高分子物理复旦大学chapter4高聚物分子量和分子量分布讲义资料.ppt

Chapt 4 Molecular Weight and Molecular Weight Distribution of Polymers 4.1 高聚物分子量和分子量分布的表示方法 4.2 分子量的测定方法 4.3 分子量分布的测定方法 4.2.1 数均分子量的测定方法 4.2.2 重均分子量的测定方法 4.2.3 粘均分子量的测定方法 Molecular weight and molecular weight distribution Distribution of molecular weights in a typical polymer 4.1 Definitions of Average MWs and MW Distribution n: total mole number; ni: mole number of ith molecule with mole mass of Mi; Ni: mole fraction of ith molecule; w: total weight of the sample; wi: weight of the ith molecule; Wi: weight fraction of ith molecule. (1) Number-average molecular weight (数均分子量): (2) Weight-average molecular weight (重均分子量): Schulz Tung Logarithm normal distribution 用简化的函数拟合 MW Distribution Width of molecular weight distribution (分子量分布宽度): Polydispersity (多分散系数): MW Distribution Function 实验测量 平均分子量 分布宽度 4.2 Measurement of Molecular Weight End group analysis (端基分析) molecular weight determination through group analysis requires that the polymer contain a known number of determinable groups per molecule. measure the number-average molecular weight, Mn ? 2.5 ? 104 Colligative property (依数性) measurement: measure the number-average molecular weight Mn vapor-pressure lowing boiling-point elevation (ebulliometry) freezing-point depression (cryoscopy) osmotic pressure (osmometry) DTb, DTf, and P are the boiling-point elevation, freezing-point depression, and osmotic pressure. r is the density of the solvent. DHv and DHf are the enthalpies of vaporization and fusion. Vapor-phase osmometry (VPO, 气相渗透法) Small temperature difference resulting from different rates of solvent evaporation from and condensation onto droplets of pure solvent and polymer solution maintained in an atmosphere of solvent vapor. Measure Mn that is too lower for membrane osmometry method. Calibrated with low-molecular weight standards: a relative method. Quasi-steady-state phenomena. care must be taken to standarize such variables as time of measurement and drop size between calibration an