Reaction mechanism study on transesterification in synthesis of thermotropic liquid crystalline polymer catalyzed by zinc(II) carboxylate: A combination of DFT and kinetics analyses

Shen, Junyao; Gao, Xinyi; Liu, Zhen; Zhao, Liang; Xi, Zhenhao; Wang, Yuan

doi:10.1016/j.cej.2022.136848

Cited by 9 publications

(5 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore, a true transition state will only have one imaginary frequency (see Table S1). − As seen from Figure a, the conformational transfer energy of DB-modified chains reduces by 0.57 kJ/mol compared to unmodified ones, which suggests that the introduction of DBs could hasten the α–γ phase transition with an increased thermodynamic driving force. As is also seen in Figure a, the activation energy for the conformational transition from TGTG to TTTG in unmodified chains is 17.71 kJ/mol, while that in DB-modified chains decreases to 11.32 kJ/mol.…”

Section: Resultsmentioning

confidence: 93%

Enhancing the Alpha-To-Gamma Phase Transition of Poly(vinylidene fluoride) via Dehydrofluorination Modification

Yuan,

Wang,

Wang

et al. 2024

Crystal Growth & Design

View full text Add to dashboard Cite

Due to the high activating energy, it is very difficult to initiate the α-to-γ phase transition of poly(vinylidene fluoride) (PVDF), resulting in an extremely slow transition rate. Here, introducing a small number of double bonds into the PVDF molecular chains through dehydrofluorination is demonstrated to markedly decrease the activating energy and enhance the phase transition efficiency. It is found that the introduced double bonds during the dehydrofluorination reaction accelerate the α-to-γ phase transition, which is reflected by the shortened induction period and increased transition rate. The α-to-γ phase transition in PVDF modified with double bonds occurs mostly from the nuclei of αspherulites rather than from the scarce boundaries initiated by γspherulites as in unmodified PVDF. Comparative analysis reveals that the energy storage performance of γ-PVDF films prepared through the phase transition surpasses that of α-PVDF ones. Compared to α-PVDF, the energy storage density of the modified γ-PVDF exhibits a remarkable enhancement of 181%, while the energy storage efficiency experiences a notable improvement of 124%. Consequently, a molecular modification strategy for the α-to-γ phase transition is introduced, enabling efficient production of γ-PVDF with enhanced energy storage properties and positioning it as an ideal material for driving technological advancements in electronic devices, electric vehicles, and renewable energy sectors.

show abstract

Section: Resultsmentioning

confidence: 93%

Enhancing the Alpha-To-Gamma Phase Transition of Poly(vinylidene fluoride) via Dehydrofluorination Modification

Yuan,

Wang,

Wang

et al. 2024

Crystal Growth & Design

View full text Add to dashboard Cite

show abstract

“…In addition, DFT calculations can be useful in designing new catalysts which have been done for other polymer systems. For example, Shen et al [25] employed DFT calculations to explore the mechanism of the catalytic polymerization process involved in the synthesis of thermotropic liquid crystalline polymers using zinc(II) carboxylates as a catalyst (Figure 11b). DFT calculations revealed that the rate-limiting step was the transesterification Figure 11.…”

Section: Pre-screening and Designing Catalystsmentioning

confidence: 99%

“…For example, Shen et al. [ 25 ] employed DFT calculations to explore the mechanism of the catalytic polymerization process involved in the synthesis of thermotropic liquid crystalline polymers using zinc(II) carboxylates as a catalyst (Figure 11b ). DFT calculations revealed that the rate‐limiting step was the transesterification between phenol and anhydride acid.…”

Section: Molecular Insights and Aided Design Of Novel Vitrimersmentioning

confidence: 99%

Next‐Generation Vitrimers Design through Theoretical Understanding and Computational Simulations

Li,

Tran,

Pan

et al. 2023

Advanced Science

View full text Add to dashboard Cite

Vitrimers are an innovative class of polymers that boast a remarkable fusion of mechanical and dynamic features, complemented by the added benefit of end‐of‐life recyclability. This extraordinary blend of properties makes them highly attractive for a variety of applications, such as the automotive sector, soft robotics, and the aerospace industry. At their core, vitrimer materials consist of crosslinked covalent networks that have the ability to dynamically reorganize in response to external factors, including temperature changes, pressure variations, or shifts in pH levels. In this review, the aim is to delve into the latest advancements in the theoretical understanding and computational design of vitrimers. The review begins by offering an overview of the fundamental principles that underlie the behavior of these materials, encompassing their structures, dynamic behavior, and reaction mechanisms. Subsequently, recent progress in the computational design of vitrimers is explored, with a focus on the employment of molecular dynamics (MD)/Monte Carlo (MC) simulations and density functional theory (DFT) calculations. Last, the existing challenges and prospective directions for this field are critically analyzed, emphasizing the necessity for additional theoretical and computational advancements, coupled with experimental validation.

show abstract

“…28,183 According to the mechanism of transesterification/esterification in section 2, the nucleophilicity and steric hindrance of different alcohols had an important influence on the reaction. 184,185 The nucleophilic and spatial effects of different alkoxy anions are as follows.…”

Section: Alcohol Type and Molar Ratiomentioning

confidence: 99%

Functionalized organic–inorganic hybrid porous coordination polymer-based catalysts for biodiesel production via trans/esterification

Zhang

Chen

et al. 2022

Green Chem.

View full text Add to dashboard Cite

show abstract

Reaction mechanism study on transesterification in synthesis of thermotropic liquid crystalline polymer catalyzed by zinc(II) carboxylate: A combination of DFT and kinetics analyses

Cited by 9 publications

References 41 publications

Enhancing the Alpha-To-Gamma Phase Transition of Poly(vinylidene fluoride) via Dehydrofluorination Modification

Enhancing the Alpha-To-Gamma Phase Transition of Poly(vinylidene fluoride) via Dehydrofluorination Modification

Next‐Generation Vitrimers Design through Theoretical Understanding and Computational Simulations

Functionalized organic–inorganic hybrid porous coordination polymer-based catalysts for biodiesel production via trans/esterification

Contact Info

Product

Resources

About