高分子近代史课件

ModernHistoryofPolymers高分子近代史郑强教授Dr.ProfQiangZHENG2004/9DevelopmentofPolymerScience高分子科学的形成与发展Whatispolymer其分子量(molecularweight)104～107小分子(smallmolecule)“点”(point)高分子(polymer)“一条链”(chain)“一串珠”(bead)MacromoleculePolymerHighPolymer高分子高分子是指其分子主链上的原子都直接以价键连接，且链上的成键原子都共享成键原子的化合物价键bond缺电子键electron-defectbond配位键coordinate-covalentbond共价键covalentbondEarlierGoodyear(1839,美)天然橡胶（naturerubble）Parks(1855,美)硝化纤维素（guncotton）樟脑（camphor）人造丝（rayon）deChardonnet(1883,法)赛璐璐(celluloid）Hyatt(1870)高分子和我们的关系Oilindustrydatashowsthatonlyabout9%ofallcrudeoilisusedforpetrochemicals.Thelargestuseofcrudeoilisinfuelfortransport(about53%).Oftheoilusedforpetrochemicals,abouthalfgoesintoplastics,sothatthecompleteabolitionofplasticswouldhaveatinyeffectonoilconsumption.Indeed,plasticsproductionusesoilfractionsthatmightotherwisebeflared;polymerizationofethylene,propylene,dienesandcyclo-olefinstolightweight,high-added-valueengineeringmaterials,whichkeepthecarboncontentlockedinasolidform,isavery“green”activity.Modern高分子科学PolymerScience高分子化学PolymerChemistry高分子物理PolymerPhysics高分子材料PolymerMaterial历史人物StoriedCharactersH.Staudinger(German，1881～1965)1.OrganicChemistandPolymerChemist1881.Mar.23,borninWorms1965.Sep.8,diedinFreeburg.1903,hestudiedatDarmstadt,MunichandHalleandobtainedhisdoctorate.1912,hewasappointedassociateprofessoratthePolytechnicinKarlsruhe,movedtoZurichandfinallytotheUniversityofFreeburgin1926.In1910,herecognisedthatthecurrenttheoriesforthestructureofnaturalrubberwereincorrect.Thecontroversiessurroundingnaturallyoccurringlargemoleculesandexperimentaldifficultiesinstudyingthemledhimtolookatmaterialsbasedonsimplermoleculessuchasstyrene.Heintroducedtheconceptofmacromolecules,atermwhichhecoined,andpolymerisationinMay1922,inareportwhichappearedinHelveticaChimicaActa.HemetWallaceCarothersataconferenceinCambridgein1935,followingwhichheincludedpolyestersinhisstudiesofthepropertiesofdilutepolymersolutions-fromwhichhediscoveredtherelationshipbetweenviscosityandmolecularweight.Towardstheendofhiscareerheturnedhisattentionbacktobiologicalmacromoleculesandwhatisnowcalledmolecularbiology.1920OnPolymer《论聚合》首次提出聚合就是小分子依靠化学键结合起来，形成大分子的过程的理论，并提出了聚苯乙烯、聚甲醛、天然橡胶的线型长链结构式1932Thehigh-molecularcompounds《高分子有机化合物》首次提出了合成大分子具有多分散性，且物理性质具有分子量依赖性，标志着高分子化学的诞生。1953NobelPrizeinChemistryForhisdiscoveriesinthefieldofmacromolecularchemistry.“链状大分子物质的发现”K.Ziegler(German，1989～1973)2.1898.Nov.26,borninHelsainGermany.1973.Aug.12,diedinottoHahn.1920,graduatedunderProf.vonAuwersattheUniversityofMarburg/Lahn.1936,hebecameProfessorandDirectoroftheChemischesInstitutattheUniversityofHalle/Saale.1943-1969,hewasDirectoroftheMax-Planck-InstitutfurKohlenforschung.OrganicChemistHisearlierworkinvolvedtheclarificationofrubbersynthesisreactions,cycliccarboncompoundsusedinperfumesandlithiuminorganicreactions.Ziegler'smostimportantdiscoverywasmadein1953fromhisworkonorgano-aluminiumcompounds.WithE.Holzkamp,astudent,hefoundthatsubstancesmadebymixingorgano-metalliccompoundswithcertainheavymetalspermittedrapidpolymerisationofethyleneatatmosphericpressure.Thissignificantcontributionestablishedthatveryhighmolecularweightpolyethylenecouldbeproducedwithlinearchainstructureandgivevaluableproduction,propertyandapplicationpotential.Thecatalystwasderivedfromtriethylaluminiumandtitaniumtetrachloride.Althoughmanyothercatalystsystemsandpolymerisationmethodsweredevised,thisworkformedthebasisoflaterdevelopmentsintheproductionoflongchainpolymersfromolefinssuchaspropyleneandbutadiene.Themodernpolyethylenerangeofspecificallystructuredpolymershasprovidedproductsreadilyformedasfilms,fibersandmouldingsapplicableinmanyareasofmodernlife.Blowmouldedbottles(egformilkandhouseholdcleaners),injectionmouldedcontainers,toysandappliancecomponentsaredailyremindersofZiegler'soutstandingandoriginalwork.•α烯烃的催化二聚作用,合成高级α烯烃•乙烯经烷基铝催化合成高级伯醇•由烯烃合成萜醇•由烷基铝经电化学或其他方法合成其他金属的烷基化合物•利用氢化烷基铝和三烷基铝做有机物官能团的还原剂•以三烷基铝与四氯化钛为催化剂(称为ziegler-natta催化剂)使乙烯在常温常压下聚合成线型聚乙烯,这项研究为高分子化学和配位催化作用开辟了广阔的研究领域。主要贡献G.Natta(Italian，1903～1979)1903.Feb.,borninImperia,Italy.1979.May,diedinBergamo.1924,hegraduatedinChemicalEngineeringatthePolytechnicofMilanandteachtherein1927.1936-1938,full-professoranddirectoroftheInstituteofIndustrialChemistryatthePolytechnicofTurin.Since1938,hehasbeenfull-professoranddirectoroftheDepartmentofIndustrialChemistryattheMilanPolytechnic.ItalianChemistProf.NattabeganhiscareerwithastudyofsolidsbymeansofX-raysandelectrondiffraction.Hethenusedthesamemethodsforstudyingcatalystsandthestructureofsomehighorganicpolymers.Hiskineticresearchonmethanolsynthesis,onselectivehydrogenationofunsaturatedorganiccompoundsandonoxosynthesisledtoanunderstandingofthemechanismofthesereactionsandtoanimprovementintheselectivityofcatalysts.Hedevelopednewusesforthecommercialsynthesisofmethanol,formaldehyde,succinicacidandbutyraldehyde.HisintensiveinterestinandstudiesofpolymersinconjunctionwiththeItalianfirmMontecatiniledin1953tohisuseofZieglercatalystsforthepolymerisationofpropylene.Healsodevelopedcatalystsystemsforproducingsyndiotacticpolypropylene.hecontributiono