Taking account of the effect ale heteroatoms iq backbone, this article dealt with the mean-square radii of gyration of polyalkyleneoxides by the approach of matrix algebra in accordance with the rotational isomeric st...Taking account of the effect ale heteroatoms iq backbone, this article dealt with the mean-square radii of gyration of polyalkyleneoxides by the approach of matrix algebra in accordance with the rotational isomeric state model, Numerical calculation with the parameters available in the literatures indicated that the dependence of [S-2] on the molecular weight can be expressed by the general formula: [S-2]=aM(b).展开更多
The mean-square radius of gyration <S^2>,the mean-square dipole moment <D^2>,the mean-square end-to-end distance <R^2> and their temperature coefficients of unsymmetrical disubstituted poly(methylphe...The mean-square radius of gyration <S^2>,the mean-square dipole moment <D^2>,the mean-square end-to-end distance <R^2> and their temperature coefficients of unsymmetrical disubstituted poly(methylphenylsiloxane) (PMPS) chains, as a function of stereochemical structure,confomational energies and length of polymers,were studied by using an improved configurational-confomational statistical method based on the rotational-isomeric-state theory.It is found that the increase in isotacticity of P...展开更多
Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystalline layered structure. Whether or not a chain disentangles may result in different crystallization mechan...Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystalline layered structure. Whether or not a chain disentangles may result in different crystallization mechanism. When compared to the crystal thickness (d(c)), the volume occupied by the chain in the melts i.e., the radius of gyration (R-g), plays a very important role in polymer crystallization. When d(c) less than or equal to R-g, crystallization does not necessitate a chain disentangling. The entanglements are just shifted into the amorphous regions. However, as d(c)>R-g, i.e., as the crystal thickness gets larger than the radius of gyration of the chain in the melt, it becomes necessary for a chain to disentangle. Then a change of crystallization mechanism occurs. Such change has been experimentally observed in the crystallization of poly(I-butene). A change in the crystal morphologies from spherulite to quadrangle, is seen via PLM, as crystallization temperatures increase. Even more, such a change is molecular weight dependent, and shifts to lower temperature as molecular weight decreases. There exists a jump of crystal thickness and crystallinity associated with morphological change, as seen via SAXS. A change of crystallization kinetics and crystallinity is further evidenced via dilatometry. The unique feature of P1b crystallization has been discussed based on the radius of gyration of chain in the melt (R-g), and very good agreement is obtained.展开更多
We present an incorporation of the kinetic Monte Carlo(kMC)simulation with the adjacency matrix(AM)method to investigate structural parameters of randomly branched polymers.The AMs of branched polymers are obtained by...We present an incorporation of the kinetic Monte Carlo(kMC)simulation with the adjacency matrix(AM)method to investigate structural parameters of randomly branched polymers.The AMs of branched polymers are obtained by the growth generation model,which is employed in the kMC simulation based on Gillespie’s algorithm.Of particular interest is the effect of the branched units on the relevant structural parameters.As an application in randomly hyperbranched polymers formed by AB_(2)type of monomers,average maximum span length,average length of sub-chains,number distribution of branched units,and meansquare radius of gyration are calculated.It is shown that the branched units can give rise to a significant effect on these physical quantities,whereby such a structure-property relationship can be employed to optimize reaction conditions and implement material designs.展开更多
A single polymer chain in solvent confined in a slit formed by two parallel plates is studied by using molecular dynamics simulation method. The square radii of gyration and diffusion behaviors of polymers are greatly...A single polymer chain in solvent confined in a slit formed by two parallel plates is studied by using molecular dynamics simulation method. The square radii of gyration and diffusion behaviors of polymers are greatly affected by the distance between the two plates, but they do not follow the same way. The chain size decays drastically with increasing h （h is the distance between two plates）, until a basin occurs, and a universal h/（Rg）o dependence for polymer chains with different degrees of polymerization can be obtained. While, for the chain＇s diffusion coefficient, it decays monotonously and there is no such basin-like behavior. Furthermore, we studied the radial distribution function of confined polymer chains to explain the reason why there is a difference for the decay behaviors between dynamic properties and static properties. Besides, we also give the degree of confinement dependence of the static scaling exponent for a single polymer chain. Our work provides an efficient way to estimate the dynamics and static properties of confined polymer chains, and also helps us to understand the behavior of polymer chains under confinement.展开更多
An improved configurational-confomational statistical method is developed and the mean-square radius of gyration for atactic poly（α-methylstyrene）（PαMS） chains is studied, in which the effect of large side group...An improved configurational-confomational statistical method is developed and the mean-square radius of gyration for atactic poly（α-methylstyrene）（PαMS） chains is studied, in which the effect of large side groups is considered. The deduced formulas, based on the rotational isomer state theory, are used to investigate the configuration-dependent properties of the atactic polymer chain, and the statistical correlation of the unperturbed polymer chain dimension and structure parameters are calculated. For the fraction of meso dyads Wm= 0.4, the dependence of the radius of gyration Rg and the intrinsic viscosity [η] on the molecule mass M are Rg = 2.63×10^-2 M^0.50 nm and [η] = 7.36 × 10^-2 M^0.497, respectively, which are in agreement with the previous experimental data for the PαMS samples. A small hump is detected in the curve of the characteristic ratio of the unperturbed mean-square radius of gyration versus the chain length for short PαMS chains. The Rg increases linearly with the temperature T, and the effects of the chain length and the tacticity on the temperature coefficient are remarkable. These are quite different from the results for PαMS chains not considering side groups or for the monosubstituted polystyrene chain.展开更多
基金This work was supported by the National Natural Science Foundation of China
文摘Taking account of the effect ale heteroatoms iq backbone, this article dealt with the mean-square radii of gyration of polyalkyleneoxides by the approach of matrix algebra in accordance with the rotational isomeric state model, Numerical calculation with the parameters available in the literatures indicated that the dependence of [S-2] on the molecular weight can be expressed by the general formula: [S-2]=aM(b).
基金supported by the National Basic Research Program (973) of China (No.10574109)the Zhejiang Provincial Science and Technology Department (No.2007G60G1120019)+1 种基金National Science Foundation of Zhejiang Province (No.Y604064)Zhejiang Gongshang University (No.08-13),China.
文摘The mean-square radius of gyration <S^2>,the mean-square dipole moment <D^2>,the mean-square end-to-end distance <R^2> and their temperature coefficients of unsymmetrical disubstituted poly(methylphenylsiloxane) (PMPS) chains, as a function of stereochemical structure,confomational energies and length of polymers,were studied by using an improved configurational-confomational statistical method based on the rotational-isomeric-state theory.It is found that the increase in isotacticity of P...
基金This work was supported by the Deutsche Forschungsgemeinschall and der Chemischen Industrierate, Alexander von Humboldt Stiffeng and the China National Distinguished Young Investigator Fund (No. 29925413).
文摘Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystalline layered structure. Whether or not a chain disentangles may result in different crystallization mechanism. When compared to the crystal thickness (d(c)), the volume occupied by the chain in the melts i.e., the radius of gyration (R-g), plays a very important role in polymer crystallization. When d(c) less than or equal to R-g, crystallization does not necessitate a chain disentangling. The entanglements are just shifted into the amorphous regions. However, as d(c)>R-g, i.e., as the crystal thickness gets larger than the radius of gyration of the chain in the melt, it becomes necessary for a chain to disentangle. Then a change of crystallization mechanism occurs. Such change has been experimentally observed in the crystallization of poly(I-butene). A change in the crystal morphologies from spherulite to quadrangle, is seen via PLM, as crystallization temperatures increase. Even more, such a change is molecular weight dependent, and shifts to lower temperature as molecular weight decreases. There exists a jump of crystal thickness and crystallinity associated with morphological change, as seen via SAXS. A change of crystallization kinetics and crystallinity is further evidenced via dilatometry. The unique feature of P1b crystallization has been discussed based on the radius of gyration of chain in the melt (R-g), and very good agreement is obtained.
基金supported by the Central Guidance on Local Science and Technology Development Fund of Hebei Province (No.236Z7601G)the Interdisciplinary Research Program of Natural Science of Hebei University, China (No.DXK202112)。
文摘We present an incorporation of the kinetic Monte Carlo(kMC)simulation with the adjacency matrix(AM)method to investigate structural parameters of randomly branched polymers.The AMs of branched polymers are obtained by the growth generation model,which is employed in the kMC simulation based on Gillespie’s algorithm.Of particular interest is the effect of the branched units on the relevant structural parameters.As an application in randomly hyperbranched polymers formed by AB_(2)type of monomers,average maximum span length,average length of sub-chains,number distribution of branched units,and meansquare radius of gyration are calculated.It is shown that the branched units can give rise to a significant effect on these physical quantities,whereby such a structure-property relationship can be employed to optimize reaction conditions and implement material designs.
基金financially supported by the National Natural Science Foundation of China (Nos.21074137,21104082 and 50930001)the Fund for Creative Research Groups (No.50921062)National Basic Research Program of China (973Program, 2012CB821500)
文摘A single polymer chain in solvent confined in a slit formed by two parallel plates is studied by using molecular dynamics simulation method. The square radii of gyration and diffusion behaviors of polymers are greatly affected by the distance between the two plates, but they do not follow the same way. The chain size decays drastically with increasing h （h is the distance between two plates）, until a basin occurs, and a universal h/（Rg）o dependence for polymer chains with different degrees of polymerization can be obtained. While, for the chain＇s diffusion coefficient, it decays monotonously and there is no such basin-like behavior. Furthermore, we studied the radial distribution function of confined polymer chains to explain the reason why there is a difference for the decay behaviors between dynamic properties and static properties. Besides, we also give the degree of confinement dependence of the static scaling exponent for a single polymer chain. Our work provides an efficient way to estimate the dynamics and static properties of confined polymer chains, and also helps us to understand the behavior of polymer chains under confinement.
文摘An improved configurational-confomational statistical method is developed and the mean-square radius of gyration for atactic poly（α-methylstyrene）（PαMS） chains is studied, in which the effect of large side groups is considered. The deduced formulas, based on the rotational isomer state theory, are used to investigate the configuration-dependent properties of the atactic polymer chain, and the statistical correlation of the unperturbed polymer chain dimension and structure parameters are calculated. For the fraction of meso dyads Wm= 0.4, the dependence of the radius of gyration Rg and the intrinsic viscosity [η] on the molecule mass M are Rg = 2.63×10^-2 M^0.50 nm and [η] = 7.36 × 10^-2 M^0.497, respectively, which are in agreement with the previous experimental data for the PαMS samples. A small hump is detected in the curve of the characteristic ratio of the unperturbed mean-square radius of gyration versus the chain length for short PαMS chains. The Rg increases linearly with the temperature T, and the effects of the chain length and the tacticity on the temperature coefficient are remarkable. These are quite different from the results for PαMS chains not considering side groups or for the monosubstituted polystyrene chain.
