简介：Thecopolymerizationsofethylenewith10-undecen-1-olhavebeeninvestigatedusingvanadiumprecatalysts,bis(imino)pyrrolylvanadium(III)complexes1-3,2,5-C4H2N(CH=NR)2VCl2(THF)2[R=C6H5(1),2,6-iPr2C6H3(2),C6F5(3)],andtheiminopyrrolylandβ-diketiminateonesforcomparison.Thepolarmonomerwaspretreatedbydiethylaluminiumchloride(presentalsoasthecocatalyst)beforethecopolymerization.ThemonomerreactivityratioswereevaluatedusingtheFineman-Rossmethod.Theligandstructureconsiderablyinfluencedthecatalyticactivityandtolerancetowardsthepolarmonomer,thepolarmonomerincorporationandthemolecularweightsoftheresultantcopolymers.Thebis(imino)pyrrolylvanadiumcomplexesexhibitedpromisingcatalyticperformanceforthecopolymerization,andahighcatalyticactivityupto3.84kg/mmolv·hwithahighcomonomerincorporationof14.0mol%wasachievedbycomplex3undermildconditions.

简介：Thiscontributionreportsethylenepolymerizationbehavioroftitaniumcomplexesincorporatingbis(phenoxyimine)ligands.Sixphenoxy-imineTi(IV)complexes{6-R1-2-[CH=N(2,6-difluoro-3,5-diR2-4-R3Ph)]C6H3O}2TiCl2(1:R1=H,R2=H,R3=H;2:R1=H,R2=H,R3=4-vinylphenyl;3:R1=CH3,R2=H,R3=H;4:R1=CH3,R2=H,R3=4-vinylphenyl;5:R1=CH3,R2=F,R3=H;6:R1=CH3,R2=F,R3=4-vinylphenyl)havebeensynthesizedandevaluatedforethylenepolymerizationusingdriedMAO(simplifiedasDMAO)ascocatalyst.AnobviouscatalyticheterogeneityofCat2(Complex2/DMAO)towardsethylenepolymerizationwasobserved,whichwasillustratedbydecreasedactivity,multimodalmolecularweightdistributionandpartiallyimprovedparticlemorphologycomparingwithCat1.Moreover,Cat3exhibits'living'characteristicsintheprocessundercertainconditions(25°C,lessthan20min).Otherwise,themoderatetohighethylenepolymerizationactivityofca.105-106gPE/(molTi·h)andhighmolecularweight(Mw=105-106)ofpolyethylenecanbeobtainedbychangingtheskeletonstructureofthesecomplexes.