衣康酸羧基的酰氯化反应中双羧酸基的作用机理

In this project, methylene butanedioyl chloride would be prepared by acylchloride reaction with itaconic acid as raw material. Then, methylene succinylamide, with bisamide group in molecule structure as polymeric monomer, would be obtained through ammonolysis reaction. The effecting law of acylchloride reagent, reaction conditions, such as the reaction temperature, the ratio of the raw materials, the feeding method, reaction time and so on, would be analysed to get the optimal conditions. On the base of these experiments, mechanism of acylchloride reaction would be studied, especially the interaction two carboxyl groups of itaconic acid and the controllability of acylchloride reaction. The physical chemistry properties of methylene butanedioyl chloride would be measured, such as melting point, boiling point and the solubility. Then, the purifying method would be put forward. The effecting law of reaction conditions would be studied in ammonolysis reaction, especially the interaction between two adjacent acyl chloride groups. And the physical chemistry properties would be obtained. Through radical polymerization, polymeric activity of methylene succinylamide would be researched. The key issue was the effect of two adjacent acylamino groups on the polymeric activity. When this project was accomplished, new derivatives of itaconic acid, originating from bio mass, would be gat. Furthermore, the influence between cyle chloride groups was announced. And the controlibility of acylchloride reaction was achieved. Meanwhile, the effecting law of two acylamido groups on the polymeric activity of the double bond would be made clear.

以衣康酸为原料，通过氯酰化反应制备新型化学品亚甲基丁二酰氯；进一步进行氨解反应获得新型带有双酰胺基团的可聚合单体亚甲基丁二酰胺。探讨不同氯酰化试剂、反应温度、物料配比等工艺条件对氯酰化反应的影响规律。通过各因素的考查，分析氯酰化反应机理，重点研究相邻羧基在氯酰化反应中的相互影响机理，分析氯酰化反应的可控性。对亚甲基丁二酰氯的熔点、沸点、溶解性等理化性质进行测试，提出合理的提纯方法。研究各工艺条件对氨解反应的影响规律，分析相邻酰氯基团的相互影响，并测试亚甲基丁二酰胺的物化性质。通过自由基聚合反应，研究亚甲基丁二酰胺分子中，双酰胺基团对不饱和双键聚合活性的影响。本项目成功实施，在获得新型化学品的同时，可以理清衣康酸分子中相邻羧基在氯酰化反应中的相互影响机理，实现氯酰化和氨解反应的可控。同时，揭示相邻酰胺基团对双键活性的影响，提出衣康酸分子中羧基转变为酰胺基后，其双键活性的变化规律。

近年来，亚甲基丁二酸的生产研究已在不少科研教育机构展开，对于亚甲基丁二酸的应用开发也已逐渐让人们重视起来，在造纸、除垢、粘着剂和防蛀剂等方面也有十分广泛的应用。随着亚甲基丁二酸的本土化发展，它的应用领域将会越来越广泛，而且还会被不断的扩大和开发出来。目前，衣康酸的应用主要是利用分子结构中的双键进行均聚，或者与其它单体进行共聚，而本文主要以衣康酸双羧基为基础，对衣康酸本身进行改性处理。先通过酰氯化反应，制备亚甲基丁二酰氯，再进一步进行氨解反应，获得新型带有双酰胺基团的可聚合单体亚甲基丁二酰胺和聚衣康酰间苯二胺。本文研究了酰氯化反应、氨解反应过程中加料方式、物料配比、反应温度和反应时间等工艺条件对合成的影响规律，同时探讨了亚甲基丁二酰氯、亚甲基丁二酰胺及聚亚甲基丁二酰间苯二胺的应用领域和应用方向。 .首先探讨了以亚甲基丁二酸为原料，用五氯化磷为酰化试剂制备了亚甲基丁二酰氯，研究了酰化剂种类、反应物原料配比、反应时间和反应温度等因素对产物纯度和收率的影响。实验结果表明：以五氯化磷为酰化剂，在亚甲基丁二酰氯和五氯化磷的摩尔比为1:2.2，温度为110℃的条件下反应2h，亚甲基丁二酰氯的收率和纯度最高，分别可达到86% 和97%以上，红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)的分析均表明所得产物为纯度较高的亚甲基丁二酰氯。.以自制的亚甲基丁二酰氯和氨水为原料，在缚酸剂的条件下合成了亚甲基丁二酰胺，并探讨了缚酸剂用量及种类、酰氯和氨水的摩尔比、反应温度、酰氯滴加时间及总反应时间对酰胺合成的影响。实验结果表明：以亚甲基丁二酰氯和氨水为原料制备亚甲基丁二酰胺时，三乙胺是最为理想的缚酸剂，并且当n(三乙胺)：n(亚甲基丁二酰氯)=2.2时，亚甲基丁二酰氯和氨水的摩尔比为1:3，在0℃下滴加时间控制为30min，再反应2h左右，可以得到较高收率的产品。根据红外光谱 (FT-IR)、核磁共振氢谱(1H-NMR)及液相色谱(LC)分析均表明，所得产品为纯度较好的亚甲基丁二酰胺。