高分子反应原理优秀PPT.ppt

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1、高分子反应原理第一页，本课件共有56页2.ControlofmolecularweightdistributionItisimportanttothepolymerproperties:Solutionproperty;Mechanicalproperties.Forexamples,PTHFinthepreparationofelasticpolyurethane,polymerprocessing,viscosityPhaseseparationintheblends第二页，本课件共有56页3.Controlofpolymerstructure1)Generalfreeradicalpol

2、ymerization:Onlysynthesisoflinearhomopolymersorcopolymers,suchas普通自由基聚合只能合成共聚物和均聚物！第三页，本课件共有56页2)Condensationpolymerization第四页，本课件共有56页3)Complicatedstructurepolymerscanbedesignedandprepared.Forexample:第五页，本课件共有56页IntroductionofPolymerStructure Linear polymers and linear block copolymers Monomer 1,Mo

3、nomer 2,Monomer 3 Monomer 1,Monomer 2,Monomer 3 Nonlinear copolymersGrafting polymer Comb polymer第六页，本课件共有56页Star block copolymerStar block copolymer Miktoarm star polymer Grafting polymer Comb polymer第七页，本课件共有56页Generalradicalpolymerizationcannotprepareblockcopolymersandothernonlinearpolymers,there

4、asonis:l lCharacteristicsoffreeradicalpolymerization.Deadmacromoleculeisformedinshorttime.第八页，本课件共有56页Well-definedblockcopolymerscannotbesynthesizedbycondensationpolymerization第九页，本课件共有56页Anyapplicationofblockcopolymersandnonlinearpolymers1.SBSisathermoplasticelastomer.2.Controlofdrugrelease:Forexam

5、ple:synthesisofamphiphiliccopolymers.第十页，本课件共有56页Synthesisofamphiphiliccopolymers 两亲性；高反应性第十一页，本课件共有56页囊泡的形成过程第十二页，本课件共有56页伴刀豆蛋白与对硝基苯酚酯的反应CON-A第十三页，本课件共有56页伴刀豆蛋白（CON A）胰岛素葡萄糖第十四页，本课件共有56页葡萄糖和胰岛素交换反应原理图葡萄糖胰岛素胰岛素糖糖糖第十五页，本课件共有56页WhydowedevelopthelivingpolymerizationControlofmolecularweightControlofmole

6、cularweightPreparepolymerswithnarrowmolecularweightPreparepolymerswithnarrowmolecularweightdistributiondistributionPreparationofcomplicatedarchitecturepolymers,suchPreparationofcomplicatedarchitecturepolymers,suchasblockcopolymers,nonlinearpolymers,includingstar,asblockcopolymers,nonlinearpolymers,i

7、ncludingstar,starblock,hyperbranched,dendrimer-likecopolymersstarblock,hyperbranched,dendrimer-likecopolymersetc.etc.第十六页，本课件共有56页1-2.ConceptofLivingPolymerizationNoterminationNochaintransferreactionInitiationrateisfasterthanpropagationrateWhat is living polymerization?第十七页，本课件共有56页Livingpolymerizat

8、ionofstyreneConversionupto100%Notermination;Notransferreactions第十八页，本课件共有56页 No termination The polymerization can continue when monomers are added.第十九页，本课件共有56页Thebigeffectofchaintransferonmolecularweightandpolydispersity,Oneexample:ChaintransferreactionsinpolymerizationofvinylchlorideNochaintransf

9、erreaction第二十页，本课件共有56页KineticsinthepresenceofchaintransferreactionWhenonlychaintransfertothemonomerexistsintheWhenonlychaintransfertothemonomerexistsinthepolymerization,suchas,AIBNusedasinitiatorinbulkpolymerization,suchas,AIBNusedasinitiatorinbulkpolymerization,theDPcanbecalculated:polymerization,

10、theDPcanbecalculated:1/Xn=2kt/kp2Rp/M2+CMDuetotherateofchaintransfertovinylchlorideismuchbiggerthanterminationrate,Rtr,MRt,thus1/Xn=Rp/(Rt+Rtr,M)Rp/Rtr,M=kp/ktr,M=1/CMMolecularweightisdeterminedbyCM,polymerizationat50oC,CM=1.35x10-3,Xn=740,whichissimilartothemeasuredMW.MWisdeterminedbyconcentrationo

11、ftransferagent,Temp;第二十一页，本课件共有56页Initiationrateisfasterthanpropagationrate C4H9Li+CH2=CH-YC4H9CH2-CH:-Li+Y=CH2=C(CH3)-,Ph,CH2=CH-,etcGenerally,alkyllithiumcaninitiateanionicpolymerizationofstyrene,1,3-butadieneetcinalkaneimmediately.第二十二页，本课件共有56页 High purity monomer High vacuum Dry reaction system

12、 Need stringent conditions第二十三页，本课件共有56页Summaryforrequirementsoflivingpolymerization1.No termination2.No chain transfer reactions.3.Initiation rate is faster thanpropagation rate4.Homogeneous system 5.Stringent conditions第二十四页，本课件共有56页1-3IdentificationofLivingPolymerizationRp=kpappM-MdM/M=kpappM-dtl

13、nM0/Mt=kpappM-t1.1.First-order kinetics第二十五页，本课件共有56页2.Molecularweightcanbecontrolled Number-average molecular weight is proportional to Number-average molecular weight is proportional to conversion,thus degree of polymerization can be calculated.conversion,thus degree of polymerization can be calcu

14、lated.DP=(M DP=(M0 0 MMt t)/M)/M-第二十六页，本课件共有56页3.Narrow molecular weight distributionPDI=Mw/Mn=1+1/DPPDIismainlyduetodifferentinitiationtime.第二十七页，本课件共有56页4.TheproducedpolymerislivingChain extending polymerization Higher molecular weight polymerHigher molecular weight polymerBlock copolymerization B

15、lock copolymerFunctionalization reaction Telechelic polymer,Macromonomer.Coupling reaction star polymer第二十八页，本课件共有56页5.Conductivitymeasurement Iffreeanionicorcationicionsexistinpolymerizationsystem,thesolutionisconductive.Conductivityismeasured,confirmingtheexistenceoffreeions.Ifnoconductivity,wecan

16、notsay“noanionicpolymerization”第二十九页，本课件共有56页1-4 Active species1.The forms of active ionic species第三十页，本课件共有56页2.The factors of influencing active site formsSolvent The polymerization is much faster in the more polar solvent,because it has much solvating power.The dielectric constant 介电常数介电常数 is not

17、 a quantitative measurement.第三十一页，本课件共有56页Table Table Effect Effect of of solvent solvent on on anionic anionic polymerization polymerization of of styrene styreneSolventDielectricconstant()Kpapp(liter/mole-sec)Benzene2.22Dioxane2.25THF7.65501,2-Dimethoxyethane5.53,800第三十二页，本课件共有56页Counterion反离子Li+1

18、602.20.94Na+801.53.4K+60-800.86.5x10419.8Rb+50-800.121.5Cs+220.0224.5CounterionPolymerizationinTHFkpforfordioxanedioxaneK Kp p K Kx10 x107 7K Kp p-TableTheeffectofcounteriononanionicpolymerizationofstyreneKisdissociationconstantfortheionpairs,thesmallertheK,thelessfreeanionicions第三十三页，本课件共有56页1-5 Te

19、rmination of active centerTerminationwithwaterevenintheatmosphereWaterisachaintransferagentandCtr,s=10第三十四页，本课件共有56页TerminationwithCO2intheairTheCOO-groupwillcombinewithotheragentsuchasH2O,formingCOOHgroup第三十五页，本课件共有56页TerminationwithO2inair第三十六页，本课件共有56页Terminationwithcompoundcontainingactivehydrog

20、en,suchasethanolandmethanol.第三十七页，本课件共有56页SpontaneousterminationThe decay for polystyryl carbanions on aging is The decay for polystyryl carbanions on aging is referred as spontaneous terminationreferred as spontaneous termination第三十八页，本课件共有56页TheterminationofpolarmonomerMMA,methyl vinyl ketone,AN e

21、tc are polar monomers,can undergo anionic polymerization,but can not undergo living polymerization第三十九页，本课件共有56页AnothersidereactionisbackbitingThiswilldecreasetheMWandpolymerizationratebecauseCH3O-islessactive第四十页，本课件共有56页Anionicpolymerizationalkylvinylketoneisverycomplicated第四十一页，本课件共有56页Summary fo

22、r identification of living polymerization Summary for identification of living polymerization First-order kineticsMolecular weight can be controlledNarrow molecular weight distributionThe produced polymer is living Chain extending polymerization Chain extending polymerization Higher molecular weight

23、 polymerHigher molecular weight polymer Block copolymerization Block copolymerization Block copolymerBlock copolymer Functionalization reaction Functionalization reaction Telechelic polymer,MacromonomerTelechelic polymer,Macromonomer Coupling reaction Coupling reaction Star polymerStar polymer第四十二页，

24、本课件共有56页1-6 Synthesis of nonlinear copolymers1.Three general methods for preparation of AnBm miktoarm star polymers by anionic polymerization Chlorosilane approach第四十三页，本课件共有56页 DPE methodDPE:DiphenylethyleneBPEB:1,3-Bis(1-phenylethenyl)Benzene第四十四页，本课件共有56页DVBmethod第四十五页，本课件共有56页2.Condensationpolym

25、erizationBranchingpolymersA-B+A3第四十六页，本课件共有56页HyperbranchedpolymersA2B+BB?A2+B3A2B第四十七页，本课件共有56页Therelationshipbetweenmolecularweightandpolymerizationtime第四十八页，本课件共有56页第四十九页，本课件共有56页The effort of overcoming the cross-linking reactionsYield=87%,Mw=285000Condensation agent第五十页，本课件共有56页Thereasonsfornoc

26、rosslinkingreactionsWhentheamountofNMPwasdecreasedfrom80mLto50mL(thetotalmonomersconcentrationwas0.31mol/Lor0.49wt%),gelformationwasobservedin2hatthesamereactionconditions.KakimotoM.,Macromolecules,1999,32:2061-NH2/-COOH=1:1(mole)Gelation-NH2/-COOH=2:3(mole)No Gelation第五十一页，本课件共有56页Proton-transferpo

27、lymerizationprocessMacromolecules,1999,32,6380-6382Journal of Polymer Science:Part A:Polymer Chemistry,38,48504869(2000)第五十二页，本课件共有56页Growthofmolecularweight(Mw)asafunctionoftime(hours)forthereactionofdiepoxide1withtriol2Thepolymerizationtemperaturewas120,sinceverylowpolymerizationrateatlowerthan100

28、.Ifthepolymerizationisallowedtocontinuethroughthefastgrowthportion,thegelationoccurred.Mw=1000;Mw/Mn=1.5-1.8.Mw=7000;Mw/Mn=5第五十三页，本课件共有56页The order of reactivity:ABCMichael addition reactionACB第五十四页，本课件共有56页Theassumptionforpredictionofgelpoint1.Thereactivityofallfunctionalgroupsofthesametypeisthesam

29、e.2.Thereactivityisindependentofmolecularsize.3.ThereisnointramolecularreactionsbetweenfunctionalgroupsonthesamemoleculeAnyoneofthethreeassumptionsisinvalid,gelationmaynotoccur.第五十五页，本课件共有56页Summaryforsynthesisofnonlinearpolymers1.Thesynthesisofmiktostarpolymersbyanionic1.Thesynthesisofmiktostarpoly

30、mersbyanionicpolymerizationspolymerizations 1)Chlorosilaneapproach;1)Chlorosilaneapproach;2)DPEmethod;2)DPEmethod;3)DVBmethod3)DVBmethod2.Branchedpolymersbycondensationpolymerization:2.Branchedpolymersbycondensationpolymerization:1)Branchingpolymers,A-B+A1)Branchingpolymers,A-B+Af f;2)Hyperbranchedpolymers,AB2)Hyperbranchedpolymers,ABmm,3)Gelation,A3)Gelation,A2 2+B+B3 3,forsynthesisofhyperbranchedpolymers,forsynthesisofhyperbranchedpolymers,AA2 2+B+B2 2B B(thereactivityofB(thereactivityofB ismuchlessthanBismuchlessthanB第五十六页，本课件共有56页