高分子鏈的結(jié)構(gòu)

高分子材料加工技術(shù)

專(zhuān)業(yè)英語(yǔ)高分子物理

高分子鏈的結(jié)構(gòu)高分子的鏈結(jié)構(gòu)1ChainStructureofPolymer1.1高分子結(jié)構(gòu)的特點(diǎn)和分類(lèi)Characteristicandclassificationofpolymerstructure1.1.1高分子的結(jié)構(gòu)特點(diǎn)Characteristicsofpolymerstructure

Polymeriscomposedofmanystructuralunitslinkedbychemicalbonds.(聚合物由許多結(jié)構(gòu)單元通過(guò)化學(xué)鍵連接而構(gòu)成。)

Themolecularweightofpolymerisveryhighandhaspolydispersity.(聚合物的分子量很大并具有多分散性。)

Themainchainsofpolymercanrotate,leadingtoflexibilityofpolymerchains.Duetothermalmotion,theshape(conformation)ofpolymerchainschangewithtime.(聚合物主鏈上的化學(xué)鍵可以旋轉(zhuǎn)，是聚合物鏈柔性的來(lái)源。同時(shí)，由于熱運(yùn)動(dòng)，聚合物鏈的形狀(構(gòu)象)會(huì)隨時(shí)間發(fā)生變化。)

TheVanderwallsforceamongstructuralunitsisveryimportant.(聚合物分子鏈間的范德華作用力非常重要！)

Crosslinkingmaygreatlychangepropertiesofpolymers.(交聯(lián)可以明顯地改變聚合物的性能。)

Theaggregatestateofpolymermaybecrystallineoramorphous.Theorderofpolymerincrystallinestateissmallerthanthatofsmallmolecules，buttheorderinamorphousstateishigherthanthatofsmallmolecules.(聚合物的聚集態(tài)結(jié)構(gòu)可以是結(jié)晶態(tài)或無(wú)定型態(tài)。聚合物結(jié)晶態(tài)的有序度比小分子晶體要低，但無(wú)定形高分子的有序度要比非晶小分子要高。)1.1.2高分子的結(jié)構(gòu)層次鏈結(jié)構(gòu)高次結(jié)構(gòu)(織態(tài)結(jié)構(gòu))聚集態(tài)結(jié)構(gòu)(三次結(jié)構(gòu))近程結(jié)構(gòu)(一次結(jié)構(gòu))遠(yuǎn)程結(jié)構(gòu)(二次結(jié)構(gòu))chemicalcompositionregioisomerismstereoisomerismbranching&crosslinkingbondingsequenceincopolymersize(molecularweightanddistribution)conformation(flexibilityandrigidity)crystallinestateliquidcrystallineamorphousstateorientationstate高分子結(jié)構(gòu)ConfigurationclassificationofpolymerstructureShortrange

structureLongrangestructureChainstructureAggregatestructuretexturalstructuretexturalstructureShortrangestructurestructuralunitsorlocalchainsegmentsareinvolvedLongrangestructureentiresinglepolymerchainsareinvolvedAggregatestructurelotsofpolymerchainsareinvolvedHowaboutdoublehelixstructureofDNA?Polymerstructuresatdifferentlevelsaredifferentbutcorrelated!!!Polymerstructureisthesumofstructuresatdifferentlevels,whichcontributetoapparentpolymerproperties.stereo-regularitystructureofmonomersequenceofcomonomermolecularweightcrystallizability;etc.conformation;liquidcrystal;etc.phaseseparation;crystallizability;etc.miscibility;meltingtemp.;etc.(低次結(jié)構(gòu)決定高次結(jié)構(gòu)?。㏑egulationandimprovementofpolymerpropertiescanbeapproachedbychangeofpolymerstructuresatdifferentlevels.

synthesis：

processing：

blending：shortrangestructureandlongrangestructurelongrangestructureandaggregatestructuretexturalstructure1.2高分子鏈的近程結(jié)構(gòu)Short-rangestructureofpolymerchain1.2.1結(jié)構(gòu)單元的化學(xué)組成

CompositionofstructuralunitStructuralunitMainchainSidechaingrouporsubstituente.g.poly(vinylchloride)-

PVCPolymerizationdegree1.2.2分子構(gòu)造單鏈SinglechainMoleculararchitecture梯型聚合物L(fēng)adderchainCarbonfiberFeaturesofladderpolymers:excellentthermalstability.Whensinglechaininaladderringisbrokenuponheating,themolecularweightofthepolymerisunaffected.BranchingEffectsonpolymerproperties:crystallinity,flexibility,hardness,density,meltingtemperature,etc.

shortbranches—regularity,crystallinity,

density,meltingtemperature

longbranches—dissolvingpropertyandrheologyinthemeltInfluenceofgraftingandcrosslinkingonthepropertiesofpolyethyleneTypePropertiesHDPELDPEXPECrystallinity,%9560~70Density,g/ml0.95~0.970.91~0.940.93~1.40Meltingpoint,

C135105Workingtemperature,

C12080~100100~135TensileStrength,MPa20~4010~2010~100Elongation,%50~40050~80050~600XPE:交聯(lián)聚乙烯Crosslinkingpolymers:un-dissolvable,un-meltablestrength,thermalstabilityThermosetresinandvulcanizedrubberarecrosslinkingpolymermaterials.交聯(lián)crosslinkingVulcanizationofrubberCureofthermosetplasticsCrosslinkingofsaturatedpolyolefins:

radicalattack(forexample：irradiationcrosslinking)1.2.3鍵接異構(gòu)BondorderisomerRegio-selectivityofstructuralunitsinpolymerization

vinylmonomers(CH2=CHR)

head-headtail-tailhead-tailaffectingcrystallizability,mechanicalpropertiesandthermalstability頭尾頭頭+ZnZnCl286%Head-tailstructureisthemajorityinpolymersofvinylmonomers.Head-to-tailHead-to-headHead-headandtail-tailstructuresleadingtomorehydroxylleft,thustheabilityofwaterabsorptionincreasesandstrengthisreduced.Dienemonomers？Howtodetermineregio-regularity?NMR,IR,chemicalreaction,Pyro-GC,etc.1.2.4立體異構(gòu)Stereoisomerism旋光異構(gòu)OpticalisomerismAfterpolymerization,achiralcarbonatomisproducedforvinylmonomers,thustherearetwoopticalisomers.(Forsinglepolymerchain,theopticalactivityisveryweakduetothesmalldifferencebetweenthetwolongchaingroup.)Howtoprepareapolymerwithopticalactivity?三種類(lèi)型Isotactic全同立構(gòu)Atactic無(wú)規(guī)立構(gòu)Syndiotactic間同立構(gòu)Polymerchainsarecomposedofsingleopticalisomers.uniformandcrystallizable.Polymerchainsarecomposedoftwoalternativeopticalisomers,uniformandcrystallizable.Polymerchainsarerandomlycomposedoftwoopticalisomers.Theformertwoarestereo-regularPP,andthelastoneisstereo-irregularPP.non-uniformand

usuallynon-crystallizableStereo-configurationaffectspolymerpropertiesPS：

isotacticPS：crystallizable，Tm=240C

，uneasytodissolve

atacticPS：softtemperature80C

，solubleinbenzenePP：

isotacticPP：Tm=175C

，highstrength,usedasfiberandengineeringplastic

atacticPP：soft,additiveforpavingasphaltIsstereoregularitythenecessaryconditionforpolymercrystallization?Undermostcasesitis,butsomeexceptions:poly(fluoroethylene)poly(vinylalcohol)poly(trichlorofluoroethylene)similarsizesofFandHstrongHbondClisslightlylargerthanF，ButstrongrepulsionbetweenFatoms.幾何(順?lè)?異構(gòu)Geometrical(cis-/trans-)isomerismFor1,4-additionofdienemonomerscis-1,4-butadiene,rubbertrans-1,4-butadiene,crystalline,plastics天然橡膠Naturalrubber杜仲膠Gutta-percha

Stereo-isomerismandregio-isomerismmayoccursimultaneously!1.2.5共聚物的序列結(jié)構(gòu)Sequencestructureofcopolymerscopolymerizationcanimprovesomespecificpropertiesofpolymers

PMMA:

poorflowbehaviorandnotsuitableforinjection-molding(strongintermolecularinteraction).

MMA+Scopolymer:

improvedflowbehavior,suitableforinjectionmolding

S+ANcopolymer:

impactresistance,thermalstabilityandchemicalresistanceareimproved(canbeusedasoil-resistantparts).

無(wú)規(guī)共聚物(randomcopolymer)Twoormoremonomerunitsdistributealongthepolymerchainrandomly

ABAABABBAAABABBAAA

Poly(A-co-B)Theinteractionamongstructuralunitsandtheintermolecularinteractionarealtered.Thesolutionproperties,crystallizabilityandmechanicalpropertiesofthecopolymeraredifferentfromthecorrespondinghomopolymers.Forexample:PEandPP

areplastics,butEPrandomcopolymerisrubber.PTFE(聚四氟乙烯)isaplastics.Moltenprocessingisimpossible,butcopolymerof

tetrafluoroethyleneandhexafluoropropyleneisathermoplastic.嵌段共聚(blockcopolymer)

AAAAAAAAABBBBBBBBB

polyA-b-polyBorpoly(A-b-B)

SBS:poly(styrene-b-butadiene-b-styrene)preparedbylivinganionicpolymerizationHardHardSoftSBS：thermoplasticelastomer

hightemp:canflowandcanbeprocessedbyinjectionmolding.lowtemp:likecrosslinkingrubber(PSchainsatbothendsareglassy,“physical”crosslinking).PSPBQuestion:IsBSBblockcopolymerathermoplasticelastomer?接枝共聚

(graftcopolymer)polyA-g-polyB

(注意順序：主鏈在前，側(cè)鏈在后)ABS(acrylonitrile-butadiene-styrene):

ternarycopolymerpreparedbycombinationofrandomcopolymerizationandgraftingpolymerization.

StructureP(BS)-g-P(SA)orP(AB)-g-PSorP(SA)-g-P(AB)-CH2-CH=CH-CH2-

Rubber-likeelasticity.HighimpactresistanceGoodformabilityChemicalresistance,hightensilestrengthandhardness交替共聚物(alternatingcopolymer)

ABABABAB

Anexample:Styrene-maleicanhydridealternatingcopolymer

Poly(A-alt-B)shortrangestructurestructureofunitcarbonchainpolymerheterochainpolymerelementaryorganic

polymerinorganicpolymermoleculararchitecturesinglechainladderchainbranchingcrosslinkingbondorderisomerismvinylmonomer：H-T;H-H;T-Tdienemonomer：1,2;1,4;3,4stereo-isomerismvinylmonomer：opticalisomerism

(isotactic,syndiotactic,atactic)dienemonomer：geometricisomersequenceofcopolymerrandomcopolymerblockcopolymergraftingcopolymeralternatingcopolymerconfiguration1.3高分子鏈的遠(yuǎn)程結(jié)構(gòu)Long-rangestructureofpolymerchain1.3.1分子量MolecularWeightSmallmolecule：definitemolecularweightforaspecificsubstancePolymer：distributionofmolecularweight(polydispersity)Forthedetails,seeChapter4OnlywhenMWreachesacertainvalue(criticalMW),polymermaterialsexhibitusefulmechanicalstrength.polarpolymer:DPcri

40non-polarpolymer:DPcri

80StrengthMolecularWeightPolarNonpolarWhenMWisveryhigh(DP>600~700),strengthreachesalimit,butmeltviscosityistoohightoprocess.Plasticsandrubber:broadMWdistribution(highMWpartscontributetostrength,lowMWpartsimproveprocessability.)Fiber:narrowMWdistribution1.3.2內(nèi)旋轉(zhuǎn)構(gòu)象ConformationalStaterotationofC－CsinglebondchangeofconformationlargerpolymerizationdegreeTEMofbacteria’sDNATherepeatingunitsinthemainchainareconnectedbycovalentbonds?noindependentmotionforsingleunit?polymerchainsare

poorinentropy.flexibility鏈段Chainsegment

consistinginmanyunits,whichcanmoveindependently.considerableconformationDuetopresenceofHandothersubstituents,energybarriermustbeovercomeforrotationofsinglebond.largerdistancesmallerrepulsionlowerenergystability:trans>gauche>cistg-g+cistrans正丁烷或聚乙烯內(nèi)旋轉(zhuǎn)位能圖gaucheForlinearPEchain,theenergylevelofall-transconformationisthelowestT=0K:planarzig-zagconformationT>0K:gaucheconformationsappearduetothermalmotion

Forawith10,000bonds,Thenumberofarrangements310,000=104,7711.3.3分子鏈的柔順性

ChainFlexibilityStaticflexibility(靜態(tài)柔順性)

flexibilityofpolymerchainatthermodynamicequilibrium

determinedbythedifferenceinthepotentialenergyof

transandgaucheconformation(

)<kT largeamountofgaucheconformation,andtheshapeofpolymerchainisrandomcoils(無(wú)規(guī)線團(tuán))

kT

transconformationisthemajority(thewholepolymerchainisflexible,butlocalisrigid.) >>kT Thepolymerchainisrigid.Dynamicflexibility(動(dòng)態(tài)柔順性)

thetransition

ratebetweendifferentconformationsdeterminedbytheenergybarrierbetweendifferentconformations(

E)

p:timefortransitionfromtranstogaucheconformationE<<kTtransitionfromtranstogaucheconformationcanbecompletedin10

11s.smallp

:gooddynamicflexibilitylargep

:poordynamicflexibilityTemperatureForceSolventExternalFacto