高分子物理Chapter 3 Properties of Polymer Solutions.pptVIP

Chapter 3 Properties of Polymer Solutions 3.1 Solubility of Polymers Polymer solution: 高聚物以分子状态分散在溶剂中形成的均匀混合物 不同类型的高聚物的溶解方式不同： 非晶态高聚物：溶剂分子容易渗入高聚物内部使之溶胀和溶解。 晶态高聚物：溶剂分子渗入高聚物内部非常困难，其溶胀和溶解困难。 非极性晶态高聚物：室温时难溶，升温至熔点附近，使晶态高聚物转变为非晶态高聚物后，再溶解。 极性晶态高聚物：室温时采用极性溶剂溶解。 Predications of Solubilities The solubility parameter is related to the cohesive energy-density, or the molar energy of vaporization of a pure liquid, ?E, as ?=(?E/V)1/2, where ?E is defined as the energy change upon isothermal vaporization of the saturated liquid to the ideal gas state at infinite dilution and V is the molar volume of the liquid. Units of ? are (cal cm-3)1/2 or (MPa)1/2. Since it is not reasonable to talk about an energy of vaporization for solid polymers, the solubility parameter of a polymer has to be determined indirectly or calculated by group-contribution methods. Experimentally, the solubility parameter of a polymer can be estimated by comparing the swelling of a crosslinked polymer sample immersed in different solvents. The solubility parameter of the polymer is taken to be that of the solvent resulting in maximum swelling. Alternatively, the solubility parameter of a polymer can be estimated by use of one of several group-contribution methods, such as those given by Small and by Hoy. An extensive presentation of group-contribution methods for estimating polymer properties, including those for solubility parameters, is given by van Krevelen. Calculation of ? by a group-contribution method requires the value of a molar attraction constant, Fi, for each chemical group in the polymer repeating-unit. The solubility parameter of a polymer is then calculated from these molar attraction constants and the molar volume of the polymer, V (units of cm3 mol-1), as: Where the summation is taken over all groups in the repeating unit. Example Problem: Estimate the solubility parameters, in units of (MPa)1/2, for poly(methyl methacrylate) (PMMA) by the method of Small. The density of PMMA is reported t