乙烯氢甲酯化合成丙酸甲酯的氢键作用机制及反应动力学研究

doi:10.11949/0438-1157.20241495

摘要/Abstract

摘要：

丙酸甲酯（MP）是一种重要的有机合成原料，也是合成甲基丙烯酸甲酯的关键中间体，在航空航天、电子信息、新能源汽车等多个领域有着广泛应用。针对MP的合成过程，构建高效的催化剂体系对满足MP需求量的快速增长具有重要的现实意义。围绕乙烯氢甲酯化的钯磷酸均相催化剂体系，本工作探究了钯前体、酸促进剂、膦/钯摩尔比和酸/钯摩尔比对催化活性的影响。通过核磁共振氢谱表征手段揭示了不同酸根阴离子与甲醇间存在氢键作用，实现对甲醇的活化脱氢，阐明了催化剂转化频率（TOF）与氢键强度的正相关关系，反应活化能与氢键强度的负相关关系。同时，优化了搅拌速度、反应压力、催化剂浓度、水含量等反应条件参数，并获得了连续反应过程中催化剂活性的变化规律，表明催化体系具有良好的稳定性。最后，通过反应动力学研究得到甲醇、一氧化碳、乙烯的反应级数分别为1.25、0.58、0。

关键词: 氢甲酯化, 酸促进剂, 核磁共振, 氢键作用, 活化作用, 反应动力学

Abstract:

Methyl propionate (MP) is an important basic raw material for organic synthesis and a key intermediate for the synthesis of methyl methacrylate, which has broad applications in various fields such as aerospace, electronics, and new energy vehicles. Aiming at the synthesis process of MP, it is of great practical significance to construct an efficient catalyst system to meet the rapid growth of MP demand. In this paper, the effects of palladium species, acid promoter, phosphine ligand/Pd(OAc)₂ ratio and p-toluenesulfonic/ Pd(OAc)₂ ratio on the catalytic activity of palladium-phosphate homogeneous catalyst system for ethylene hydroesterification were investigated. Through proton nuclear magnetic resonance (NMR) characterization, hydrogen bonding interactions between different anions and methanol are revealed, which activated methanol dehydrogenation, and highlighting a positive correlation between the catalyst's turnover frequency (TOF) and hydrogen bond strength, as well as a negative correlation between activation energy and hydrogen bond strength. At the same time, the optimal reaction conditions such as stirring speed, reaction pressure, catalyst concentration and water content were obtained, and the variation law of catalyst's TOF during continuous reaction process was investigated. The reaction order of methanol, carbon monoxide and ethylene was 1.25, 0.58 and 0, respectively.

Key words: hydroesterification, acid promoter, NMR, hydrogen bond, activation, reaction kinetics

中图分类号:

TQ 032.4

赵清萍, 张敏, 赵辉, 王刚, 邱永福. 乙烯氢甲酯化合成丙酸甲酯的氢键作用机制及反应动力学研究[J]. 化工学报, DOI: 10.11949/0438-1157.20241495.

Qingping ZHAO, Min ZHANG, Hui ZHAO, Gang WANG, Yongfu QIU. Hydrogen bond effect and kinetic studies on hydroesterification of ethylene to methyl propionate[J]. CIESC Journal, DOI: 10.11949/0438-1157.20241495.

图/表 13

图1 乙烯氢甲酯化合成丙酸甲酯反应式

Fig.1 Synthesis of methyl propionate by ethylene hydroesterification

表1 相关文献对比

Table 1 Comparison of relevant literatures

序号	催化剂组成	反应温度/℃	反应压力/MPa	转化频率TOF/h^-1	选择性/%	产率/%
1^[29]	Pd(OAc)₂:PPh₃:TsOH=1:30:20	115	4.5	5000	98	—
2^[30]	Pd(PPh₃)₂(TsO)₂:PPh₃:TsOH=1:6:8	120	4	5700	—	—
3^[31]	cis-[Pd(SO₄)(PPh₃)₂]:PPh₃:H₂SO₄=1:107:8	100	0.6	2168	—	98
4^[32]	Pd(OAc)₂:TPP:MSA:SATA=1:10:5:60	100	2	—	98	—
5^[33]	Pd(OAc)₂:dtbpp:MSA =1:1.2:2.5	120	4	25000	97.4	—
6^[34]	Pd(acac)₂:py^tbpx:p-TsOH=1:1.2:2.5	120	4	—	99	97
7^[28]	Pd(acac)₂:py^tbpf:p-TsOH=1: 2:16	100	3	46000	99	—
8^[35]	Pd(OAc)₂:dtbpx:P-[VSpIm][CH₃C₆H₄SO₃]_0.5=1:5:4	80	—	—	100	94.4
9^[36]	Pd(OAc)₂:dtbpx:[SBMI][p-TsOH]	80	2.2	—	—	99
10^[37]	Pd(OAc)₂:dtbpx:SiO₂-[SBMI][p-TsOH]	85	0.5	650	—	—
本工作	Pd(OAc)₂:dtbpx: p-TsOH=1: 2: 5 (温和的反应条件)	60	2	9359	约100	—

图2 钯前体对乙烯氢甲酯化反应催化活性的影响

Fig.2 Effect of palladium species on catalytic activity of ethylene hydroesterification reaction

图3 酸促进剂对乙烯氢甲酯化反应催化活性的影响

Fig.3 Effect of acid promoter on catalytic activity of ethylene hydroesterification reaction

图4 (a) 甲醇以及酸促进剂作用下甲醇中羟基氢的1HNMR化学位移、(b) 酸与甲醇羟基氢通过氢键作用对甲醇的活化脱氢

Fig4 (a) 1HNMR chemical shift of hydroxyl hydrogen in methanol under the action of methanol and acid promoter, (b) Activated dehydrogenation of methanol by hydrogen bonding between acid and hydroxyl hydrogen of methanol

图5 氢键强度对乙烯氢甲酯化反应催化活性的影响

Fig.5 Effect of hydrogen bond strength on catalytic activity of ethylene hydroesterification reaction

图6 不同酸促进剂组成的催化剂体系的活化能

Fig.6 Activation energy of catalyst system composed of different acid promoters

图7 氢键强度对乙烯氢甲酯化反应活化能的影响

Fig.7 Effect of hydrogen bond strength on activation energy of ethylene hydroesterification reaction

图8 膦/钯摩尔比对乙烯氢甲酯化反应活性的影响

Fig.8 Effect of dtbpx/Pd molar ratio on hydrogenation activity of ethylene

图9 酸/钯摩尔比对乙烯氢甲酯化反应活性的影响

Fig.9 Effect of p-TsOH/Pd molar ratio on hydrogenation activity of ethylene

图10 (a) 搅拌转速、(b) 反应压力、(c) Pd(OAc)2浓度、(d) 水含量对乙烯氢甲酯化反应的影响

Fig.10 Effect of reaction condition on the hydroesterification of ethylene (a) stirring speed, (b) reaction pressure, (c) Pd(OAc)2 concentration, and (d) water content

图11 (a) 甲醇浓度、(b) 乙烯分压、(c) CO分压对反应速率的影响

Fig.11 Effect of reaction conditions on reaction rate (a) methanol concentration, (b) C2H4 partial pressure, and (c) CO partial pressure

图12 (a) TOF随反应时间的变化趋势、(b) MP含量对乙烯氢甲酯化反应催化活性的影响

Fig.12 (a) Trend of TOF with reaction time, (b) Effect of MP concentration on catalytic activity of ethylene hydroesterification reaction,

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