The Behaviour Of β-Triketimine Nickel Complexes In Ethylene Polymerization

  • Sultan Alshmimri

Student thesis: Phd


Seven β-triketimine nickel complexes C1-C7 with composition [L1-7Ni(μ-Br)2NiL1- 7][BArF4]2, where L1 = HC{C(Me)=N(2,4,6-Me3C6H2)}3, L2 = HC{C(Me)=N(2,6- Me2C6H3)}3, L3 = HC{C(Me)=N(2,4-Me2C6H3)}3, L4 = HC{C(Me)=N(2-MeC6H4)}3, L5 = HC{C(Me)=N(2,4,6-Me3C6H2)}2{C(Me)=N(2,6-Me2C6H3)}, L6 = HC{C(Me)=N(2,4,6-Me3C6H2)}{C(Me)=N(2,6-Me2C6H3)}2, and L7 = HC{C(Me)=N(2,4,6-Me3C6H2)}{C(Me)=N(2,6-iPr2C6H3)}2 were synthesized from the interaction of nickel(II) bromide with L1-7 in the presence of NaBArF (BArF = [(3,5- (CF3)2C6H3)4B]-). These complexes were then fully characterized by single-crystal X- ray diffraction (XRD), MALDI-MS and elemental analysis. From XRD results, they were found to be five-coordinated dimeric bromide-bridged species [LNi(μ- Br)2NiL][BArF]2. The geometry at nickel was distorted square pyramidal, with the τ parameter in the range 0.05 to 0.28. In addition, an enamine-diimine nickel complex C8: (L2-NiBr2) was synthesized from triketimine ligand L2 and nickel dibromide in THF, thus lacking the weakly co-ordinating BArF anion. This complex was found to be pseudotetrahedral, where only two of the three imine nitrogen atoms co-ordinated. These two nitrogen atoms and two bromine atoms formed the coordination shell of Ni(II). The six-membered ring [Co-N1-C2-C3-C4-N2] adopted a boat conformation. These complexes (C1-C7) were screened in the polymerization of ethylene monomer using methylaluminoxane (MAO) as cocatalyst in toluene as solvent at 30°C. It was observed that the steric and electronic variations conferred on the complexes by ligands L1-7 had a strong influence on the activity and also on the properties of the produced polyethylene. The catalytic activity decreased in the order C2>C1>C6>C5>C7 in the range 3229 to 271 kg PE (mol Ni)-1 h-1 for a standard set of conditions (3 bar ethylene, 30 ̊C, Al:Ni 2000), while the catalysts C3 and C4, bearing only a single ortho substituents, were inactive under identical conditions. Those conditions also had strong influences on catalyst activity and polymer properties: Al:Ni ratio in the range 500 to 3000 maximized activity at 2000. For the polymerization temperature in the range 20 to 50 °C, the activity was maximized at 30 °C, while the number of branches increased with temperature while Mn decreased due to increased chain transfer. Increasing the polymerization pressure resulted in fewer branches while the molecular weight increased because of high concentration of ethylene monomer.The effect of the nature of the counterion on polymerization activity and on the polymer properties was investigated when ethylene was polymerized by C8 (N,N-Ni) and C2 (N,N,N-Ni). It was found that polyethylene produced by C8 had significantly greater crystallinity (Tm 59 ̊C, 35 branches per 1000 carbons) than that produced by C2 (Tm 36 ̊C, 53 branches per 1000 carbons). The presence of the weakly nucleophilic counterion (BArF) as in C2, may have facilitated chain walking, resulting in a branched polymer, whereas [MeMAO]- (C8) was a slightly more nucleophilic counterion impeding chain walking. Furthermore, activity was also much greater for C2 than for C8. This is the first report of an anion effect on branching.
Date of Award1 Aug 2016
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorFrancis Mair (Supervisor)


  • Ethylene Polymerization
  • Nickel catalyst

Cite this