Process for the preparation of ethylene copolymer compositions in the presence of an oligomerization catalyst

A process for the preparation of an ethylene copolymer composition having a polydispersity index Mw/Mn of from 3 to 100, comprising:

• a) feeding ethylene to at least one polymerization reactor;
• b) performing in the at least one polymerization reactor an oligomerization of ethylene in the presence of an oligomerization catalyst component (C) to produce a comonomer;
• c) performing simultaneously in the at least one polymerization reactor polymerization reactions in the presence of catalyst components (A) and (B) producing, respectively, a first and a second polyethylene fraction, wherein the weight average molecular weight Mw of the first polyethylene fraction produced by catalyst component (A) is less than the Mw of the second polyethylene fraction produced by catalyst component (B) and the comonomer incorporation ability of catalyst component (B) is higher than the comonomer incorporation ability of catalyst component (A);
• and
• d) withdrawing the ethylene copolymer composition from the polymerization reactor,
• wherein catalyst component (A) is an iron or cobalt complex of general formula (I):
• wherein
• L1A and L2A are each, independently of one another, nitrogen or phosphorus,
• E1A to E3A independently of one another are carbon, nitrogen or phosphorus,
• R1A to R3A are each, independently of one another, hydrogen, C1-C22-alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl which may in turn bear C1-C10-alkyl groups as substituents, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and 6 to 20 carbon atoms in the aryl part, —NR4A2, —OR4A, or —SiR5A3 or a five-, six- or seven-membered heterocycle, which comprises at least one atom from the group consisting of nitrogen, phosphorus, oxygen and sulfur, where the radicals R1A to R3A may also be substituted by halogen, —NR4A2, —OR4A, or —SiR5A3 and/or two radicals R1A to R3A, together with the atoms connecting them may be joined to form a ring or a heterocycle which comprises at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur, where
• R4A can be identical or different and can each be hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, or —SiR5A3 where the radicals R4A may be substituted by halogen, and/or two radicals R4A may be joined to form a 5-, 6- or 7-membered ring,
• R5A can be identical or different and can each be hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part and/or two radicals R5A may be joined to form a 5-, 6- or 7-membered ring,
• u independently of one another are 0 for E1A to E3A being nitrogen or phosphorus and 1 for E1A to E3A being carbon,
• R6A and R7A are each, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and 6 to 20 carbon atoms in the aryl part, —NR5A2, or —SiR4A3, where the radicals R6A and R7A may be substituted by halogen and/or two radicals R6A and R7A, may be joined to form a ring or a heterocycle which comprises at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur,
• v independently of one another, are 0 or 1, and when v is 0 the bond between L2A and the carbon atom bearing radical R6A is a double bond,
• R8A is, halogen, —NR13A2, —OR13A or —SiR13A3,
• R9A to R12A are each, independently of one another, C1-C20-alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, halogen, —NR13A2, —OR13A or —SiR13A3, where the organic radicals R8A to R12A may be substituted by halogens and/or two vicinal radicals R8A to R12A may be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R8A to R12A are joined to form a five-, six- or seven-membered heterocycle which comprises at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur,
• or
• R10A to R12A are, independently of one another, hydrogen,
• the radicals R13A are each, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C40-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, where the organic radicals R13A may be substituted by halogens or nitrogen- and oxygen-comprising groups and two radicals R13A may be joined to form a five- or six-membered ring,
• MA is iron or cobalt,
• XA independently of one another are fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10-alkenyl, C6-C40-aryl, arylalkyl having 1 to 16 carbon atoms in the alkyl part and 6 to 20 carbon atoms in the aryl part, —NR14A2, —OR14A, —SR14A, —SO3R14A, —OC(O)R14A, —CN, —SCN, β-diketonate, —CO, BF4−, PF6− or bulky non-coordinating anions, wherein the organic radicals XA can be substituted by halogens and/or at least one radical R14A, and the radicals XA are optionally bonded with one another,
• R14A independently of one another are hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having 1 to 16 carbon atoms in the alkyl part and 6 to 20 carbon atoms in the aryl part, or SiR15A3, wherein the organic radicals R14A can be substituted by halogens, and/or in each case two radicals R14A can be bonded with one another to form a five- or six-membered ring,
• R15A independently of one another are hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C40-aryl, arylalkyl having 1 to 16 carbon atoms in the alkyl part and 6 to 20 carbon atoms in the aryl part, wherein the organic radicals R15A can be substituted by halogens, and/or in each case two radicals R15A can be bonded with one another to form a five- or six-membered ring,
• s is 1, 2, 3 or 4,
• DA is an uncharged donor, and
• t is 0 to 4, and
• at least one radical of the group consisting of R8A, R9A and R11A is fluorine, chlorine, bromine, iodine, —OR13A or —CF3, and
• catalyst component (C) is an iron or cobalt complex of general formula (V):
• wherein
• L1C and L2C are each, independently of one another, nitrogen or phosphorus,
• E1C to E3C independently of one another are carbon, nitrogen or phosphorus,
• R1C to R3C are each, independently of one another, hydrogen, C1-C22-alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl which may in turn bear C1-C10-alkyl groups as substituents, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and 6 to 20 carbon atoms in the aryl part, —NR4C2, —OR4C, or —SiR5C3 or a five-, six- or seven-membered heterocycle, which comprises at least one atom from the group consisting of nitrogen, phosphorus, oxygen and sulfur, where the radicals R1C to R3C may also be substituted by halogen, —NR4C2, —OR4C, or —SiR5C3 and/or two radicals R1C to R3C, together with the atoms connecting them may be joined to form a ring or a heterocycle which comprises at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur, where
• R4C can be identical or different and can each be hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, or —SiR5C3 where the radicals R4C may be substituted by halogen, and/or two radicals R4C may be joined to form a 5-, 6- or 7-membered ring,
• R5C can be identical or different and can each be hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part and/or two radicals R5C may be joined to form a 5-, 6- or 7-membered ring,
• u independently of one another are 0 for E1C to E3C being nitrogen or phosphorus and 1 for E1C to E3C being carbon,
• R6C and R7C are each, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and 6 to 20 carbon atoms in the aryl part, —NR5C2, or —SiR4C3, where the radicals R6C and R7C may be substituted by halogen and/or two radicals R6C and R7C, may be joined to form a ring or a heterocycle which comprises at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur,
• v independently of one another, are 0 or 1, and when v is 0 the bond between L2C and the carbon atom bearing radical R6C is a double bond,
• R8C are each hydrogen,
• R9C to R12C are each, independently of one another, C1-C20-alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, halogen, —NR13C2, —OR13C or —SiR13C3, where the organic radicals R8C to R12C may be substituted by halogens and/or two vicinal radicals R8C to R12C may be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R8C to R12C are joined to form a five-, six- or seven-membered heterocycle which comprises at least one atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur,
• or
• R10C to R12C are, independently of one another, hydrogen,
• the radicals R13C are each, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C40-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, where the organic radicals R13C may be substituted by halogens or nitrogen- and oxygen-comprising groups and two radicals R13C may be joined to form a five- or six-membered ring,
• MC is iron or cobalt,
• XC independently of one another are fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10-alkenyl, C6-C40-aryl, arylalkyl having 1 to 16 carbon atoms in the alkyl part and 6 to 20 carbon atoms in the aryl part, —NR14C2, —OR14C, —SR14C, —SO3R14C, —OC(O)R14C, —CN, —SCN, β-diketonate, —CO, BF4−, PF6− or bulky non-coordinating anions, wherein the organic radicals XC can be substituted by halogens and/or at least one radical R14C, and the radicals XC are optionally bonded with one another,
• R14C independently of one another are hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C40-aryl, arylalkyl having 1 to 16 carbon atoms in the alkyl part and 6 to 20 carbon atoms in the aryl part, or SiR15C3, wherein the organic radicals R14C can be substituted by halogens, and/or in each case two radicals R14C can be bonded with one another to form a five- or six-membered ring,
• R15C independently of one another are hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C40-aryl, arylalkyl having 1 to 16 carbon atoms in the alkyl part and 6 to 20 carbon atoms in the aryl part, wherein the organic radicals R15C can be substituted by halogens, and/or in each case two radicals R15C can be bonded with one another to form a five- or six-membered ring,
• s is 1, 2, 3 or 4,
• DC is an uncharged donor, and
• t is 0 to 4,
• wherein at least one olefin is fed to the at least one polymerization reactor as an additional comonomer beside ethylene and from 5% by weight to 90% by weight of the structural units of the ethylene copolymer composition, which results from the incorporated comonomer, result from olefin, which was fed to the at least one polymerization reactor, and from 10% by weight to 95% by weight of the structural units of the ethylene copolymer composition, which results from the incorporated comonomer, result from comonomer, which was obtained by oligomerization of ethylene according to step b).