高分子化学英文版本第一章.ppt

Chapter 2 Radical Chain polymerization; Whether monomer could be polymerized firstly depends on the thermondynamic perspective, in which we discuss the possibility, direction and balance of chemical reaction. Its aim is to judge the possibility of polymerization from structures which is crucial to the investigation of new polymers. ;The possibility and direction of a reaction depends on its ΔG。; Polymerization and depolymerizatin are in balance, when the temperature TC is the ceiling temperature of polymerization.; Polymerization heat is the heat released when the C = C double bond transferred into a CC single bond, which is generally about -90kJ/mol. Its size depends on the structure of the monomer.;At standard thermodynamic conditions (1atm, 25 ℃, activity = 1);;R*(reactive species) （external course） Initiator species--- to provide active species in the polymer chemistry.;Monomer is easy to attacked by the active species（internal cause） ; Homolysis ;Carbonyl monomer: HCHO;carbon-carbon double bond ： Both homolysis and heterolysis，radical polymerization or ionic polymerization; Carbon-oxygen double bond: can be initiated by cationic and anionic initiator, can’t carry out the radical polymerization.;2.1.4.2 Selections of polymerization mode of vinyl monomer ;No substituent：ethylene;electron-donating substituent Such as alkyl、phenyl、vinyl Will increase the electron cloud density of C = C double bond , which is beneficial to be attacked by cation; electron-donating group enable the growth of electron cloud of carbon cation hence stablize the resonance stabilization);propylene、butylene: Electron donating and conjugate effects are weak and can only obtain oligomers.;electron-withdrawing substituent Such as cyano group, carbonyl, ester, carboxyl, aldehyde, ketone, etc. reduce the double bond electron cloud density and increase anionic increaser conjugate stability; Vinyl monomer with Electron withdrawing groups, such as