Incorporation of Polar Comonomers Into High Density Polyethylene With a Cyclopentadienyl-Amido Titanium Catalyst

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Vettese, Gregory
polymer , polyethylene , titanium , constrained geometry , cyclopentadienyl-amido , copolymerization , polar comonomer
The purpose of this research was to synthesize the constrained geometry catalyst Ti[(C5Me4)SiMe2(tBuN)]Cl2 (1) with MAO as a cocatalyst for ethylene homopolymerization and copolymerizations with 1-TMSO-alkenes to produce a copolymer with polar functionality. Three 1-alkenols of varying length were purchased and derivatized and used for the copolymerization experiments: 2-propen-1-ol, 3-buten-1-ol and 9-decen-1-ol. Several variables were tested to determine their effects on comonomer incorporation such as temperature, equivalents of comonomer, equivalents of MAO and two different solvents. Higher catalytic activities were correlated with fewer equivalents of polar comonomer, lower temperatures, and no fewer than 1000 equivalents of MAO. Toluene was found to be a far more effective reaction solvent than dichloromethane, as polymer yields were on average thirteen times higher. All polymer samples were analyzed by high temperature 1H NMR spectroscopy and selected samples were analyzed by DSC and IR spectroscopy. DSC determined that the polyethylene produced by 1 was substantially linear HDPE with long chain branching and that comonomer incorporation reduced the Tc and Tm, probably due to increased short chain branching. 1-TMSO-9-Decene was the most effective comonomer, as it had the highest incorporation rates (8.0 mol%) of all three of the polar comonomers. The two shorter comonomers exhibited no incorporation at all. This confirmed the hypothesis that polar comonomers with longer chains would be less prone to poisoning the electrophilic catalyst.
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