Kinetics of initiation, propagation, and termination for the [rac-(C(2)H(4)(1-indenyl)(2))ZrMe][MeB(C(6)F(5))(3)]-catalyzed polymerization of 1-hexene.
Metallocene-catalyzed polymerization of 1-alkenes offers fine control of critical polymer attributes such as molecular weight, polydispersity, tacticity, and comonomer incorporation. Enormous effort has been expended on the synthesis and discovery of new catalysts and activators, but elementary aspects of the catalytic processes remain unclear. For example, it is unclear how the catalyst is distributed among active and dormant sites and how this distribution influences the order in monomer for the propagation rates, for which widely varying values are reported. Similarly, although empirical relationships between average molecular weights and monomer have been established for many systems, the underlying mechanisms of chain termination are unclear. Another area of intense interest concerns the role of ion-pairing in controlling the activity and termination mechanisms of metallocene-catalyzed polymerizations. Herein we report the application of quenched-flow kinetics, active site counting, polymer microstructure analysis, and molecular weight distribution analysis to the determination of fundamental rate laws for initiation, propagation, and termination for the polymerization of 1-hexene in toluene solution as catalyzed by the contact ion-pair, [rac-(C(2)H(4)(1-indenyl)(2))ZrMe][MeB(C(6)F(5))(3)] (1) over the temperature range of -10 to 50 degrees C. Highly isotactic (>99% mmmm) poly-1-hexene is produced with no apparent enchained regioerrors. Initiation and propagation processes are first order in the concentrations of 1-hexene and 1 but independent of excess borane or the addition of the contact ion-pair [PhNMe(3)][MeB(C(6)F(5))(3)]. Active site counting and the reaction kinetics provide no evidence of catalyst accumulation in dormant or inactive sites. Initiation is slower than propagation by a factor of 70. The principal termination process is the formation of unsaturates of two types: vinylidene end groups that arise from termination after a 1,2 insertion and vinylene end groups that follow 2,1 insertions. The rate law for the former termination process is independent of the 1-hexene concentration, whereas the latter is first order. Analysis of (13)C-labeled polymer provides support for a mechanism of vinylene end group formation that is not chain transfer to monomer. Deterministic modeling of the molecular weight distributions using the fundamental rate laws and kinetic constants demonstrates the robustness of the kinetic analysis. Comparisons of insertion frequencies with estimated limits on the rates of ion-pair symmetrization obtained by NMR suggest that ion-pair separation prior to insertion is not required, but the analysis requires assumptions that cannot be validated.
Liu
Z
Z
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
Somsook
E
E
White
C B
CB
Rosaaen
K A
KA
Landis
C R
CR
D000475:Alkenes / Q000737:chemistry*; D001665:Binding Sites; D002384:Catalysis; D007192:Indenes / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D008970:Molecular Weight; D009942:Organometallic Compounds / Q000737:chemistry*; D011090:Polyenes / Q000737:chemistry*; D013816:Thermodynamics; D015040:Zirconium / Q000737:chemistry*
D000475:Alkenes; D007192:Indenes; D009942:Organometallic Compounds; D011090:Polyenes; C117224:1-hexene; D015040:Zirconium