线性聚乙烯的制备Ziegler-Natta催化剂（1953年）Table 8-3Components of Ziegler-Natta InitiatorsGroup I-lll MetalTransition Metal(C,H,)AlTiCla(C,H,)AICITiClsTiBts(C-Hs)-AIBrVCl.(C,Hs)AIC)vCl,(i-C,H,)pAl(C,Hs),Be(C,H,),TiCl2(C-Hs),Mg(CH,COCHCOCH,),VCaH,LiTi(OC,H,)Ti(OH)4(C,Hs),ZnMocls(O,N),AINioOMgBrCrCi(CHs)AILiZrCl4CsHuNaWCl6(C,Hs),CdMnCl2(CaHs)Ga
线性聚乙烯的制备 ◼ Ziegler-Natta 催化剂 （1953年）
Ziegler-Natta催化剂的负载(100)Site-llSite-1(110)Site-lllFig.2.Plausible active Tispecies on the MgCl2 surfaces as proposed by Busicoeta30
Ziegler-Natta催化剂的负载
聚合机理InitiationhycrocarbonsolveatTCl4(CH,CH2)AICl2+Ticlon the crystalcocatalystcatalystcrystal?surface(alkylationagent)(powder)suspensionparticleCHcoordination=CHCHinsertionOPropagationn CHz=CH2coordinationandinsertionTermination(chain-transferreacdon)PEβ-hydrideeliminationCH2=CHPEW口H26HCHa-CH-PE
聚合机理
茂金属催化剂（1970-80年发明）CH3CH3MAOMAO.CI(CIMAO)-Ti0CPClCCH3CpCsHs(MAO)orgenericcyclopentadienylAI-0十,(Me,Si),N(Me,Si)2NCp - CsHsCsH,Me-CpCsMes -Cpor generic cyclopentadienylCH,CMeE8THI-SBI-Me2C(Cp)(Flu)cthylone-bis(totrahydroindenyl)Me2Si-bis(indenyl)
茂金属催化剂（1970-80年发明）
Table3.Homopolymerizationofetheneat30*C,2.5bareithenepressure,6.25x10-mol/metalloceneconcentration,molarratioMAO/metallocene250.EAO=ethylaluminoxan,iBAO-trisobutylaluminoxanActivitymol.mass茂金属制备线性聚乙烯活性与分子量Ref.No(kgPe/molZr-h-[Et])(g/mol)Catalysts56160900620000Cp,ZrCl,Nm34200400000Cp,TiCl,4200*700000CP,HICI,53427000*440000Cp,TiMecl53573000014000*Cp,ZrMe25312006500000Cp.TiMe:85573600*550000CP,HIMe,82.500550000Cp,ZrCl,/EAO5795400390000CPZrCl/iBAO1300150000010(C,Mesh,ZrCl25845000*60000011(Ind),ZrCl,5612122001000000(neomenthyiCp),ZrCl)8000001318800(C,Me,Et),ZrCl)9300001457800[O(SiMe,Cp),]ZrCl700001511700[O(SiMe;tBuCp),JZrCl,561641100140000[En(Ind),JZrCl,56290048000017[En(Ind),jHfCl,4000018[En(Fluh,jZrCl,-1978000190000[En(2.4.7Me,Ind),]ZrCl5620222001000000[En(IndHa),]ZrC]562136900260000[Me,Si(Ind),]ZrC12562220200320000[Ph,Si(Ind),JZrCl2562312200350000[Bz,Si(Ind),]ZrCl25000024111900[Me,Si(2.4,7Me,Ind),JZrCl一3020090000025[Me,Si(IndH.),]ZrCl)1860073000026[Me,Si(2Me4,6iPrlnd),JZrCl2716600730000[Me,Si(2Me4PhInd),JZrCl)287600450000[Me,Si(2Me4,Sbenzoind)]ZrCl33301800029[Ph,C(IndXCp)]ZrC]5615502500030[Me,C(IndXCp]]ZrC]2562.7003000031[Me,C(IndX3MeCp]]ZrCl)289063000032[Ph,C(FluXCp]]ZrCl56200050000033(MeC(FluxCpljZrCl,89056000034[Me,C(FluxCp)]HICl'Calculatedvaluesfromliterature
茂金属制备线性聚乙烯活性与分子量