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1、[理学]《聚合反应原理专论》chapter1中科大研究生教学课件2.ControlofmolecularweightdistributionItisimportanttothepolymerproperties:Solutionproperty;Mechanicalproperties.Forexamples,PTHFinthepreparationofelasticpolyurethane,polymerprocessing,viscosityPhaseseparationintheblends3.Control
2、ofpolymerstructure1)Generalfreeradicalpolymerization:Onlysynthesisoflinearhomopolymersorcopolymers,suchasStarblockcopolymerMiktoarmstarpolymerGraftingpolymerCombpolymerGeneralradicalpolymerizationcannotprepareblockcopolymersandothernonlinearpolymers,thereasoni
3、s:Characteristicsoffreeradicalpolymerization.Deadmacromoleculeisformedinshorttime.Well-definedblockcopolymerscannotbesynthesizedbycondensationpolymerizationAnyapplicationofblockcopolymersandnonlinearpolymersSBSisathermoplasticelastomer.2.Controlofdrugrelease:
4、Forexample:synthesisofamphiphiliccopolymers.Synthesisofamphiphiliccopolymers★两亲性;★高反应性囊泡的形成过程伴刀豆蛋白与对硝基苯酚酯的反应CON-A伴刀豆蛋白(CONA)胰岛素葡萄糖葡萄糖和胰岛素交换反应原理图葡萄糖胰岛素糖糖WhydowedevelopthelivingpolymerizationControlofmolecularweightPreparepolymerswithnarrowmolecularweightdistrib
5、utionPreparationofcomplicatedarchitecturepolymers,suchasblockcopolymers,nonlinearpolymers,includingstar,starblock,hyperbranched,dendrimer-likecopolymersetc.1-2.ConceptofLivingPolymerizationNoterminationNochaintransferreactionInitiationrateisfasterthanpropagati
6、onrateWhatislivingpolymerization?LivingpolymerizationofstyreneConversionupto100%Notermination;NotransferreactionsNoterminationThepolymerizationcancontinuewhenmonomersareadded.Thebigeffectofchaintransferonmolecularweightandpolydispersity,Oneexample:Chaintransfe
7、rreactionsinpolymerizationofvinylchlorideNochaintransferreactionKineticsinthepresenceofchaintransferreactionWhenonlychaintransfertothemonomerexistsinthepolymerization,suchas,AIBNusedasinitiatorinbulkpolymerization,theDPcanbecalculated:1/Xn=2kt/kp2·Rp/[M]2+CMDu
8、etotherateofchaintransfertovinylchlorideismuchbiggerthanterminationrate,Rtr,M>Rt,thus1/Xn=Rp/(Rt+Rtr,M)~Rp/Rtr,M=kp/ktr,M=1/CMMolecularweightisdeterminedbyCM,polymerizationat50oC,C