Theoretical study on the mechanism of hydrolysis/alcoholysis/ammonolysis of butanediol terephthalate dimer

doi:10.11949/0438-1157.20221121

Abstract

Abstract:

Using the density functional theory M06-2X/6-311G(d) method, the quantum chemical theory of the hydrolysis/alcoholysis/ammonolysis reaction mechanism of butylene terephthalate dimer was studied. The possible reaction paths of the hydrolysis/alcoholysis/ammonolysis process were proposed, and the geometric structure optimization and frequency calculation of various intermediates, transition states and products involved in the reaction were carried out to obtain the thermodynamic and kinetic parameter values. The calculation results show that the reaction activation energy of the cracking process of butanediol terephthalate dimer can be reduced under the condition of hydrolysis/alcoholysis/ammonolysis, which makes the reaction easier, the reaction energy barriers of the main elemental reaction steps in hydrolysis/alcoholysis/ammonolysis are about 170.0, 155.0 and 165.0 kJ/mol, respectively. The hydrolysis products of butanediol terephthalate dimer are mainly terephthalic acid and 1,4-butanediol, and the alcoholysis products of butanediol terephthalate dimer are dimethyl terephthalate and 1,4-butanediol, ammonolysis products mainly include aromatic nitrile and 1,4-butanediol, among which 1,4-butanediol will be further degraded to form tetrahydrofuran. In the process of butanediol terephthalate dimer hydrolysis/alcoholysis/ammonolysis, the decomposition reaction in methanol medium is better than that in ammonia atmosphere, and the reaction in ammonia atmosphere is better than that in water molecular environment, and the increase of reaction temperature can increase its spontaneity.

Key words: butanediol terephthalate dimer, density functional theory, hydrolysis, alcoholysis, ammonolysis, kinetics, thermodynamics

摘要：

采用密度泛函理论M06-2X/6-311G（d）方法，对对苯二甲酸丁二醇酯二聚体的水/醇/氨解反应机理进行了量子化学理论研究。提出了各种可能的水/醇/氨解反应路径，对各反应的中间体、过渡态及产物进行了几何结构优化和频率计算以获得热力学与动力学参数值，分析了对苯二甲酸丁二醇酯二聚体主链酯键中的酰氧键位置水/醇/氨降解的反应机理。计算结果表明：水/醇/氨解条件下能够降低对苯二甲酸丁二醇酯二聚体主链酯键中的酰氧键裂解的反应活化能，使反应更易于进行，水/醇/氨解中主要基元反应步的反应能垒分别约为170.0、155.0和165.0 kJ/mol。对苯二甲酸丁二醇酯二聚体水解产物主要为对苯二甲酸和1,4-丁二醇，醇解产物主要为对苯二甲酸二甲酯和1,4-丁二醇，氨解产物主要为芳香腈和1,4-丁二醇等，其中1,4-丁二醇会进一步降解形成四氢呋喃。在对苯二甲酸丁二醇酯二聚体水/醇/氨解反应过程中，甲醇介质中的裂解反应优于氨气气氛中的反应、氨气气氛中的反应优于水分子环境中的反应，且反应温度的升高可以增加其自发性。

关键词: 对苯二甲酸丁二醇酯二聚体, 密度泛函理论, 水解, 醇解, 氨解, 动力学, 热力学

CLC Number:

TQ 519

Xiaosong LUO, Jinbao HUANG, Mei ZHOU, Xin MU, Weiwei XU, Lei WU. Theoretical study on the mechanism of hydrolysis/alcoholysis/ammonolysis of butanediol terephthalate dimer[J]. CIESC Journal, 2022, 73(11): 4859-4871.

罗小松, 黄金保, 周梅, 牟鑫, 徐伟伟, 吴雷. 对苯二甲酸丁二醇酯二聚体水/醇/氨解机理的理论研究[J]. 化工学报, 2022, 73(11): 4859-4871.

Figures/Tables 15

Fig.1 Possible reaction paths for hydrolysis of butanediol terephthalate dimer

Fig.2 Schematic diagram of reaction energy barrier for hydrolysis of butanediol terephthalate dimer

Fig.3 Optimized structure of transition state of butanediol terephthalate dimer during initial hydrolysis

Fig.4 Possible reaction paths for alcoholysis of butanediol terephthalate dimer

Fig.5 Schematic diagram of reaction energy barrier for alcoholysis of butanediol terephthalate dimer

Fig.6 Optimum structure of transition state of butanediol terephthalate dimer during initial alcoholysis

Fig.7 Possible reaction paths for ammonolysis of butanediol terephthalate dimer

Fig.8 Schematic diagram of reaction energy barrier for ammonolysis of butanediol terephthalate dimer

Fig.9 Optimum structure of transition state of butanediol terephthalate dimer during initial ammonolysis

Fig.10 Possible reaction paths for degradation of 1,4-butanediol

Fig.11 Reaction energy barrier diagram for degradation of 1,4-butanediol

Table 1 Activation energy of initial reaction steps in pure pyrolysis and hydrolysis/alcoholysis/ammonolysis processes of butanediol terephthalate dimer at different temperatures

Temperature/K	Hydrolysis[Path(1)]/ (kJ/mol)			Alcoholysis[Path(2)]/ (kJ/mol)			Ammonolysis[Path(3)]/ (kJ/mol)			Pure pyrolysis/ (kJ/mol)
Temperature/K	1→TS1(1-a)	1→TS4(1-b)	1→TS5(1-c)	1→TS7(2-a)	1→TS10(2-b)	1→TS12(2-c)	1→TS15(3-a)	1→TS22(3-b)	1→TS24(3-c)	Six-membered ring			Four-membered ring
298	171.6	172.9	169.0	154.8	154.9	156.6	162.5	160.1	168.4	217.4	214.1	211.8	279.5	279.9	281.5
400	172.2	172.8	168.8	154.7	153.3	156.5	162.5	160.1	168.4	217.7	213.6	210.5	280.8	280.5	282.0
500	173.4	173.2	168.8	154.9	151.8	156.6	162.9	160.6	168.8	217.9	213.2	209.2	282.1	280.9	282.5
600	174.8	173.8	169.8	155.2	150.5	156.9	163.7	161.3	169.5	218.1	212.7	207.8	283.2	281.3	282.9
700	176.5	174.7	170.7	155.5	149.2	157.2	164.6	162.3	170.4	218.3	212.2	206.4	284.2	281.6	283.1
800	178.3	175.7	171.7	155.9	147.9	157.5	165.7	163.3	171.5	218.4	211.5	204.9	285.1	281.7	283.2
900	180.2	176.8	172.7	156.3	146.7	157.9	166.8	164.5	172.6	218.4	210.8	203.3	285.9	281.7	283.2

Fig.12 Relationship between activation energy of initial reaction steps in hydrolysis/alcoholysis/ammonolysis processes of butanediol terephthalate dimer and temperature

Table 2 ΔH/ΔG/ΔS of initial reaction steps in hydrolysis/alcoholysis/ammonolysis processes of butanediol terephthalate dimer at different temperatures

Temperature/K	Hydrolysis[Path(1)]			Alcoholysis[Path(2)]			Ammonolysis[Path(3)]
Temperature/K	ΔH/ (kJ/mol)	ΔG/ (kJ/mol)	ΔS/ (J/(mol·K))	ΔH/ (kJ/mol)	ΔG/ (kJ/mol)	ΔS/ (J/(mol·K))	ΔH/ (kJ/mol)	ΔG/ (kJ/mol)	ΔS/ (J/(mol·K))
298	19.4	-6.1	85.6	-11.7	-27.0	51.1	83.0	55.8	91.3
400	17.3	-14.4	79.4	-10.8	-32.3	53.7	82.9	46.5	91.0
500	16.1	-22.2	76.6	-9.9	-37.8	55.7	83.5	37.4	92.3
600	15.5	-29.8	75.5	-9.0	-43.4	57.4	84.5	28.0	94.1
700	15.2	-37.3	75.1	-8.1	-49.2	58.8	85.6	18.6	95.7
800	15.3	-44.9	75.2	-7.2	-55.2	60.0	86.7	8.9	97.3
900	15.5	-52.4	75.4	-6.3	-61.2	61.0	87.8	-0.9	98.6

Fig.13 Relationship between ΔH/ΔG/ΔS in hydrolysis/alcoholysis/ammonolysis processes of butanediol terephthalate dimer and temperature

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