The present invention relates to a method for oligomerizing olefins including the steps of: carrying out an oligomerization reaction of olefins by injecting an oligomerization transition metal catalyst, a cocatalyst, an olefin monomer and a solvent into a reactor; and injecting, into the reaction product of the oligomerization reaction, a catalyst inactivator including a gaseous inorganic material that contains oxygen.

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.

Catalyst systems suitable for tetramerizing ethylene to form 1-octene may include a catalyst including a reaction product of a chromium compound and a ligand having the structure according to Formula (II). In Formula (II), A and C may be independently chosen from phosphorus, arsenic, antimony, bismuth, and nitrogen; B may be a linking group between A and C; and R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may be independently chosen from a (C.sub.1-C.sub.50) hydrocarbyl or a (C.sub.1-C.sub.50) heterohydrocarbyl. The catalyst system may include a co-catalyst including a reaction product of an organoaluminum compound and an antifouling compound. The antifouling compound may include one or more quaternary salts; one or more organic acids, organic acid salts, esters, anhydrides, or combinations of these; one or more chlorinated hydrocarbons, chloro-aluminum alkyls, or combinations of these; one or more polyether alcohols; or one or more non-polymeric ethers.

Catalyst systems suitable for tetramerizing ethylene to form 1-octene may include a catalyst having a structure according to Formula (VI) or Formula (VII). In Formulas (VI) and (VII), X is a halogen, a (C.sub.2-C.sub.30) carboxylate, acetylacetonate, or a (C.sub.1-C.sub.30) hydrocarbyl; L.sub.1 is a neutral coordinating ligand; n is an integer from 0 to 6; Y is a (C.sub.6-C.sub.20)fluorine-substituted aryl, a (C.sub.6-C.sub.20)fluorine-substituted aryloxy, or a (C.sub.1-C.sub.20)fluorine-substituted alkoxy; and L∩L is a bidentate chelating ligand. The catalyst system may also include an aluminum containing agent which includes a reaction product of an organoaluminum compound and an antifouling compound. The antifouling compound may include one or more quaternary salts.

Catalyst systems suitable for tetramerizing ethylene to form 1-octene may include a catalyst having a structure according to Formula (VI) or Formula (VII). In Formulas (VI) and (VII), X is a halogen, a (C.sub.2-C.sub.30) carboxylate, acetylacetonate, or a (C.sub.1-C.sub.30) hydrocarbyl; L.sub.1 is a neutral coordinating ligand; n is an integer from 0 to 6; Y is a (C.sub.6-C20)fluorine-substituted aryl, a (C.sub.6-C.sub.20)fluorine-substituted aryloxy, or a (C.sub.1-C.sub.20)fluorine-substituted alkoxy; and L∩L is a bidentate chelating ligand. The catalyst system may also include an aluminum containing agent which includes a reaction product of an organoaluminum compound and an antifouling compound. The antifouling compound may include one or more chlorinated hydrocarbons, chloro-aluminum alkyls, or combinations of these.

Catalyst systems suitable for tetramerizing ethylene to form 1-octene may include a catalyst having a structure according to Formula (VI) or Formula (VII). In Formulas (VI) and (VII), X is a halogen, a (C.sub.2-C.sub.30) carboxylate, acetylacetonate, or a (C.sub.1-C.sub.30) hydrocarbyl; L.sub.1 is a neutral coordinating ligand; n is an integer from 0 to 6; Y is a (C.sub.6-C.sub.20)fluorine-substituted aryl, a (C.sub.6-C.sub.20)fluorine-substituted aryloxy, or a (C.sub.1-C.sub.20)fluorine-substituted alkoxy; and L∩L is a bidentate chelating ligand. The catalyst system may also include an aluminum containing agent which includes a reaction product of an organoaluminum compound and an antifouling compound. The antifouling compound may include one or more organic acids, organic acid salts, esters, anhydrides, or combinations of these.

Catalyst systems suitable for tetramerizing ethylene to form 1-octene may include a catalyst having a structure according to Formula (VI) or Formula (VII). In Formulas (VI) and (VII), X is a halogen, a (C.sub.2-C.sub.30) carboxylate, acetylacetonate, or a (C.sub.1-C.sub.30) hydrocarbyl; L.sub.1 is a neutral coordinating ligand; n is an integer from 0 to 6; Y is a (C.sub.6-C.sub.20)fluorine-substituted aryl, a (C.sub.6-C.sub.20)fluorine-substituted aryloxy, or a (C.sub.1-C.sub.20)fluorine-substituted alkoxy; and L∩L is a bidentate chelating ligand. The catalyst system may also include an aluminum containing agent which includes a reaction product of an organoaluminum compound and an antifouling compound. The antifouling compound may include one or more polyether alcohols or one or more non-polymeric ethers.

The present invention describes a catalyst composition for use as a catalyst system for an ethylene oligomerization, providing high activity and produce linear oligomer product having broad weight percent distribution i.e. C.sub.4 to C.sub.16. The catalyst composition comprises a zirconium amide compound, an organoaluminum compound and an additive. The present invention also provides a process for preparation of the zirconium amide compound comprising reacting a zirconium component having formula ZrX.sub.m.nTHF, wherein X is halogen atom; m is an integer having value equal or less than 4 and n is a number equal or less than 2, and a substituted amide of formula RCONR′R″, wherein R, R′ and R″ are saturated or unsaturated aliphatic C.sub.1-C.sub.10 hydrocarbon or aromatic C.sub.6-C.sub.14 hydrocarbon, in the presence of an organic solvent.

The invention relates to a process for oligomerization of ethylene, preferably for selective trimerization of ethylene to hex-1-ene, comprising simultaneously bringing ethylene into contact with the components of a catalytic composition based on chromium.

Processes to produce tunable mixtures of 1-hexene and 1-octene are described. The process includes contacting a mixture of a 1-hexene catalyst and a 1-octene catalyst with ethylene under conditions sufficient to produce a composition that includes a desired amount 1-hexene and 1-octene are described.