乙醇酸甲酯偶联反应的研究进展

详细介绍了有关甲醛、甲酸甲酯偶联合成乙醇酸甲酯的合成方法及反应机理的研究进展     

甲酸甲酯与甲醇钠合成碳酸二甲酯反应研究

通过对不同溶剂存在下甲酸甲酯与甲醇钠非催化合成碳酸二甲酯反应的研究,发现四氢呋喃比质子性溶剂甲醇和极性非质子性溶剂二甲基甲酰胺等更适合该合成反应,它兼有两者的优点,对两者的缺点又有不同程度的克服。本文重点考察了甲醇和一氧化碳对催化合成DMC反应的影响,结果发现当反应体系中有甲醇存在时,甲醇会与甲氧基负离子通过氢键结合,降低甲氧基负离子的亲核活性,影响反应生成DMC的速率。与甲醇不同,一氧化碳能有效抑制甲酸甲酯的分解反应,当使用CO/O2作氧化剂时,得到了较好的DMC收率和选择性。     

甲酸甲酯合成技术进展

介绍甲酸甲酯的合成方法，即甲醇酯化法、甲醇气相催化脱氢法、甲醇羰基化法、合成气直接合成法最新技术进展，并分析了这几种方法的优劣。     

我国甲酸甲酯合成技术新进展

综述甲醇羰基化法、甲醇脱氢法、合成气直接合成法三种甲酸甲酯 ( MF)合成技术最近几年的开发研究情况。     

甲酸甲酯合成技术新进展

综述甲醇羰基化法、甲醇脱氢法、合成气直接合成法3种甲酸甲酯合成技术最近几年的开发研究情况。     

由含CO的尾气净化合成甲酸甲酯

介绍了甲醇羰基化合成甲酸甲酯的研究进展 ,并着重指出由含CO的工业尾气与甲醇合成甲酸甲酯工艺的经济性及对环境的友好性。     

低温低压液相催化制甲醇,甲酸甲酯

甲醇是大宗化工产品,甲酸甲酯(MF)是新一代C_1化工产品的基础中间体之一。本文介绍以合成气为原料,低温低压液相催化联产甲醇和MF的新工艺,该工艺反应温度低,利用浆态床反应器。与ICI公司的通用合成甲醇工艺及甲醇羰化法制造甲酸甲酯工艺相比,均显示了操作条件温和、成本低等优点,在国际上亦处于领先地位,这一新工艺的开发将会提升我国有关产品的国际竞争能力。     

甲酸甲酯合成工艺及其下游化学品的开发

综述甲醇羰基化法,甲醇脱氢法,合成气直接合成法３种甲酸甲酯（ＭＦ）合成工艺及丙酸甲酯、乙醇酸甲酯、丙烯酸甲酯、甲醇等下游化学品最近几年的开发研究情况。     

甲基橙褪色光度法测定亚硝酸根的研究

以亚硝酸根在酸性介质中能使甲基橙褪色为基础,建立了一种测定亚硝酸根的新的光度法。该方法在室温下进行,操作方便,选择性好。该方法的线性范围为0.1～10.0μg/mL,检出限为0.08μg/mL。用于水样中亚硝酸根的测定,RSD为<5.3%,加标回收率在95%～103%之间。     

一氧化碳、甲醇液相羰基化合成甲酸甲酯的助催化剂研究

在间歇釜式反应器中,进行一氧化碳与甲醇羰基化合成甲酸甲酯的合成,考察甲醇钠碱性催化体系对反应的影响。结果表明:以甲醇钠为主催化剂,添加吡啶作为助剂,有较好的助催化剂的作用。     

甲酸甲酯的应用及制备

本文介绍了甲酸甲酯下游产品的开发利用及甲酸甲酯的制备方法。以MeF作为有机合在中间体,可进行多种反应,生成各种衍生物,成为C化学工业发展有效途径之一,具有广泛的工业应用前景,值得进一步开发利用。     

Methyl formate as a new building block in C1 chemistry

Methyl formate has been proposed as a building block molecule in C₁ chemistry. This paper examines the potential of this concept by reviewing the processes of synthesis of the molecule and the chemical reactions that it undergoes. Methyl formate can be produced by a variety of routes from a number of feedstocks. The reaction between methanol and carbon monoxide is an efficient process, used commercially. Combination of an efficient synthesis of methyl formate and its facile decomposition allows the molecule to be used as a means for separation, storage and transport of synthesis gas. The number of reactions that convert methyl formate to other chemicals is large. In particular, the synthesis of large volume chemicals such as methanol, acetic acid and ethylene glycol deserves serious consideration. Examples are provided of applications in the chemical and energy industries involving methyl formate. The reactions involved in the synthesis and transformation of methyl formate are mostly catalytic in nature. Many currently known catalytic systems are not efficient to compete with conventional routes involving methanol or synthesis gas. Fundamental research to understand the catalytic chemistry involved is highly desirable in order to improve the performance of the catalytic systems.     

一氧化碳、甲醇羰基化液相合成甲酸甲酯工艺条件的初步研究

在甲醇钠为主催化剂的条件下,研究了甲醇与CO羰基化事成甲酸甲酯,考察了反应温度、CO分压、催化剂浓度、助催化剂浓度以及原料甲醇含水量等因素对反应的影响,并用正交试验方法确定了一定工艺范围内的最佳工艺操作点。     

甲醇羰基化法合成甲酸甲酯流程模拟

采用流程模拟的方法对甲醇羰基化法合成甲酸甲酯的进料条件及反应压力等工艺条件对反应强度、动力消耗等参数的影响给出了定量的分析结果 ,并提出了在过程设计和生产操作中根据甲酯产率及消耗确定适宜工艺参数的方法     

氯甲酸三氯甲酯合成工艺路线的选择研究

本文对甲酸甲酯和氯甲酸甲酯二条原料路线合成氯甲酸三氯甲酯的研究作了详细介绍，通过模试和小试验证试验，认为在生产中，氯化反应器很难实现气相区使甲酸甲酯气体和氯气避开爆鸣和自燃浓度范围。为使生产安全起见，应采用氯甲酸甲酯为原料的合成路线为宜。     

Pushing Boundaries—Selective Cooling Crystallization as Tool for Selectivity Compensation and Product Purification Using a Recyclable Pd/Xantphos Catalyst in the Methoxycarbonylation of Methyl 10-Undecenoate

The homogeneously catalyzed methoxycarbonylation of methyl 10-undecenoate allows for the synthesis of dimethyl 1,12-dodecandioate as an interesting bio-based drop-in alternative for 1,12-dodecandioic acid as polymer building block. Although the benchmark catalyst system of Pd/1,2-bis((di-tert-butylphosphino)methyl)benzene and methane sulfonic acid is very active and selective, long-term stability over a potential catalyst recycling is limited. In this work, modifications of this catalyst system in terms of protonation of the ligand and its replenishment during recycling are first investigated, proving that the reaction system is tolerant against minor changes. Finally, the commercially available ligand Xantphos, featuring higher stability but comes with a rather low l:b selectivity of 70:30, is applied. However, through the application of cooling crystallization, 58 g product (52% isolated yield) with an overall purity of 94% is obtained from the crude reaction solution without further treatment and a ∑TON of 4000 after ten reaction runs, while catalyst loss into the product is low. Practical Applications: Selective syntheses on the basis of renewable resources are a powerful tool for the production of value products in terms of green chemistry. Thereby, homogeneous transition metal catalysts are beneficial regarding selectivity. However, their separation and recycling are challenging due to their limited stability. The combination of a stable, commercially available catalyst with a selective purification method allows for isolation and purification from a crude reaction mixture without the need for any auxiliary or further purification steps. In this work, cooling crystallization is applied for subsequent purification of the linear diester dimethyl 1,12-dodecandioate. Thereby, a lower selectivity from the methoxycarbonylation reaction using the stable Xantphos ligand is compensated and combined with recycling of the homogeneous catalyst. Thus, the development of an integrated process covering a stable catalyst system in the reaction, and high selectivity in the purification is the key toward an efficient homogeneous catalyst recycling.     

固体碱催化丙酮和碳酸二甲酯合成乙酰乙酸甲酯

以碳酸二甲酯(DMC)与丙酮为原料,在固体碱上合成乙酰乙酸甲酯,并考察了反应温度、反应时间、催化剂用量和原料摩尔比等因素对反应结果的影响。结果表明,以固体酸为催化剂时,无乙酰乙酸甲酯的生成,而具有中强碱位的K/MgO对反应具有较好的催化性能。当以K/MgO为催化剂,在反应温度为240℃,反应时间5h,催化剂用量为反应物总质量的1.5%,原料摩尔比为n(丙酮)∶n(DMC)=1∶4时,丙酮的转化率和乙酰乙酸甲酯的选择性分别达到41.2%和50.3%。反应的主要副产物为丙酮自身缩合的产物(二丙酮醇、4-甲基-3-烯基-2-戊酮、4-甲基-4-烯基-2-戊酮)以及醚化产物(2-甲氧基丙烯)等。     

甲基橙反应体系新用途——光度法测定亚硝酸根

基于亚硝酸根重氮化反应后生成甲基橙 ,用分光光度法进行测定。与传统甲基橙合成反应不同的是 ,此反应可在常温下短时间内快速完成。有色物质的摩尔吸光系数为 4.38× 1 0 4L/( mol·cm) ,方法的相对标准偏差为 0 .2 1 % ,方法回收率 1 0 0 .5 % ,亚硝酸氮的浓度在 0 .0 1 6～ 0 .1 6μg/m L与吸光度有良好的线性关系。     

固体碱催化苯乙酮和碳酸二甲酯合成苯甲酸甲酯

以固体酸碱为催化剂,研究了碳酸二甲酯与苯乙酮合成苯甲酸甲酯的反应,考察了反应温度、反应时间、催化剂用量和原料摩尔配比等因素对反应结果的影响。实验结果表明,固体酸催化剂不利于苯甲酸甲酯的生成,而具有中强碱位的MgO对反应有较好的催化活性。当以MgO为催化剂,在反应温度为260℃,反应时间5 h,催化剂用量为反应物总质量的1.5%,n(苯乙酮)∶n(DMC)=1∶4的条件下,苯乙酮的转化率和苯甲酸甲酯的选择性分别达72.0%和59.8%。另外,反应的副产物主要为乙酸甲酯、少量苯乙酮缩合的产物、甲基化及醚化产物等。     

杂多酸催化合成甲基叔丁基醚的研究

介绍了以叔丁醇和甲醇为原料,在杂多酸催化下合成甲基叔丁基醚（ＭＴＢＥ）的方法,探索了反应温度、催化剂用量、反应摩尔比等诸因素对合成工艺、催化剂活性和选择性的影响,确定了适宜的工艺条件。