高分子物理（浙江大学） 3 高分子溶液 Polymer Solutions-2.pptVIP

3 Polymer Solutions 高分子溶液 Study on dilute solution is of key importance on the formation of polymer science 3.1 Dissolution of polymers 3.1.1Characteristics of Polymer Dissolution 高分子的溶解特点 Crosslinked polymers can only be swollen (溶胀)，not be dissolved (溶解) . Polymer-polymer mutual solutions are even more difficult to attain. Free energy of dissolution 溶解自由能 Non-polar crystalline polymers Firstly heating to the temperature near Tm to destroy the crystal lattice, then dissolved in the solvent. HDPE( Tm＝135?C), T 120?C in decalin sPP(Tm＝134 ?C) and iPP(Tm＝170?C) T130?C, in decalin. Polar crystalline polymers Can be dissolved at room temperature! The solvent first interacts with amorphous parts. The produced heat can destroy the crystal lattice and the crystalline is dissolved gradually. PA can be dissolved in MeOH or 4％ H2SO4，or 60% HCOOH at room temperature. ★ Crystallinity dissolution 3.1.2 Selection of solvent溶剂的选择 Similar polarity (极性相似原则) Similar solubility parameter (溶度参数相近原则) Solvation (溶剂化原则) ★ combinatorial consideration of above three points! Similar polarity：相似相溶(定性) For small molecules: The smaller the difference in polarity, the easier the dissolution. For polymers: also applicable Natural rubber (non-polar): petroleum, benzene, hexane and petroleum ether (non-polar) PS (weak polarity) ：toluene, chloroform, aniline(苯胺)(weak polarity) and benzene (non-polar) PMMA (polar) ：acetone (polar) PVA (polar) ：water (polar) PAN (strong polarity) ：DMF, acetonitrile(乙腈)(strong polarity) 溶度参数相近原则(定量) 非极性高聚物，其溶解过程一般吸热?HM0，所以只有在 |?HM| T|?SM| 时，才能满足 ?G0。也就是说只增大 T 或减小?HM时才能使体系自发溶解，那么?HM又如何得知呢？ 非极性高聚物与溶剂相互混合时的混合热可以借助小分子的溶度公式来计算。 Definitions of Solubility parameter溶度参数的定义 Solubility parameter and solubility 溶度参数与溶解度 Solubility parameter of polymers Solubility parameter of solvents Mixed solvent 混合溶剂 (1)小分子溶剂的溶度参数由Clapeyron-Clausius公式计算： ①先求得?Hv(摩尔蒸发热) ②再根据热