五元环状碳酸酯的制备及其应用

发布时间：2018-07-05 02:44

  本文选题：环状碳酸酯 + 碳酸甘油酯　； 参考：《沈阳工业大学》2017年硕士论文

【摘要】：环状碳酸酯由于具有高溶解性、高沸点、低毒、可降解等优异的物化性能,被广泛应用于混合物的萃取分离、纺织、电化学、有机合成以及高聚物的制备等领域。因此,环状碳酸酯是一类非常重要的化合物。碳酸甘油酯(GC)是一种非常重要的环状碳酸酯,被广泛应用于溶剂、化妆品、电解质、涂料以及聚酯、聚碳酸酯等领域。将生物柴油的副产物甘油转化为GC,不仅提高了甘油的附加值,而且还会促进生物柴油的发展。其中,以GC为原料生产的非异氰酸酯型聚氨酯(NIPU)不仅避免了聚氨酯生产制备过程中异氰酸酯对人体和环境的伤害,而且比传统的聚氨酯具有更好的耐水解稳定性和加工性能,因此GC型NIPU受到人们的广泛关注。针对催化制备GC过程中催化剂易失活、难回收的问题,本课题的主要目的是寻找一种可用于催化制备GC的高效、易分离且可循环使用的固体碱催化剂。首先采用酯交换法,以甘油和碳酸二甲酯(DMC)为原料,考察了400℃煅烧的各种无水硅酸盐催化剂对反应的影响。发现无水硅酸钠的催化活性最高,甘油的转化率、GC的选择性和收率分别高达97.7%、94.0%和91.8%。然后将Na2SiO3·9H2O经焙烧、研磨、过筛等工艺制得了系列无水Na2SiO3固体碱催化剂,并将其用于催化甘油与DMC的酯交换反应,探讨了无水硅酸钠催化剂的制备条件对反应的影响。采用TG-DTG、XRD、FT-IR、BET、FESEM和Hammett指示剂法对系列无水硅酸钠催化剂进行了表征。实验结果表明,煅烧温度对催化剂的碱量和强碱含量有较大影响,但是强碱的增加会促进副产物缩水甘油的产生,进而降低GC的选择性和收率。催化剂的最佳制备工艺为Na2SiO3·9H2O经200℃煅烧2h后,经研磨、过筛,选取粒度为120目的组分。甘油与DMC的最佳反应条件为:催化剂的加入量为反应物质量的5%、甘油与DMC的摩尔比为1:4时,75℃常压反应2.5h。甘油的转化率和GC的选择性分别为97.8%和97.6%。催化剂连续使用5次后,催化活性并没有明显的降低。此外,以GC与癸二酸为原料,4-二甲氨基吡啶和N,N'-二环己基碳二亚胺为催化剂,室温反应16h后得到了双(1,10-环碳酸甘油酯)癸二酸酯。然后将得到的双五元环状碳酸酯与多元胺在有机碱的催化下,150℃下反应4h后得到了NIPU。通过对比双五元环状碳酸酯与不同的胺反应得到的NIPU的性能,发现三聚氰胺型NIPU的性能较好。
[Abstract]:Because of their high solubility, high boiling point, low toxicity and biodegradability, cyclic carbonates are widely used in the fields of mixture extraction, separation, textile, electrochemistry, organic synthesis and polymer preparation. Therefore, cyclic carbonate is a very important class of compounds. Glycerol carbonate (GC) is a very important cyclic carbonate, which is widely used in solvents, cosmetics, electrolytes, coatings, polyester, polycarbonate and other fields. The conversion of glycerol, the by-product of biodiesel, to GCnot only increases the added value of glycerol, but also promotes the development of biodiesel. Among them, the non-isocyanate polyurethane (NIPU), which is produced by GC as raw material, not only avoids the harm of isocyanate to human body and environment, but also has better hydrolytic stability and processability than traditional polyurethane. Therefore, GC type NIPU has attracted wide attention. In order to solve the problem that the catalyst is easy to deactivate and difficult to recover in the process of catalytic preparation of GC, the main purpose of this paper is to find a solid base catalyst which can be used in the preparation of GC with high efficiency, separation and recycling. The effects of various anhydrous silicate catalysts calcined at 400 鈩，

本文编号：2098573