聚合反应原理Chapter3.ppt

Chapter 3 Nitroxide Mediated Living radical polymerization 3-1 Basic concept of nitroxide-mediated living free radical polymerization In this reaction, selecting suitable stable radical is key point. In many stable radicals, N-O and alkoxylamines free radicals are the best Low molecular weight polymer or oligomers are obtained by polymerization at 80-100oC When polymerization of acrylate at 80-100oC in the presence of BPO and hindered nitroxide, low MW or oligomer was obtained. This can not be considered living 3-2. initiation 1 Bimolecular process 2 Unimolecular initiator The poorly defined nature and unknown concentration of the initiating species in the bimolecular process prompted the development of a single molecule initiating system The function of each specie 3 Design of initiator Necessity b. For more monomers applicable in living radical polymerization Change the structure of TEMPO · For increasing the polymerization rate c. The use of alicyclic nitroxides he most significant breakthrough in the design of improved nitroxTides was the use of alicyclic nitroides The striking difference is the presence of a hydrogen atom on one of the d-carbons, in contrast to the two quaternary d-carbons present in TEMPO A wide variety of monomer families, such as acrylates, acrylamides, 1,3-dienes and acrylonitrile can be polymerized with accurate control of MWs and polydispersity as low as 1.05 Control the formation of random and block copolymers from a wide selection of monomer units containing reactive functional groups such as amino, carboxylic acid, glycidyl 3-3 Synthesis of N-O stable free radicals 1. Polymerization method 2. Oxidation method Alkyl radical is produced in the presence of peroxides, then combined with stable radical 3. Single electron transfer Controlled generation of carbon-centered radicals followed by trapping of radical-like intermediates Cu2+-promoted single electron transfer reactions with enolate anions to provide carbon-centered free radical