Relationship between Tranlational and Rotational Diffusions of Polymer Chains

聚合物链的平移和旋转扩散之间的关系

• 批准号: 04453106
• 负责人: ADACHI Keiichiro
• 金额: $ 4.61万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453106/
• 关键词: translation diffusion; rotational diffusion; end-to-end vector; polyisoprene; relaxation time; tube model; Rouse theory; polybutadiene; 重心拡散係数; 散乱レーリー散乱法; 誘電的ノーマルモード過程; 回転緩和時間; 二乗平均末端間距離; からみ合い状態; 高分子; 並進拡散; 回転拡散; 強制レーリー散乱; 誘電緩和; Rouse

Measurements of the translational diffusion coefficient D and the relaxation time tau for reorientation of the end-to-end vector of polyisoprene (PI) were carried by means of forced Rayleigh scattering and dielectric methods, respectively. From the dielectric relaxation strength we also determined the mean square end-to-end distance <r^2>. From the data of D, tau, and <r^2> over wide range of molecular weight M, the values of a dimensionless quantity Dtau/<r^2> were determined and compared with the Rouse theory and tube model.In monodisperse polyisoprene, D decreased with increasing M in proportion to M^<-2.8> in the range of 10000 < M < 40000 but the exponent decreased slight in 40000 < M.This behavior does not agree with the tube model which predicts D * M^<-2.0>. In a binary blends in which a trace amount of labeled PI is dissolved in a matrix of non-labeled PIs, D depended strongly on the M of the matrix PI,i.e., D * M^<-1.0> when the M of the diffusant is much higher than that of matrix and D * M^<-2.5> wehn the matrix has much higher M than the diffusant. The former behavior agrees with the Rousse theory. The value of Dtau/<r^2> in the monodisperse system is calpha one order smaller than the prediction of the Rouse and tube models both of which predict Dtau/<r^2> = 1/3pi^2. On the other hand, in the binary blends of low molecular weight matrix, Dtau/<^2> agreed well with the Rouse theory.

采用强迫瑞利散射法和介电法分别测量了聚异戊二烯（PI）端到端矢量重定向的平移扩散系数D和弛豫时间tau。根据介质弛豫强度，我们还确定了端到端距离的均方<r^2>。根据D、tau和<r^2>在大分子量M范围内的数据，确定了一个无因次量Dtau/<r^2>的值，并与劳斯理论和管模型进行了比较。在单分散聚异戊二烯中，在10000 < M < 40000范围内，D随M^<-2.8>的增大而减小，但在40000 < M时指数略有下降，这与预测D * M^<-2.0>的管状模型不一致。在二元共混物中，微量标记PI溶解在非标记PI的矩阵中，D强烈依赖于矩阵PI的M，即。当扩散剂的M远大于基体的M时，D * M^<-1.0>；当基体的M远大于扩散剂时，D * M^<-2.5>。前一种行为符合卢斯理论。在单分散体系中，Dtau/<r^2>的值比Rouse和tube模型的预测值小1阶，两者都预测Dtau/<r^2> = 1/3pi^2。另一方面，在低分子量矩阵的二元共混体系中，Dtau/<^2>符合Rouse理论。

项目成果

O.Urakawa: "Dielectric Normal Mode Relaxation of Probe Polyisoprene in Semidilute Polybutadiene Solutions.2.Dynamic Behavior" Macromolecules. 26. 2042-2049 (1993)

O.Urakawa：“半稀聚丁二烯溶液中探针聚异戊二烯的介电常模弛豫。2.动态行为”大分子。

O.Urakawa: "Calculation of Type-A Dipole Moments with a Rotational Isomeric State Model." Rep.Progr.Polym.Phys.Jpn.36. 113-116 (1993)

O.Urakawa：“使用旋转异构态模型计算 A 型偶极矩。”

O.Urakawa, K.Adachi and T.Kotaka: "Dielectric Normal Mode Relaxation of Probe Polyisoprene in Semidilute Polybutadiene Solutions.1. End-to End Distance" Macromolecules. Vol.26 No.8. 2036-2041 (1993)

O.Urakawa、K.Adachi 和 T.Kotaka：“半稀聚丁二烯溶液中探针聚异戊二烯的介电常模弛豫。1. 端到端距离”大分子。

H.Hirano, K.Adachi and T.Kotaka: "Dielectric Normal Mode Relaxation in Dilute and Semidilute Solutions of Butadiene-Isoprene Block Copolymer" Rep. Progr. Polym. Phys. Jpn.Vol.36. 109-112 (1993)

H.Hirano、K.Adachi 和 T.Kotaka：“丁二烯-异戊二烯嵌段共聚物的稀溶液和半稀溶液中的介电常模弛豫”Rep. Progr。

O.Urakawa,K.Adachi T.Kotaka: "Dielectric Normal Mode Relaxation of Probe Polyisoprene Chain in Semidilute Solutions.1. End-to-End Distance" Macromolecules. 26. (1993)

O.Urakawa，K.Adachi T.Kotaka：“半稀溶液中探针聚异戊二烯链的介电常模弛豫。1.端到端距离”大分子。