Journal
MACROMOLECULES
Volume 50, Issue 23, Pages 9151-9161Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.7b01341
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Funding
- U.S. Department of Energy [DE-FG02-03ER15466]
- National Science Foundation through Purdue University [TG-CTS070034N]
- Henry B. Hass Fellowship
- U.S. Department of Energy (DOE) [DE-FG02-03ER15466] Funding Source: U.S. Department of Energy (DOE)
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A zirconium amine bis(phenolate) catalyst that is capable of simultaneously producing both oligomers and polymers of 1-hexene was investigated. It was found that the polymer produced has more branching than the commonly encountered poly(1-hexene), suggesting an oligomer macro-monomer enchainment. The polymer weight fraction and molecular weight are weakly dependent on conversion and are not affected by increasing the concentration of free oligomer macromonomers in solution. After considering a number of possible mechanisms, the most plausible supported by spectroscopic and kinetic data is a second-order reaction between an oligomer forming site and a polymer forming site, resulting in the transfer of oligomer macro-monomers into the growing polymer chain. The ratio between oligomer and polymer products can be precisely tuned by varying the precatalyst activation conditions.
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