Effect of the polar group content on the glass transition temperature of ROMP copolymers

Li, Yilin; Jia, Xiang‐Meng; Zhang, Xu-Ze; Lu, Zhong‐Yuan; Qian, Hu-Jun

doi:10.1039/d2sm01229d

Cited by 8 publications

(12 citation statements)

References 71 publications

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“…The same conclusion has been drawn in a previous study of the Stockmayer fluid in which the interacting particles exhibit both LJ and charge (dipole) interactions . In the corresponding case of polymeric liquids, Li et al have found that the cohesive energy density of a coarse-grained polar polymer melt increases linearly with increasing the polar group content, and our previous work has likewise indicated that the cohesive energy density increases with increasing the charge interaction strength . Our simulation results indeed suggest that glass formation in charged polymers at least roughly corresponds to uncharged polymers with a modified short-range attractive interparticle interaction strength ϵ LJ , supporting our hypothesis that the effective LJ interaction is renormalized by the charge interactions.…”

Section: Resultssupporting

confidence: 90%

“…Dashed−dotted lines are fits to the linear equation T x (P) = T x (0) + a x P with x = A, c, g, or 0, where the fitting parameters (a A , a c , a g , a 0 ) are determined to be 6.66 × 10 −2 , 3.24 × 10 −2 , 2.86 × 10 −2 , and 2.61 × 10 −2 and 6.00 × 10 −2 , 3.83 × 10 −2 , 3.52 × 10 −2 , and 3.00 × 10 −2 for uncharged and charged polymer melts, respectively. of polymeric liquids, Li et al 86 have found that the cohesive energy density of a coarse-grained polar polymer melt increases linearly with increasing the polar group content, and our previous work has likewise indicated that the cohesive energy density increases with increasing the charge interaction strength. 24 Our simulation results indeed suggest that glass formation in charged polymers at least roughly corresponds to uncharged polymers with a modified short-range attractive interparticle interaction strength ϵ LJ , supporting our hypothesis that the effective LJ interaction is renormalized by the charge interactions.…”

Section: T H I S C O N T E N T Imentioning

confidence: 62%

“…Finally, we point out that there are other important molecular factors that potentially influence the glass formation of charged polymers. In practice, many polymers are polar, and the glass formation of polymers has been shown to be affected by the degree of polarizability in a complex manner. , It would thus be of great interest to investigate the role of polarizability in determining the collective motion and other characteristic properties of glass formation of charged polymers from both experimental and computational perspectives.…”

Section: Discussionmentioning

confidence: 99%

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Molecular Dynamics Investigation of the Pressure Dependence of Glass Formation in a Charged Polymer Melt

Yang

Douglas

et al. 2023

Macromolecules

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Most commodity polymers are derived from petroleum raw materials, and correspondingly, these materials are normally uncharged and nonpolar, attributes that make this class of material relatively insoluble in water and relatively slow to breakdown in the environment. Natural and synthetic charged polymer materials often do not exhibit these drawbacks, thereby offering the potential for being more sustainable. As with all polymer materials, properties related to glass formation play a central role in the design and characterization of materials. Here, we investigate the influence of a crucial processing variable, the pressure P, on the glass formation of a coarse-grained charged polymer melt using molecular dynamics simulation. We find that the temperature (T) dependence of the thermodynamics and segmental dynamics under variable P conditions largely resemble the trends observed before for uncharged polymer liquids. In particular, we are able to organize all our segmental relaxation data as functions of both T and P in terms of the conventional phenomenology for uncharged polymer melts, namely, the Vogel–Fulcher–Tammannn temperature dependence of the structural relaxation time τα and a pressure analog of this equation, etc. Moreover, we can quantitatively describe all our simulation data for both charged and uncharged polymer melts with the string model of glass formation. Importantly, our results indicate that the main effect of charge on the dynamics of polymeric glass-forming liquids is to “renormalize” the cohesive interaction strength. This opens the possibility of applying theories of neutral polymer melts to describe the glass formation of synthetic and natural charged polymer melts, ionic fluids, and possibly even polar polymer melts, once an accounting is made for how charge modifies the effective cohesive interaction strength.

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Section: Resultssupporting

confidence: 90%

Section: T H I S C O N T E N T Imentioning

confidence: 62%

Section: Discussionmentioning

confidence: 99%

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Molecular Dynamics Investigation of the Pressure Dependence of Glass Formation in a Charged Polymer Melt

Yang

Douglas

et al. 2023

Macromolecules

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“…The presence of polar functional groups is known to affect mechanical properties and increase glass transition temperatures for many types of polymer materials . In order to separately consider the polar effects resulting from installation of the ketone with any effects that are specific to the vinyl C–H hydrogen bond, we prepared a control polymer in which the ketone was maintained but the conjugated alkene was removed.…”

Section: Resultsmentioning

confidence: 99%

“…The presence of polar functional groups is known to affect mechanical properties and increase glass transition temperatures for many types of polymer materials. 53 In order to separately consider the polar effects resulting from installation of the ketone with any effects that are specific to the vinyl C−H hydrogen bond, we prepared a control polymer in which the ketone was maintained but the conjugated alkene was removed. As shown in Scheme 3, the control polymer (oxaPDCPD RD ; 5 p ) was efficiently synthesized through regioselective zinc-promoted reduction of the enone monomer (4 m ) 54 followed by polymerization with the Grubbs second-or third-generation catalyst.…”

Section: Computational Analysis and Comparison To Experimental Datamentioning

confidence: 99%

A Single-Atom Upgrade to Polydicyclopentadiene

et al. 2023

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Chemical cross-links within polymers increase mechanical strength and rigidity. Such cross-links can be either irreversible (e.g., those derived from carbon–carbon bonds) or reversible (e.g., those that depend on X–H···O hydrogen bonds). Here we describe a ketone-functionalized derivative of polydicyclopentadiene that establishes an unprecedented network of vinyl C–H···O hydrogen bonds within the polymer. The resulting thermoset displays a significantly increased glass transition temperature relative to the unfunctionalized polymer, together with enhancements to storage modulus, Young’s modulus, and compression strength.

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Star‐Shaped Organic Semiconductor with Extraordinary Thermomechanical Property and Solution Processability for Stable Perovskite Solar Cells

Wei,

Zhang,

Ren

et al. 2023

Adv Funct Materials

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Achieving the desired thermomechanical properties for highly solution‐processable organic semiconductors is challenging but crucial for heat tolerance of emerging optoelectronic devices. To this end, the successful synthesis of triphenylene–ethylenedioxythiophene‐dimethoxytriphenylamine (TP–ETPA), a star‐shaped organic semiconductor, is reported through a direct arylation reaction that involves ETPA, an electron donor, being grafted densely onto TP, which possesses six electron‐equivalent functionalization sites. Remarkably, TP–ETPA exhibits significantly improved hole mobility compared to 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenyl‐amine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) at a given hole density, owing to its lower energetic disorder, larger average centroid distance, and smaller reorganization energy. TP–ETPA, with a molecular weight of 2888 Da and lacking flexible chains, demonstrates extraordinary solubility in nonpolar solvents, enabling the formation of dense, pinhole‐free films through solution codeposition with an air‐doping promoter. By utilizing the p‐doped TP–ETPA composite as the hole transport layer, perovskite solar cells with an average power conversion efficiency of 23.4% are successfully fabricated. Notably, these devices display significantly enhanced operational stability and thermal stability at 85 °C. Molecular dynamics simulations reveal that the TP–ETPA‐based hole transport layer possesses a high cohesive energy density, resulting in a large elastic modulus and slow diffusion of external species.

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Effect of the polar group content on the glass transition temperature of ROMP copolymers

Abstract: Polar groups have long been recognized to greatly influence the glass transition temperature (Tg) of polymers, but understanding the underlying physical mechanism remains a challenge. Here, we study the glass...

Cited by 8 publications

References 71 publications

Molecular Dynamics Investigation of the Pressure Dependence of Glass Formation in a Charged Polymer Melt

Molecular Dynamics Investigation of the Pressure Dependence of Glass Formation in a Charged Polymer Melt

A Single-Atom Upgrade to Polydicyclopentadiene

Star‐Shaped Organic Semiconductor with Extraordinary Thermomechanical Property and Solution Processability for Stable Perovskite Solar Cells

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