高分子物理浙江大學(xué)Introduction2

polymerphysics高分子物理徐君庭，沈烈teachers任課教師徐君庭高分子大樓419;87953164xujt@沈烈高分子大樓310;87953712

shenlie@booksandreferences

教材與參考書(shū)方征平，宋義虎，沈烈 高分子物理(polymerphysics) 浙江大學(xué)出版社,杭州,2008何曼君，陳維孝，董西俠 高分子物理(修訂版) 復(fù)旦大學(xué)出版社，上海，1990金日光，華幼卿 高分子物理(第二版) 化學(xué)工業(yè)出版社，北京，2000l.h.sperling introductiontophysicalpolymersciencep.j.flory

pricinplesofpolymerchemistry網(wǎng)絡(luò)課件地址：

/polymerphysics/或

:8080/ka/index.htm

省級(jí)精品課程(2009年)

電子教案實(shí)驗(yàn)教學(xué)特色教學(xué)學(xué)習(xí)資料概念圖解(完善中，歡迎同學(xué)參加！)教學(xué)課件名詞解釋教學(xué)大綱實(shí)驗(yàn)內(nèi)容實(shí)驗(yàn)儀器教學(xué)研究學(xué)生作業(yè)習(xí)題introduction緒論polymersarelong-chainmoleculesofveryhighmolecularweight,oftenmeasuredinthehundredsofthousands高分子是由成千上萬(wàn)個(gè)結(jié)構(gòu)單元以共價(jià)鍵重復(fù)連接而成的長(zhǎng)鏈分子definitionsofpolymers

高分子的定義macromolecularhypothesis(1920)theoriginofmodernpolymersciencehermanstaudinger1953nobelprizeawarderpolymer,ormacromoleculelargemoleculeconsistingofrepeatingsmallerunits(calledmonomer).e.g.(poly=many;mer=unit)polymer 聚合物macromolecule大分子highpolymer高聚物nomenclature

高分子術(shù)語(yǔ)monomer單體

molecule小分子oligomer

齊(低)聚物classificationofsyntheticpolymersclassificationaccordingto:physicalstructurethermalbehaviour

usepreparationmethodphysicalstructurelinearpolymersmayberepresentedbyachainwithtwoends.branchedpolymers

havesidechains,orbranches,ofsignificantlengthwhicharebondedtothemainchainatbranchpoints,andarecharacterizedintermsofthenumberandsizeofthebranches.

polymerswithwell-controlledmodesofbranching:

comblikepolymers,starpolymers,dendrimers,etc.networkpolymers

havethree-dimensionalstructuresinwhicheachchainisconnectedtoallothers,andarecharacterizedbytheircrosslinkingdensityordegreeofcrosslinking(numberofjunctionpointsperunitvolume).shortbranchingpolymercomblikepolymerstarpolymerdendrimer

hyperbranchpolymercore1stgeneration2ndgeneration3rdgenerationthermalbehaviorthermosetsrigidmaterialsandnetworkpolymersinwhichchainmotionisgreatlyrestrictedbyahighdegreeofcrosslinking.intractableonceformed.degraderatherthanmeltuponheating.thermoplastics(plastics)linearorbranchedpolymerswhichcanbemeltedupontheapplicationofheat.(largestproportionofthepolymersusedinindustry.)crystallinepolymers

invariablydonotformperfectcrystallinematerialsbutinsteadaresemicrystallinewithbothcrystallineandamorphousregions.

thecrystallinephaseofsuchpolymersarecharacterizedbytheirmeltingtemperature(tm).

amorphouspolymers

characterizedbytheirglasstransitiontemperature(tg),thetemperatureatwhichtheytransformabruptlyfromtheglassstate(hard)totherubberystate(soft).thistransitioncorrespondstotheonsetofmotionofchainsegments.plastics塑料rubber橡膠fiber纖維adhesive膠粘劑paint涂料leather皮革…use三大合成材料photoelectricpolymers光電高分子biomedicalpolymers生物醫(yī)用高分子conductivepolymers導(dǎo)電高分子ion-exchangeresins離子交換樹(shù)脂…structuralpolymers結(jié)構(gòu)高分子functionalpolymers功能高分子preparationmethod2typesofpreparationmethods:additionpolymerscondensationpolymersdifferences:condensationproducesabyproduct,e.g.watercondensationpolymersoftenhavenon-catomsinbackbonechainsadditionpolymersformedbyaddingmanymonomerunitstogetherthroughchemicalbondse.g.polyethylenench2=ch2

-[ch2-ch2]-n ethylenemonomer polyethyleneotheradditionpolymers:polypropylene,poly(methylmethacrylate),polystyrene,poly(vinylchloride)condensationpolymerstwomoleculescombinewiththeformationandlossofanothersmallermoleculee.g.poly(ethyleneterephthalate)(pet)terephthalicacidethyleneglycolcopolymerstatisticalcopolymersarecopolymersinwhichthesequentialdistributionoftherepeatunitsobeysknownstatisticallaws.randomcopolymersareaspecialtypeofstatisticalcopolymerinwhichthedistributionofrepeatunitsistrulyrandom.

~~-b-a-b-b-a-b-a-a-b-a-b-b-b-a-~~

(forsimplicity,illustrationisforcopolymerscontainingonlyaandb.)alternatingcopolymershaveonlytwodifferenttypesofrepeatunitandthesearearrangedalternatelyalongthepolymerchain:

~~-a-b-a-b-a-b-a-b-a-b-a-b-a-b-~~

blockcopolymersarelinearcopolymersinwhichtherepeatunitsexitonlyinlongsequences,orblocks,ofthesametype.e.g.,abdiblockcopolymers~~-a-a-a-a-a-a-a--a-a-b-b-b-b-b-b-b~~abatriblockcopolymers~~-a-a-a-a-a-a-b-b-b-b-b--b-a-a-a-a-a-~~graftcopolymersarebranchedpolymersinwhichthebrancheshaveadifferentchemicalstructuretothatofthemainchain.

b-b-b-b-b-b-bb-b

b-b-b-b-b-b-b-b-b-b-b

b

b

~~-a-a-a-a-a-a-a-a-a-a-a-a-a-a-a-a-a-a-a-a-a-a-a-a-a--a-a-a-

b

b

b-b-b-b-b-b-b-b-b-b-b

b-b-b-b-b-b-b-b-b-b-b

fromlittlemoleculestobigmolecules

從小分子到大分子numberofcarbonsinchainstateandpropertiesofmaterialuse,dependentonchainlength1-4simplegasbottledgasforcooking5-11simpleliquidgasoline9-16medium-viscosityliquidkerosene16-25high-viscosityliquidoilandgrease25-50simplesolidparaffinwaxcandles1000-3000toughplasticsolidpolyethylenebottlesandcontainerspolyethylenemeltingtemperaturemolecularweightthemolecularweight-meltingtemperaturerelationshipforthealkaneserieslog0criticalmolecularweight(a)(b)entanglementofpolymerchainslowmolecularweight,noentanglement.(b)highmolecularweight,chainsareentangled.thetransitionbetweenthetwoisoftenatabout600backbonechainatoms.

highmwstrongintermolecularinteractionlargenumberofconformationmultiplemotionunitsentanglementviscosity;rheologicalbehavior;mechanicalpropertiestime(frequency)andtemperaturedependencestrength;novaporstateflexibility;elasticitychainfolding(incrystal)cryst