Process for generating linear apha olefin comonomers

A method for preparing linear alpha olefin comonomers from ethylene monomer comprising the following steps:

• providing one or more comonomer synthesis reactors configured in series, one or more downstream gas/liquid phase separators configured in series, and one or more distillation columns configured in series;
• feeding an ethylene monomer, and a catalyst in a solvent and or diluent to said one or more comonomer synthesis reactors;
• reacting in said one or more comonomer synthesis reactors said ethylene monomer and said catalyst in solvent and or diluent under reaction conditions to produce an effluent stream comprising unreacted ethylene monomer, said catalyst in a solvent and or diluent, and comonomer;
• passing said effluent stream to said one or more downstream gas/liquid phase separators to form a gas stream of said unreacted ethylene monomer, and a liquid stream of said comonomer and said catalyst in a solvent and or diluent;
• passing said liquid stream of said comonomer and said catalyst in a solvent and or diluent to said one or more distillation columns to separate said comonomer from said catalyst in a solvent and or diluent;
• recycling to said one or more comonomer synthesis reactors said unreacted ethylene monomer and said catalyst in a solvent and or diluent;
• and
• storing said comonomer for subsequent processing;
• wherein said comonomer is selected from the group consisting of 1-butene, 1-hexene, 1-octene, 1-decene and mixtures thereof, wherein the catalyst comprises
• the combination of:
• 1) a ligand represented by the formula:
• wherein:
• N is nitrogen;
• R1 and R20 are each independently selected from the group consisting of consisting of hydrogen and optionally substituted hydrocarbyl, heteroatom containing hydrocarbyl and silyl, provided that R1 or R20 do not equal T-J, alternately R1 and R20 are each independently a ring having from 4 to 8 atoms in the ring selected from the group consisting of substituted cycloalkyl, heterocycloalkyl, aryl and heteroaryl);
• T is a bridging group, preferably represented by the formula -(T′R2R3)-, where T′ is carbon or silicon, R2 and R3 are each independently selected from the group consisting of hydrogen, halogen, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, alkylthio, arylthio, and combinations thereof, provided that two or more R2 and/or R3 groups may be joined together to form one or more optionally substituted ring systems having from 3 to 50 non-hydrogen atoms (for example, T is cyclopropyl, where T′=C, and R2 and R3 together form —CH2—CH2—;
• or T is cyclohexyl, where T′=C and the two R2 groups together form —CH2—CH2—CH2—CH2—);
• J is an optionally substituted six-membered heterocycle, containing at least one nitrogen atom as part of the ring, or J is an optionally substituted five-membered heterocycle, containing at least one nitrogen atom as part of the ring;
• or a ligand represented by the formula:
• wherein
• P is phosphorus;
• each of R1*, R2*, R3*, R4*, R5*, R6*, R7*, R8*, R9*, R10*, R11*, R12*, R13*, R14*, R15*, and R16* is, independently, selected from the group consisting of hydrogen, halogen, optionally substituted hydrocarbyl and optionally substituted heteroatom containing hydrocarbyl;
• each of Z1, Z2, Z3 or Z4 is, independently, selected from the group consisting of hydrogen, a hydrocarbyl, alkoxy, aryloxy, alkylthio, arylthio, hydroxyl, mercapto and amino;
• Q is a bridging group selected from the group consisting of optionally substituted hydrocarbyl having from 2 to 20 carbon atoms;
• 2) a metal precursor compound characterized by the general formula Cr(L)n where each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, ether, thioether, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulfates, ethers, thioethers and combinations thereof, wherein two or more L groups may be combined in a ring structure having from 3 to 50 non-hydrogen atoms;
• and n is 1, 2, 3, 4, 5, or 6;
• and
• 3) optionally, one or more activators.

A method for preparing linear alpha olefin comonomers from ethylene monomer comprising the following steps:

• providing a combination comonomer synthesis reactor and gas/liquid phase separator into a single vessel;
• feeding an ethylene monomer, and a catalyst in a solvent and or diluent to said combination comonomer synthesis reactor and gas/liquid phase separator;
• reacting in said combination comonomer synthesis reactor and gas/liquid phase separator said ethylene monomer and said catalyst in solvent and or diluent under reaction conditions to produce an effluent stream comprising a gas stream of unreacted ethylene monomer and a liquid stream of comonomer and catalyst in a solvent and or diluent;
• recycling to said combination comonomer synthesis reactor and gas/liquid phase separator said gas stream and a portion of said liquid stream;
• and
• storing a remaining portion of said liquid stream for subsequent processing of said comonomer;
• wherein said comonomer is selected from the group consisting of 1-butene, 1-hexene, 1-octene, 1-decene and mixtures thereof, wherein the catalyst comprises
• the combination of:
• 1) a ligand represented by the formula:
• wherein:
• N is nitrogen;
• R1 and R20 are each independently selected from the group consisting of consisting of hydrogen and optionally substituted hydrocarbyl, heteroatom containing hydrocarbyl and silyl, provided that R1 or R20 do not equal T-J, alternately R1 and R20 are each independently a ring having from 4 to 8 atoms in the ring selected from the group consisting of substituted cycloalkyl, heterocycloalkyl, aryl and heteroaryl);
• T is a bridging group, preferably represented by the formula -(T′R2R3)-, where T′ is carbon or silicon, R2 and R3 are each independently selected from the group consisting of hydrogen, halogen, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, alkylthio, arylthio, and combinations thereof, provided that two or more R2 and/or R3 groups may be joined together to form one or more optionally substituted ring systems having from 3 to 50 non-hydrogen atoms (for example, T is cyclopropyl, where T′=C, and R2 and R3 together form —CH2—CH2—;
• or T is cyclohexyl, where T′=C and the two R2 groups together form —CH2—CH2—CH2—CH2—);
• J is an optionally substituted six-membered heterocycle, containing at least one nitrogen atom as part of the ring, or J is an optionally substituted five-membered heterocycle, containing at least one nitrogen atom as part of the ring;
• or a ligand represented by the formula:
• wherein
• P is phosphorus;
• each of R1*, R2*, R3*, R4*, R5*, R6*, R7*, R8*, R9*, R10*, R11*, R12*, R13*, R14*, R15*, and R16* is, independently, selected from the group consisting of hydrogen, halogen, optionally substituted hydrocarbyl and optionally substituted heteroatom containing hydrocarbyl;
• each of Z1, Z2, Z3 or Z4 is, independently, selected from the group consisting of hydrogen, a hydrocarbyl, alkoxy, aryloxy, alkylthio, arylthio, hydroxyl, mercapto and amino;
• Q is a bridging group selected from the group consisting of optionally substituted hydrocarbyl having from 2 to 20 carbon atoms;
• 2) a metal precursor compound characterized by the general formula Cr(L)n where each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, ether, thioether, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulfates, ethers, thioethers and combinations thereof, wherein two or more L groups may be combined in a ring structure having from 3 to 50 non-hydrogen atoms;
• and n is 1, 2, 3, 4, 5, or 6;
• and
• 3) optionally, one or more activators.