下，所得产物软化点为 124℃，剪切强度为 6.7MPa。
南京工业大学 硕士学位论文 二聚酸型聚酰胺树脂的合成及性能研究 姓名：袁源 申请学位级别：硕士 专业：应用化学 指导教师：姚成
20060601
摘要
二聚酸是由不饱和脂肪酸或不饱和脂肪酸酯在一定条件下聚合而成的，因 其具有特殊的分子结构，所以可生成许多性能优异的衍生物，聚酰胺树脂就是其 中最重要的一种。由二聚酸合成的聚酰胺树脂具有较好的柔韧性和粘结性，以及 适宜的软化点，故可用作热熔性胶粘剂和印刷油墨的连接料。本文主要对二聚酸 型聚酯酰胺、含哌嗪聚酰胺树脂、醇溶性聚酰胺树脂的合成及性能进行了研究。
研究了以醇溶性聚酰胺树脂为原料所制备的聚酰胺树脂醇溶液。对聚酰胺树 脂醇溶液不同涂法的防腐性能测定进行了考察，结果表明聚酰胺树脂醇溶液具有 耐酸、耐碱、耐盐、耐油的性能。
关键词：二聚酸 聚酰胺 热熔胶 油墨
ABSTRACT
Dimer acid is polymerization by the unsaturated fatty acid or the unsaturated fatty acid ester under the certain condition. Because it has the special molecular structure, therefore dimer acid may produce many derivatives with outstanding property, the polyamide resin is the one of the most important kind. By dimer acid synthesis is polyamide resins have the good flexibility and cohesiveness, as well as is suitable melting point, so may use as the hot-melting adhesive and the printing ink connection material. This paper’s objective is mainly to study on synthesis and performance of the dimer acid-based polyester-amide, the polyamide resins containing piperazine, and the alcohol soluble polyamide resins.
二聚酸具有与一般不饱和脂肪酸相似的化学性质，可与碱金属反应生成金属盐， 也可衍生成酰氯、酰胺、酯、二异氰酸酯等产物。例如，(1)氢化反应：在钠或亚铬酸 铜的催化作用下，二聚酸高压加氢可以得到饱和二聚醇。二聚醇为粘性流体，与水形 成乳状液，可有效防止二聚酸氧化；(2)与碱金属氢氧化物或两性氢氧化物反应：与钠、 钾的氢氧化物反应生成具有强乳化作用的金属皂化物；与铝、锌的氢氧化物等反应， 则生成不溶于水的金属盐；(3)酯化反应：与醇在强酸催化剂作用下生成的酯具有低粘 度，可溶于各种有机溶剂。(4)与卤化物反应：与 PCl3 反应生成酰氯，这是一种非常 有用的中间体，可用于制备其他二聚酸的衍生物。二聚酰氯还可以直接用作金属防腐 剂；(5)与胺反应：在不同条件下，可分别生成盐、酰胺、亚胺等；(6)与环氧乙烷反 应：与环氧乙烷反应生成羟乙酯，在一定条件下可继续进行反应，直至生成链状聚氧 乙烯酯；(7)聚合反应：二聚酸能与二胺或多元胺反应生成聚酰胺；与多元醇反应生成 聚酯多元醇，聚酯多元醇可再与二异氰酸酯反应生成聚氨酯[3]。这些反应都已在工业 中得到广泛的应用。
piperazine is below 1/1, the softening point of obtained product is 124℃ and the shearing strength is 6.7 MPa.
Study on synthesis of the alcohol soluble polyamide resins has been carried on the copolycondensation reaction, which taking dimer acid, the butyric acid, the isobutyric acid, 1, 6-hexamethylene-diamines as the raw material. The effects of the acid composition in the raw material, the reaction temperature and the reaction time on the product performance, as well as effects of the ratio of reactive materials and different reaction conditions on gel time and viscosity of the prepared alcohol solution of polyamide resins have been investigated. The optimized reaction conditions are that the reaction temperature is 235℃, reaction time is 5 h, the mole ratio of dimer acid and the copolymerization acid is between 70/30 and 60/40, the softening point is 110℃, the viscosity is 77.5 cst under 25℃ condition, the cold point is -4℃.
研究了以涤纶树脂为原料经醇解后，与二聚酸、己二胺等进行共缩聚反应， 制得织物用聚酯酰胺热熔胶。考察了涤纶树脂用量与乙二醇用量比、原料中酸组 成、温度及时间对产物性能的影响。得到的优化反应条件为：反应温度为 235℃， 缩聚反应时间为 2h，m 涤纶：m 乙二醇＝1.8:1。所得产物软化点为 122℃，水洗后剥 离强度保持率为 87％，干洗后剥离强度保持率为 83％。
Keywords：dimer acid , polyamide , hot-melt adhesive , ink
硕士学位论文
第一章 文献综述
1.1 二聚酸及其应用
1.1.1 二聚酸的概述
二聚酸(Dimer Acid)是 C18 不饱和脂肪酸二聚物的简称，由不饱和脂肪酸或不饱和 脂肪酸酯通过 Diels－Alder 反应生成 C－C 键，或以单环、双环形式结合起来的二 元酸。它是多种异构体的混合物，其中还含有单酸和三聚酸。二聚酸性能优良，在涂 料、热熔胶、油墨、固化剂、润滑剂、表面活性剂、复合固体火箭燃料等方面的生产 中，显示出越来越重要的地位[1]。纯二聚酸为淡褐色的透明粘稠状液体，有较好的热 稳定性，在-20℃低温下不结晶、不失透明度和流动性，250℃不蒸发，不凝胶化。二 聚酸的相对分子质量较大，不溶于水，但能与各种溶剂互溶，如可溶于丙酮、乙醇、 乙醚、氯仿、苯以及脂肪族石油系列溶剂[2]。
Study on synthesis of dimer acid-based polyamide resins containing piperazine have been carried on the copolycondensation reaction, which taking dimer acid, the adipic acid, the 1, 6-hexamethylenediamine and piperazine as the raw materials for the purpose of hot-melting adhesive. The effects of the synthesis composition, the softening point, the shearing strength relations temperature well as reaction time have been investigated. The optimized reaction conditions are that the reaction temperature is 230℃, reaction time is 4 h, the mole ratio of dimer acid and the copolymerization acid is 4~6, the mole ratio of 1, 6-hexamethylenediamine and