catalyst system

Abstract

The present invention provides a catalyst system for producing ethylene copolymers in a high temperature solution process, comprising: (i) an optionally substituted metallocene complex of a Group 4 transition metal comprising at least one ligand selected from cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands; and (ii) Solid alkylaluminum oxide promoter The present invention relates to the above catalyst system, comprising: The present invention also relates to a method for preparing the catalyst system, a method for using the catalyst system in a high temperature solution process, and a method for producing ethylene and C in a high temperature solution process in the presence of the catalyst system. 4~10 and an alpha-olefin comonomer.

Description

[Technical Field]

[0001] The present invention relates to a novel catalyst system capable of producing polyethylene copolymers in a high-temperature solution polymerization process. The novel catalyst system comprises a substituted bridged metallocene complex of a Group 4 transition metal combined with a specific cocatalyst in solid form. This combination significantly results in a catalyst system with an improved balance of productivity, comonomer incorporation capability, and molecular weight capability. [Background technology]

[0002] Metallocene catalysts have been used to produce polyolefins for decades. Countless scientific and patent publications describe the use of these catalysts in olefin polymerization. Metallocenes are used industrially today, and polypropylene and polyethylene are often produced using cyclopentadienyl-based catalyst systems with different substitution patterns.

[0003] Some of these metallocene catalysts have been described in several patent documents for use in solution polymerization to produce polyethylene homopolymers or copolymers.

[0004] For example, WO 2000 / 024792 describes a catalyst system comprising a hafnocene catalyst complex derived from a biscyclopentadienylhafnium organometallic compound having i) at least one unsubstituted or fused aromatic ring-substituted cyclopentadienyl ligand, ii) one substituted or unsubstituted fused aromatic ring-substituted cyclopentadienyl ligand, and iii) a covalent bridge connecting the two cyclopentadienyl ligands.

[0005] The bridge can be a single carbon substituted with two aryl groups, each of which is C1-C6 20It is substituted with a hydrocarbyl or hydrocarbylsilyl group, whereby at least one of these substituents is a linear C3 or greater substituent.

[0006] In addition, the catalyst system includes an activating cocatalyst, which is a precursor ionic compound containing a halogenated tetraaryl-substituted Group 13 anion, typically a perfluorinated borate compound, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, which is used in all examples.

[0007] Also, numerous scientific publications have disclosed the influence of ligand structure on high temperature ethylene homo- and copolymerization with various Cp-Flu metallocenes. Summary of the Invention [Problem to be solved by the invention]

[0008] Perfluorinated borate activators for single-site catalysts are widely used, especially in high-temperature solution polymerizations, where they have been shown to provide satisfactory performance in polymerizations. However, these activators have very low solubility in aliphatic hydrocarbons and must be either dissolved in an aromatic solvent or slurried in an aliphatic solvent to be delivered to the polymerization process. Both solutions have the following disadvantages: aromatic solvents are undesirable in the process due to their toxicity, and solid slurries require more than stoichiometric amounts of activator relative to the metallocene complex, resulting in waste of expensive components.

[0009] Likewise, the metallocene complex must also have relatively high solubility in aliphatic hydrocarbons.

[0010] There are commercially available activators for use with single-site catalysts based on methylalumoxane (MAO) or mixtures thereof with aluminum alkyls, such as MAO / triisobutylaluminum (MAO / TIBA), modified MAO (MMAO), etc., i.e., not based on perfluorinated borates.

[0011] Metallocene / MAO based catalyst systems would be desirable potential replacements for currently used metallocene / borate systems, provided they could be prepared without aromatic solvents such as toluene.

[0012] An advantage of using an activated metallocene / MAO catalyst system can be that complexes with lower solubility in aliphatic hydrocarbons can also be used because the solubility is provided by the solvating power of MAO itself. However, while MAO is commercially available as a toluene solution, toluene-free MMAO is less efficient at activating such less soluble complexes.

[0013] Therefore, there is a need to find new solutions for catalyst activation. [Means for solving the problem]

[0014] It is therefore an object of the present invention to provide a metallocene-based catalyst system comprising a metallocene complex and a cocatalyst, wherein the solubility of the metallocene is not a limiting feature for the use of such catalyst systems in high temperature solution processes, and it is therefore an object of the present invention to provide a novel catalyst system in which no aromatic solvent is required for the catalyst system.

[0015] It is a further object of the present invention to provide a metallocene-based catalyst system in which fluorinated borates are not used as activators, yet productivity remains at a good level or is even improved without the use of such borates as activators.

[0016] It is yet another object of the present invention to provide a metallocene-based catalyst system capable of producing polyethylene polymers in a high temperature solution process with an improved balance of molecular weight capability and comonomer incorporation capability.

[0017] Additionally, it is an object of the present invention to provide a method for preparing the catalyst system described herein.

[0018] Additionally, a method for producing ethylene copolymers in a high temperature process in the presence of the catalyst system described herein is an object of the present invention.

[0019] For a process to produce ethylene copolymers to be effective, it is important that the catalyst system used must meet a set of requirements as disclosed above: comonomer incorporation, capacity for higher comonomers (C4 to C12 comonomers) (comonomer reactivity), molecular weight capacity of the catalyst, and thermal stability of the catalyst must be within the range of 0.85 g / cm. 3 The catalyst molecular weight capability must ensure the production of copolymers with densities up to 0.5 and melt indices MI2 (190°C, 2.16 kg) up to 0.3 g / 10 min, and with high productivity. The catalyst molecular weight capability means the lowest achievable melt index for a given polymer density, monomer concentration and polymerization temperature.

[0020] Therefore, although much research has been conducted in the field of metallocene catalyst systems, there is still a need to find new metallocene-based catalyst systems for ethylene copolymerization in high-temperature solution processes. Such catalyst systems should be capable of producing polymers with desirable properties and should have an improved balance of productivity, comonomer incorporation capability, and molecular weight capability. Furthermore, there should be no limitation in using different metallocenes with different solubility characteristics.

[0021] In order to solve the problems indicated above, the present inventors have attempted to develop a novel catalyst system which has a polymerization behavior superior to the above-mentioned polymerization catalyst systems in terms of productivity, comonomer incorporation capacity and molecular weight capability. In addition, the limitations caused by low metallocene solubility are no longer an issue with the catalyst system of the present invention.

[0022] The present inventors have now discovered a new class of olefin polymerization catalyst systems that can solve the problems disclosed above. According to the present invention, the novel catalyst system comprises a metallocene complex in combination with a specific cocatalyst selected from solid alkylaluminum oxides. Thus, the use of a borate cocatalyst can be avoided in the catalyst system. Thus, according to a preferred embodiment, the catalyst system of the present invention is a combination of one or more metallocene complexes and one or more cocatalysts selected from solid alkylaluminum oxides, more preferably a combination of a metallocene and a cocatalyst selected from solid alkylaluminum oxides.

[0023] The phrases "activator" and "cocatalyst" have the same meaning and are interchangeable in this application.

[0024] Thus, in one aspect, the present invention provides a catalyst system for producing ethylene copolymers in a high temperature solution process at temperatures above 100°C, comprising: (i) an optionally substituted metallocene complex of a Group 4 transition metal comprising at least one ligand selected from cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands; and (ii) Solid alkylaluminum oxide promoter The present invention relates to a catalyst system as described above, comprising:

[0025] Viewed from a second aspect, the present invention provides a catalyst system for producing ethylene copolymers in a high temperature solution process at temperatures above 100°C, comprising: (i) an optionally substituted metallocene complex of a Group 4 transition metal comprising at least one ligand selected from cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands; and (ii) Aliphatic C5~C 24 A solid alkylalumoxane cocatalyst provided as a suspension in a hydrocarbon solvent or a mixture of such aliphatic hydrocarbon solvents. The present invention relates to the above catalyst system comprising:

[0026] Viewed from another aspect, the present invention is a process for preparing an ethylene copolymer, the process comprising reacting ethylene and C in a high temperature solution process at a temperature above 100°C in the presence of a catalyst system. 4~12 and an alpha-olefin comonomer, wherein the catalyst system comprises: (i) an optionally substituted metallocene complex of a Group 4 transition metal comprising at least one ligand selected from cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands; and (ii) solid alkylalumoxane cocatalyst The method includes:

[0027] In yet another aspect, the present invention is a process for preparing an ethylene copolymer, the process comprising reacting ethylene and C in a high temperature solution process at a temperature above 100°C in the presence of a catalyst system. 4~12 and an alpha-olefin comonomer, wherein the catalyst system comprises: (i) an optionally substituted metallocene complex of a Group 4 transition metal comprising at least one ligand selected from cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands; and (ii) Aliphatic C5~C 24 A solid alkylalumoxane cocatalyst provided as a suspension in a hydrocarbon solvent or a mixture of such aliphatic hydrocarbon solvents. The method includes:

[0028] Viewed from a further aspect, the present invention relates to ethylene C produced by the process defined hereinabove. 4~12 Alpha-olefin copolymers are provided.

[0029] From another perspective, the present invention provides a method for producing ethylene C in a high temperature solution process at temperatures above 100°C. 4~12 1. Use of a catalyst system for preparing an alpha-olefin copolymer, the catalyst system comprising: (i) an optionally substituted metallocene complex of a Group 4 transition metal comprising at least one ligand selected from cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands; and (ii) solid alkylalumoxane cocatalyst The present invention provides a use of the above catalyst system, which comprises:

[0030] From yet another perspective, the present invention provides a method for producing ethylene C12 in a high temperature solution process at temperatures above 100°C. 4~12 1. Use of a catalyst system for preparing an alpha-olefin copolymer, the catalyst system comprising: (i) an optionally substituted metallocene complex of a Group 4 transition metal comprising at least one ligand selected from cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands; and (ii) Aliphatic C5~C 24 A solid alkylalumoxane cocatalyst provided as a suspension in a hydrocarbon solvent or a mixture of such aliphatic hydrocarbon solvents. The present invention provides a use of the above catalyst system, which comprises:

[0031] Alkyl aluminum oxide and alkyl alumoxane have the same meaning and are interchangeable terms in this application. DETAILED DESCRIPTION OF THE INVENTION

[0032] Metallocene Complexes Ethylene C 4~12The single-site metallocene complexes used for the production of alpha-olefin copolymers are metallocene complexes of Group 4 transition metals, which contain at least one ligand selected from optionally substituted cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands, and which may have a covalent bridge connecting two of the ligands.

[0033] Such unbridged metallocene complexes are metallocene complexes of formula (A) below:

[0034] [ka]

[0035] where Z is a ligand that coordinates to Mt, Mt is Ti, Zr, Hf, or a mixture of Zr and Hf; X is a sigma ligand, R 1 ~R 5 are independently a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic C1-C 10 Hydrocarbyl groups, C6-C 10 Aryl groups, C6-C 20 Alkylaryl group or C6-C 20 arylalkyl groups, which may contain one or two heteroatoms or silicon atoms; or R 1 ~R 5 Any two adjacent groups among these may form a ring having 4 to 8 ring atoms, wherein the atoms that are part of the formed ring are saturated or unsaturated, straight or branched, C1 to C 10 Hydrocarbyl groups, C5-C 10 Aromatic group, C6~C 20 Alkylaryl group or C6-C 20 one or more R selected from arylalkyl groups; 12 groups, and one or more R 12The group may have one or two heteroatoms or silicon atoms.

[0036] Mt is Ti, Zr, Hf or a mixture of Zr and Hf, which means that the complex of formula (A) may comprise a mixture of complex (A) with Zr or Hf metal. Accordingly, Mt is a mixture of Ti, Zr, Hf or Zr and Hf, where said mixture of Zr and Hf is a mixture of the complex of formula (A) with Zr or Hf metal.

[0037] In particular, it is provided that in more than 50 mol % of the complexes of formula (A), Mt is Hf.

[0038] According to one embodiment, R 1 ~R 5 are independently a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic C1-C 10 Hydrocarbyl groups, C6-C 10 Aryl groups, C6-C 20 Alkylaryl group or C6-C 20 an arylalkyl group, wherein up to two C atoms in the aryl ring(s) may be replaced by up to two heteroatoms and may have substituents attached to those ring atoms, and such substituents may have one or two heteroatoms or silicon atoms, or R 1 ~R 5 Any two adjacent groups among these may form a ring having 4 to 8 ring atoms, wherein the atoms that are part of the formed ring are saturated or unsaturated, straight or branched, C1 to C 10 Hydrocarbyl groups, C5-C 10 Aromatic group, C6~C 20 Alkylaryl group or C6-C 20 one or more R selected from arylalkyl groups; 12 groups, and one or more R 12 The group may have one or two heteroatoms or silicon atoms.

[0039] The ligand Z may be an organic or inorganic ligand and may be selected from a wide variety of groups, for example Z may be an unsubstituted or substituted cyclopentadienyl group, a hydrocarbyl group, an amino group, an imino group, an oxygen atom, a phosphimine group, an alkylsilyl group, an alkoxy group.

[0040] The heteroatom belongs to groups 15 to 16, and is in particular N, P, O or S of formula (A).

[0041] According to another embodiment, ethylene C 4~12 The single-site metallocene complexes used to prepare the alpha-olefin copolymers are metallocene complexes of a Group 4 transition metal comprising at least one ligand selected from optionally substituted cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands, a ligand Z, and a covalent bridge connecting two of the ligands.

[0042] Such metallocenes having a bridge are metallocenes of formula (B) below:

[0043] [ka]

[0044] where Z is a ligand that coordinates to Mt, Mt is Ti, Zr, Hf, or a mixture of Zr and Hf as defined in the metallocene of formula (A); X is a sigma ligand, R 2 ~R 5 is as defined in the metallocene of formula (A), L is a covalent bridge connecting the ligands; Z is as defined in the metallocene of formula (A).

[0045] According to a preferred embodiment, the present invention can be realized by a metallocene complex of a Group 4 transition metal, which comprises two ligands selected from the group consisting of cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands, which may be substituted.

[0046] According to a more preferred embodiment, the present invention can be realized by a metallocene complex of a Group 4 transition metal containing two ligands selected from an optionally substituted cyclopentadienyl (Cp) ligand, an indenyl (Ind) ligand, and a fluorenyl (Flu) ligand, and a covalent bridge connecting the two ligands.

[0047] According to a preferred embodiment, the invention is provided by a metallocene complex of formula (I) below,

[0048] [ka]

[0049] where: Mt is Zr, Hf, or a mixture of Hf and Zr; X is a sigma ligand, Y is Formula-WR y 2 - is a bridge of n is 1, 2 or 3, preferably 1 or 2, more preferably 1; W is C or Si; Each R y are independently a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic C1-C 10 Hydrocarbyl groups, C6-C 10 Aryl groups, C6-C 20 Alkylaryl group or C6-C 20 arylalkyl groups, any of which may contain one or two heteroatoms or silicon atoms; or Linear, branched or cyclic, saturated or unsaturated C1-C20 a saturated or unsaturated ring having 3 to 7 ring atoms and containing a heteroatom, which may be substituted with a hydrocarbyl group; R 2 ~R 5 and R 2' ~R 5' are independently a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic C1-C 10 Hydrocarbyl groups, C6-C 10 Aryl groups, C6-C 20 Alkylaryl group or C6-C 20 arylalkyl groups, which may contain one or two heteroatoms or silicon atoms; or R 1 ~R 5 and / or R 1' ~R 5' Any two adjacent groups among these may form a ring having 4 to 8 ring atoms.

[0050] The atoms that are part of the formed ring may be saturated or unsaturated, straight or branched, C1-C 10 Hydrocarbyl, C6-C 10 Aryl groups, C6-C 20 Alkylaryl group or C6-C 20 one or more R selected from arylalkyl groups; 12 may be further substituted by a group, and said one or more R 12 The group may have one or two heteroatoms or silicon atoms.

[0051] Mt is Zr, Hf or a mixture of Zr and Hf, which means that the complex of formula (I) may comprise a mixture of complex (I) with Zr or Hf metal. Accordingly, Mt is Zr, Hf or a mixture of Zr and Hf, where said mixture of Zr and Hf is a mixture of the complex of formula (I) with Zr or Hf metal.

[0052] In particular, it is provided that in more than 50 mol % of the complexes of formula (I), Mt is Hf.

[0053] The heteroatom belongs to group 15-16, and is in particular N, P, O or S of formula (I).

[0054] According to one embodiment, R of formula (I) 1 ~R 5 and R 2' ~R 5' are independently a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic C1-C 10 Hydrocarbyl groups, C6-C 10 Aryl groups, C6-C 20 Alkylaryl group or C6-C 20 an arylalkyl group, in which up to two C atoms in the aryl ring(s) may be replaced by up to two heteroatoms and may have substituents attached to those ring atoms, and such substituents may have one or two heteroatoms or silicon atoms, or R 1 ~R 5 and / or R 2' ~R 5' Any two adjacent groups among may form a ring having 4 to 8 ring atoms, wherein the atoms that are part of the formed ring are saturated or unsaturated, straight or branched, C1 to C 10 Hydrocarbyl, C5-C 10 Aromatic group, C6~C 20 Alkylaryl group or C6-C 20 one or more R selected from arylalkyl groups; 12 groups, and one or more R 12 The group may have one or two heteroatoms or silicon atoms.

[0055] In formula (A), formula (B) and formula (I), each X may be the same or different and is a sigma ligand, preferably a hydrogen atom, a halogen atom, R 14 , OR 14 , OSO2CF3, OCOR 14 , S.R. 14 , N.R. 142 or PR 14 There are two units, and this allows R 14 is a linear or branched, cyclic or acyclic C1-C alkyl group which may have one or more heteroatoms belonging to Group 15 or 16; 20 -Alkyl, C2-C 20 -Alkenyl group, C2-C 20 -Alkynyl group, C6-C 20 -aryl group, C7-C 20 -Alkylaryl group or C7-C 20 -arylalkyl group, or SiR 14 3. SiHR 14 2 or SiH2R 14 This gives R 14 is preferably C 1~6 - an alkyl, phenyl or benzyl group.

[0056] The term halogen includes fluorine, chlorine, bromine and iodine atoms, preferably chlorine atoms.

[0057] More preferably, each X is independently a halogen atom or R 14 group or OR 14 group, whereby R 14 is C 1~6 - an alkyl group, a phenyl group or a benzyl group.

[0058] Most preferably, X is a methyl group, a chlorine atom or a benzyl group. Even more preferably, both X groups are the same.

[0059] According to a further preferred embodiment, the invention is provided by a metallocene complex of formula (II) below:

[0060] [ka]

[0061] where: Mt is Zr, Hf, or a mixture of Hf and Zr, wherein said mixture of Hf and Zr is a mixture of the complex of formula (II) with Zr or Hf metal; X is a sigma ligand, Y is Formula-WR y 2 - is a bridge of n is 1, 2 or 3, preferably 1 or 2, more preferably 1; W is C or Si; Each R y is as defined in formula (I), R 2 ~R 11 are independently a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic C1-C 10 Hydrocarbyl groups, C6-C 10 Aryl groups, C6-C 20 Alkylaryl group or C6-C 20 arylalkyl groups, which may have up to two heteroatoms or silicon atoms; or R 2 ~R 11 Any two adjacent groups among these may form a ring containing 4 to 8 atoms, and the atoms that are part of the formed ring may be saturated or unsaturated, linear or branched, C1 to C 10 Hydrocarbyl, C5-C 10 Aromatic group, C6~C 20 Alkylaryl group or C6-C 20 one or more R selected from arylalkyl groups; 12 may be further substituted by a group, and said one or more R 12 The group may have up to two heteroatoms or silicon atoms.

[0062] In formula (II), each X is as defined in formula (A), formula (B) and formula (I).

[0063] More preferably, each X is independently a halogen atom or R 14 group or OR 14group, whereby R 14 is C 1~6 - an alkyl group, a phenyl group or a benzyl group.

[0064] Most preferably, X is a methyl group, a chlorine atom or a benzyl group. Preferably, both X groups are the same.

[0065] In particular, it is provided that in more than 50 mol % of the complexes of formula (II), Mt is Hf.

[0066] According to one embodiment, R of formula (II) 5 ~R 11 are independently a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic C1-C 10 Hydrocarbyl groups, C6-C 10 Aryl groups, C6-C 20 Alkylaryl group or C6-C 20 an arylalkyl group, wherein up to two C atoms in the aryl ring(s) may be replaced by up to two heteroatoms and may have substituents attached to those ring atoms, and such substituents may have one or two heteroatoms or silicon atoms, or R 2 ~R 11 Any two adjacent groups among may form a ring having 4 to 8 ring atoms, wherein the atoms that are part of the formed ring are saturated or unsaturated, straight or branched, C1 to C 10 Hydrocarbyl, C5-C 10 Aromatic group, C6~C 20 Alkylaryl group or C6-C 20 one or more R selected from arylalkyl groups; 12 groups, and one or more R 12 The group may have one or two heteroatoms or silicon atoms.

[0067] According to a more preferred embodiment, the invention is provided by a metallocene complex of formula (III)

[0068] [ka]

[0069] where: Mt, X, and R 2 ~R 4 and R 6 ~R 11 is as defined in formula (II), Y is Formula-WR y 2 - The bridge is the law of nature, W is C or Si; Each R y is as defined in formula (I).

[0070] According to an even more preferred embodiment, the metallocene complex has the following formula (IV):

[0071] [ka]

[0072] where Mt, X, Y and R 4 , R 6 , R 7 , R 10 and R 11 is as defined in formula (III).

[0073] According to an even more preferred embodiment, the metallocene complex has the following formula (V):

[0074] [ka]

[0075] where Mt, X, Y, and R 6 and R 11 is as defined in formulas (III) and (IV).

[0076] In formula (V), most preferably, R 6 and R 11 is a tertiary alkyl group, such as a tert-butyl group, and X is a methyl group or a chlorine atom.

[0077] Mt is preferably Hf.

[0078] In formulas (I) to (V), each R y is more preferably a saturated or unsaturated linear, branched or cyclic C4-C 10 Hydrocarbyl groups, C6-C 10 Aryl group, or saturated or unsaturated linear, branched or cyclic C3-C 10 It is an unsaturated ring having a heteroatom of 3 to 7 ring atoms substituted with a hydrocarbyl group.

[0079] Representative preferred complexes applicable to the present invention are: Dimethylmethylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl Methyl(phenyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl (3-buten-1-yl)(methyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl (3-buten-1-yl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl (Cyclohexyl)(methyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl (Cyclohexyl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl Diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl (5-n-butylthienyl)(methyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl (5-n-butylthienyl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl (5-Methylthienyl)(methyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl (5-methylthienyl)(n-butyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl (5-Methylthienyl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl Dimethylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride Methyl(phenyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride (3-Buten-1-yl)(methyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride (3-buten-1-yl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride (Cyclohexyl)(methyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride (Cyclohexyl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride Diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride (5-n-butylthienyl)(methyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride (5-n-butylthienyl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride (5-Methylthienyl)(methyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride (5-Methylthienyl)(n-butyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride (5-Methylthienyl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride Dimethylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl Methyl(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl (3-buten-1-yl)(methyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl (3-buten-1-yl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl (Cyclohexyl)(methyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl (Cyclohexyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl Diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl (5-n-butylthienyl)(methyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl (5-n-butylthienyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl (5-Methylthienyl)(methyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl (5-methylthienyl)(n-butyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl (5-methylthienyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl Dimethylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride Methyl(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (3-buten-1-yl)(methyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (3-buten-1-yl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (Cyclohexyl)(methyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (Cyclohexyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride Diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (5-n-butylthienyl)(methyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (5-n-butylthienyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (5-Methylthienyl)(methyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (5-Methylthienyl)(n-butyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (5-methylthienyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride, and their zirconium analogues.

[0080] cocatalyst To form an active catalytic species, it is usually necessary to use a cocatalyst, as is well known in the art. It has now been discovered that the use of certain aluminum-containing cocatalysts in metallocene-based catalyst systems provides advantageous performance in high-temperature solution processes for producing ethylene copolymers.

[0081] The aluminum-containing cocatalyst used in accordance with the present invention is a solid alkylalumoxane (AlkAO), also known as alkylaluminum oxide, in which the alkyl group is C1-C6 alkyl, preferably C1-C3 alkyl. Most preferably, the cocatalyst is solid methylalumoxane (solid MAO). It is essential that the AlkAO be a solid compound.

[0082] The solid AlkAO used in the present invention as a cocatalyst is a solid aliphatic hydrocarbon insoluble C1-C6 alkylalumoxane, more preferably solid MAO.

[0083] The solid AlkAO is preferably provided as a suspension in an aliphatic hydrocarbon solvent or a mixture of aliphatic hydrocarbon solvents. Preferably, the solvent is one or more C5-C 24 Aliphatic hydrocarbons, preferably one or more C6-C 12 aliphatic hydrocarbons, including

[0084] According to a more preferred embodiment, the cocatalyst comprises one or more C5-C 24 As a suspension in an aliphatic hydrocarbon, more preferably one or more C6-C 12 Solid MAO provided as a suspension in an aliphatic hydrocarbon, particularly as a slurry in decane or a mixture of decane and hexane.

[0085] In one preferred embodiment, decane and hexane are used as a mixture of 50 to 70% by weight of decane and 50 to 30% by weight of hexane.

[0086] C5~C 24 The average particle size (APS) of the solid MAO in the aliphatic hydrocarbon or mixture thereof may vary and is preferably in the range of 2 to 20 μm, more preferably in the range of 4 to 12 μm, especially in the range of 4 to 10 μm.

[0087] The solid AlkAO suspension, preferably the solid MAO suspension, used in the present invention in the preparation of the catalyst system preferably has a solid MAO content in the range of 3 to 30 wt.%, preferably in the range of 6 to 20 wt.%, more preferably in the range of 8 to 15 wt.%.

[0088] The Al content in the solid MAO is preferably in the range of 25 to 60% by weight, preferably in the range of 30 to 50% by weight, particularly in the range of 35 to 45% by weight.

[0089] An example of such a solid MAO is commercially available from Tosoh Finechem Corporation, and its preparation is described, for example, in European Patent Application No. 2360191.

[0090] Furthermore, additional aluminum alkyl compounds can be added to the polymerization process or the catalyst composition slurry as scavengers or additional alkylating agents. Suitable aluminum alkyl compounds are compounds of the formula AlR3, where R is a linear or branched C2-C8 alkyl group.

[0091] Preferred aluminum alkyl compounds are triethylaluminum, tri-isobutylaluminum, tri-isohexylaluminum, tri-n-octylaluminum and tri-isooctylaluminum.

[0092] Thus, according to a preferred embodiment, the present invention is a catalyst system for producing ethylene copolymers in a high temperature solution process at temperatures above 100°C, said catalyst system comprising: (i) a metallocene complex of a Group 4 transition metal selected from the metallocene complexes defined in any one of formulas (I) to (V), which may be substituted and which contains two ligands selected from a cyclopentadienyl (Cp) ligand, an indenyl (Ind) ligand, and a fluorenyl (Flu) ligand; and (ii) solid alkylalumoxane cocatalysts (AlkAOs) in which the alkyl group (Alk) is a C1-C6 alkyl, preferably a C1-C3 alkyl. The catalyst system includes:

[0093] In particular, the solid alkylalumoxane cocatalyst (AlkAO) (ii) is an aliphatic C5-C 24 It is provided as a suspension in a hydrocarbon solvent or in a mixture of such aliphatic hydrocarbon solvents.

[0094] Thus, according to a preferred embodiment, the present invention provides a process for preparing an ethylene copolymer, which comprises reacting ethylene and C in a high temperature solution process at a temperature above 100° C. in the presence of a catalyst system. 4~12 and an alpha-olefin comonomer, wherein the catalyst system comprises: (i) a metallocene complex of a Group 4 transition metal selected from the metallocene complexes defined in any one of formulas (I) to (V), which may be substituted and which contains two ligands selected from a cyclopentadienyl (Cp) ligand, an indenyl (Ind) ligand, and a fluorenyl (Flu) ligand; and (ii) an aliphatic C5-C alkyl group in which the alkyl group (Alk) is C1-C6 alkyl, preferably C1-C3 alkyl; 24 A solid alkylalumoxane cocatalyst (AlkAO) provided as a suspension in a hydrocarbon solvent or a mixture of such aliphatic hydrocarbon solvents. The method includes:

[0095] From another perspective, the present invention provides, in a preferred embodiment, a method for producing ethylene C in a high temperature solution process at a temperature above 100°C. 4~12 1. Use of a catalyst system for preparing an alpha-olefin copolymer, the catalyst system comprising: (i) an optionally substituted metallocene complex of a Group 4 transition metal selected from the metallocene complexes defined in any one of formulas (I) to (V), which comprises two ligands selected from a cyclopentadienyl (Cp) ligand, an indenyl (Ind) ligand, and a fluorenyl (Flu) ligand; and (ii) an aliphatic C5-C alkyl group in which the alkyl group (Alk) is C1-C6 alkyl, preferably C1-C3 alkyl; 24 A solid alkylalumoxane cocatalyst provided as a suspension in a hydrocarbon solvent or a mixture of such aliphatic hydrocarbon solvents. The present invention provides a use of the above catalyst system, which comprises:

[0096] Preferably, the metallocene complexes used according to the present invention are the above metallocene complexes of formula (II) to formula (V), more preferably formula (III), formula (IV) and formula (V), even more preferably in particular formula (IV) and formula (V), especially formula (V).

[0097] Preparation of the catalyst system According to the present invention, the metallocene complex is capable of reacting ethylene with C in a high temperature solution polymerization process. 4~12 In combination with one or more of said cocatalysts as a catalyst system for the polymerization of alpha-olefin comonomers.

[0098] The catalyst system of the present invention comprises: a) providing solid AlkAO, preferably solid MAO, as a suspension in one or more liquid aliphatic hydrocarbon solvents; b) contacting said suspension with said metallocene complex in solid form; c) stirring the suspension for at least 2 hours; d) Obtaining the product in the form of a slurry of a solid catalyst supported on an alkylalumoxane. It is prepared by

[0099] The product from step b) or step c) may optionally be mixed with a light hydrocarbon solvent, such as a C6-C 12 It can be diluted with an alkane or a mixture thereof, whereby a diluted suspension is obtained in step d).

[0100] The product obtained from step d) is introduced into a polymerization reactor in the form of a slurry of the solid catalyst supported on the alkylalumoxane.

[0101] Thus, the catalyst system is prepared by first providing a solid AlkAO, preferably solid MAO, as a suspension in an aliphatic hydrocarbon (step a), as defined above, which suspension is then contacted with the desired solid metallocene complex (step b) in an amount to achieve the desired molar ratio of Al to metal (Al / Mt).

[0102] The suspension is then stirred at a temperature of -20 to 100°C, preferably 0 to 50°C, most preferably 20 to 40°C for at least 2 hours (aging time) to allow the metallocene complex to transfer from the solution to the solid alkylalumoxane (step c).

[0103] The suspension may be diluted with a light hydrocarbon solvent, such as a C6-C 12 It can optionally be further diluted with an alkane or mixture thereof to achieve the desired solids concentration in the slurry.

[0104] The product obtained is then in the form of a slurry of solid catalyst supported on alkylalumoxane, preferably a slurry of solid catalyst supported on MAO (step d).

[0105] Suitable amounts of cocatalyst (defined by the molar ratio Al / Mt, where Mt is the transition metal in the metallocene complex) are well known to those skilled in the art.

[0106] In the resulting catalyst system, the molar ratio of aluminum to metal ion (Mt) of the metallocene (Al / Mt) can be in the range of 100 to 650 mol / mol, preferably in the range of 150 to 450 mol / mol, and more preferably in the range of 200 to 400 mol / mol.

[0107] polymer The polymers to be produced using the catalyst system of the present invention are polymers of ethylene and C 4~12 Alpha-olefin comonomers, preferably C 4~10Copolymers with alpha-olefin comonomers such as 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc. or mixtures thereof. Preferably, 1-butene, 1-hexene or 1-octene, most preferably 1-octene, is used as the comonomer.

[0108] The comonomer content in such polymers may be up to 45 mol %, preferably 1-40 mol %, more preferably 1.5-35 mol %, and even more preferably 2-25 mol %.

[0109] The density of the polymer (measured according to ISO 1183-187) is 0.850 g / cm 3 ~0.930g / cm 3 in the range of 0.850 g / cm 3 ~0.920g / cm 3 and more preferably 0.850 g / cm 3 ~0.910g / cm 3 It is in the range of.

[0110] The melting point of the polymer to be produced (measured using DSC according to ISO 11357-3:1999) is below 130°C, preferably below 120°C, more preferably below 110°C, and more preferably below 100°C.

[0111] polymerization The catalyst system of the present invention is used to prepare ethylene copolymers as defined above in a high temperature solution polymerization process at temperatures above 100°C.

[0112] In view of the present invention, such a process is essentially based on the polymerization of a monomer and a suitable comonomer in a liquid hydrocarbon solvent in which the resulting polymer is soluble. The polymerization is carried out at a temperature above the melting point of the polymer, resulting in a polymer solution. This solution is flashed to separate the polymer from unreacted monomer and solvent. The solvent is then recovered and recycled to the process.

[0113] Solution polymerization processes are known for their short reactor residence times (compared to gas phase or slurry processes), thus allowing for very rapid grade transitions and significant flexibility in producing a wide product range in short production cycles.

[0114] According to the present invention, the solution polymerization process used is a high temperature solution polymerization process using a polymerization temperature of 100° C. or higher. Preferably, the polymerization temperature is at least 110° C., more preferably at least 150° C. The polymerization temperature can be up to 250° C.

[0115] The pressure used in the solution polymerization process according to the present invention is preferably in the range of from 10 to 100 bar, preferably from 15 to 100 bar, and more preferably from 20 to 100 bar.

[0116] The liquid hydrocarbon solvent used is preferably a linear, branched or cyclic aliphatic C 5~12 Hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha. More preferably, 6~10 A hydrocarbon solvent is used.

[0117] Advantages The novel catalyst system comprising component (i) and component (ii) can be advantageously used for the copolymerization of ethylene in a high temperature solution polymerization process.

[0118] The catalyst system according to the present invention, when used for ethylene copolymerization in the high-temperature solution polymerization process, exhibits an improved balance of productivity, comonomer incorporation capability, and molecular weight capability. The novel catalyst system broadens the range of possible metallocene complexes, allowing for a wider range of metallocene choices, since the solubility of the metallocene complexes is no longer an issue. Thus, the novel catalyst system allows for the selection of a desired complex based on the desired properties and performance, while not forgetting the cost and availability of suitable complexes.

[0119] Additionally, by using the catalyst system of the present invention, the use of borate-based cocatalysts, such as perfluorinated borates, is avoided. Furthermore, aromatic solvents are not required in preparing the catalyst system of the present invention.

[0120] Purpose The polymers produced by the catalyst systems of the present invention are useful for all kinds of finished articles, such as pipes, films (cast or blown), fibers, molded articles (e.g., injection molded, blow molded, rotomolded), extrusion coatings, and the like.

[0121] The invention will now be illustrated by reference to the following non-limiting examples.

[0122] Working Example: method

[0123] Determination of comonomer content by NMR spectroscopy Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers.

[0124] quantitative 13 C{ 1 The {H} NMR spectrum 1 H and 13 All spectra were recorded in the melt using a Bruker Advance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for C, respectively. All spectra were recorded at 150 °C, using nitrogen gas for all pneumatics. 13 Recordings were made using a C-optimized 7 mm magic-angle spinning (MAS) probehead. Approximately 200 mg of material was loaded into a 7 mm outer diameter zirconia MAS rotor and spun at 4 kHz. This configuration was chosen primarily for the high sensitivity required for rapid identification and accurate quantification. [1],[2],[3],[4] Standard single-pulse excitation was used, utilizing a transient NOE and RS-HEPT decoupling scheme with a short recycle delay of 3 s.[6],[7] A total of 1024 (1k) transients were acquired per spectrum. This configuration was chosen for its high sensitivity to low comonomer content.

[0125] quantitative 13 C{ 1 H} NMR spectra were processed, integrated, and quantitative characteristics were determined using a custom automated spectral analysis program. All chemical shifts were internally referenced to the bulk methylene signal (δ) at 30.00 ppm. [8] .

[0126] A characteristic signal corresponding to the incorporation of 1-octene was observed. [8],[9],

[10] ,

[11] ,

[12] , and all comonomer contents were calculated relative to all other monomers present in the polymer.

[0127] A characteristic signal resulting from isolated 1-octene incorporation, i.e., EEOEE comonomer sequence, was observed. Isolated 1-octene incorporation was quantified using the integral of the signal at 38.32 ppm. This integral corresponds to the integrals of the isolated (EEOEE) and isolated double non-consecutive (EEOEOEE) 1-octene sequences, respectively. * B6 region and * The two βB6B6 sites are assigned to uncleaved signals corresponding to both the * To compensate for the influence of the βB6B6 site, the integral of the ββB6B6 site at 24.7 ppm is used. O=I *B6+*βB6B6 -2 * I ββB6B6

[0128] A characteristic signal resulting from successive 1-octene incorporations, i.e., the EEOOEE comonomer sequence, was also observed and quantified using the integral of the signal at 40.48 ppm assigned to the ααB6B6 moiety, which accounts for the number of reporting sites per comonomer. OO=2* I ααB6B6

[0129] A characteristic signal resulting from isolated non-sequential 1-octene incorporation, i.e., the EEOEOEE comonomer sequence, was also observed and quantified using the integral of the signal at 24.7 ppm assigned to the ββB6B6 moiety, which accounts for the number of reporting sites per comonomer. OEO=2 * I ββB6B6

[0130] A characteristic signal resulting from isolated triple consecutive 1-octene incorporations, i.e., the EOOOOEE comonomer sequence, was also observed and quantified using the integral of the signal at 41.2 ppm assigned to the ααγB6B6B6 moiety, which accounts for the number of reporting sites per comonomer. OOO=3 / 2 * I ααγB6B6B6

[0131] If no other signals indicative of other comonomer sequences were observed, the total 1-octene comonomer content was calculated based only on the amounts of isolated (EEOEE), isolated doubly consecutive (EEOOEE), isolated non-consecutive (EEOEOEE), and isolated triple consecutive (EEOOOEE) 1-octene comonomer sequences. O 合計 =O+OO+OEO+OOO

[0132] Characteristic signals resulting from saturated end groups were observed. Such saturated end groups were quantified using the average integrals of two resolved signals at 22.84 and 32.23 ppm. The integral at 22.84 ppm is assigned to the unresolved signal corresponding to 1-octene and both the 2B6 and 2S moieties of the saturated chain ends, respectively. The integral at 32.23 ppm is assigned to the unresolved signal corresponding to 1-octene and both the 3B6 and 3S moieties of the saturated chain ends, respectively. The total 1-octene content is used to compensate for the influence of the 2B6 and 3B6 1-octene moieties. S=(1 / 2) * (I 2S+2B6 +I 3S+3B6 -2 * O total )

[0133] Ethylene comonomer content was quantified using the integral of the bulk methylene (bulk) signal at 30.00 ppm. This integral is a function of the γ and 4B6 moieties from 1-octene and δ + The total ethylene comonomer content was calculated based on the bulk integrals and compensated for the observed 1-octene sequences and end groups. E 合計 =(1 / 2) * [I バルク +2 * O+1 * OO+3 * OEO+0 * OOO+3 * S]

[0134] It should be noted that compensation of the bulk integral for the presence of isolated triple-incorporated (EEOOOEE) 1-octene sequences is not necessary, as the number of underestimated ethylene units is equal to the number of overestimated ethylene units.

[0135] The total mole fraction of 1-octene in the polymer was then calculated as follows: fO=(O 合計 / (E 合計 +O 合計 )

[0136] Total comonomer incorporation of 1-octene in weight percent was calculated from the above mole fractions in the standard manner. O[weight%]=100 * (fO * 112.21) / ((fO * 112.21)+((1-fO) * 28.05))

[0137] [1] Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol.Chem.Phys.2006;207:382. [2] Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol.Chem.Phys.2007;208:2128. [3] Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373 [4] NMR Spectroscopy of Polymers: Innovative Strategies for Complex Macromolecules,Chapter 24,401 (2011) [5] Pollard, M., Klimke, K., Graf, R., Spiess, HW, Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004;37:813. [6] Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239 [7] Griffin, JM, Tripon, C., Samoson, A., Filip, C., and Brown, SP, Mag.Res.in Chem.2007 45,S1,S198 [8] J.Randall,Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201. [9] Liu, W., Rinaldi, P., McIntosh, L., Quirk, P., Macromolecules 2001,34,4757

[10] Qiu, X., Redwine, D., Gobbi, G., Nuamthanom, A., Rinaldi, P., Macromolecules 2007,40,6879

[11] Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun.2007,28,1128

[12] Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J.Mag.Reson.187 (2007) 225

[0138] Gel Permeation Chromatography (GPC) The average molecular weights (Mz, Mw and Mn), molecular weight distribution (MWD) and their breadth, described by the polydispersity index, PDI=Mw / Mn, where Mn is the number average molecular weight and Mw is the weight average molecular weight, were determined by gel permeation chromatography (GPC) in accordance with ISO 16014-1:2003, ISO 16014-2:2003, ISO 16014-4:2003 and ASTM D6474-12.

[0139] A high-temperature GPC instrument equipped with either an infrared (IR) detector (IR4 or IR5 from PolymerChar (Valencia, Spain) or a differential refractometer (RI) from Agilent Technologies equipped with 3x Agilent-PLgel Olexis and 1x Agilent-PLgel Olexis Guard columns) was used. 1,2,4-Trichlorobenzene (TCB) stabilized with 250 mg / L of 2,6-ditertbutyl-4-methyl-phenol was used as the solvent and mobile phase. The chromatographic system was operated at 160°C with a constant flow rate of 1 mL / min. 200 μL of sample solution was injected per analysis. Data collection was performed using either Agilent Cirrus software version 3.3 or PolymerChar GPC-IR control software.

[0140] The column set was calibrated using 19 narrow MWD polystyrene (PS) standards ranging from 0.5 kg / mol to 11,500 kg / mol using universal calibration (according to ISO 16014-2:2003). The PS standards were dissolved at room temperature for several hours. Conversion of polystyrene peak molecular weights to polyolefin molecular weights was achieved using the Mark Houwink equation and the following Mark Houwink constants: K PS =19×10 -3 mL / g, α PS =0.655, K PE =39×10 -3 mL / g, α PE =0.725

[0141] A third order polynomial fit was used to fit the calibration data.

[0142] All samples were prepared in the concentration range of 0.5-1 mg / ml and dissolved at 160°C for 3 h under gentle continuous shaking.

[0143] Determination of the relative comonomer reactivity ratio R Since the total pressure is kept constant by feeding ethylene during the polymerization, the ethylene concentration in the liquid phase can be considered constant. The C8 / C2 ratio in the solution at the end of the polymerization is calculated by subtracting the amount of octene contained in the polymer from the measured composition of the latter (1-octene wt%). The reactivity ratio R of each catalyst is calculated as follows: R=[(C8 / C2) pol ] / [(C8 / C2) 液相における平均 ] where (C8 / C2) 液相における平均 is ((C8 / C2) final + (C8 / C2) 供給 ) / 2.

[0144] Average particle size (APS): Malvern Method A sample consisting of dried catalyst powder is mixed so that a representative test portion can be obtained. Approximately 50 mg of sample is placed in a 20 ml crimp-cap vial in an inert atmosphere, and the exact weight of the powder is recorded. A test solution is prepared by adding white mineral oil to the powder so that the mixture maintains a concentration of approximately 0.5 to 0.7% by weight. After the test solution is carefully mixed, an aliquot is taken and placed in a measuring cell suitable for the instrument. The measuring cell should have a distance of at least 200 μm between the two optically transparent glass plates.

[0145] Image analysis is performed at room temperature in a Malvern Morphologi 3G system. The measurement cell is placed on a microscope stage that moves precisely in all directions. Physical size measurements in the system are standardized against an internal grating or by using an external calibration plate. An area of ​​the measurement cell is selected so that the particle distribution is representative of the test solution. This area is recorded in overlapping images by a CCD camera, and the images are saved in system-specific software via a microscope with a sufficient working distance and an objective lens with 5x magnification. A diascopic light source is used, and the illumination intensity is adjusted before each run. All images are recorded using a set of four focal planes across the selected area. The collected images are analyzed by software, where the particles are individually identified by comparing them with the background using a predefined grayscale setting of the material. A classification scheme is applied to the individually identified particles, and the collected particle population can then be identified as belonging to a physical sample. Based on selection by the classification scheme, further parameters may be attributed to the sample.

[0146] Particle size is calculated as the circular equivalent (CE) diameter. The size range of particles included in the distribution is 6.8 to 200 μm. The distribution is calculated as a numerical moment ratio density function distribution, and statistical descriptors are calculated based on the numerical distribution. The numerical distribution for each bin size can be recalculated for an estimate of the volume-transformed distribution.

[0147] All graphical representations are based on 11-point smoothing functions, and the statistical descriptors of the cluster are based on the unsmoothed curves. The mode is manually determined as the peak of the smoothed frequency curve. The span is calculated as (CE D[x,0.9]-CE D[x,0.1]) / CE D[x,0.5].

[0148] chemicals Solid MAO (sMAO) was provided by Tosoh Finechem Corporation with the following information: The solid MAO (sMAO) was prepared as a slurry having 13.7 wt% sMAO, 56 wt% decane, and 30.3 wt% C6-rich cut, the average particle size (APS) of the sMAO was 5.6 microns, and the Al content in the sMAO was 42.1 wt%.

[0149] Modified MAO (MMAO-3A in heptane) was provided by Akzo.

[0150] The following metallocene complexes were used: MC1: Diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl MC2: (phenyl)(5-n-butylthienyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl

[0151] 1-Octene (99%, Sigma Aldrich) as comonomer was dried over molecular sieves and degassed with nitrogen before use.

[0152] Heptane and decane (99.9%, Sigma Aldrich) were dried under molecular sieves and degassed with nitrogen before use.

[0153] Isopar E was provided by ExxonMobil.

[0154] Triethylaluminum (TEA) was provided by Sigma Aldrich.

[0155] Cyclopentadienyl magnesium bromide was prepared according to the procedure described in the following literature [John R. Stille and Robert H. Grubbs, Intramolecular Diels-Alder Reaction of α,β-Unsaturated Ester Dienophiles with Cyclopentadiene and the Dependence on Tether Length, J. Org. Chem 1989, 54, 434-444].

[0156] Catalyst Preparation Example

[0157] a) Complex preparation:

[0158] Complex-MC1 Diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl Diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride was synthesized according to Hopf, A, Kaminsky, W., Catalysis Communications 2002;3:459.

[0159] [ka]

[0160] In a mixture of 50 ml of toluene and 50 ml of ether, [1-(η 5 -cyclopentadien-1-yl)-1-(η 5To a solution of 3.78 g (5.0 mmol) of [1-(2,7-di-tert-butylfluorenyl)-1,1-diphenylmethane]hafnium dichloride was added 7.0 mL (14.77 mmol) of 2.11 M MeMgBr in ether. The resulting mixture was refluxed for 30 minutes and then evaporated to approximately 25 mL. The resulting mixture was heated to 80-90°C and filtered while hot through a glass frit (G4) to remove insoluble magnesium salts. The filter cake was further washed with 5 x 20 mL of warm hexane. The combined filtrate was evaporated to approximately 5 mL, and then 20 mL of hexane was added to the residue. The yellow powder that precipitated from this solution was collected and dried in vacuo. This procedure yielded 3.14 g (88%) of pure [1-(η 5 -cyclopentadien-1-yl)-1-(η 5 (2,7-di-tert-butylfluorenyl)-1,1-diphenylmethane]hafnium dimethyl Elemental analysis:C 41 H 44 Calculated values ​​of Hf: C, 68.85; H, 6.20. Found values: C, 69.10; H, 6.37. 1 H NMR(CDCl3):δ8.07(d,J=8.9Hz,2H),7.95(br.d,J=7.9Hz,2H),7.85(br.d,J=7.9Hz,2H),7.44(dd,J=8.9Hz,J=1.5Hz,2H),7.37(td,J=7.6Hz,J=1.2 Hz,2H),7.28(td,J=7.6Hz,J=1.2Hz,2H),7.24~7.17(m,2H),6.26(s,2H), 6.20(t,J=2.7Hz,2H),5.45(t,J=2.7Hz,2H),1.03(s,18H),-1.90(s,6H). 13 C{ 1 H} NMR(CDCl3,):δ148.46,145.75,129.69,128.63,128.46,126.73,126.54,123.29,122.6 2,120.97,118.79,116.09,111.68,107.76,101.56,76.47,57.91,37.61,34.88,30.84.

[0161] Complex-MC2 (5-n-butyl-2-thienyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride Step 1: Synthesis of 2-butylthiophene

[0162] [ka]

[0163] in hexane n BuLi (2.43 M, 176 mL, 427.7 mmol) was added dropwise over 40 minutes to a solution of thiophene (35.2 g, 418.3 mmol) in 200 mL of THF cooled to -78°C. The mixture was stirred at 0°C for 1 hour, cooled to -40°C, and 60.2 g (439.4 mmol) of 1-bromobutane was added over 5 minutes. The reaction mixture was allowed to warm to room temperature and stirred at this temperature overnight. It was then quenched with 500 mL of water, and the resulting mixture was extracted with 3 x 250 mL of ether. The combined extracts were dried over NaSO and concentrated under reduced pressure, and the residue was distilled in vacuo to give 37.0 g (63%) of 2-butylthiophene as a slightly yellowish liquid. bp 49-50°C / 5 mmHg. 1 H NMR(600MHz, CDCl3): δ7.08(dd,J=5.1Hz,J=1.2Hz,1H),6.90(dd,J=5.1Hz,J=3.4Hz,1H),6.7 7(m,1H),2.82(t,J=7.7Hz,2H),1.70~1.62(m,2H),1.43~1.35(m,2H),0.93(t,J=7.4Hz,3H).

[0164] Step 2: Synthesis of (5-butyl-2-thienyl)(phenyl)methanone

[0165] [ka]

[0166] AlCl3 (43.8 g, 328.5 mmol) was added in aliquots over 1 h to a solution of 2-butylthiophene (41.4 g, 295.2 mmol) and benzoyl chloride (45.6 g, 324.4 mmol) in 600 mL of dichloromethane cooled in an ice-water bath. The reaction mixture was stirred for an additional 1 h at +5 °C (ice-water bath) and then poured onto 500 g of crushed ice. The organic layer was separated, and the aqueous layer was extracted with 2 × 150 mL of dichloromethane. The combined organic extracts were washed with 10% K2CO3 and dried over K2CO3. After removal of the solvent, the residue was distilled in vacuo to give 54.8 g (76%) of (5-butyl-2-thienyl)(phenyl)methanone as a yellowish liquid. bp 165-175 °C / 5 mmHg. 1 H NMR (600MHz, CDCl3): δ7.85~7.79(m,2H),7.58~7.52(m,1H),7.50~7.43(m,3H),6.85~6.83 (m,1H),2.87(t,J=7.7Hz,2H),1.74~1.66(m,2H),1.45~1.37(m,2H),0.94(t,J=7.4Hz,3H). 13 C{ 1 H} NMR(CDCl3): δ187.88,156.44,140.98,138.27,135.38,131.85,128.95,128.24,125.47,33.36,30.30,22.06,13.67.

[0167] Step 3: Synthesis of 6-phenyl-6-(5-butyl-2-thienyl)fulvene

[0168] [ka]

[0169] Cyclopentadienylmagnesium bromide (26.4 g, 154.75 mmol, 1.25 equiv.) in 200 mL of THF was added in one portion to a solution of (5-butyl-2-thienyl)(phenyl)methanone (30.16 g, 123.43 mmol) in 50 mL of THF. The resulting red mixture was stirred overnight at room temperature to give a dark red solution, which was poured into 1000 mL of water. 500 mL of ether was added, followed by 10% HCl to a slightly acidic pH. The ether extract was separated and dried over Na2SO4. Removal of the solvent under vacuum gave a dark red oil. The product was isolated by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate = 200:1, by volume). This procedure gave 14.0 g (39%) of 6-phenyl-6-(5-butyl-2-thienyl)fulvene as a red oil. 1 H NMR (600MHz, CDCl3): δ7.43~7.33(m,5H),6.90(m,1H),6.85(m,1H),6.75(m,1H),6.61(m,1H),6.47(m,1H), 6.01(m,1H),2.82(t,J=7.6Hz,2H),1.67(quintet,J=7.5Hz,2H),1.40(sextet,J=7.4Hz,2H),0.93(t,J=7.3Hz,3H). 13 C{ 1 H} NMR(CDCl3):δ152.37,144.49,141.85,141.28,141.02,133.47,132.61,131.55 ,130.79,128.65,127.38,125.13,124.86,122.76,33.50,30.11,22.21,13.76.

[0170] Step 4: Synthesis of (phenyl)(5-n-butyl-2-thienyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (one-pot reaction forms fulvene)

[0171] [ka]

[0172] in hexane n BuLi (2.43 M, 19.7 mL, 47.87 mmol) was added in one portion to a solution of 2,7-di-tert-butylfluorene (13.33 g, 47.88 mmol) in 250 mL of ether cooled to -30°C. The mixture was stirred at room temperature for 4 hours. The resulting orange solution was cooled to -30°C, and a solution of 14.0 g (47.87 mmol) of 6-phenyl-6-(5-butyl-2-thienyl)fulvene in 150 mL of ether was added in one portion. After stirring overnight at room temperature, the red reaction mixture was cooled to -50°C and 2.43 M hexanes solution was added. n 19.7 ml (47.87 mmol) of BuLi was added in one portion. The mixture was stirred at room temperature for 6 hours. The resulting dark red solution was cooled to -60 °C, and 15.34 g (47.89 mmol) of HfCl4 was added. The mixture was stirred at room temperature for 24 hours. The resulting dark red mixture was evaporated to near dryness, the residue was dried with 100 ml of n-hexane, and the resulting suspension was filtered while hot (G3). The filtrate was evaporated to dryness, and the residue was triturated with 60 ml of n-pentane. The precipitate that formed was filtered off (G3) and recrystallized from a toluene / n-hexane mixture. This procedure gave 5.8 g (15%) of (5-n-butyl-2-thienyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride. Elemental analysis:C 41 H 44 Calculated values ​​for Cl2HfS: C, 60.18; H, 5.42. Found values: C, 60.33; H, 5.64. 1H NMR(CDCl3):δ8.03(d,J=8.8Hz,2H),7.98~7.90(m,2H),7.62(dd,J=8.8Hz,J=1.4Hz,1H),7.58(dd,J= 8.8Hz,J=1.4Hz,1H),7.49(td,J=7.7Hz,J=1.2Hz,1H),7.44(br.s,1H),7.36(br.d,J=6.3Hz,2H),6.8 8~6.58(m,2H),6.37~6.28(m,3H),6.04~5.91(m,1H),5.60(dd,J=5.3Hz,J=2.7Hz,1H),2.88~2.67(br .s,2H),1.78~1.58(br.s,2H),1.50~1.35(br.s,2H),1.19(s,9H),1.06(s,9H),1.01~0.87(br.m,3H).

[0173] Step 5: Synthesis of (phenyl)(5-n-butyl-2-thienyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl

[0174] [ka]

[0175] MeMgBr (3.0 M in ether, 5.7 mL, 17.1 mmol) was added to a solution of (5-n-butyl-2-thienyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (3.5 g, 4.28 mmol) in a mixture of 25 mL of toluene and 25 mL of ether. The resulting mixture was stirred at room temperature for 3 hours and then evaporated to approximately 25 mL. The resulting suspension was filtered through a glass frit (G3) to remove insoluble magnesium salts. The filter cake was further washed with 2 x 10 mL of toluene. The combined filtrates were evaporated to near dryness, and 20 mL of n-hexane was added to the residue. The resulting mixture was filtered once again through a glass frit (G4). The mother liquor was evaporated to dryness, and the residue was dissolved in 10 mL of n-pentane. The yellow powder that precipitated from this solution overnight at −25° C. was collected and dried in vacuo. This procedure gave 2.4 g (72%) of pure (5-n-butyl-2-thienyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl as a solvate with 0.5 moles of n-hexane. Elemental analysis:C 43 H 50 HfS x 0.5 n-C6H 14 Calculated values: C, 67.34; H, 7.00. Measured values: C, 67.68; H, 7.19. 1H NMR(CDCl3):δ8.06(d,J=8.8Hz,2H),7.97~7.82(m,2H),7.47(dd,J=8.8Hz,J=1.5Hz,1H), 7.45~7.36(m,2H),7.36~7.20(m,3H),6.76~6.42(m,2H),6.26~6.13(m,3H),5.75(br.s,1H) ),5.39(dd,J=5.2Hz,J=2.7Hz,1H),2.83~2.60(br.s,2H),1.71~1.51(br.s,2H),1.47~1.2 9(br.s,2H),1.15(s,9H),1.02(s,9H),0.97~0.15(br.m,3H),-1.85(s,3H),-1.91(s,3H).

[0176] MMAO 3A Activation Procedure (Comparative Example) The catalyst solution is prepared by dissolving the desired amount of complex in the MMAO solution so that the Al / Hf molar ratio reaches 300.

[0177] For polymerization tests, aliquots of the desired solution are further diluted to 4 mL with isopar E and then injected into the polymerization reactor after different contact times.

[0178] Solid MAO Activation Procedure (for Examples of the Invention) The catalyst system is prepared by contacting a sMAO suspension with the solid complex to reach approximately 300 mol / mol sMAO / Hf and further diluting it with isopar-E. The suspension is then stirred for at least 18 hours before use.

[0179] During the first preparation, it was observed that color appeared to form in the liquid phase immediately after adding the complex to the sMAO suspension. The color disappeared after a few hours, and after 18 hours the liquid was completely colorless, indicating that all of the complex had been transferred from the solution to the solid MAO.

[0180] For the polymerization tests, the desired slurry volume of 4 mL is adjusted with isopar-E before injection into the reactor (glove box).

[0181] Polymerization procedure The same polymerization conditions were used for all complexes tested with both activators. The polymerizations were carried out in a 125 mL reactor equipped with a bottom valve. Various catalyst loadings were evaluated to achieve good temperature and pressure control and sufficient polymer production.

[0182] The reactor is charged with 71 mL of solvent (isopar E) containing a scavenger (TEA, 35 μmol) and 9 mL of 1-octene at room temperature. The temperature is then increased to 160°C, and the reactor is carefully pressurized with ethylene (25-28 bar-g). When conditions stabilize, the ethylene pressure is adjusted to 30 bar-g, and the mixture is stirred at 750 rpm for 10 minutes while feeding ethylene to maintain a constant pressure to determine the residual ethylene uptake.

[0183] After this time, the catalyst system is injected into the reactor by nitrogen overpressure. The pressure is then kept constant by feeding ethylene, and after 10 minutes, the polymerization is quenched by adding 3-4 bar of CO2 as a killing agent. The reactor is then evacuated, the temperature is reduced, and the contents are discharged into an aluminum pan. The reactor is then washed twice with isopar E, and the washings are collected in an aluminum pan. A few milligrams of Irganox 1076 (approximately 500 ppm with respect to the copolymer produced) are added. The pan is placed under a well-ventilated fume hood until the volatiles evaporate, and the residue is then dried overnight at 55°C in a vacuum oven. The product was analyzed by HT-SEC, DSC, and NMR according to the methods described in the polymer analysis section.

[0184] The results of the polymerization are shown in Table 1 below, and the polymer analysis is disclosed in Table 2 below.

[0185] [Table 1] (1) The average (C8 / C2) in the liquid phase is calculated using Aspen plus as ((C8 / C2) final + (C8 / C2) feed) / 2

[0186] [Table 2]

[0187] As can be seen from the results, the catalyst system of the present invention has a significantly higher productivity than the comparative catalyst system, and also has a higher comonomer incorporation capacity than the comparative example.

[0188] Typically, higher comonomers, such as 1-hexene or 1-octene, have lower reactivity than ethylene, which means that the polymerization catalyst will produce copolymers with a lower comonomer content than the comonomer content of the reactor liquid phase. This means that an efficient polymerization catalyst must also have as high a comonomer incorporation capacity as possible.

[0189] In addition, the molecular weight of the copolymer tends to decrease with increasing comonomer content, especially at the high polymerization temperatures and conversions typical of solution polymerization. As a result, the range of melt index values ​​(molecular weights) achievable at the lowest densities (highest comonomer contents) is often limited to an upper (lower) range.

[0190] This means that for a polymerization catalyst to be efficient, the decrease in copolymer molecular weight with increasing comonomer content should be as small as possible.

[0191] For MC1, very similar Mw is achieved with both activators, but MC1 / sMAO shows higher C8 incorporation. For MC2, testing with MMAO as the activator resulted in a lower Mw compared to sMAO at the same C8 content. The present invention may be configured as follows. [Section 1] 1. A catalyst system for producing ethylene copolymers in a high temperature solution process at temperatures above 100°C, comprising: (i) an optionally substituted metallocene complex of a Group 4 transition metal comprising at least one ligand selected from cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands; and (ii) Aliphatic C 5 ~C 24 A solid alkylalumoxane cocatalyst provided as a suspension in a hydrocarbon solvent or a mixture of such aliphatic hydrocarbon solvents. The catalyst system comprising: [Section 2] Item 1, wherein the metallocene complex in (i) has the following formula (A) or (B):

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Claims

1. Ethylene-C 4 ~C 12 1. A process for the preparation of an alpha-olefin copolymer, comprising: (i) an optionally substituted metallocene complex of a Group 4 transition metal comprising at least one ligand selected from cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands; and (ii) Aliphatic C 5 ~C 24 In hydrocarbon solvents or aliphatic C 5 ~C 24 A solid alkylalumoxane cocatalyst provided as a suspension in a mixture of hydrocarbon solvents In a high temperature solution process at temperatures above 100°C, ethylene and C are reacted in the presence of a catalyst system containing 4～12 and an alpha-olefin comonomer, The method.

2. 2. The method of claim 1, wherein the metallocene complex in (i) has the following formula (A) or (B): 【Chemistry 1】 where: Z is a ligand that coordinates to Mt, Mt is Ti, Zr, or Hf; X is a sigma ligand, L is a covalent bridge; R 1 ~R 5 are independently hydrogen atoms, C 1 ~C 10 Hydrocarbyl group, C 6 ~C 10 Aryl group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 arylalkyl groups, which may contain one or two heteroatoms or silicon atoms, where the heteroatoms belong to group 15 or 16, or R 1 ~R 5 Any two adjacent groups may form a ring having from 4 to 8 ring atoms, wherein the atoms that are part of the formed ring are selected from linear C 1 to C 10 hydrocarbyl groups, branched C 3 to C 10 Hydrocarbyl group, C 5 ~C 10 Aromatic group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 one or more R selected from arylalkyl groups; 12 group, and one or more R 12 The group may have one or two heteroatoms or silicon atoms, where the heteroatoms belong to group 15 or 16.

3. 2. The method of claim 1, wherein the metallocene complex in (i) has the following formula (A) or (B): 【Chemistry 2】 where: Z is a ligand that coordinates to Mt, Mt is Ti, Zr, or Hf; X is a sigma ligand, L is a covalent bridge; R 1 ~R 5 are independently hydrogen atoms, C 1 ~C 10 Hydrocarbyl group, C 6 ~C 10 Aryl group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 Arylalkyl groups, in which up to two C atoms in the one or more aryl rings may be replaced by up to two heteroatoms belonging to group 15 or 16 and may have substituents attached to those ring atoms, and such substituents may have one or two heteroatoms or silicon atoms, in which the heteroatoms belong to group 15 or 16, or R 1 ~R 5 Any two adjacent groups may form a ring having from 4 to 8 ring atoms, wherein the atoms that are part of the formed ring are selected from linear C 1 to C 10 hydrocarbyl, branched C 3 to C 10 Hydrocarbyl, C 5 ~C 10 Aromatic group, C 6 ~C 20 Alkylaryl or C 6 ~C 20 one or more R selected from arylalkyl groups; 12 group, and one or more R 12 The group may have one or two heteroatoms or silicon atoms, where the heteroatoms belong to group 15 or 16.

4. 2. The method of claim 1, wherein the metallocene complex in (i) has the following formula (I): 【Transformation 3】 where: Mt is Zr or Hf; X is a sigma ligand, Y is the formula -WR y 2 - is a bridge of n is 1, 2 or 3; W is C or Si; Each R y are independently hydrogen atoms, C 1 ~C 10 Hydrocarbyl group, C 6 ~C 10 Aryl group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 arylalkyl groups, each of which may contain one or two heteroatoms or silicon atoms, where the heteroatoms belong to group 15 or 16; or C 1 ~C 20 a saturated or unsaturated ring having 3 to 7 ring atoms and containing a heteroatom of Group 15 or 16, optionally substituted with a hydrocarbyl group; R 2 ~R 5 and R 2' ~R 5' are independently a hydrogen atom or C 1 ~C 10 Hydrocarbyl group, C 6 ~C 10 Aryl group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 arylalkyl groups, which may contain one or two heteroatoms or silicon atoms, where the heteroatoms belong to group 15 or 16; or R 2 ~R 5 and / or R 2' ~R 5' Any two adjacent groups may form a ring having from 4 to 8 ring atoms, the atoms that are part of the formed ring being selected from linear C 1 to C 10 hydrocarbyl, branched C 3 to C 10 Hydrocarbyl, C 5 ~C 10 Aromatic group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 one or more R selected from arylalkyl groups; 12 may be further substituted by a group, and one or more R 12 The group may have one or two heteroatoms or silicon atoms, where the heteroatoms belong to group 15 or 16, or R 2 ~R 5 and R 2’ ~R 5’ are independently hydrogen atoms, C 1 ~C 10 Hydrocarbyl group, C 6 ~C 10 Aryl group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 Arylalkyl groups, in which up to two C atoms in the one or more aryl rings may be replaced by up to two heteroatoms belonging to group 15 or 16, and may have substituents attached to those ring atoms, and such substituents may have one or two heteroatoms or silicon atoms, in which the heteroatoms belong to group 15 or 16, or R 2 ~R 5 and / or R 2' ~R 5' Any two adjacent groups may form a ring having from 4 to 8 ring atoms, wherein the atoms that are part of the formed ring are selected from linear C 1 to C 10 hydrocarbyl, branched C 3 to C 10 Hydrocarbyl, C 5 ~C 10 Aromatic group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 one or more R selected from arylalkyl groups; 12 group, and one or more R 12 The group may have one or two heteroatoms or silicon atoms, where the heteroatoms belong to group 15 or 16. Each X may be the same or different and is a sigma ligand.

5. 2. The method of claim 1, wherein the metallocene complex in (i) has the following formula (II): 【Chemistry 4】 where: Mt is Zr or Hf; Y is the formula -WR y ２ - is a bridge of n is 1, 2 or 3; W is C or Si; Each R y are independently hydrogen atoms, C 1 ~C 10 Hydrocarbyl group, C 6 ~C 10 Aryl group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 arylalkyl groups, each of which may contain one or two heteroatoms or silicon atoms, where the heteroatoms belong to group 15 or 16; or C 1 ~C 20 a saturated or unsaturated ring having 3 to 7 ring atoms and containing a heteroatom of Group 15 or 16, optionally substituted with a hydrocarbyl group; each X is a sigma ligand; R 2 ~R 11 are independently a hydrogen atom or C 1 ~C 10 Hydrocarbyl group, C 6 ~C 10 Aryl group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 arylalkyl groups, which may have up to two heteroatoms or silicon atoms, where the heteroatoms belong to Group 15 or 16; or R 2 ~R 11 Any two adjacent groups may form a ring containing from 4 to 8 atoms, the atoms that are part of the formed ring being selected from linear C 1 to C 10 hydrocarbyl, branched C 3 to C 10 Hydrocarbyl, C 5 ~C 10 Aromatic group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 one or more R selected from arylalkyl groups; 12 may be further substituted by a group, and one or more R 12 The group may have up to two heteroatoms or silicon atoms, where the heteroatoms belong to group 15 or 16, or R 2 ~R 11 are independently hydrogen atoms, C 1 ~C 10 Hydrocarbyl group, C 6 ~C 10 Aryl group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 Arylalkyl groups, in which up to two C atoms in the one or more aryl rings may be replaced by up to two heteroatoms belonging to group 15 or 16 and may have substituents attached to those ring atoms, and such substituents may have one or two heteroatoms or silicon atoms, in which the heteroatoms belong to group 15 or 16, or R 2 ~R 11 Any two adjacent groups may form a ring having from 4 to 8 ring atoms, wherein the atoms that are part of the formed ring are selected from linear C 1 to C 10 hydrocarbyl, branched C 3 to C 10 Hydrocarbyl, C 5 ~C 10 Aromatic group, C 6 ~C 20 Alkylaryl or C 6 ~C 20 one or more R selected from arylalkyl groups; 12 group, and one or more R 12 The group may have one or two heteroatoms or silicon atoms, where the heteroatoms belong to group 15 or 16.

6. 1. A catalyst system for producing ethylene copolymers in a high temperature solution process at temperatures above 100°C, comprising: (i) a metallocene complex having the formula (II): 【Chemistry 4】 where: Mt is Zr or Hf; Y is the formula -WR y ２ - is a bridge of n is 1, 2 or 3; W is C or Si; Each R y are independently hydrogen atoms, C 1 ~C 10 Hydrocarbyl group, C 6 ~C 10 Aryl group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 arylalkyl groups, each of which may contain one or two heteroatoms or silicon atoms, where the heteroatoms belong to group 15 or 16; or C 1 ~C 20 a saturated or unsaturated ring having 3 to 7 ring atoms and containing a heteroatom of Group 15 or 16, optionally substituted with a hydrocarbyl group; each X is a sigma ligand; R 2 ~R 11 are independently a hydrogen atom or C 1 ~C 10 Hydrocarbyl group, C 6 ~C 10 Aryl group, C 6 ~C 20 Alkylaryl group or C 6 ~C 20 arylalkyl groups, which may have up to two heteroatoms or silicon atoms, where the heteroatoms belong to Group 15 or 16; and (ii) Aliphatic C 5 ~C 24 In hydrocarbon solvents or aliphatic C 5 ~C 24 A solid alkylalumoxane cocatalyst provided as a suspension in a mixture of hydrocarbon solvents The catalyst system comprising:

7. 7. The catalyst system of claim 6, wherein the metallocene complex in (i) has the formula (V): 【Transformation 5】 where Mt, X, Y, and R 6 and R 11 is as defined in claim 6.

8. The solid alkylalumoxane cocatalyst in (ii) is a cocatalyst in which the alkyl group is C 1 ~C 6 8. The catalyst system according to claim 6 or 7, which is a solid alkylalumoxane (AlkAO) in which Alk is alkyl.

9. 9. The catalyst system according to any one of claims 6 to 8, wherein the co-catalyst is solid methylalumoxane (MAO).

10. 10. The catalyst system of claim 9, wherein the Al content in the solid MAO is in the range of 25 to 60 wt.%.

11. The solid alkylalumoxane cocatalyst comprises one or more C 6 ~C 12 The catalyst system of any one of claims 6 to 10, provided as a suspension in an aliphatic hydrocarbon solvent.

12. 7. The catalyst system of claim 6, wherein the solid alkylalumoxane cocatalyst in suspension has an average particle size of from 2 to 20 μm.

13. 7. The catalyst system of claim 6, wherein the content of solid alkylalumoxane (AlkAO) in the suspension is in the range of 3 to 30% by weight.

14. 1. A method for preparing a catalyst system, comprising: a) 1 or more C 5 ~C 24 providing a solid alkylalumoxane (AlkAO) as a suspension in a liquid aliphatic hydrocarbon solvent; b) contacting the suspension of step a) with the metallocene complex as defined in any one of claims 1 to 7 in solid form, c) stirring the suspension for at least 2 hours; d) Obtaining the product in the form of a slurry of a solid catalyst supported on an alkylalumoxane. The method comprising:

15. The product from step b) or step c) is C 6 ~C 12 15. The process of claim 14, wherein the solvent is diluted with a light hydrocarbon solvent selected from alkanes or mixtures thereof.

16. Ethylene and C 4～12 16. Use of the catalyst system according to any one of claims 6 to 13 or the catalyst system prepared by the method according to claim 14 or 15 in a high temperature solution process at temperatures above 100°C for copolymerizing alpha-olefin comonomers.

17. 10. The method of claim 1, wherein the polymerization comprises: a) at a polymerization temperature of at least 110°C, b) at a pressure in the range of 10 to 100 bar, and c) Unsubstituted or C 1～4 substituted by alkyl groups, C 5～12 In a liquid hydrocarbon solvent selected from the group of hydrocarbons The method is carried out.

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