Chevron Phillips Chemical Company LP

Other

Daniel Halsell Ess

Orson L Sydora

Steven M Bischof

Uriah J Kilgore

Doo-Hyun Kwon

Jack T Fuller, Iii

Qing R Yang

John Russell Falck

Richard M Buck

Graham R Lief

Jawahar Lal Jat

Laszlo Kurti

Steven M Maley

Nicholas K Rollins

Disclosed is a heteroatomic ligand-metal compound complex transition-state model which has been developed for activity, purity, and/or selectivity for selective ethylene oligomerizations, and density functional theory calculations for determining heteroatomic ligand-metal compound complex reactivity, product purity, and/or selectivity for ethylene trimerizations and/or tetramerizations. Using reaction ground states and transition states, and/or reaction ground states and transition states in combination with the energetic span model, this disclosure reveals that a chromium chromacycle mechanism, there are multiple ground states and multiple transition states, which can account for activity, purity, and/or selectivity for selective ethylene oligomerizations. Based on the reaction ground states and transition states, and/or reaction ground states and transition states in combination with the energetic span model, the methods disclosed herein can qualitatively and semi-quantitatively used to predict relative heteroatomic ligand-metal compound complex activity, purity, and/or selectivity and lead to a successful process for catalyst design and implementation, in which new ligands can be successfully identified and experimentally validated.

Machine learning and statistical analysis for catalyst structure prediction and design

This disclosure provides new methods for the design and development of ethylene polymerization catalysts, including Group 4 metallocene catalysts such as zirconocenes, which are based on an improved ability to adjust co-monomer incorporation into the polymer. Computational analyses with and without dispersion corrections revealed that designing catalyst scaffolds which induce stabilizing non-covalent dispersion type interactions with incoming α-olefin co-monomers can be used to modulate co-monomer selectivity into the polyethylene chain. Demonstrated herein is a lack of correlation of computed ΔΔGvalues against experimental ΔΔGvalues when the dispersion correction (D3BJ) was disabled, and B3LYP was used in the absence of Grimme's D3 dispersion and Becke-Johnson (BJ) dampening, but a correlation of computed against experimental ΔΔGwith B3LYP+D3BJ, which are used to design new catalyst scaffolds.

Modulating co-monomer selectivity using non-covalent dispersion interactions in group 4 olefin polymerization catalysts

The present disclosure relates to a catalyst system comprising i) (a) a bicyclic 2-[(phosphinyl)aminyl] cyclic imine chromium salt or (b) a chromium salt and a bicyclic 2-[(phosphinyl)aminyl] cyclic imine and ii) an organoaluminum compound. The present disclosure also relates to a process comprising: a) contacting i) ethylene; ii) a catalyst system comprising (a) a 2-[(phosphinyl)aminyl] cyclic imine chromium salt complex or (b) a chromium salt and a bicyclic 2-[(phosphinyl)aminyl] cyclic imine; ii) an organoaluminum compound, and iii) optionally an organic reaction medium; and b) forming an oligomer product in a reaction zone.

Chromium phosphinyl hydroisoindole amidine complexes for tetramerization of ethylene

The present disclosure relates to a catalyst system comprising i) (a) an N-phosphinyl bicyclic amidine chromium salt or (b) a chromium salt and an N-phosphinyl bicyclic amidine and ii) an organoaluminum compound. The present disclosure also relate to a process comprising: a) contacting i) ethylene; ii) a catalyst system comprising (a) an N-phosphinyl bicyclic amidine chromium salt complex or (b) a chromium salt and an N-phosphinyl bicyclic amidine; ii) an organoaluminum compound, and iii) optionally an organic reaction medium; and b) forming an oligomer product in a reaction zone.

Chromium bicyclic phosphinyl amidine complexes for tetramerization of ethylene

The present disclosure relates to a catalyst system comprising i) (a) a bicyclic 2-[(phosphinyl)aminyl] cyclic imine chromium salt or (b) a chromium salt and a bicyclic 2-[(phosphinyl)aminyl] cyclic imine and ii) an organoaluminum compound. The present disclosure also relate to a process comprising: a) contacting i) ethylene; ii) a catalyst system comprising (a) a 2-[(phosphinyl)aminyl] cyclic imine chromium salt complex or (b) a chromium salt and a bicyclic 2-[(phosphinyl)aminyl] cyclic imine; ii) an organoaluminum compound, and iii) optionally an organic reaction medium; and b) forming an oligomer product in a reaction zone.

Chromium phosphinyl isoindole amidine complexes for tetramerization of ethylene

A composition comprising an N-phosphinylamidine chromium salt complex having Structure FNPACr I:  

Fluorinated N-phosphinyl amidine compounds, chromium salt complexes, catalyst systems, and their use to oligomerize ethylene

A composition comprising a perfluoro-N-phosphinylamidine chromium salt complex having Structure PFAHNPACr I: wherein Ris a substituted phenyl group comprising alkyl groups at the 2 and 6 positions and at least one fluoro group or perfluoroalkyl group at the 3, 4, and/or 5 positions, Ris a Cto Corganyl group, Rand Rare each independently a Cto Corganyl group, and CrXis a chromium salt where X is a monoanion, and p is an integer from 2 to 6.

[object Object]

A catalyst system comprising an N-phosphinylamidine chromium salt complex having Structure PFHNPACr I: wherein Rf, Rf, Rf, and Rfare independently selected from a perfluorohydrocarbyl group; and CrXis a chromium salt; X is a monoanion, and p is an integer from 2 to 6. A process comprising a) contacting i) ethylene, ii) a catalyst system comprising an N-phosphinylamidine chromium salt complex having Structure PFHNPACr I: wherein each Rf, Rf, Rf, and Rfare independently selected from a perfluorohydrocarbyl group and CrXis a chromium salt; X is a monoanion and p is an integer from 2 to 6, and iii) optionally an organic reaction medium; and b) forming an oligomer product in a reaction zone.

Perfluorohydrocarbyl-N2-phosphinyl amidine compounds, chromium salt complexes, catalyst systems, and their use to oligomerize ethylene

A method for the direct stereospecific conversion of structurally diverse mono-, di-, tri- and tetra-substituted olefins to N&#x2014;H, N-alkyl, N-cycloalkyl, or N-aralkyl aziridines using a hydroxylamine amination agent with transition metal catalyst. The method is operationally simple (i.e., one-pot), scalable and fast at ambient temperature.

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Provo, UT, United States of America

Daniel Halsell Ess