Theoretical study on hydrolysis/alcoholysis/ammonolysis mechanisms of ethylene terephthalate dimer

doi:10.19491/j.issn.1001-9278.2023.01.014

Abstract

Abstract:

The mechanisms for the hydrolysis/alcoholysis/ammonolysis reactions of ethylene terephthalate dimer was studied by using the density functional theory B3P86/6⁃31++G（d，p） method. The possible reaction paths in the hydrolysis/alcoholysis/ammonolysis degradation process were proposed. The geometric structures of various intermediates， transition states， and products involved in the reaction were optimized， and their frequencies were calculated to get the thermodynamic and kinetic parameters. The reaction mechanism for the hydrolysis/alcoholysis/ammonolysis degradation in the acyl⁃oxygen bond position in the backbone chain of ethylene terephthalate dimer was analyzed. The results indicated that the hydrolysis/alcoholysis/ammonolysis reactions reduced the activation energy of the acyl⁃oxygen bond cleavage in the main chain ester bond of ethylene terephthalate dimer， resulting in an easier reaction. The main element reaction in the hydrolysis had the highest energy barrier of 169.0 kJ/mol， whereas the ammonolysis reaction had the lowest energy barrier of 153.0 kJ/mol. The alcoholysis reaction exhibited an energy barrier of 155.0 kJ/mol.

Key words: ethylene terephthalate dimer, density functional theory, hydrolysis, alcoholysis, ammonolysis, reaction mechanism

CLC Number:

TQ316.3

ZHOU Mei, LI Sijia, XU Weifeng, HUANG Jinbao, LUO Xiaosong, WU Lei. Theoretical study on hydrolysis/alcoholysis/ammonolysis mechanisms of ethylene terephthalate dimer[J]. China Plastics, 2023, 37(1): 90-98.

Figures/Tables 11

Fig.1. Possible reaction paths for ethylene terephthalate dimer hydrolysis

Fig.2. Energy barrier of ethylene terephthalate dimer hydrolysis reaction

Fig.3. Initial hydrolysis transition state optimization structure of ethylene terephthalate dimer

Fig.4. Possible reaction paths for ethylene terephthalate dimer alcoholysis

Fig.5. The energy barrier of ethylene terephthalate dimer alcoholysis reaction

Fig.6. Optimal structure of initial alcoholysis transition state of ethylene terephthalate dimer

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

Fig.8. Ammonolysis reaction barrier of ethylene terephthalate dimer

Fig.9. Optimization of transition state for initial ammonolysis of ethylene terephthalate dimer

温度/K	水解/醇解/氨解反应［路径（1）/路径（2）路径（3）］
温度/K	ΔH/ kJ·mol^-1	ΔG/ kJ·mol^-1	ΔS/ J·（mol·K）^-1	ΔH/ kJ·mol^-1	ΔG/ kJ·mol^-1	ΔS/ J·（mol·K）^-1	ΔH/ kJ·mol^-1	ΔG/ kJ·mol^-1	ΔS/ J·（mol·K）^-1
298	20.8	5.0	53.0	-15.9	-19.9	13.2	24.2	5.2	63.8
400	18.1	0.2	44.7	-16.0	-21.2	12.9	23.4	-1.1	61.4
500	16.2	-4.1	40.5	-16.0	-22.5	12.9	23.2	-7.3	60.9
600	14.8	-8.0	38.0	-16.0	-23.8	12.9	23.2	-13.4	61.0
700	13.9	-11.7	36.5	-16.0	-25.1	12.9	23.4	-19.5	61.2
800	13.1	-15.3	35.6	-16.0	-26.4	13.0	23.6	-25.6	61.5
900	12.6	-18.8	34.9	-16.0	-27.7	13.0	23.8	-31.8	61.7

Tab.1. ΔH/ΔG/ΔS of ethylene terephthalate dimer during hydrolysis/alcoholysis/ammonolysis processes at different temperature

Fig.10. Relationship between ΔH，ΔG and ΔS in hydrolysis/alcoholysis/ammonolysis processes of ethylene terephthalate dimer and temperature

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