Zn-La复合氧化物催化剂用于甲醇与碳酸乙烯酯酯交换反应的研究

ZnO、La₂O₃和Zn-La复合氧化物催化剂用于甲醇与碳酸乙烯酯反应制备碳酸二甲酯和乙二醇。催化剂采用共沉淀法进行制备,并用BET、XRD、TG-DSC、CO₂-TPD和Hammett滴定等对催化剂进行表征。考察了Zn-La物质的量比、焙烧温度,反应条件（反应温度、反应时间、催化剂用量等）对催化剂活性的影响。结果表明,ZnLa复合氧化物物质的量比为2：1,焙烧温度为500℃时,催化剂表现了较好的催化效果。催化剂的活性与催化剂表面的碱性强度和碱量有关,碱量越多催化剂的活性越好。     

Lanthanum nitrate as an efficient and recoverable homogeneous catalyst for the transesterification of dimethyl carbonate with ethanol

Lanthanum nitrate was an efficient and recoverable homogeneous catalyst for the transesterification of dimethyl carbonate (DMC) with ethanol. It was reused 5 times for the transesterification without loss of its catalytic activity.     

Mg-Al-O-t-Bu hydrotalcite as an efficient catalyst for the transesterification of dimethyl carbonate with ethanol

Mg-Al-O-t-Bu hydrotalcite was synthesized and characterized by XRD, FT-IR and TGA-DTA. It was proved to be an active heterogeneous catalyst for the transesterification of dimethyl carbonate (DMC) with ethanol. When the reaction was carried out over Mg-Al-O-t-Bu hydrotalcite at 80°C, 7 h, molar ratio of ethanol to DMC 5:1, 1.0 wt.% of catalyst, the conversion of DMC was 86.4%, the selectivity to diethyl carbonate (DEC) was 61.2%. This heterogeneous catalyst could be used 5 times without loss of its activity.     

Mg/Al水滑石催化碳酸二甲酯与苯酚酯交换反应

Mg/Al水滑石催化碳酸二甲酯与苯酚酯交换反应     

Synthesis of polycarbonate from dimethyl carbonate and bisphenol-a through a non-phosgene process

A novel nonphosgene process for producing bisphenol-A polycarbonate (PC) was developed through a transesterification between bisphenol-A (BPA) and dimethyl carbonate (DMC) and a melt-polycondensation of the resulting bisphenol-A bismethylcarbonate (1). The transesterification was carried out by heating bisphenol A in dimethylcarbonate in the presence of Lewis acid catalysts, removing the by-producing methanol using molecular shieves 4A. Among various catalysts, a combination of (Bu₂SnCl)₂O and dimethylaminopyridine gave the best results to produce 1 in 22% yield for 48 h. Using a larger amount of the molecular sieves further improved the yield to 80% in 120 h. The resulting 1 was heated under reduced pressure in the presence of titanium catalysts to produce PC in good yields. The resulting PC had high weight average molecular weight (M_w) of 75,000. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2087–2093, 1999     

不同催化剂上碳酸乙烯酯与对苯二甲酸二甲酯的酯交换反应

 将碳酸乙烯酯与甲醇酯交换合成碳酸二甲酯的反应和乙二醇与对苯二甲酸二甲酯酯交换合成聚对苯二甲酸乙二醇酯(PET)的反应偶合,建立了同时合成碳酸二甲酯和PET的新方法. 探索了有机锡、钛酸酯、乙酸盐和金属氧化物等不同催化剂对合成碳酸二甲酯和PET的影响. 二丁基氧化锡的催化效果最佳,其碳酸二甲酯的收率达68.4%.     

Ca-Al催化剂上甘油与碳酸二甲酯酯交换合成碳酸甘油酯

生物柴油是一种环保、可再生、使用安全、可替代石化柴油的新型液体燃料,其产量和使用范围正逐年扩大。然而生物柴油生产过程中的主要副产物甘油严重过剩,因此甘油资源化转化和利用已经成为近年研究热点。甘油可以作为一种平台化合物实现向多种高附加值化学品的转化,例如通过催化氢解合成1,2-丙二醇,通过发酵和催化氧化制备二羟基丙酮,通过脱水制备丙烯醛和羟基丙酮,通过酯交换反应生成甘油酯等。其中,以甘油为原料合成的碳酸甘油酯(GC)具有很好的工业应用前景。以碳酸二甲酯(DMC)为原料与甘油进行酯交换合成GC是近年内比较有工业发展潜力的合成路线。前期研究发现,固体碱对该反应具有很好的催化活性,而且随着催化剂碱性增强,甘油转化率明显增加,然而当催化剂(如NaOH, KOH和K2CO3等)碱性过强时,产物选择性明显降低。水滑石类化合物是一种常见的碱性温和的固体催化剂,而且其碱性与结构可以调节,因此我们选择了一种常见水滑石——水铝钙石作为本研究的重点。 本文通过共沉淀法制备了一系列不同Ca/Al比(1–6)的Ca-Al水滑石,并以此作为前驱体制备了新型的固体碱催化剂。 XRD结果表明,当Ca/Al比为1–6时,所有样品都出现了明显的水滑石特征衍射峰,但当铝含量过高时会出现氢氧化铝杂相。 SEM结果发现,当Ca/Al =2–4时,样品中水滑石的结晶度高,有较完整的水滑石晶片, Ca/Al =6的样品中水滑石晶片较小, Ca/Al =1的样品中有明显的无定形氧化铝杂相。 TG-DSC结果表明, Ca/Al =2的样品除了几个与水滑石相关的特征失重峰以外,在786oC还检测到明显的热吸收峰,说明此时钙铝石已经发生分解,生成了单独的Ca12Al14O33晶相和氧化钙,这与SEM结果一致。这些水滑石经焙烧后用于温和条件下催化甘油与DMC酯交换生成GC的反应,发现上述催化剂对该反应具有很高的催化活性和目的产物选择性。当DMC与甘油的摩尔比为3时,70oC反应3 h后,甘油转化率达到93%, GC选择性高于97%。表征结果显示,甘油转化率主要取决于焙烧后Ca-Al催化剂中强碱性中心数量。其中经800oC焙烧后Ca/Al =2的样品中强碱性中心数量最多,因而表现出最高的催化活性。焙烧后催化剂中形成的Ca12Al14O33晶相在多次重复使用后仍可以稳定存在,但是表面CaO易流失,可能会降低催化剂的重复使用活性。     

Mg-Al水滑石催化甘油与碳酸二甲酯的酯交换反应简

报道了温和条件下甘油和碳酸二甲酯在一系列不同Mg/Al比（0.5-6）的Mg-Al水滑石催化下合成碳酸甘油酯（GC）的反应. 发现,Mg-Al水滑石对该反应具有很高的GC选择性,其中Mg/Al=2经400℃处理所得水滑石催化效率最高：70 ℃反应3 h甘油转化率达66.9%时,GC选择性维持在97%以上. 表征结果表明,水滑石样品的比表面积、孔径、结晶度和表面碱性对其催化活性影响很大.     

Transesterification of dimethyl oxalate with phenol over Ti-containing phosphate catalysts

The transesterification of dimethyl oxalate (DMO) with phenol is studied on various Ti-containing phosphate (Ti-P-O) catalysts. The weak acid-base characteristics of Ti-P-O catalysts are responsible for the high activity and selectivity to methyl phenyl oxalate (MPO) and diphenyl oxalate (DPO).     

Synthesis of dimethyl adipate from cyclopentanone and dimethyl carbonate over solid base catalysts

A facile route for the synthesis of dimethyl adipate (DAP) from cyclopentanone and dimethyl carbonate (DMC) in the presence of solid base catalysts has been developed.It was found that the intermediate carbomethoxycyclopentanone (CMCP) was produced from cyclopentanone with DMC in the first step,and then CMCP was further converted to DAP by reacting with a methoxide group.The role of the basic catalysts can be mainly ascribed to the activation of cyclopentanone via the abstraction of a proton in the α-position by base sites,and solid bases with moderate strength,such as MgO,favor the formation of DAP.     

氧化钙室温催化碳酸丙烯酯和甲醇的酯交换合成碳酸二甲酯

 在室温条件下用氧化钙催化碳酸丙烯酯（PC）和甲醇的酯交换反应，高收率、高选择性地合成了碳酸二甲酯（DMC）．在假设羟丙基甲基碳酸酯（HPMC）是反应中间产物的基础上，计算了甲醇、PC和HPMC的电荷分布，并推论出可能的副反应PC的聚合．通过考察反应温度对DMC选择性和收率的影响，证明了关于中间体HPMC和副反应PC聚合的假设．考察了加料顺序、反应温度对DMC生成速率的影响，并在此基础上提出了氧化钙催化PC和甲醇酯交换合成DMC的可能机理．     

Liquid-liquid equilibria of ternary mixtures of dimethyl carbonate, diphenyl carbonate, phenol and water at 358.15 K

The ternary liquid-liquid equilibria (LLE) of the following systems were analytically determined at 358.15 K at atmospheric pressure using stirred and thermo-regulated cells: {dimethyl carbonate (DMC) + diphenyl carbonate (DPC) + water}, {DMC + phenol + water} and {DPC + phenol + water}. The experimental ternary LLE data were correlated with the NRTL and UNIQUAC activity coefficient models. Additionally, the Bachman-Brown correlation was used to ascertain the reliability of the experimental data for each system.     

KF/MgO 催化碳酸二甲酯与月桂醇酯交换合成碳酸二月桂酯

 研究了 KF/MgO 催化剂对碳酸二甲酯 (DMC) 与月桂醇酯交换反应制备碳酸二月桂酯 (DDC) 的催化性能. 考察了催化剂 KF 负载量及焙烧温度对反应的影响, 并采用 X 射线衍射、傅里叶变换红外光谱、扫描电镜和 N2 吸附-脱附等对催化剂进行了表征. 结果表明, 催化剂 KF/MgO 在空气中较高温度焙烧后生成新相 K2MgF4 和 K2CO3, 它们为催化剂的主要活性组分. 催化性能测试结果表明, 该催化剂具有良好的催化活性, KF 的最佳负载量为 30%, 催化剂的最佳焙烧温度为 873 K. 还考察了反应条件对 KF/MgO 催化剂性能的影响. 当在反应物月桂醇:DMC 摩尔比 = 4, 催化剂用量为反应物总质量的 0.75%, 反应时间为 4 h 的条件下, 反应性能最佳, DMC 转化率和 DDC 收率分别为 86.7% 和 86.2%.     

碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的热力学性质及均相催化剂

在298.15K,101.325kPa条件下,液态碳酸二甲酯(DMC)的标准Gibbs自由能和熵分别估算为-472.3kJ*mol-1和245.2J*mol-1*K-1.在298K～523K计算了由DMC和苯酚生成碳酸二苯酯(DPC)和苯甲醚反应的热力学性质(ΔrH0m,ΔrS0m,ΔrG0m和平衡常数).计算出的热力学性质表明,DMC和苯酚酯交换合成DPC反应是吸热的,并且在热力学上是不利的.研究了n-Bu2SnO, Ti(OC4H9)4, AlCl3和ZnCl2四种酯交换法合成DPC反应的催化剂,其中n-Bu2SnO具有最高的催化活性.热力学计算和实验结果均表明,合成DPC反应的最佳温度为453K.当以n-Bu2SnO为催化剂,n(苯酚)∶n(DMC)＝4∶1时,DPC的产率和选择性分别为43.0%和88.7%.     

钛酸酯催化碳酸二甲酯与苯酚酯交换反应

The transesterification of phenol and dimethyl carbonate (DMC) to diphenyl carbonate (DPC) was studied using tetrabutyl titanate and tetraphenyl titanate as catalysts. The main product was found to be methyl phenyl carbonate (MPC) which is an intermediate of the reaction. The selectivity for DPC was improved when increasing the phenol/DMC molar ratio or prolonging the reaction time. The phenol conversion, selectivity for MPC and DPC were 47 4%, 90 9% and 9 14%, respectively, when the transesterification reaction approached equilibrium under the conditions of 175 ℃, 25 h and DMC∶phenol∶ Ti(OBu) 4 molar ratio of 1 5∶1∶0 05. The selectivity for DPC could reach 12.2% when the reaction time was 30 h. The tetrabutyl titanate catalyst showed a higher catalytic activity than tetraphenyl titanate.     

催化剂对碳酸二甲酯与苯酚酯交换反应的影响

甲基苯基碳酸酯;碳酸二苯酯;催化剂对碳酸二甲酯与苯酚酯交换反应的影响     

二丁基氧化锡催化碳酸二甲酯与苯酚酯交换反应机理研究

研究了二丁基氧化锡催化碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的反应机理, 发现原料苯酚和产物DPC都能与二丁基氧化锡生成同一种中间体, 并测定了其晶体结构. 该晶体属于单斜晶系, P2₁/n空间群; 晶胞参数: a＝1.3336(2) nm, b＝1.7208(2) nm, c＝1.3759(3) nm, β＝101.00(2)°; V＝3.0993(9) nm³; D_c＝1.432 g/cm³; Z＝4; F(000)＝1352; μ＝1.635 mm^－1. 分析结果显示该中间体是一种新型的二聚四烃基二锡氧烷化合物[Bu₂Sn(OPh)OSnBu₂O(Ph)]₂ (I), 该化合物具有中心对称的层状结构. MS和XPS结果证实I在酯交换反应条件下能稳定存在. 基于实验结果, 本文提出了一个合理的酯交换反应机理.     

有机阴离子柱撑水滑石催化酯交换合成碳酸二苯酯

 A series of organic anion-pillared hydrotalcites were synthesized by the ion exchange method and characterized by X-ray diffraction and Fourier transform infrared spectroscopy. The hydrotalcite precursor and pillared hydrotalcites with different anions was tested as catalysts in transesterification of dimethyl carbonate (DMC) with phenol. The results show that the catalytic selectivity of this transesterification reaction over these organic anion-pillared hydrotalcites is significantly improved. The catalytic selectivities of C4H4O4-, C6H8O4-, C10H16O4-, 1,4-C8H4O4-, and C7H5O2-pillared hydrotalcites for transesterified products (diphenyl carbonate and methyl phenyl carbonate) are all greater than 90%, at least 10% higher than that of the hydrotalcite precursor. Under the conditions of n(phenol)/n(DMC)=4, catalyst amount=1.5%, and t=10 h, the C6H8O4-pillared hydrotalcite presents the best catalytic performance, and the DMC conversion and the selectivity for transesterified products reach 43.8% and 93.2%, respectively.     

碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的HPLC分析

用HPLC分析碳酸二甲酯与苯酚酯交换合成的碳酸二苯酯，克服了GC法分析由于高温导致碳酸二苯酯分解造成含量偏低的问题，建立了针对性强、操作简单、精密度和准确度高的HPLC分析方法。     

MoO3催化碳酸二甲酯与乙酸苯酯合成碳酸二苯酯

采用焙烧法制备了MoO3催化剂并将其用于碳酸二甲酯(DMC)与乙酸苯酯(PA)合成碳酸二苯酯(DPC)反应,考察了焙烧温度对催化荆性能的影响,并用X射线衍射(XRD)对催化剂结构进行了表征.结果发现,在400或500℃焙烧的催化剂具有良好的催化性能,DMC转化率为73.9%,DPC和甲基苯基碳酸酯的选择性分别为39.5%和56.5%.XRD结果表明,该催化剂物相组成为正交晶系MoO3,且(021)或/和(110)晶面有利于酯交换反应.催化剂使用5次后DMC转化率从73.9%降至10.2%,多次重复使用后的催化剂在窄气气氛中于400或500℃焙烧即可再生,再生后催化剂的性能几乎和新鲜催化剂相当.