In-line process for generating comonomer

An in-line method for generating comonomer for input to a polyethylene polymerization reactor comprising the following steps:

• providing an in-line comonomer synthesis reactor prior to a polyethylene polymerization reactor, wherein the reactor is a fixed bed type with a catalyst in a fixed position;
• feeding ethylene monomer to said comonomer synthesis reactor;
• reacting said ethylene monomer and said catalyst under reaction conditions to produce an effluent stream comprising ethylene monomer and comonomer selected from the group consisting of 1-hexene, 1-octene;
• 1-decene and mixtures thereof;
• and
• directing said effluent stream to said polyethylene polymerization reactor to provide a comonomer source, 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.

An in-line method for generating comonomer for input to a polyethylene polymerization reactor comprising the following steps:

• providing an in-line comonomer synthesis reactor and a downstream gas/liquid phase separator prior to a polyethylene polymerization reactor;
• feeding ethylene monomer and a catalyst in a solvent and or diluent to said comonomer synthesis reactor;
• reacting said ethylene monomer and said catalyst in solvent and or diluent under reaction conditions to produce an effluent stream comprising ethylene monomer and comonomer selected from the group consisting of 1-hexene, 1-octene;
• 1-decene and mixtures thereof;
• passing said effluent stream from said comonomer synthesis reactor to said downstream gas/liquid phase separator to separate a gas stream from a bottom stream, wherein said gas stream is a mixture of ethylene monomer, and said comonomer;
• and
• transporting without isolation or storage said gas stream to said polyethylene polymerization reactor to provide a comonomer source, 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.