堿金屬有機(jī)化合物的結(jié)構(gòu)高分子合成-陰離子聚合反應(yīng)

堿金屬有機(jī)化合物的結(jié)構(gòu)及陰離子聚合反應(yīng)胡愛國背景知識金屬有機(jī)化合物的定義及金屬有機(jī)化學(xué)發(fā)展歷史金屬有機(jī)化合物中的結(jié)構(gòu)和化學(xué)鍵化合價、

氧化態(tài)、d電子數(shù)、

飽和度、有機(jī)配體、配位數(shù)和18電子規(guī)則空間點(diǎn)群（PointGroup）、立體構(gòu)型價鍵理論（ValencebondTheory）、晶體場理論（CrystalFieldTheory）分子軌道理論（MolecularOrbitalTheory）金屬有機(jī)化合物的反應(yīng)

配合反應(yīng)氧化加成反應(yīng)和還原消除反應(yīng)（OxidativeAddition&ReductiveElimination）遷移插入和消除反應(yīng)（MigrationInsertion&Elimination）、配體上的反應(yīng)金屬有機(jī)化學(xué)在高分子合成中的應(yīng)用

陰離子聚合反應(yīng)(AnionicPolymerization)配位聚合反應(yīng)(CoordinationPolymerization)卡賓配合物和烯烴復(fù)分解聚合反應(yīng)（OlefinMetathesisPolymerization）交叉偶聯(lián)反應(yīng)及相關(guān)聚合反應(yīng)(CrossCouplingPolymerization)原子轉(zhuǎn)移自由基聚合反應(yīng)(AtomTransferRadicalPolymerization)金屬有機(jī)高分子化合物（新型功能高分子）教學(xué)大綱PeriodTableOrganometalliccompoundsarenormallynamedassubstitutedmetals,e.g.alkylmetaloralkylmetalhalide.GroupIandIImetalalkylsarenormallyusedinanionicpolymerizationOrganolithiumCompoundsSynthesisoforganolithiumcompounds1930ZieglerandGillmanCommonstartingmaterials:CH3Cl,CH3Br,butylchloridesSomecommerciallyavailablecompounds:–nBuLi: 100mLto35.000L 15-90%inHexane 20%inCyclohexane,Toluene–sec-BuLi: 100mLto35.000L 10%inIsopentane–tBuLi: 100mLto… 15%inPentane,Hexane–MeLi: 1L(pertruck!!!) 5%inEt2OLimitedstabilityofnBuLietalOrganolithiumCompoundsb-EliminationofalkeneandLithiumhydrideReactionwithsolventlithiumalkylsaretypicallystoredinhexaneorotheralkanesolventsAssayofOrganolithiumSolutionsOrganolithiumCompounds?SolutionsmaycontainLiOHandalkoxides(LiOR)causedby:–Hydrolysis–EthercleavageorreactionofLiRwithO2?AsLiR,LiORandLiOHareallbasic,titrationwithacidsuggestsaLiRcontentthatistoohigh?Gillmandoubletitrationshouldbeemployed–1.DirecttitrationwithacidprovidestotalLicontent–2.LiRisremovedbyachemicalreaction:titrationgivesLiOH+LiOR–3.Thedifferencebetweentitration1and2givesLiRnoreactionwithLiOHorLiORStructureofOrganolithiumCompoundsOrganolithiumCompoundsOrganolithiumcompoundsareoftenschematicallydepictedasmonomericspecieswithonelithiumatomandacarbanionicgroup,suchasMeLiornBuLi.However,thestructuresofthesecompoundsaremuchmorecomplicatedandtheunderstandingoftheseprinciplesisnecessaryfordescribingthereactivityAbuildingprincipleofthesestructuresisthearrangementofthelithiumatomstoLi3triangles,whichjoineachothertoformlithiumpolyhedra4c-2ebondingCarstenStrohmannetalChem.Eur.J.2009,15,3320–3334StructureofOrganolithiumCompoundsMethylLithium

infinitepolymer----octetruleLeft:staggeredconformationof(MeLi)4tetrahedron.Right:Subsetofthethree-dimensionalnetwork.常用的和鋰試劑組合的多胺StructureofOrganolithiumCompoundsDeaggregation

ofmethyllithium----breakingdownpolymerchainLewisbaseslikeTHF,arenotabletobreakthemethyllithiumtetramer.Inthesolidstatestructuresofsuchsolvents,the(MeLi)4unitisretained,suchasin(MeLi·THF)4;(R,R)-TMCDA,however,canfurtherbreakMeLidowntodimerStructureofOrganolithiumCompoundsMeLi?

monomericmethyllithiumhasnotbeenisolatedsofarInthismolecularstructureasinglemethylgroupcoordinatesataLi3surface,whichisstabilisedbythedonoratomsoftheligandandtheethermoleculesDietmarStalkeetalChem.Eur.J.2001,7,1417StructureofOrganolithiumCompoundsn-ButylLithium

hexamerdimern-Butyllithiumisthemostwidelyusedalkyllithiumbase.WithoutadditionofLewisbasesnBuLiformsahexamericparentstructurewiththecharacteristicLi6octahedronDeaggregationtodimericsolid-statestructuresisachievedbythecoordinationof(R,R)-TMCDA(asshowninthisfigure),whichshowthetypicalLi-C-Li-Cfour-memberedringwithfourcontactstoeachlithiumatomStructureofOrganolithiumCompoundsn-ButylLithium

pseudo-monomer,realn-BuLiisstillunknownThisinterestingadductconsistsoftwomonomericnBuLi·PMDTAunitscoordinatedtothelithiumcentresofthecentralLi-C-Li-Cfour-memberedring.ThemonomericnBuLiunitsshowshortenedLi-Cdistancesincomparisonwithdimericorganolithiumcompounds.SuchashortenedLi-Cdistanceincomparisontodimersortetramersisthecharacteristicfeatureofmonomericlithiumorganics.StructureofOrganolithiumCompoundstert-ButylLithium

spatialfactormatters!tert-butyllithiumisthemostreactivealkyllithiumduetoitshighcarbanioniccharacter.Thespatialdemandofthetert-butylgroupeasesthedeaggregationtosmalladducts.Thetetramericparentstructure(tBuLi)4isdeaggregatedbyadditionofdiethyletherresultingintheformationofdimeric(tBuLi·Et2O)2StructureofOrganolithiumCompoundstert-ButylLithiummonomer

easy!Cleavageofmonomerictert-butyllithiumthroughthisprocedure?WorldofPolymerHowdoesthewidthofmolarmassdistributioninfluencethemechanicalpropertiesofapolymer?Whatistheeffectofbranchingonpolymerproperties?WhatprotectingeffectisexertedbysolublegraftsonaninsolublebackboneinGraftCopolymers?Whatisthesizeofacyclicmacromoleculeascomparedwiththatofthelinearhomologue?HowdoescompositionalheterogeneityaffectthepropertiesofaCopolymer?Whataretheconditionsrequiredforablockcopolymertoexhibitphaseseparation?WorldofPolymerSomeproblemsthatrequirewell-definedpolymers

microscopicrespectM.M.SzwarcMichaelM.SzwarcU.S.A.1909~2000

MacromolecularChemist;Professor,UniversityofSouthernCaliforniaAchemistwhohasmadeanoutstandingcontributiontoresearchanddevelopmentofpolymericmaterialsformaterialsscience,heisbestknownfordiscovering"livingpolymerization,"pavingthewayfornewfunctionalmaterialswithindispensableapplicationsinadvancedtechnology,andprovidingmanyscientistsandengineers(particularlypolymerscientists)withsignificantandunprecedentedmethodologiesforthedesignandsynthesisofnewpolymericmaterials.1909BorninPoland1932GraduatedfromWarsawPolytechnicCollege,Poland1942Ph.D.,OrganicChemistry,HebrewUniversity,Israel1947D.Sc.,PhysicalChemistry,UniversityofManchester,England1953Professor,TheStateUniversityofNewYork

Director,ThePolymerResearchCenter,TheStateUniversityofNewYork-2000Professor,TheHydrocarbonResearchInstitute,UniversityofSouthernCaliforniahttp://www.inamori-f.or.jp/laureates/k07_a_michael/prf_e.htmlLivingAnionicPolymerizationAnionicpolymerizationofstyreneusingsodiumnaphthalenideasinitiatorinTHFBaskaran,D.;Mueller,A.H.

E.Prog.Polym.Sci.2007,32,173–219ReactorusedtodemonstratethelivingnatureofstyrenepolymerizationusingsodiumnapthalenideinTHFThisspeciallydesignedapparatushas:A:MainreactorB:THFsolutionofinitiatorC:THFsolutionofstyreneD:THFsolutionofsecondarymonomerE:Build-inviscometerAfterdeterminingtherelativeviscosityofthefirstpolymerizedsolutionatitsfullconversion,thesolutionwaspouredbacktothemainreactor,andanotherportionofsecondarymonomerwasadded.Therelativeviscosityoftheresultingsolutionwasagainmeasuredwhichshowedasubstantialincrease(10times)ascomparedtothatofthefirstsolution.Thisobservationprovedconclusivelythatthereactivityoftheterminalchain-endsremainsactiveevenaftercompletemonomerconsumptionandthechainextensionoccurswithafreshadditionofasecondportionofstyrenewithoutthechain-endsundergoingtransferandtermination.

MichaelSzwarccharacterizedthisbehaviorofthepolymerizationas‘‘livingpolymerization’’andcalledthepolymersas‘‘livingpolymers’’Szwarc,M.etal.JACS

1956,78,2656.LivingAnionicPolymerizationLivingAnionicPolymerizationMacromolecules2014,47,1883-1905.LivingAnionicPolymerizationSBSRubber

blockcopolymer—onestonefortwobirdsPolystyreneisatoughhardplastic,andthisgivesSBSitsdurability.Polybutadieneisarubberymaterial,andthisgivesSBSitsrubber-likeproperties.SinceSBScontainsrubberandplastic,itactslikebothmaterials.LivingAnionicPolymerizationInitiator

mostlyalkalinemetalalkylsTwoelectronwithdrawinggroupsaresoeffectiveinstabilizinganionsthatevenwatercaninitiatecyanoacrylate("SuperGlue").Weakbases(suchasthoseontheproteinsinskin)workevenbetter.-----Morphology,Composition,FunctionalityAschematicrepresentationofpolymerstructuresthatcanbepreparedusingcontrolledpolymerizationtechniques.LivingPolymerization-----Morphology,Composition,FunctionalityLivingPolymerizationEndGroupmodificationCharacterizationMethodstobeusedtodeterminethestructuralparametersorthebehaviorofComplexMacromolecularArchitecturesLivingAnionicPolymerizationInsolution,inthebulk!StaticandDynamicLightScatteringTogetMolarMass,Mw,andRadiusofGyrationandHydrodynamicRadius,…

SizeExclusionChromatography(SECorGPC)Detectorsrequired*DifferentialRefractometry:togetc*UVSpectrometrytocheckforthepresenceofachromophore*LightscatteringtogetMw*Viscometry(necessaryforuniversalcalibration)

NMR,UVSpectrometry(microstructure,composition,functionality)MALDI-TOFMSAFM X-Raymeasurements

w-undecenylw-allyl

w-styrenylDeactivationLivingAnionicPolymerizationCharacterization:Molarmass:SEC:Mnexp=Mn

th,(1000to10000g.mol-1)Sharpmolarmassdistribution,nocouplingFunctionalization:1HNMRChemicalTritrationMALDI-TOFPS(atactic):undecenylendgroupAnionicPolymerizationofOxiraneWithK(andnotNaorLi)RT

WellfunctionalizedHeterofunctionalPolymerOHDeactivationalsopossibleforPEOInitiationnotpossibleforPSmacromonomersLivingAnionicPolymerizationValuablepolymericmaterialsconstitutedofapolymerbackbonePoly(A)carryinganumberofgraftsofdifferentchemicalnaturePoly(B)distributedatrandomPSPEOLivingAnionicPolymerizationINTEREST:ArisesfromtheincompatibilitybetweenbackboneandgraftsHighsegmentdensitybecauseofthebranchedstructureHightendencytoformintramolecularphaseseparationMicellesareformedinapreferentialsolventofthegrafts(surfacemodification,compatibiliziers,micelles….)(enhancingordepressingsurfacetension,makingasurfacehydrophobicorhydrophilicBottleBrushesGraftingfrom:GraftingbyanionicinitiationfromsitescreatedonthebackboneGraftingonto:AnionicdeactivationoflivingchainsbyelectrophilicfunctionslocatedonapolymericbackboneGraftingthrough:Useofdanglingunsaturationstoattachgraftsontoapolymericbackbone(Macromonomerfreeradicalpoly).ThreestrategiesInGraftCopolymersavarietyofMolecularParameterscanbevaried -Mainchainandsidechainpolymertype -Degreeofpolymerizationandpolydispersitiesofthemainandsidechain -Graftdensity(averagespacingdensitybetweensidechains) -Distributionofthegrafts(graftuniformity)BottllebrushstructureDP>80Star-shapedDP<80MorphologyBottleBrushesSEC:SmallerhydrodynamicvolumeSEC:Transitioncomb-shaped/Starbottlebrushtypegraftpolymersaredenserthantheirlinearcounterparts,inSEC(GPC)analysis,thesepolymersshowlongerretentiontimecomparingwithlinearPSstandardstarshapedgraftpolymersareevenmoreunliketheirlinearcounterparts,inSECanalysis,theyshowevenlongerretentiontimeBottleBrushesLivingAnionicPolymerizationStarShapedPolymersArm-firstMethodsSynthesisofaw-livingpolymer(PS,PI)reactingitwithaplurifunctionalelectrophileinstoechiometricamountTypicalmoleculesusedascoreStarshapedpolymerscouldalsobepreparedbyusingthecarbanionicsitesofthearmtoinitiatethepolymerizationasmallamountofbiunsaturatedmonomersuchasDVB,DEMAPS,PI,PMMAAdvantages: -Lowfluctuationsinmolarmass -Lowcompositionheterogeneity(copo) -Characterizationoftheindividualbranches -AveragenumberofbranchesaccessibleFunctionalizationattheouterendofthebranchesnotpossibleStarShapedPolymersArm-firstMethods6-6bond5-6bondStarShapedPolymersArm-firstMethodsC60starpolymer

C60isconstitutedof12pentagonsand20hexagons,Smallmolecule(d10?)andpolyfunctional(30doublebonds)*Controlthenumberofgrafts*Controlofthepolymerchain:

-ThechainendmustbeabletoreactwithC60

-Controlmolarmassandpolymolecularity-Graftingofblockcopolymers..

AnionicPolymerizationModelarchitectures:StarShapedPolymersC60starpolymer

limitednumberoffunctionalation

C60beingaconjugatedmolecule,charge(introducedbythecarbanionpresentatthelivingchainend)delocalizes.Thereforeasecondlivingchaincannotbeaddedontopyracycleneunitsandhexagonesh1toh4.(additiontothe6-6ringdoublebonds)ChargedelocalisationandgeometricalformofC60limitthenumberofgraftsto6(molarmassesupto2*106gmol-1)

hexafunctionalStar-shapedpolymersStarShapedPolymersC60starpolymer

limitednumberoffunctionalation

PolyfunctionalInitiators:Core-FirstMethod

Metal

organicsitestendtostronglyassociate,eveninaproticpolarsolvents

Aggregateformationisfrequent:somesitesmayremainhidden

AspolymerizationofthemonomerproceedsgelationofthereactionmediumistobeexpectedHowevermolarmassnotdirectlyaccessibleStarShapedPolymers+A+BBifunctionalcouplingagentPolyfunctionalInitiators:Core-FirstMethodStarShapedPolymersMorphologyandFunctionalityLivingPS,PI,diblockWell-definedstar-shapedorrelatedbranchedstructuresbaseonanionicpolymerizationButverytimeconsumingsynthesis,fractionated,interestingmorphologiesStarShapedPolymersMorphologyandFunctionalityL