01Advances in Non-Metallocene Olefin Polymerization Catalysi

01Advances in Non-Metallocene Olefin Polymerization Catalysis

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Advances in Non-Metallocene Olefin Polymerization Catalysis

Vernon C. Gibson, and Stefan K. Spitzmesser

Chem. Rev., 2003, 103 (1), 283-316 DOI: 10.1021/cr980461r

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Chemical Reviews is published by the American Chemical Society. 1155 Sixteenth

01Advances in Non-Metallocene Olefin Polymerization Catalysis

Chem.Rev.2003,103,283 315283

AdvancesinNon-MetalloceneOlefinPolymerizationCatalysis

VernonC.Gibson*andStefanK.Spitzmesser

DepartmentofChemistry,ImperialCollege,ExhibitionRoad,London,SW72AY,U.K.

ReceivedJuly16,2002

Contents

I.

II.

III.

IV.IntroductionandDevelopmentoftheFieldScopeofReviewGroup3CatalystsGroup4Catalysts

A.CpandOtherCarbon-DonorLigands

1.Cp-BasedPrecatalystswithanAdditionalNeutralDonor

2.Cp-BasedPrecatalystswithanAdditionalAnionicDonor

3.Metallocene-RelatedPrecatalysts

4.Non-CpCarbon-BasedLigands

B.ChelatingAmidesandRelatedLigands

1.DiamideLigands

2.DiamideLigandswithanAdditionalDonor

3. -DiketiminatesandRelatedSix-MemberedChelateLigands

4.IminopyrrolidesandRelatedFive-MemberedChelateLigands

5.AmidinatesandRelatedFour-MemberedChelateLigands

6.AmideLigandsFormingThree-MemberedChelates

C.ChelatingAlkoxides,Aryloxides,andRelatedLigands

1.SalicylaldiminatoLigands

2.Bis(phenoxy)AmineLigands

3.OtherAryloxide,Alkoxide,andThiolateLigands

4.AryloxideandAlkoxideLigandsinCombinationwithCp

Group5Catalysts

A.Precatalystsinthe+VOxidationState

B.Precatalystsinthe+IVOxidationState

C.Precatalystsinthe+IIIOxidationState

Group6Catalysts

A.Cp-BasedLigands

B.Non-Cp-BasedAmide,Amine,andPhenoxyLigands

Group7Catalysts

Group8Catalysts

A.NeutralBis(imino)pyridineandRelatedLigands

B.AnionicLigands

Group9Catalysts283284286286286286286288289289289290291291292293293293294294294295295296296297297298300300300302302X.Group10CatalystsA.NeutralLigands1.R-DiimineandRelatedLigands2.OtherNeutralNitrogen-BasedLigands3.ChelatingPhosphorus-BasedLigandsB.MonoanionicLigands1.[PO]Chelates2.[NO]Chelates3.OtherMonoanionicLigands4.Carbon-BasedLigandsXI.Group11CatalystsXII.Group12CatalystsXIII.Group13CatalystsXIV.SummaryandOutlookXV.GlossaryXVI.References303303303304304305305306306306307307307308308308I.IntroductionandDevelopmentoftheFieldThefieldofolefinpolymerizationcatalysishasexperiencedaphenomenalaccelerationinresearchactivityoverthepast5years,withmanyacademicandindustrialresearchlaboratoriesengaginginthedesignofcoordinationand/ororganometallicprecata-lystsforthecontrolledsynthesisofpolyolefinprod-ucts.TheseedsofthisactivityaretraceabletoadvancesinGroup4metallocenesystemsandtheirrelatedhalf-sandwichtitaniumamide(“constrainedgeometry”)catalystsduringthe1980s.1Duringthatperiod,studiesontheGroup4metallocenesaffordedmuchneededinsightintothenatureoftheactivatedspecies,andthepossibilitiesforcontrollingthenatureofthepolyolefinproductsweremostelegantlydemonstratedbythecapacityofansa-metallocenestructurestopolymerizepropylenewithhighiso-orsyndiotacticcontrol.2Changestotheligandskeletonprovidedaccesstomoreunusualmaterials,suchashemi-isotacticpolypropylene(PP)andstereo-block(isotactic-atactic)materials.3Contemporaneously,thehalf-sandwichtitaniumamidesystem,oftenalsoreferredtoasa“metallocene”system,wasshowntopossessanunparalleledcapacitytoincorporatelongerchainR-olefincomonomerswiththesamedegreeofincorporationovertheentiremolecularweightrangeofthepolyolefinproduct.1

Duringthefirsthalfofthe1990s,interestgrewin

developingnewgeneration“non-metallocene”cata-

lysts,partlytoavoidthegrowingpatentminefield

inGroup4cyclopentadienylsystems,butalsotoV.VI.VII.VIII.IX.*Towhomcorrespondenceshouldbeaddressed.E-mail:v.gibson@ic.ac.uk.Phone:+44(0)2075945830.Fax:+44(0)2075945810.

01Advances in Non-Metallocene Olefin Polymerization Catalysis

284ChemicalReviews,2003,Vol.103,No.1

VernonGibsonwasborninGrantham,England,in1958.HereceivedhisB.Sc.degreefromtheUniversityofSheffieldin1980,andhisD.Phil.degreefromtheUniversityofOxfordin1984,withMalcolmGreen.HewasaNATOpostdoctoralfellowwithJohnBercawatCaltechfrom1984to1986,beforebeingappointedtoalectureshipinInorganicChemistryattheUniversityofDurham,England.HewaspromotedtoFullProfessoratDurhamin1992,andin1995movedtoImperialCollege,wherehenowholdstheSirEdwardFranklandBPChairofInorganicChemistry.Hisresearchinterestsincludefundamentalaspectsofmetalcoordinationandorganometallicchemistry,andapplicationsofdiscretemetalcomplexesinpolymersynthesis.

StefanSpitzmesser,borninBu¨hl,Germany,beganstudyingChemistryin1991attheUniversityofKonstanzinGermany.Duringhisstudies,healsospentoneyearasanundergraduateresearchassistantwithK.P.C.VollhardtattheUniversityofCalifornia,Berkeley.In1997,hegraduatedfromKonstanzwithadiplomathesisonansa-zirconocenesunderthedirectionofH.-H.Brintzinger.Afterabriefspellasabusinessconsultant,hejoinedthegroupofV.C.GibsonatImperialCollegeinLondonin1998.HewasrecentlyawardedaPh.D.forhisworkonthedevelopmentofnewnon-metalloceneolefinpolymerizationcatalysts.

harnessthepotentialofothermetalstopolymerize

ethyleneonitsownandwithotherolefinicmono-

mers.Itwasadiscoveryinthemid-1990sthatwas

tohaveagalvanizingeffectonresearchersinthe