高分子化学（浙江大学） polymer2-1 Radical Chain Polymerization.pptVIP

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高分子化学（浙江大学） polymer2-1 Radical Chain Polymerization.ppt

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高分子化学（浙江大学） polymer2-1 Radical Chain Polymerization

* 4 Initiation * 4.1 Thermal initiators 1 initiator A. azo compounds ( -N=N-，偶氮化合物) Release of nitrogen * B. Peroxides (-O-O-，过氧化合物) The rate of decomposition of peroxide initiators is a function of their chemical structure: ( R COR ROCO) The nature of the solvent may also affect the rate of decomposition: tert-butyl peroxide higher in acetonitrile than in cyclohexane inorganic * C. Redox initiators （氧化还原引发剂） Usually two components low Ea for polymerization at low temperature * 2. Kinetics of decomposition Unimolecular decomposition and first order kinetics for azo and peroxides. Integration leads to an expression that describes the decreasing initiator concentration as a function of time. Two parameters: kd and t 1/2 = ln2 / kd (half life of initiator) kd(s-1, min-1, or h-1 ) is the rate coefficient of initiator decomposition Rd (mol/L·s ) is the rate of initiator decomposition * 3 Initiation Efficiency ( f ) Cage effect As an initiator molecule decomposes, the resulting geminate radicals can either react with one another inside the ‘‘solvent cage’’ or diffuse out of the cage to participate in other reactions, mainly addition to monomer. This so called ‘‘cage effect’’ is the main reason that the initiator efficiency f is lower than unity (another reason is primary radical termination) . * Efficiency of AIBN as initiator (solution styrene:toluene 50% v/v, 70 oC) Moad et al., Makromol,Chem.Rapid.Commun 1984, 5, 793 ▲ cumulativeO instantaneous di-tert-butylperoxide AIBN di-tert-butylperoxalate f = 0.65 f = 0.75 f=0.95 * 4 Selection of initiator According to the polymerization method Bulk, solution polymerization organic Emulsion, aqueous polymerization water-soluble or redox According to polymerization temperature kd or t1/2 * 4.2 Self-initiation/Thermal-initiation (热引发) Only proven to occur with st