(精)非平衡缩聚.pptVIP

* Non-Equilibrium Polycondensation 1 Introduction 1.1 Classification of polycondensation 1.1.1 By the kinds of monomer 1) homopolycondensation H2NRCOOH ?-amino acid 2) heteropolycondensation H2NRNH2 + HOOCR?COOH diamine diacid 3) copolycondensation H2NRCOOH + H2NR?COOH H2NRNH2 + H2NR?NH2 + HOOCR??COOH 1.1.2 By the structure of polymer 1) linear polycondensation 2-system, 2-2 system 2) network (three dimensional) polycondensation 2-3 or 2-4 system 1.1.3 By the types of the functional group polyesterification -COO- polyamidation -CONH- polyetherification -O- polyurethanation -OCONH- 1.1.4 By the thermodynamic characteristics of reaction n a-A-a + n b-B-b a [ AB ] b + (n-1) ab equilibrium polycondensation (reversible) degradation or exchange reaction K=k1/k2 small non-equilibrium polycondensation (irreversible) no degradation or exchange reaction K103 ex. Kevlar, poly(p-phenylene terephthalamide) n ClOC- -COCl + n H2N- -NH2 terephthaloyl chloride p-phenylene diamine k1 k2 n n [ NH- -NH-CO- -CO ] + 2n HCl 1.2 Factors causing non-equilibrium polycondensation 1) chemical factors * highly-active functional groups of monomer: -COCl COOH acyl chloride carboxy * more stable product: Kevlar high decomposition temperature 500℃ soluble in concentrated H2SO4 only * add some reagent to promote positive reaction such as tertiary amine to react with HCl in Kevlar reaction 2) physical factors * lower the reaction temperature * interfacial polycondensation 2 Types of non-equilibrium polycondensation 2.1 Controlled by chemical factors 1) diacyl chloride reacts with diol or diamine O HOOC-R-COOH + Cl-S-Cl ClOC-R-COCl + H2SO3 dichloro sulfoxide very active, larger K n HOOC- -COOH + n HO(CH2)4OH PBT n ClOC- -COCl + n HO(CH2)4OH 2) oxidative dehydropolyc