Modified Group Contribution Scheme to Predict the Glass-Transition Temperature of Homopolymers through a Limiting Property Dataset

Yang, Yang; Zou, Xiong; Ye, Haotian; Wei-xuan, Zhu; Dong, Hongguang; Bi, Mingshu

doi:10.1021/acsomega.0c04499

Cited by 11 publications

(10 citation statements)

References 51 publications

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“…It is worth mentioning that polymers with side chains are also attractive targets in recent machine learning studies aiming at making accurate predictions of T g of polymers. 33,34 The present work utilizes the GET and molecular dynamics (MD) simulation to investigate the influence of side-chain length and the relative rigidities of the backbone and side chains on the glass formation of branched polymers with a fixed molecular mass. In particular, we study the crossover from linear polymers to comb polymers with side chains of moderate length to bottlebrush polymers, where the side chains can dominate the properties of the polymer material.…”

Section: Introductionsupporting

confidence: 52%

“…These interesting experimental observations, in conjunction with the practical importance of bottlebrush polymers, naturally invite attempts at a theoretical explanation and require simulation to better understand the glass formation of branched polymers at the molecular scale. It is worth mentioning that polymers with side chains are also attractive targets in recent machine learning studies aiming at making accurate predictions of T g of polymers. , …”

Section: Introductionmentioning

confidence: 99%

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Influence of Side-Chain Length and Relative Rigidities of Backbone and Side Chains on Glass Formation of Branched Polymers

Douglas

2021

Macromolecules

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Molecular branching is a common characteristic of both synthetic and natural polymers that plays a key role in determining their physical properties, but a fundamental understanding of how this molecular factor influences polymer glass formation remains incomplete. Here, we utilize the generalized entropy theory (GET) and molecular dynamics simulation to investigate the influence of side-chain length on the glass formation of general classes of branched polymers with a fixed molecular mass, as characterized by the relative rigidities of the backbone and side chains. We consider the crossover from linear polymers to comb polymers with side chains of moderate length to bottlebrush polymers. The relative rigidities of the backbone and side chains are shown to be key factors in dictating the general trends of the characteristic properties of polymer glass formation in variation with the side-chain length. Both the glass transition temperature and fragility are predicted by the GET to decrease on increasing the side-chain length in the polymer class with a relatively stiff backbone and flexible side chains, whereas the trends are reversed in the other classes of polymers. Simulation results of a coarse-grained polymer model are shown to be largely consistent with the predictions from the GET, although some differences between the GET and simulation are also observed. An analysis based on simulation results reveals the presence of a power-law relationship between the average segmental structural relaxation time and the structural relaxation times corresponding to different parts in the monomers of branched polymers, indicating that it is adequate to utilize the average segmental structural relaxation time to discuss many aspects of glass formation in branched polymers. Our work demonstrates that the GET can be a convenient theoretical vehicle for studying the glass formation of branched polymers.

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Section: Introductionsupporting

confidence: 52%

Section: Introductionmentioning

confidence: 99%

Influence of Side-Chain Length and Relative Rigidities of Backbone and Side Chains on Glass Formation of Branched Polymers

Douglas

2021

Macromolecules

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“…It is generally recognized that when the average molecular weight is really high, some bulk properties will reach their asymptotic value (The trend can be found in eq ). As molecular weight distribution is the main factor that influences properties, for these properties, it is suggested to use the limiting value instead of the original property value: where f ( X (∞)) is the function of certain limiting property X (∞), and C i (∞) is the limiting contribution of the i group, which occurs N i times. In this work, eq is used to calculate glass transition temperature and surface tension.…”

Section: Improved Computer-aided Polymer Design Methodologymentioning

confidence: 99%

“…The results are shown in Table 2 and Figure 2. The contribution of groups for glass transition temperature and surface tension can be found in a previous work 32 and Table S1 in the Supporting Information, respectively.…”

Section: Improved Computer-aided Polymer Designmentioning

confidence: 99%

Polymer Product Design: Considering Detailed Polymer Attributes and Production Guidelines

Yang

Wei-xuan

et al. 2021

Ind. Eng. Chem. Res.

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Because polymer properties are influenced by numerous complex structural factors, repeat unit structures provided by previous polymer designs are not sufficient for the production guidelines. In addition, neither the phase state nor the working temperature is considered when determining product attributes in previous studies. Considering these deficiencies, an improved polymer product design framework is proposed. Target polymer repeat unit structures with an average molecular weight range and difficulty of synthesis are provided under target properties, working temperatures, and phase states. First, the molecular weight and temperature-dependent properties are classified; then, limiting properties determined using the group contribution method are introduced to describe molecular weightproperty relationship. Finally, van der Waals volume is introduced to predict molar volume at a certain working temperature so that temperature-dependent properties can be determined. Advantages of the proposed framework are discussed and compared with the traditional polymer design, and a practical binder design example for coating is presented to demonstrate the applicability.

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“…It was found that the predicted result was very close to the experimental data. Yang et al 12 established a new data set containing 198 polymers to predict Tg ∞ (Tg of limit degree of polymerization (DP)) using the improved GC method which showed a good correlation. Karteek et al 13 created the density functional theory (DFT) forcefield and improved the traditional polymer consistent force field (PCFF) to obtain a wider applicable modified PCFF (m-PCFF), and the Tg values for Calculation of the glass transition temperature (Tg) from different methods of poly-(p-phenylenediamine-alt-2,6-diformyl tetraphenyl) (PPDM-4) a number of yet-to-be-synthesized polyhydroxyalkanoates (PHA)-based polymers with a diverse set of functional groups on the polymer side chains were predicted by using this forcefield.…”

Section: Introductionmentioning

confidence: 99%

Using the group contribution method and molecular dynamics to predict the glass transition temperatures and mechanical properties of poly-(p-phenylenediamine-alt-2, 6-diformyl multiphenyl)

et al. 2021

Journal of Chemical Research

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This article reports the glass transition temperatures of poly-( p-phenylenediamine-alt-2,6-diformyl multiphenyl) predicted by both the group contribution method and the molecular dynamics simulations. The related modeling method and the degree of polymerization, density, specific volume, radius of volume, radius of rotation, and non-bonding energy terms with temperature are analyzed in depth. The bulk modulus, shear modulus, compressibility, Young’s modulus, and Poisson’s ratio of poly-( p-phenylenediamine-alt-2,6-diformyl multiphenyl) at room temperature are simulated by molecular dynamics. The results show that the simulated glass transition temperatures of poly-( p-phenylenediamine-alt-2,6-diformyl multiphenyl) are greater than 480 K, which indicates that poly-( p-phenylenediamine-alt-2,6-diformyl multiphenyl) can be expected to be used as a high-temperature-resistant material. As the number of rigid benzene rings on the molecular side chain increases, the glass transition temperature decreases, with an average decrease of 10 K for each additional benzene ring. The free volume theory can explain the glass transitions of poly-( p-phenylenediamine-alt-2,6-diformyl multiphenyl). The modulus and density of poly-( p-phenylenediamine-alt-2,6-diformyl multiphenyl) change accordingly with an increase of rigid benzene rings on the side chain, probably due to the fact that the flexibility of the polymers changes accordingly as the number of benzene rings on the side chain increases.

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Modified Group Contribution Scheme to Predict the Glass-Transition Temperature of Homopolymers through a Limiting Property Dataset

Cited by 11 publications

References 51 publications

Influence of Side-Chain Length and Relative Rigidities of Backbone and Side Chains on Glass Formation of Branched Polymers

Influence of Side-Chain Length and Relative Rigidities of Backbone and Side Chains on Glass Formation of Branched Polymers

Polymer Product Design: Considering Detailed Polymer Attributes and Production Guidelines

Using the group contribution method and molecular dynamics to predict the glass transition temperatures and mechanical properties of poly-(p-phenylenediamine-alt-2, 6-diformyl multiphenyl)

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