醇解技术在制备皮革加脂剂方面的研究进展

本文介绍了醇解反应的动力学、影响醇解反应收率的因素以及醇解反应在合成加脂剂方面的应用。     

废聚酯饮料瓶裂解制备聚酯清漆

叙述了以废聚酯饮料瓶为原料,经过醇解、酯化以及缩聚等工艺过程,制成透明聚酯清漆。该法为废饮料瓶回收利用开辟了可行之路,也为聚酯清漆找到了廉价的原材料。     

Synthesis of 2‐monoglycerides by alcoholysis of palm oil and tuna oil using immobilized lipases

Commercial immobilized lipases were used for the synthesis of 2‐monoglycerides (2‐MG) by alcoholysis of palm and tuna oils with ethanol in organic solvents. Several parameters were studied, i.e., the type of immobilized lipases, water activity, type of solvents and temperatures. The optimum conditions for alcoholysis of tuna oil were at a water activity of 0.43 and a temperature of 60 °C in methyl‐tert‐butyl ether for ～12 h. Although immobilized lipase preparations from Pseudomonas sp. and Candida antarctica fraction B are not 1, 3‐regiospecific enzymes, they were considered to be more suitable for the production of 2‐MG by the alcoholysis of tuna oil than the 1, 3‐regiospecific lipases (Lipozyme RM IM from Rhizomucor miehei and lipase D from Rhizopus delemar). With Pseudomonas sp. lipase a yield of up to 81% 2‐MG containing 80% PUFA (poly‐unsaturated fatty acids) from tuna oil was achieved. The optimum conditions for alcoholysis of palm oil were similar as these of tuna oil alcoholysis. However, lipase D immobilized on Accurel EP100 was used as catalyst at 40 °C with shorter reaction times (<12 h). This lead to a yield of ～60% 2‐MG containing 55.0‐55.7% oleic acid and 18.7‐21.0% linoleic acid.     

Enzymatic production of alkyl esters through alcoholysis: A critical evaluation of lipases and alcohols

This paper focuses on a detailed evaluation of commercially available immobilized lipases and simple monohydric alcohols for the production of alkyl esters from sunflower oil by enzymatic alcoholysis. Six lipases were tested with seven alcohols, including straight and branched-chain primary and secondary alcohols. The reactions were conducted in a batch stirred reaction vessel using stoichiometric amounts of substrates under solvent-free conditions. Dramatic differences in alcoholysis performance were observed among the different lipases. For most of the alcohols, Novozym 435 produced the highest yield of FA alkyl esters, with yields well over 90% for methanol, absolute ethanol, and 1-propanol. Overall, 96% ethanol was the preferred alcohol for all lipases except Novozym 435, and ethanolysis reactions reached the maximal conversion efficiency. Increasing the water content in the system resulted in an increased degree of conversion for all lipases except Novozym 435. The secondary alcohol 2-propanol significantly reduced the alcoholysis reaction with all lipases; however, the branch-chain isobutanol was more advantageous than linear 1-butanol for Novozym 435, Lipozyme RMIM, and Lipase PS-C. Many commercial immobilized lipases are highly efficient and promising for the production of alkyl esters, offering high reaction yields and a simple operation process.     

低相对分子质量的聚乙烯醇的合成研究

聚乙烯醇(PVA)是重要的水溶性聚合物.低相对分子质量的PVA被广泛应用于化妆品、食品、医药和农业等领域.采用溶液聚合法,以醋酸乙烯为单体,偶氮二异丁腈为引发剂,甲醇为溶剂,加入分子量调节剂,通过多次实验优化实验条件,合成低相对分子质量的聚醋酸乙烯(PVAc),后者以NaOH为催化剂,经醇解得到了外观为白色粉末状、平均聚合度为600,醇解度为80%的低相对分子质量的PVA产品.     

聚酯醇解反应动力学研究

根据聚酯醇解的反应规律,建立了该反应的动力学数学模型,用恒温实验数据确定了以醋酸盐化合物为催化剂条件下的醇解动力学参数,求得反应的活化能和频率因子分别为220KJ/mol和8.865×10~(22);探讨了催化剂机理及影响反应的各项因素,如乙二醇的加入量及反应温度.研究发现(1)在一定温度范围内升高反应温度,有利于反应的进行,但应避免前期温度过高,引起乙二醇的挥发;(2)乙二醇过量的情况下,醇解产物全部为BHET。     

2-furyloxirane: II. Reduction,hydrolysis, alcoholsis and the uncatalysed polymerization induced by OH groups

The reduction of furyloxirane (FO) with different reducing agents was conducted under various experimental conditions and occurred essentially by the α-opening of the oxirane ring. It was also shown that the presence of Lewis acids favoured this mode of ring opening. The hydrolysis of furanic oxiranes was accompanied by oligomerization even in the absence of a catalyst. Moreover, very small quantities of water induced the oligomerization of FO giving degrees of polymerization of 40–50. This behaviour is unique since aliphatic and aromatic oxiranes are not activated by water alone. The alcoholysis of FO catalysed by metal alkoxides showed variable extents of α- and β-opening of the oxirane ring, depending on the steric hindrance of the alkoxide used.     

尿素和甲醇反应制氨基甲酸甲酯的研究

尿素和甲醇在自制催化剂作用下制备氨基甲酸甲酯（MC）,通过测试分析计算MC的收率,比较不同方法制备出的负载型金属氧化物催化剂的催化活性,并对活性好的催化剂进行SEM和XRD表征。实验结果表明,金属氧化物负载型催化剂中ZnO-KOH对合成氨基甲酸甲酯具有较高的催化活性,其反应优化条件为：n(甲醇)∶n(尿素)＝60、催化剂ZnO-KOH用量为甲醇和尿素质量的4％、反应时间为8 h和反应温度为185 ℃,MC的收率可达84.46％。     

稀乙酸对聚乙烯醇水溶液静电纺丝性能的影响

采用质量分数3%乙酸水溶液作为高醇解度聚乙烯醇(PVA)的溶剂,研究了PVA稀乙酸溶液的性质及其静电纺丝工艺。结果表明:加入质量分数3%乙酸,PVA溶液粘度下降,表面张力及电导率提高;纺丝液浓度对PVA稀乙酸溶液的静电纺丝性能影响最大;当PVA稀乙酸溶液质量分数为8%～13%,固化距离15mm,纺丝电压14～18kV时,可制得形态良好的PVA超细纤维无纺毡。     

加脂剂合成中的醇解反应

本文论述以阴离子层柱材料作催化剂,进行醇解反应制备皮革加脂剂中间体。以植物油为原料进行酯交换反应,制得脂酸甲酯,甘油单双酯,或甲基丙烯酸甲酯醇解制甲基丙烯酸高级醇酯。可进一步合成LWF结合型加脂剂,改性菜油加脂剂,磷酸酯加脂剂,丙烯酸加脂复鞣剂。