一类新型的nn二齿镍配合物的合成及催化乙烯齐聚聚合研究-synthesis of a new type of nn bidentate nickel complex and its catalytic effect on ethylene oligomerization polymerization.docxVIP

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一类新型的nn二齿镍配合物的合成及催化乙烯齐聚聚合研究-synthesis of a new type of nn bidentate nickel complex and its catalytic effect on ethylene oligomerization polymerization.docx

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一类新型的nn二齿镍配合物的合成及催化乙烯齐聚聚合研究-synthesis of a new type of nn bidentate nickel complex and its catalytic effect on ethylene oligomerization polymerization

AbstractAbstractThisdissertationfocusesondesigningandsynthesisof凡。哪Substituted-5，6，7-trihydroquinolin-8-ylidene)啊lamino嗣basedN，蝴Ni(II)complexesandtheirapplicationonethyleneoligomerizationlpolymerization.Allthosenickelcomplexesweresynthesizedbyhigh-efficiencyone-potreaction，meanswhile，therawmaterialarenotveryexpensiveandcanbeobtainedconveniently.SomerespectivecomplexesweredeterminedbuX-raydiffraction，themolecularstruc阳resshowedthatthecoordinatenumberforthenickelcentervariedaccordingtothebulkinessofthesubstitentsintheligands.Thecatalyticbehaviorsofthosecomplexeswereinvestedanddiscussedindetailwithvariouscocatalysts、reωtionparameters(suchasmolarratioofAlINi，reactiontemp阴阳reandtime)andthena阳reofdifferentligandstoelucidatetheirinfluenceon由ecatalyticactivityforethylenepolymerization.IntheprecenceofEASC，alltitlecomplexesshowedhighactivityinethyleneoligomerizationwithproducingbutanesandhexenesinhighalphaselectivity(99%).η町eemainp町ts阳eincludedinthisdissertation:Part1:ηleprogressofcatalystsusedinpolymerizationand/oroligomerizationofethyleneissummarized，especiallyfornickelcomplexes.Part11:ThetentativesynthesisofN-。帽Substi阳ted-5，6，7-trihydroquinolin-8-ylidene)aη恤nino.However，由econdensationofketonewithanilineproducesimineaswellasanisomer(amine).Hence，one-potreactionwasutilizedtoproceedthiswork.AseriesofN-(2-Substituted-5，6，7-trihydroquinolin-8-ylidene)arylaminonickeldichloridesw，即synthesizedbyone-potstoichiometricreactionatarelativelyhighyield.Allnickelcomplexeswerecharacterizedbyelementalandspectroscopicanalysis.丁hemolecularstructuresofrepresentativenickelcomplexes，determinedbythesingle-crystalX咽ydi俯action，indicatethedifferentcoordinationnumbersaroundnickeleitherfo町withmorebulkyligandsorfivewithlessbulkyligands.PartIII:Upontreatmentwithethylaluminiumsesquichloride(Et3AhC13)，allthosenickelcomplexesshowhighactivitytowardethyleneoligomerizationwi由optimizingthereactionconditions(reactiontempera阳reandtìme)，AlINimolarratioaswellasthen副山eoftheligands.KeyWords:Catalyst;Latetransitionme