共聚物速率方程：引发、增长与终止及其影响.pptxVIP

Part4TheRateEquationofcopolymerizationInitiation,propagationandterminationTheeffectofterminationrateoncopolymerizationrate：Thechemicalcontrolledtermination;Thediffusioncontrolledtermination.

5.4.1TherateequationofchemicalcontrolledterminationSincethedispearrateofmonomerisdeterminedbypropagation,theoverallpropagationrateisthesumoffourkindsofpropagation.

Twokindsofsteadyasumption：1.Theconcentrationofallkindsofradicalsareinthesteadystate，then：2.Thetotalconcentrationofradicalskeepconstant,I.e.theinitiationrateequalstotheterminationrate：Ri=Rt=2kt11[M1·]2+2kt12[M1·][M2·]+2kt22[M2·]2

φ＞1isprefertothecrosstermination

5.4.2TherateequationofdiffusioncontrolledterminationTheterminationrateisdependsontheviscosityofsystemastheviscosityislow.Intheotherword，thechainterminationiscontrolledbychaindiffusionfromthelowconversionon.Therefore,thetotoalpropagationrateequationis：

(5-36)

Theterminationrateconstantcanberegardedasthefunctionofterminationrateconstantofhomopolymerizationasfellows,

Eq.(6-29)Eq.(6-30)Figure5-7VAc-MMAsolventcopolymerization(60℃)