【作者】 耿涛；

【导师】 李瑞丰； 李秋小；

【作者基本信息】 太原理工大学 ， 化学工程与技术， 2010， 博士

【摘要】 酯基季铵盐作为一种生物降解性优良的阳离子表面活性剂,已广泛应用于纺织、印染、皮革、合成纤维、造纸和机械行业等领域,是目前“绿色柔软剂”的典型代表。但因其生产工艺的限制,存在产品质量不高、制备工艺有待改进、制备过程中使用剧毒季铵化剂等问题。碳酸二甲酯(DMC)是近年来颇受重视的一种用途广泛的绿色化学品,由于其分子中含有甲基基团,故可作为季铵化试剂使用。本文主要是对酯基季铵盐的制备工艺进行绿色化改进,并对碳酸二甲酯的季铵化反应进行研究,为拓展碳酸二甲酯在阳离子表面活性剂制备中的绿色化应用奠定一定的基础。开发了环路反应装置制备酯胺的新工艺路线,成功合成了质量较高的酯胺产品。在相同的反应条件下同传统釜式搅拌工艺进行了多方面对比,结果表明环路反应装置具有较高的传质传热效率,不仅使反应时间缩短1/3,而且产品质量高、色泽好,能源及氮气消耗低,它具有的气相自循环特性实现了反应过程的零排放。为解决传统酯胺化反应催化剂的残留和回用问题,进一步提高酯胺产品的选择性,开发了适用于酯胺化反应的负载硫酸锆(ZS)的SBA-15固体酸催化剂(ZS/SBA-15)。通过ZS/SBA-15与传统催化剂比较,发现当以20%ZS/SBA-15(6)作为酯胺化反应的催化剂时,不仅可有效提高原料的转化率和产品中单双酯含量,而且解决了催化剂的残留和回用问题,提高了酯胺产品的内在质量。研究了碳酸二甲酯与酯胺的季铵化反应,并确定了其较优的反应条件。1H-NMR表征结果说明成功合成了新的绿色酯基季铵盐产品—双硬脂酸乙酯基羟乙基甲基碳酸甲酯铵(EQDMC)。反应中过量碳酸二甲酯和溶剂回收后不需经过任何处理即可循环使用。通过EQDMC与传统柔软剂—双硬脂酸乙酯基羟乙基甲基碳酸甲酯铵(EQDMS)和D1821的比较,发现EQDMC在性能上可替代EQDMS和D1821,是一种新的绿色柔软剂产品。研究了碳酸二甲酯与不同碳链长度的单、双烷基叔胺季铵化反应的优化条件。结果表明:相同反应条件下,单烷基叔胺的反应速率和季铵化率与其碳链长度无关,其季铵化率均在99%左右;而双烷基叔胺的反应速率和季铵化率与其碳链长度有很大关系,碳链长度越长反应速率越慢。通过分子空间结构模拟发现,引起这种差异的主要原因是空间位阻的不同。同时,利用甲基碳酸酯季铵盐和盐酸反应合成了1831,证明了甲基碳酸酯季铵盐可以作为合成多种负离子季铵盐的原料,为丰富季铵盐的种类提供了前期试验基础。更多还原

【Abstract】 Ester quaternary ammonium salt (EQ) as an excellent biodegradable cationic surfactant, has been widely used in textile, printing and dyeing, leather, synthetic fiber, paper making and machinery industries, which is a typical kind of“green softener”. However, some defects, existing in the production process of EQ, cause the product quality and preparation process should be improved. Further more, quaternary ammonium agent used in the production process of EQ was toxic, which should be improved too. Dimethyl carbonate (DMC), which is a kind of green reagent, has received much attention in recent years. The molecule of DMC containing methyl group can be used as a new type of quaternization agent. This article mainly investigated the green improvement of EQ preparation process and the application of dimethyl carbonate as a quaternization agent, which would lay the foundation for the application of dimethyl carbonate in the preparation of green cationic surfactant.Loop reactor process had been developed to prepare esteramine, and the high quality of esteramine was successfully synthesized. Compared with the conventional stirred tank process under the optimal experimental conditions, the results showed that the loop reactor process not only had higher heat and mass transfer efficiency with 1/3 reaction time being shortened and low consumption of energy and nitrogen, but also obtained higher quality and lighter color of the products. Further more, there was no emission in the reaction process.To overcome the problems for the homogenous catalysts that catalysts remained in the products and can not be reused, and improve the selectivity of esteramine, zirconium sulfate (ZS) supported on SBA-15 mesoporous molecular sieve solid acid catalyst (ZS/SBA-15) were developed for esteramine synthesis. In comparison with the traditional catalyst, ZS/SBA-15 showed better catalytic activity and selectivity. When 20%ZS/SBA-15(6) was taken as the catalyst of esteramine synthesis, it not only could improve the conversion of raw materials, but also increased the content of mono-esteramine and di-esteramine. Moreover, this kind of improvement could solve the catalyst residues and be reused effectively, and benefit the intrinsic quality of ester amine products.The quaternization of DMC and esteramine was studied. The reaction conditions were optimized by orthogonal test method. The characterization results of 1H-NMR indicated that the new green EQDMC (Di-alkyl diester hyroxylethyl methyl ammonium methyl carbonate) was synthesized successfully. Excessive dimethyl carbonate and the solvent could be recovered and recycled without any extra-treatment. EQDMC could replace the traditional softener as a new green softener.The quaternization reaction conditions of dimethyl carbonate and alkyl tertiary amine with different carbon chain lengths of single and double were also optimized. The results showed that: the reaction rate and conversion of the single alkyl tertiary amine had nothing to do with the carbon chain length at the same reaction conditions, and the conversions were about 99%, but the reaction rate and conversion of dual alkyl tertiary amine had a lot to do with carbon chain lengths, and the reaction rate slowed with the longer carbon chain. Based on the molecular space structure simulations, a conclusion was drawn that the difference was mainly due to the space steric hindrance.At the same time, 1831 was synthesized by the reaction of quaternary ammonium salt methyl carbonate and hydrochloric acid, which proved that quaternary ammonium methyl carbonate could be used as the materials of preparing various counter ion of quaternary ammonium salts. During this, a pre-test foundation has been built for enriching the types of quaternary ammonium salts.更多还原