聚合反应工程基础（全套课件）.ppt

谢 谢！ * 表明：速率关系式仍然存在，但转化率表达式、共聚物组成式有变化。 * （4）半连续乳液聚合中的聚合速率 * 习题：以过氧化二苯甲酰作引发剂，60℃下进行St的本体聚合。动力学参数如下： * t j * Chap 6 Step Growth Polymerization(Polycondensation) 6.1 Introduction 6.2 AB Polycondensation 6.3 A2+B2 Polycondensation 6.4 Reversible Polycondensation * 6.1 Introduction Polymn. mechanism Chain polymn. Step growth polymn. Active chain end (ACE) Activated monomer (AM) coordination Polyaddition Polycondensation radical anionic cationic condensate * Activated monomer (AM) mechanism 2. Carbene catalyzed ROP of lactone 1. alkali catalyzed ROP of caprolactam 酰化内酰胺 酰化内酰胺开环 质子交换反应 * 1. Nylon (Polyamide) 2. Polyester 3. Aromatic polyester Examples for polycondensation polymers 4. Polycarbonate 其它：酚醛、尿醛，…… 缩聚方法 熔融缩聚 溶液缩聚 界面缩聚 * 聚酯家族 全芳香聚酯 半芳香聚酯 半芳香聚酯 脂肪族聚酯 饱和聚酯 不饱和聚酯或交联聚酯 聚酯 醇酸树脂 (苯酐＋甘油) 马来苯酐(苯酐)＋多元醇：玻璃钢 醇酸树脂(苯酐＋甘油)：涂料 脂肪族交联聚酯(柠檬酸+甘油)：医用弹性体 * 6.2 AB Polycondensation nylon 11 characteristics : Reaction occurs between group A and B other than chain end and monomer, therefore, what is concerned is consumption rate of group other than of monomer examples PLA In general * (6.1) (6.2) [A],[B]: concentration of group A and B, respectively; Pi: polymer chain with i structural units, Pi means ARiB, P1 means monomer ARB; [Pi]: concentration of Pi; [P]: concentration of all polymer chains (6.4) (6.3) 由于每条聚合物链Pi均含有1个A官能团、1个B官能团， * (6.5) (6.6) (6.7) (6.8) (相当于官能团的转化率) 注意反应程度与单体转化率的区别！ 由式6.14 * (6.9) (6.10) Why a factor of 2 appears in the disappearance items? 如何求分子量分布函数？先写出关于[Pi]的微分方程： (6.12) (6.11) generate disappear * If i ? j, there are two distinguishable reactions, in each reaction an i-mer disappears by reacting with a j-mer, but in one the A group is lost on the i-mer, and in the other on the j-mer. Therefore, a factor of 2 is reasonable for the i ? j case. If i = j, although the two reactions are no longer distinguishable, however, two i-mers disappear. Therefore, a factor of 2 is also reasonable for the i = j case. Why no