Theoretical study on thermal degradation mechanism of polybutylene terephthalate dimer

LUO Xiao-song; HUANG Jin-bao; WU Lei; JIN Li; XU Wei-wei; YAN Xia

doi:10.1016/S1872-5813(22)60043-4

Volume 51 Issue 3

Mar. 2023

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Article Navigation > Journal of Fuel Chemistry and Technology > 2023 > 51(3): 388-404

LUO Xiao-song, HUANG Jin-bao, WU Lei, JIN Li, XU Wei-wei, YAN Xia. Theoretical study on thermal degradation mechanism of polybutylene terephthalate dimer[J]. Journal of Fuel Chemistry and Technology, 2023, 51(3): 388-404. doi: 10.1016/S1872-5813(22)60043-4

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LUO Xiao-song, HUANG Jin-bao, WU Lei, JIN Li, XU Wei-wei, YAN Xia. Theoretical study on thermal degradation mechanism of polybutylene terephthalate dimer[J]. Journal of Fuel Chemistry and Technology, 2023, 51(3): 388-404. doi: 10.1016/S1872-5813(22)60043-4

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Theoretical study on thermal degradation mechanism of polybutylene terephthalate dimer

doi: 10.1016/S1872-5813(22)60043-4

School of Mechatronics Engineering, Guizhou Minzu University, Guiyang 550025, China

Funds: The project was supported by the Construction Project of Characteristic Key Laboratory in Guizhou Colleges and Universities [KY(2021)003], the Science and Technology Funds of Guizhou province [ZK(2021)278, ZK[2022]198], Youth Science and Technology Talent Project in Guizhou Colleges and Universities under [KY(2021)120]

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Corresponding author: Tel: 18212008607, E-mail: huangjinbao76@ 126.com
Received Date: 2022-05-24
Accepted Date: 2022-06-10
Rev Recd Date: 2022-06-09

Available Online: 2022-10-25

Publish Date: 2023-03-15

Abstract

Abstract

Thermal degradation mechanism of polybutylene terephthalate (PBT) dimer was studied by density functional theory (DFT) method M06-2X/6-311G(d). Eight possible reaction paths were designed for the thermal decomposition of PBT dimer, and the thermodynamic and kinetic parameters of elementary reaction steps in each reaction path were calculated. Calculation results show that, in the initial pyrolysis process of PBT, the energy barrier of concerted reaction occurring on the main chain is significantly lower than that of the radical reaction, so terephthalic acid, monobutenyl terephthalate, dibutenyl terephthalate and diterephthalate-1,4-butadiester formed by concerted reaction are main products in PBT initial pyrolysis. The energy barrier of the main chain fracture through the six-membered cyclic transition state is lower than that through the four-membered cyclic transition state, and the main chain fracture of PBT is mainly through the concerted reaction with six-membered cyclic transition state. In addition, the secondary degradation reaction of the main products of PBT pyrolysis was also discussed. It is found that the main products such as 1,3-butadiene, tetrahydrofuran, benzene, CO₂ and benzoic acid are mainly generated through concerted reaction in the processes of secondary degradation.
- PBT dimer,
- density functional theory,
- pyrolysis,
- reaction mechanism

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References(41)

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