The invention relates to oligomerization of olefins, such as ethylene, to higher olefins, such as a mixture of 1-hexene and 1-octene, using a catalyst system that comprises a) a source of chromium b) one or more activators and c) a phosphacycle-containing ligating compound. Additionally, the invention relates to a phosphacycle-containing ligating compound and a process for making said compound.

The invention relates to oligomerization of olefins, such as ethylene, to higher olefins, such as a mixture of 1-hexene and 1-octene, using a catalyst system that comprises a) a source of chromium b) one or more activators and c) a phosphacycle-containing ligating compound. Additionally, the invention relates to a phosphacycle-containing ligating compound and a process for making said compound.

A process includes periodically or continuously introducing an olefin monomer and periodically or continuously introducing a catalyst system or catalyst system components into a reaction mixture within a reaction system, oligomerizing the olefin monomer within the reaction mixture to form an oligomer product, and periodically or continuously discharging a reaction system effluent comprising the oligomer product from the reaction system. The reaction system includes a total reaction mixture volume and a heat exchanged portion of the reaction system comprising a heat exchanged reaction mixture volume and a total heat exchanged surface area providing indirect contact between the reaction mixture and a heat exchange medium. A ratio of the total heat exchanged surface area to the total reaction mixture volume within the reaction system is in a range from 0.75 in.sup.−1 to 5 in.sup.−1, and an oligomer product discharge rate from the reaction system is between 1.0 (lb)(hr.sup.−1)(gal.sup.−1) to 6.0 (lb)(hr.sup.−1)(gal.sup.−1).

A process includes periodically or continuously introducing an olefin monomer and periodically or continuously introducing a catalyst system or catalyst system components into a reaction mixture within a reaction system, oligomerizing the olefin monomer within the reaction mixture to form an oligomer product, and periodically or continuously discharging a reaction system effluent comprising the oligomer product from the reaction system. The reaction system includes a total reaction mixture volume and a heat exchanged portion of the reaction system comprising a heat exchanged reaction mixture volume and a total heat exchanged surface area providing indirect contact between the reaction mixture and a heat exchange medium. A ratio of the total heat exchanged surface area to the total reaction mixture volume within the reaction system is in a range from 0.75 in.sup.−1 to 5 in.sup.−1, and an oligomer product discharge rate from the reaction system is between 1.0 (lb)(hr.sup.−1)(gal.sup.−1) to 6.0 (lb)(hr.sup.−1)(gal.sup.−1).

The present disclosure relates to a catalyst system comprising i) (a) an N.sup.2-phosphinyl bicyclic amidine chromium salt or (b) a chromium salt and an N.sup.2-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.sup.2-phosphinyl bicyclic amidine chromium salt complex or (b) a chromium salt and an N.sup.2-phosphinyl bicyclic amidine; ii) an organoaluminum compound, and iii) optionally an organic reaction medium; and b) forming an oligomer product in a reaction zone.

The present disclosure relates to a catalyst system comprising i) (a) an N.sup.2-phosphinyl bicyclic amidine chromium salt or (b) a chromium salt and an N.sup.2-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.sup.2-phosphinyl bicyclic amidine chromium salt complex or (b) a chromium salt and an N.sup.2-phosphinyl bicyclic amidine; ii) an organoaluminum compound, and iii) optionally an organic reaction medium; and b) forming an oligomer product in a reaction zone.

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.

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.

Catalyst systems for tetramerizing ethylene to form 1-octene may include a catalyst which may include a chromium compound coordinated with a ligand and a co-catalyst which may include an organoaluminum compound. The ligand may have a chemical structure according to Chemical Structure (I), wherein R.sub.5 is a (C.sub.1-C.sub.15) alkyl group, a (C.sub.3-C.sub.15) cyclohydrocarbyl group, a (C.sub.3-C.sub.15) cycloheterohydrocarbyl group, or a (C.sub.1-C.sub.15) aryl group, and R.sub.A, R.sub.B, R.sub.C, R.sub.D, R.sub.E, R.sub.F, R.sub.G, R.sub.H, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7, R.sub.8, and R.sub.9 are independently chosen from a hydrogen atom, a (C.sub.1-C.sub.50) hydrocarbyl group, or a (C.sub.1-C.sub.50) heterohydrocarbyl group.

Catalyst systems for tetramerizing ethylene to form 1-octene may include a catalyst which may include a chromium compound coordinated with a ligand and a co-catalyst which may include an organoaluminum compound. The ligand may have a chemical structure according to Chemical Structure (I), wherein R.sub.5 is a (C.sub.1-C.sub.15) alkyl group, a (C.sub.3-C.sub.15) cyclohydrocarbyl group, a (C.sub.3-C.sub.15) cycloheterohydrocarbyl group, or a (C.sub.1-C.sub.15) aryl group, and R.sub.A, R.sub.B, R.sub.C, R.sub.D, R.sub.E, R.sub.F, R.sub.G, R.sub.H, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7, R.sub.8, and R.sub.9 are independently chosen from a hydrogen atom, a (C.sub.1-C.sub.50) hydrocarbyl group, or a (C.sub.1-C.sub.50) heterohydrocarbyl group.