Improved preparation of catalyst systems

Abstract

Improved process for the preparation of silica-supported catalyst systems comprising a specific class of metallocene complexes in combination with a boron-containing cocatalyst and an aluminoxane cocatalyst; and uses of the novel improved catalyst systems.

Description

[0001] The present invention relates to an improved process for preparing a silica-supported catalyst system comprising a specific class of metallocene complexes in combination with a boron-containing cocatalyst and an aluminoxane cocatalyst. The present invention also relates to the use of the novel, improved catalyst system.

[0002] Metallocene catalysts have been used for many years to make polyolefins. Numerous academic and patent publications describe the use of these catalysts in olefin polymerization. Metallocenes are now used industrially, especially to produce polyethylene and polypropylene, usually using cyclopentadienyl-based catalyst systems with different substitution patterns.

[0003] In order to obtain some desired polymer properties, metallocene catalysts are used in propylene polymerization. Suitable metallocene catalysts should have high activity and high productivity. Several attempts have been described in the patent literature.

[0004] WO 2002 / 040549 discloses an olefin polymerization catalyst comprising a metallocene compound, a supported activator such as MAO, an ionizing activator such as dimethylanilinium tetrakis(pentafluorophenyl)borate and triphenylcarbonium tetrakis(pentafluorophenyl)borate and a carrier.

[0005] US Patent Publication No. 2006 / 0116490 discloses a metallocene catalyst for olefin polymerization, which comprises a combination of a carrier and an ionic compound such as aluminoxane and tetrakis(pentafluorophenyl)borate as a cocatalyst, and a metallocene compound. These catalysts have the disadvantage of low activity.

[0006] As an improvement, EP2545084 proposes to provide a highly active supported metallocene catalyst, in which a metallocene compound having a ligand substituted by an alkoxide or an aryl oxide is incorporated into a conventional supported metallocene catalyst, and a borate compound is incorporated as a second co-catalyst to exhibit a significantly superior catalyst activity.

[0007] The catalyst system comprises a carrier, a first co-catalyst (e.g., MAO) layer laminated on the carrier, a first metallocene compound layer laminated on the first co-catalyst layer; and a second co-catalyst layer laminated on the first metallocene compound layer, wherein the second co-catalyst layer is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0008] Although compared with the catalyst described in WO 2002 / 040549 and US 2006 / 0116490, this catalyst system shows improved catalyst activity, can produce polyolefin (especially polyethylene) with high molecular weight, narrow molecular weight distribution and prevent fouling in the preparation process, from the perspective of even higher activity and productivity, there is still room for improvement in catalyst behavior. In addition, from the perspective of EP2545084, it is desirable to simplify the preparation process, for example to reduce the number of preparation steps.

[0009] Thus, especially in the case of copolymerization between propylene and α-olefins having 4 to 8 C atoms and / or ethylene to form propylene copolymers, it is desirable to find catalyst systems that provide high activity and productivity. In the production of high molecular weight polypropylene polymers, especially homopolymers, the desired catalysts should also have improved performance. Various prior art references target one or more of these features.

[0010] WO 02 / 02576 describes, inter alia, rac-Me2Si[2-Me-4-(3,5-Me2Ph)Ind]2ZrCl2 and its use in the production of high molecular weight and high melting point polypropylene.

[0011] The metallocene catalyst activated with MAO or borate of WO 02 / 02576 is carried on a silica support and gives iPP with Tm between 156°C and 159°C at a polymerization temperature of 60°C or 70°C but with poor catalyst activity.

[0012] WO 2013 / 007650 describes certain asymmetric catalysts containing an alkoxy group in the 5-position of one of the rings, such as dimethylsilylene (η5-6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)-(η5-6-tert-butyl-2-methyl-4-phenyl-1H-inden-1-yl) zirconium dichloride. The catalyst is prepared using a specific emulsion / solidification technique and activated only with MAO.

[0013] Despite its good performance, the catalyst based on this reference is limited in terms of polypropylene homopolymer melting temperature, productivity at low MFR. In addition, the overall productivity of the catalyst still needs to be improved. In addition, it is desired to simplify the production of the catalyst system. According to WO 2013 / 007650, an additional prepolymerization step is required before the catalyst system can be used.

[0014] WO 2018 / 122134 describes in particular the complex rac-trans-dimethylsilanediyl[2-methyl-4-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-dicyclopentadienylbenzo-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, which is activated solely with MAO and supported on silica.

[0015] WO 2014 / 060540 describes in particular the use of the complex dimethylsilylene(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butyl-phenyl)indenyl)zirconium dichloride in combination with MAO and a borate cocatalyst. The catalyst is prepared using a special emulsion / curing technique as described above, which includes an off-line prepolymerization step before the catalyst system is used. In addition, the activity of the prepolymerized catalyst system is quite low.

[0016] Although a great deal of work has been done in the field of metallocene catalysts, some problems still exist, which are mainly related to the productivity or activity of the catalysts. In addition, a straightforward and cost-effective catalyst preparation procedure is desired.

[0017] The present inventors have identified an improved process for the preparation of a silica supported catalyst system consisting of a specific class of metallocene complexes in combination with a boron-containing cocatalyst and an aluminoxane cocatalyst which results in improved polymerization behavior, higher catalyst productivity, improved performance in the production of high molecular weight propylene polymers such as propylene homopolymers and propylene random copolymers and is therefore ideal for the production of high molecular weight propylene homopolymers, propylene random copolymers, especially propylene-ethylene random copolymers, and also suitable heterophasic propylene copolymers. The specific catalyst system provides a higher degree of flexibility / freedom in the design of propylene polymers compared to the catalyst systems of the prior art.

[0018] Additionally, the new preparation procedure is more robust and requires fewer steps than existing techniques. Summary of the invention

[0019] From one aspect, the present invention provides a method for preparing a supported catalyst system, wherein the catalyst system comprises

[0020] (i) metallocene complexes;

[0021] (ii) a cocatalyst system comprising a boron-containing cocatalyst and an aluminoxane cocatalyst; and

[0022] (iii) a porous inorganic support,

[0023] The method comprises the following steps

[0024] a) reacting the porous inorganic carrier with an aluminoxane co-catalyst in a hydrocarbon solvent to obtain an aluminoxane co-catalyst treated carrier;

[0025] b) reacting a metallocene complex with an aluminoxane cocatalyst in a hydrocarbon solvent, wherein the amount of the aluminoxane cocatalyst added in step a) is 75.0 wt % to 97.0 wt % of the total amount of the aluminoxane cocatalyst, and the amount of the aluminoxane cocatalyst added in step b) is 3.0 wt % to 25.0 wt % of the total amount of the aluminoxane cocatalyst;

[0026] c) adding the boron-containing cocatalyst to the solution obtained in step b) to obtain a solution of a metallocene complex, a boron-containing cocatalyst and an aluminoxane cocatalyst, wherein the boron-containing cocatalyst is added in an amount such that the boron / M molar ratio of the feed amount reaches a range of 0.1:1 to 10:1;

[0027] d) adding the solution obtained in step c) to the aluminoxane cocatalyst treated support obtained in step a) and optionally

[0028] e) drying the supported catalyst system thus obtained.

[0029] In one embodiment, the metallocene complex is an optionally bridged biscyclopentadienyl type metallocene complex or a constrained geometry metallocene complex. Preferred metallocene complexes are those having formula (I)-(III):

[0030] (Cp)2MXr (II) or

[0031] wherein each X is independently a σ donor ligand;

[0032] M is Ti, Zr, Hf, Y, Sc, La or a lanthanide, preferably Ti, Zr or Hf;

[0033] Each Cp is independently an unsubstituted or substituted cyclopentadienyl-containing ligand or an unsubstituted or substituted fused cyclopentadienyl-containing ligand;

[0034] Q is -O or -NW or -PW;

[0035] W is an organic group or H;

[0036] L is a carbon, silicon or germanium based bridge with one to four backbone atoms connecting the ligands; and

[0037] r is an integer such that the oxidation state of the metal is satisfied.

[0038] Any Cp ligand is preferably a substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted dicyclopentaphenyl ligand or a substituted or unsubstituted fluorenyl ligand.

[0039] L is preferably a divalent bridge based on carbon, silicon or germanium, wherein one or two backbone atoms connect the ligands.

[0040] Viewed from another aspect, the present invention provides a method for preparing a supported catalyst system, wherein the catalyst system comprises

[0041] (i) a metallocene complex having the formula (IV):

[0042]

[0043] in

[0044] Each X is independently a σ donor ligand,

[0045] M is Zr or Hf;

[0046] L is a divalent bridge based on carbon, silicon or germanium, wherein one or two backbone atoms connect the ligands;

[0047] Each Ar is an aryl or heteroaryl group having 3 to 20 carbon atoms, such as a phenyl ring or a 5-membered or 6-membered heteroaryl ring;

[0048] Each R 1 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - a hydrocarbon group, and optionally, two adjacent R 1 The groups may be part of a ring including the carbon to which they are bonded,

[0049] Each R 2 are independently the same or may be different and are CHR 8’ -R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 -aryl or optionally substituted by one to three R 11 A heteroaryl group having 3 to 20 carbon atoms substituted by a group, and R 8’ Is H or C 1-6 alkyl;

[0050] R 3It is a straight chain or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -Alkaryl or C6-C 20 - aryl;

[0051] R 4 is C(R 9 )3 groups, wherein R 9 is a straight-chain or branched C1-C6-alkyl group;

[0052] R 5 is hydrogen or an aliphatic C1-C ... 20 - hydrocarbon group;

[0053] R 6 is hydrogen or an aliphatic C1-C ... 20 - a hydrocarbon group; or

[0054] R 5 and R 6 can be formed together optionally by n R 10 A 5-membered saturated carbon ring substituted with a radical, wherein n is 0 to 4;

[0055] Each R 10 Same or different, and can be C1-C 20 -hydrocarbon, or a C1-C ... 20 - hydrocarbon group;

[0056] R 7 is H or linear or branched C1-C6-alkyl or optionally substituted by one to three R 11 A substituted aryl or heteroaryl group having 3 to 20 carbon atoms, such as a phenyl ring or a 5-membered or 6-membered heteroaryl ring; and

[0057] Each R 11 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - hydrocarbon group;

[0058] (ii) a cocatalyst system comprising a boron-containing cocatalyst and an aluminoxane cocatalyst; and

[0059] (iii) a porous inorganic support,

[0060] The method comprises the following steps

[0061] a) reacting the porous inorganic carrier with an aluminoxane co-catalyst in a hydrocarbon solvent to obtain an aluminoxane co-catalyst treated carrier;

[0062] b) reacting a metallocene complex having formula (IV) with an aluminoxane cocatalyst in a hydrocarbon solvent, wherein the amount of the aluminoxane cocatalyst added in step a) is 75.0 wt % to 97.0 wt % of the total amount of the aluminoxane cocatalyst, and the amount of the aluminoxane cocatalyst added in step b) is 3.0 wt % to 25.0 wt % of the total amount of the aluminoxane cocatalyst;

[0063] c) adding the boron-containing cocatalyst to the solution obtained in step b) to obtain a solution of a metallocene complex having formula (IV), a boron-containing cocatalyst and an aluminoxane cocatalyst, wherein the boron-containing cocatalyst is added in an amount such that the molar ratio of boron / M in the feed amount reaches a range of 0.1:1 to 10:1;

[0064] d) adding the solution obtained in step c) to the aluminoxane cocatalyst treated support obtained in step a); and optionally

[0065] e) drying the supported catalyst system thus obtained.

[0066] From one aspect, the present invention provides a method for preparing a supported catalyst system, the catalyst system comprising

[0067] (i) a metallocene complex having the formula (V):

[0068]

[0069] in

[0070] M is Zr or Hf,

[0071] Each X is independently a σ donor ligand,

[0072] L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C ... 20 - a hydrocarbon group, or, optionally, two R' groups together may form a ring,

[0073] Each R 1 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -Alkaryl or C 6-20-aryl or OY group, where Y is C 1-10 - a hydrocarbon group, and optionally, two adjacent R 1 The groups may be part of a ring including the phenyl carbon to which they are bonded,

[0074] Each R 2 are independently the same or may be different and are CH2-R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C3-8-cycloalkyl, C 6-10 - aryl,

[0075] R 3 It is a straight chain or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -Alkaryl or C6-C 20 - aryl,

[0076] R 4 is C(R 9 )3 groups, wherein R 9 is a straight-chain or branched C1-C6-alkyl group,

[0077] R 5 is hydrogen or an aliphatic C1-C ... 20 - hydrocarbon group;

[0078] R 6 is hydrogen or an aliphatic C1-C ... 20 - a hydrocarbon group; or

[0079] R 5 and R 6 can be optionally replaced by n R 10 The group is substituted with the indenyl ring fused to a portion of the 5-membered ring, n is 0 to 4;

[0080] Each R 10 Same or different, and can be C1-C 20 -hydrocarbon, or a C1-C ... 20 - hydrocarbon group;

[0081] R 7 is H or linear or branched C1-C6-alkyl or optionally substituted by one to three R 11 a radical-substituted aryl or heteroaryl group having 6 to 20 carbon atoms,

[0082] Each R11 are independently the same or may be different and are hydrogen, straight or branched C6-C 20 -alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - a hydrocarbon group,

[0083] (ii) a cocatalyst system comprising a boron-containing cocatalyst and an aluminoxane cocatalyst; and

[0084] (iii) a silica support,

[0085] The method comprises the following steps

[0086] a) reacting the silica carrier with an aluminoxane co-catalyst in a hydrocarbon solvent to obtain an aluminoxane co-catalyst treated carrier;

[0087] b) reacting a metallocene complex having formula (V) with an aluminoxane cocatalyst in a hydrocarbon solvent, wherein the amount of the aluminoxane cocatalyst added in step a) is 75.0 wt% to 97.0 wt% of the total amount of the aluminoxane cocatalyst, and the amount of the aluminoxane cocatalyst added in step b) is 3.0 wt% to 25.0 wt% of the total amount of the aluminoxane cocatalyst;

[0088] c) adding the boron-containing cocatalyst to the solution obtained in step b) to obtain a solution of a metallocene complex having formula (V), a boron-containing cocatalyst and an aluminoxane cocatalyst, wherein the boron-containing cocatalyst is added in an amount such that the boron / M molar ratio of the feed amount reaches a range of 0.1:1 to 10:1;

[0089] d) adding the solution obtained in step c) to the aluminoxane cocatalyst treated support obtained in step a); and

[0090] e) drying the supported catalyst system thus obtained.

[0091] By preparing the catalyst system according to the invention, very high catalyst system activities and productivity can be achieved.

[0092] Thus, according to a further embodiment, the present invention relates to a process for producing olefin polymers using the specific catalyst system of the present invention, wherein the olefin comprises an olefin having 2 to 12 C atoms, preferably 2 to 8 C atoms, or a mixture thereof, typically ethylene or propylene olefin, with a comonomer of a selected monomer having 2 to 6 C atoms. In particular, the present invention relates to a process for producing propylene polymers, such as propylene homopolymers, propylene random copolymers or heterophasic propylene copolymers, using the specific catalyst system as defined above.

[0093] definition

[0094] Throughout this specification, the following definitions apply.

[0095] The term "C 1-20 -alkyl" includes C 1-20 -alkyl, C 2-20 -Alkenyl, C 2-20 -Alkynyl, C 3-20 -cycloalkyl, C 3-20 -cycloalkenyl, C 6-20 -Aryl, C 7-20 -alkylaryl or C 7-20 - aralkyl or mixtures of these groups, for example cycloalkyl substituted by alkyl. Straight-chain and branched hydrocarbon groups cannot contain cyclic units. Aliphatic hydrocarbon groups cannot contain aromatic rings.

[0096] Unless otherwise stated, the preferred C 1-20 -The hydrocarbon group is C 1-20 -alkyl, C 4-20 -cycloalkyl, C 5-20 -cycloalkyl-alkyl, C 7-20 -Alkaryl, C 7-20 -aralkyl or C 6-20 -Aryl, especially C 1-10 -alkyl, C 6-10 -Aryl or C 7-12 -aralkyl, such as C 1-8 -alkyl. The most particularly preferred hydrocarbon radicals are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C 5-6 - cycloalkyl, cyclohexylmethyl, phenyl or benzyl.

[0097] When referring to the complex definition, the term "halogen" includes fluorine, chlorine, bromine and iodine groups, especially chlorine or fluorine groups.

[0098] Any group containing "one or more heteroatoms belonging to Groups 14-16 of the Periodic Table of the Elements" preferably represents O, S or N. The N group may be in the form of -NH- or -NR"-, wherein R" is C1-C 10 -alkyl. For example, there may be 1 to 4 heteroatoms. A group containing one or more heteroatoms belonging to Groups 14 to 16 of the Periodic Table of the Elements may also be an alkoxy group, for example C1-C 10 -alkoxy, whereby the heteroatom may be located at the end of the group and bonded to an adjacent atom.

[0099] The oxidation state of a metal ion is determined primarily by the nature of the metal ion in question and the stability of each metal ion's respective oxidation state.

[0100] It will be appreciated that in the complexes of the invention the metal ion M is coordinated by the ligand X in order to satisfy the valence of the metal ion and to fill its available coordination sites. The nature of these σ-ligands may vary widely.

[0101] The term "C4 phenyl ring" relates to a substituted phenyl ring attached to the 4-position of an indenyl or dicyclopentaphenyl ring, respectively. The numbering of these rings will be apparent from the structures indicated herein.

[0102] Catalyst activity is defined in this application as the amount of polymer produced / g catalyst / h. Catalyst metal activity is defined here as the amount of polymer produced / g metal / h. The term productivity is sometimes also used to indicate catalyst activity, but here it means the amount of polymer produced per unit weight of catalyst.

[0103] Unless otherwise stated, the term "molecular weight" is used herein to refer to the weight average molecular weight Mw. DETAILED DESCRIPTION

[0104] The present invention relates to an improved process for the preparation of a supported catalyst system comprising a metallocene complex in combination with a boron-containing cocatalyst and an aluminoxane cocatalyst, thus being an ideal catalyst system for propylene polymerization.

[0105] The metallocene catalyst complexes of the present invention may be symmetrical or asymmetrical. Asymmetrical simply means that the two ligands forming the metallocene are different, i.e., each ligand carries a chemically different set of substituents.

[0106] Metallocene catalyst complex of the present invention can be the chiral racemic bridged bis-indenyl metallocene in its trans configuration.Metallocene of the present invention is C2 symmetric, or C1 symmetric.When they are C1 symmetric, they still keep pseudo-C2 symmetry, because they keep C2 symmetry near metal center, but not so around ligand.According to their chemical property, in the synthesis process of complex, meso form and racemic enantiomer pair (in the case of C2 symmetric complex) or trans and cis enantiomer pair (in the case of C1 symmetric complex) are formed.For purposes of the present invention, racemic-trans refers to that two indenyl ligands are oriented in opposite directions relative to cyclopentadienyl-metal-cyclopentadienyl plane, and racemic-cis refers to that two indenyl ligands are oriented in the same direction relative to cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the figure below.

[0107]

[0108] The chemical formulae herein are intended to encompass both the cis and trans configurations.Preferred metallocene catalyst complexes are in the trans configuration.

[0109] The metallocene catalyst complex of the present invention can adopt the form of racemic-trans isomer.Therefore, it is desirable that at least 95% mol, such as at least 98% mol, and especially at least 99% mol of the metallocene catalyst complex is in the racemic-trans isomer form.

[0110] In the metallocene catalyst complex of the present invention, the following are preferably applicable.

[0111] The metallocene complex may be any biscyclopentadienyl-type complex, especially a bridged biscyclopentadienyl-type complex, or it may be a constrained geometry metallocene catalyst.

[0112] In any of the formulae of the present invention, the following preferred features apply.

[0113] M may be any Group 3 or Group 4 metal or a lanthanide metal. M is preferably Zr or Hf, preferably Zr.

[0114] Each X is independently a sigma donor ligand. Thus, each X may be the same or different and is preferably a hydrogen atom, a halogen atom, a linear or branched, cyclic or acyclic C 1-20 -alkyl or -alkoxy, C 6-20 -Aryl, C 7-20 -Alkaryl or C 7-20 - aralkyl; optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table.

[0115] In one embodiment, the X group can be a trihydrocarbylsilyl group, a C 1-10 -alkoxy, C 1-10 Alkoxy-C 1-10 -alkyl- or amide-.

[0116] The term halogen includes fluorine, chlorine, bromine and iodine groups, preferably chlorine groups. The term heteroatom belonging to Groups 14 to 16 of the periodic table includes, for example, Si, N, O or S.

[0117] More preferably, each X is independently a hydrogen atom, a halogen atom, a linear or branched C 1-6 -alkyl or C 1-6 - alkoxy, phenyl or benzyl.

[0118] Still more preferably, each X is independently a halogen atom, a linear or branched C 1-4 -alkyl or C 1-4 -alkoxy, phenyl or benzyl.

[0119] Most preferably, each X is independently chloro, benzyl or methyl.

[0120] Preferably, the two X groups are identical.

[0121] The most preferred options for the two X groups are two chlorides, two methyl groups or two benzyl groups.

[0122] W is preferably C 1-20 Hydrocarbons, especially C 1-10 alkyl.

[0123] L is a bridge based on carbon, silicon or germanium. Between the two ligands there are one to four, for example one or two main chain connecting atoms, for example structures such as ligand-C-ligand (one main chain atom) or ligand-Si-Si-ligand (two main chain atoms).

[0124] The bridging atom may carry other groups. For example, suitable bridging ligands L are selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C2-atom optionally containing one or more heteroatoms of Groups 14-16 of the Periodic Table or fluorine atoms. 20 - a hydrocarbon group, or, optionally, two R' groups together may form a ring. In one embodiment, R' may be an alkyl group having 1 to 10 carbon atoms substituted by an alkoxy group having 1 to 10 carbon atoms.

[0125] The term heteroatom belonging to Groups 14 to 16 of the periodic table includes, for example, Si, N, O or S.

[0126] Preferably, L is -R'2Si-, ethylene or methylene.

[0127] In the formula -R'2Si-, each R' is preferably independently C1-C 20 -hydrocarbon group. Therefore, the term C 1-20 -Hydrocarbon includes C 1-20 -alkyl, C 2-20 -Alkenyl, C 2-20 -Alkynyl, C 3-20 -cycloalkyl, C 3-20 -cycloalkenyl, C 6-20 -Aryl, C 7-20 -alkylaryl or C 7-20 -aralkyl or of course mixtures of these groups, for example cycloalkyl substituted by alkyl. Unless otherwise specified, preferred C 1-20 -The hydrocarbon group is C 1-20 -alkyl, C 4-20 -cycloalkyl, C 5-20 -cycloalkyl-alkyl, C 7-20 -Alkaryl, C 7-20 -aralkyl or C 6-20 -Aryl.

[0128] In one embodiment, the formula -R'2Si-, represents a silacycloalkanediyl group, such as silacyclobutane, silacyclopentane or 9-silafluorene.

[0129] Preferably, the two R' groups are the same. Preferably, if R' is C1-C 10 -Hydrocarbon or C6-C 10 - aryl, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C 3-8 -cycloalkyl, cyclohexylmethyl, phenyl or benzyl, then more preferably, both R' are C1-C6-alkyl, C 5-6 -cycloalkyl or C6-aryl, and most preferably, both R' are methyl, or one is methyl and the other is cyclohexyl. Most preferably, the bridge is -Si(CH3)2-.

[0130] Ar is an aryl or heteroaryl group having 3 to 20 carbon atoms, such as a phenyl ring or a 5- or 6-membered heteroaryl ring; Ar is preferably a phenyl group or a 5- or 6-membered heteroaryl ring, such as a furanyl, phenylthio or pyridyl ring. However, it is preferred if the Ar group is a phenyl group.

[0131] Preferably, when the Ar group is phenyl, then the R1 substituents are located at the 3, 4, 5-positions of the ring (with the 1-position being attached to the indenyl ring).

[0132] Each R 1 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -Alkaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - a hydrocarbon group, and optionally, two adjacent R 1 The groups may be part of a ring including the phenyl carbon to which they are bonded.

[0133] Preferably, each R 1 are independently identical or may be different and are hydrogen, or straight-chain or branched C1-C6-alkyl, such as methyl or tert-butyl.

[0134] For example, it is possible that the Ar ring, such as the C4-phenyl ring, is unsubstituted (ie, R 1 is hydrogen), or is substituted only at the para position, such as 4'-tert-butylphenyl, or is disubstituted at the 3' and 5' positions, such as 3',5'-dimethylphenyl or 3',5'-di-tert-butylphenyl. In addition, the two phenyl rings may have the same substitution pattern, or the two phenyl rings may have different substitution patterns.

[0135] Therefore, if one or both R 1If two R1 groups are H, the remaining R1 group is preferably in the para position. If one R 1 If the group is H, then the remaining R 1 The group is preferably in the meta position.

[0136] Each R 2 are independently the same or may be different and are CHR 8 '-R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 -aryl, optionally substituted by one to three R 11 A heteroaryl group having 3 to 20 carbon atoms substituted by a group, and R 8’ Is H or C 1-6 alkyl.

[0137] R 8’ Preferred is H or methyl, especially H.

[0138] Each R 2 Preferably, they are independently the same or may be different and are CH2-R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C3-8-cycloalkyl, C 6-10 -Aryl.

[0139] Preferably, the two R 2 Same and CH2-R 8 Group, where R 8 is H or a linear or branched C1-C4-alkyl group, more preferably, two R 2 Same and CH2-R 8 Group, where R 8 is H or a linear or branched C1-C3-alkyl group. Most preferably, both R 2 They are all methyl.

[0140] R 3 It is a straight chain or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -Alkaryl or C6-C 20 -Aryl.

[0141] R 3 Preferably it is a straight-chain or branched C1-C6-alkyl or C 6-20- aryl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably straight-chain C1-C4-alkyl, more preferably C1-C2-alkyl, most preferably methyl.

[0142] R 4 Preferably C(R 9 )3 groups, wherein R 9 is a straight-chain or branched C1-C6-alkyl group. 9 The same or different, where R 9 is a straight-chain or branched C1-C4-alkyl group, more preferably R 9 are identical and are C1-C2-alkyl. Most preferably, R 4 is tert-butyl, and therefore all R 9 The groups are all methyl.

[0143] In one embodiment of the present invention, R 5 and R 6 are independently the same or may be different and are hydrogen or an aliphatic C1-C2 optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table of the Elements. 20 - a hydrocarbon group, such as an alkyl group or an alkoxy group, for example C1-C 10 -alkyl or -alkoxy.

[0144] Preferably, R 5 and R 6 are independently identical or may be different and are hydrogen or a linear or branched C1-C6 alkyl or C1-C6 alkoxy group.

[0145] More preferably, R 5 and R 6 are independently identical or may be different and are hydrogen or straight-chain or branched C1-C4-alkyl or C1-C4-alkoxy.

[0146] In another embodiment, R 5 and R 6 can be optionally replaced by n R 10 The 5-membered ring fused to the indenyl ring is substituted with a group, n is 0 to 4, preferably 0 or 2, and more preferably 0, wherein each R 10 Can be the same or different and can be C1-C 20 -hydrocarbon, or a C1-C ... 20 - Hydrocarbyl; preferably straight-chain or branched C1-C6-alkyl.

[0147] R 7 is H or linear or branched C1-C6-alkyl or optionally substituted by 1 to 3 R11 The aryl or heteroaryl group is substituted with a radical and has 6 to 20 carbon atoms.

[0148] Preferably, R 7 is H or optionally 1 to 3 R 11 A substituted aryl group having 6 to 10 carbon atoms, more preferably R 7 is H or optionally 1 to 3 R 11 A phenyl group substituted with a group.

[0149] In R 7 In the case of an optionally substituted aryl group having 6 to 10 carbon atoms such as phenyl, each R 7 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 -hydrocarbon group. If R 7 Other than hydrogen, it is most preferred.

[0150] If R 7 is optionally replaced by 1-3 R 11 The most preferred is a phenyl group substituted with a group, and more preferably, R 7 Is 1 to 2 R 11 A phenyl group substituted with a group.

[0151] Preferably, each R 11 are independently identical or different and are hydrogen, straight-chain or branched C1-C6-alkyl or C 6-20 -aryl or OY-group, where Y is C 1-4 More preferably, each R 11 are independently identical or different and are hydrogen or a straight-chain or branched C1-C4-alkyl group or an OY-group, where Y is C 1-4 -hydrocarbyl. Even more preferably, each R 11 are independently identical or may be different and are hydrogen, methyl, ethyl, isopropyl, tert-butyl or methoxy, in particular hydrogen, methyl or tert-butyl.

[0152] Even more preferably, each R 11 are independently identical or may be different and are methyl, ethyl, isopropyl, tert-butyl or methoxy, in particular methyl or tert-butyl.

[0153] If an aryl group such as a phenyl group is substituted, it is preferably substituted by 1 or 2 R 11 Groups such as non-hydrogen R 11 Group substitution.

[0154] If the 4-position group and R 7 The groups are the same, which is most preferred. 7 is 3,5-dimethylphenyl, then the group at position 4 of the ligand should be 3,5-dimethylphenyl. This is particularly true when the ring is a dicyclopentaphenyl ring.

[0155] In a preferred embodiment, the metallocene complex is one of formula (I)-(III):

[0156] (Cp)2MXr(II) or

[0157] wherein each X is independently a σ donor ligand,

[0158] M is Ti, Zr, Hf, Y, Sc, La or a lanthanide element, preferably Ti, Zr or Hf, more preferably Zr or Hf;

[0159] Each Cp is independently an unsubstituted or substituted cyclopentadienyl-containing ligand and / or a fused unsubstituted or substituted cyclopentadienyl-containing ligand;

[0160] Q is -O or -NW or -PW;

[0161] W is an organic group or H;

[0162] L is a carbon, silicon or germanium based bridge with one to four backbone atoms connecting the ligands; and

[0163] r is an integer such that the oxidation state of the metal is satisfied. If M is Ti, Zr or Hf, then r is 2.

[0164] The term cyclopentadienyl-containing ligand refers to any ligand in which a cyclopentadienyl ring is present, which may be cyclopentadienyl by itself or cyclopentadienyl fused to other rings, similar to indenyl.

[0165] In a more preferred embodiment, the metallocene complex is one of formula (VI)

[0166]

[0167] Each X is independently a σ donor ligand,

[0168] M is a Group 4 metal, such as Zr or Hf;

[0169] L is a carbon, silicon or germanium based bridge with one to four backbone atoms connecting the ligands; and

[0170] Each Ind is a substituted or unsubstituted indenyl, or a substituted or unsubstituted fused indenyl, such as a substituted or unsubstituted dicyclopentaphenyl ligand or a substituted or unsubstituted fluorenyl ligand.

[0171] Further preferred metallocenes have the formula (VII)

[0172]

[0173] wherein each X is independently a σ donor ligand;

[0174] M is a Group 4 metal, such as Zr or Hf;

[0175] L is a divalent bridge based on carbon, silicon or germanium, wherein one or two backbone atoms connect the ligands;

[0176] R 2 and R 2’ are independently H, -OSi(C 1-10 -alkyl)3, CHR 8’ -R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 - aryl or optionally substituted heteroaryl having 3 to 20 carbon atoms, and

[0177] R 8’ Is H or C 1-6 alkyl;

[0178] R 4-6 independently hydrogen or optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table of the Elements. 20 - hydrocarbon group;

[0179] R 4’-6’ independently hydrogen or optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table of the Elements. 20 - a hydrocarbon group; or

[0180] R 5 and R 6 may together form an optionally substituted 5-membered or 6-membered carbocyclic ring; and / or

[0181] R 5’ and R 6’ may together form an optionally substituted 5- or 6-membered carbocyclic ring;

[0182] R 7 is hydrogen or optionally contains up to two silicon atoms or heteroatoms C 1-20 a hydrocarbon group; and

[0183] R 7’ It is hydrogen, C 1-3 Hydrocarbon or C 1-10 Alkoxy.

[0184] Further preferred metallocenes have the formula (VIII)

[0185]

[0186] wherein each X is independently a σ donor ligand;

[0187] M is a Group 4 metal, such as Zr or Hf;

[0188] L is a divalent bridge based on carbon, silicon or germanium, wherein one or two backbone atoms connect the ligands;

[0189] R 2 and R 2’ are independently H, -OSi(C 1-10 -alkyl)3, CHR 8’ -R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 -aryl or optionally substituted heteroaryl having 3 to 20 carbon atoms, and R 8’ Is H or C 1-6 alkyl;

[0190] R 5-6 independently hydrogen or optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table of the Elements. 20 - hydrocarbon group;

[0191] R 5’-6’； independently hydrogen or optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table of the Elements. 20 - a hydrocarbon group; or

[0192] R 5 and R 6 can be formed together optionally by n R 10 A 5-membered saturated carbocyclic ring substituted with a group, wherein n is 0 to 4; or

[0193] R 5’ and R 6’ can be formed together optionally by n R 10 A 5-membered saturated carbon ring substituted with a radical, wherein n is 0 to 4;

[0194] Each R 10Same or different, and can be C1-C 20 -hydrocarbon, or a C1-C ... 20 - hydrocarbon group;

[0195] R 7 is hydrogen or optionally contains up to two silicon atoms or heteroatoms C 1-20 Hydrocarbon;

[0196] R 7’ It is hydrogen, C 1-3 Hydrocarbon or C 1-10 Alkoxy.

[0197] Ar and Ar' are independently C6-C 22 Aryl, or optionally substituted with up to 5 R 1 C3-C 20 heteroaryl; and

[0198] R 1 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - Hydrocarbyl.

[0199] Further preferred metallocenes have the formula (IX)

[0200]

[0201] wherein each X is independently a σ donor ligand,

[0202] M is a Group 4 metal, such as Zr or Hf;

[0203] L is a divalent bridge based on carbon, silicon or germanium, wherein one or two backbone atoms connect the ligands;

[0204] R 2 and R 2’ are independently H, -OSi(C 1-10 -alkyl)3, CHR 8’ -R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 - aryl or optionally substituted heteroaryl having 3 to 20 carbon atoms; and

[0205] R 8’ Is H or C 1-6alkyl;

[0206] R 5-6 independently hydrogen or optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table of the Elements. 20 - hydrocarbon group;

[0207] R 5’-6’； independently hydrogen or optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table of the Elements. 20 - a hydrocarbon group; or

[0208] R 5 and R 6 can be formed together optionally by n R 10 A 5-membered saturated carbocyclic ring substituted with a group, wherein n is 0 to 4; or

[0209] R 5’ and R 6’ can be formed together optionally by n R 10 A 5-membered saturated carbon ring substituted with a radical, wherein n is 0 to 4;

[0210] Each R 10 Same or different, and can be C1-C 20 -hydrocarbon, or a C1-C ... 20 - hydrocarbon group;

[0211] Ar and Ar' are phenyl, naphthyl, anthracenyl, pyridyl, phenylthio, 2-alkylphenylthio, benzophenylthio, pyrrolyl, furanyl, 2-alkylfuranyl, optionally substituted with up to 5 R 1 group substitution; and

[0212] R 1 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -Alkaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - Hydrocarbyl.

[0213] Further preferred metallocenes have the formula (X)

[0214]

[0215] Each X is independently a σ donor ligand;

[0216] M is a Group 4 metal, such as Zr or Hf;

[0217] L is a divalent bridge based on carbon, silicon or germanium, wherein one or two backbone atoms connect the ligands;

[0218] R 2 and R 2’ are independently H, -OSi(C 1-10 -alkyl)3, CHR 8’ -R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 - aryl or optionally substituted heteroaryl having 3 to 20 carbon atoms, and

[0219] R 8’ Is H or C 1-6 alkyl;

[0220] R 5-6 is hydrogen or a C1-C ... 20 - hydrocarbon group;

[0221] R 5’-6’； is hydrogen or a C1-C ... 20 - a hydrocarbon group; or

[0222] R 5 and R 6 can be formed together optionally by n R 10 A 5-membered saturated carbocyclic ring substituted with a group, wherein n is 0 to 4; or

[0223] R 5’ and R 6’ can be formed together optionally by n R 10 A 5-membered saturated carbon ring substituted with a radical, wherein n is 0 to 4;

[0224] Each R 10 Same or different, and can be C1-C 20 -hydrocarbon, or a C1-C ... 20 - hydrocarbon group;

[0225] Ar is composed of up to 5 R 1 phenyl substituted with a radical;

[0226] Ar' is phenyl, naphthyl, anthracenyl, pyridyl, phenylthio, 2-alkylphenylthio, benzophenylthio, pyrrolyl, furanyl, 2-alkylfuranyl, optionally substituted with up to 5 R 1 group substitution; and

[0227] R 1 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - Hydrocarbyl.

[0228] Further preferred metallocenes have the formula (XI)

[0229]

[0230] Each X is independently a σ donor ligand,

[0231] L is a divalent bridge based on carbon, silicon or germanium, wherein one or two backbone atoms connect the ligands;

[0232] Each R 1 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - a hydrocarbon group, and optionally, two adjacent R 1 The groups may be part of a ring including the phenyl carbon to which they are bonded,

[0233] Each R 2 and R 2’ are independently the same or may be different and are CHR 8’ -R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 -aryl or optionally substituted by one to three R 11 A heteroaryl group having 3 to 20 carbon atoms substituted by a group, and

[0234] R 8’ Is H or C 1-6 alkyl;

[0235] R 5 is hydrogen or an aliphatic C1-C ... 20 - hydrocarbon group;

[0236] R 6 is hydrogen or an aliphatic C1-C ...20 - a hydrocarbon group; or

[0237] R 5 and R 6 can be formed together optionally by n R 10 A 5-membered saturated carbon ring substituted with a radical, wherein n is 0 to 4;

[0238] R 5 ' is hydrogen or an aliphatic C1-C ... 20 - hydrocarbon group;

[0239] R 6 ' is hydrogen or an aliphatic C1-C ... 20 - a hydrocarbon group; or

[0240] R 5’ and R 6’ can be formed together optionally by n R 10 A 5-membered saturated carbocyclic ring substituted with a group, wherein n is 0 to 4; and

[0241] Each R 10 Same or different, and can be C1-C 20 -hydrocarbon, or a C1-C ... 20 - Hydrocarbyl.

[0242] In a more preferred embodiment, the metallocene complex may have the formula (XII)

[0243]

[0244] Each X is independently a σ donor ligand,

[0245] M is Zr or Hf;

[0246] L is a divalent bridge based on carbon, silicon or germanium, wherein one or two backbone atoms connect the ligands;

[0247] Each Ar is an aryl or heteroaryl group having 3 to 20 carbon atoms, such as a benzene ring or a 5-membered or 6-membered heteroaryl ring;

[0248] Each R 1 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - a hydrocarbon group, and optionally, two adjacent R1 The groups may be part of a ring including the phenyl carbon to which they are bonded,

[0249] Each R 2 are independently the same or may be different and are CHR 8’ -R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 -aryl or optionally substituted by one to three R 11 A heteroaryl group having 3 to 20 carbon atoms substituted by a group, and R 8’ Is H or C 1-6 alkyl;

[0250] R 3 It is a straight chain or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -Alkaryl or C6-C 20 - aryl;

[0251] R 4 is C(R 9 )3 groups, wherein R 9 is a straight-chain or branched C1-C6-alkyl group;

[0252] R 5 is hydrogen or an aliphatic C1-C ... 20 - hydrocarbon group;

[0253] R 6 is hydrogen or an aliphatic C1-C ... 20 - a hydrocarbon group; or

[0254] R 5 and R 6 can be formed together optionally by n R 10 A 5-membered saturated carbon ring substituted with a radical, wherein n is 0 to 4;

[0255] Each R 10 Same or different, and can be C1-C 20 -hydrocarbon, or a C1-C ... 20 - hydrocarbon group;

[0256] R 7 is a linear or branched C1-C6-alkyl group or optionally substituted by one to three R 11a radical-substituted aryl or heteroaryl group having 3 to 20 carbon atoms, for example a phenyl ring or a 5-membered or 6-membered heteroaryl ring;

[0257] Each R 11 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - Hydrocarbyl.

[0258] In a more preferred embodiment, the metallocene complex may have the formula (XIII)

[0259]

[0260] Each X is independently a σ donor ligand,

[0261] M is Zr or Hf;

[0262] L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C ... 20 - a hydrocarbon group, or, optionally, two R' groups together may form a ring,

[0263] Each R 1 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 Aralkyl, C 7-20 Alkyl or C 6-20 Aryl or OY group, where Y is C 1-10 A hydrocarbon group, and optionally, two adjacent R 1 The groups may be part of a ring including the phenyl carbon to which they are bonded,

[0264] Each R 2 are independently the same or may be different and are CH2-R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C3-8 cycloalkyl, C 6-10 Aryl,

[0265] R 3 It is a straight chain or branched C1-C6-alkyl, C 7-20 Aralkyl, C 7-20 Alkyl or C6-C 20 - aryl,

[0266] R 4 is C(R 9 )3 groups, wherein R 9 is a straight chain or branched C1-C6 alkyl group,

[0267] R 5 is hydrogen or an aliphatic C1-C ... 20 Hydrocarbon;

[0268] R 6 is hydrogen or an aliphatic C1-C ... 20 Hydrocarbyl; or

[0269] R 5 and R 6 can be formed together optionally by n R 10 A 5-membered saturated carbon ring substituted with a radical, wherein n is 0 to 4;

[0270] Each R 10 Same or different, and can be C1-C 20 A hydrocarbon group, or a C1-C ... 20 Hydrocarbon;

[0271] R 7 is a linear or branched C1-C6-alkyl group or optionally substituted by 1 to 3 R 11 a radical-substituted aryl or heteroaryl group having 6 to 20 carbon atoms,

[0272] Each R 11 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 Aralkyl, C 7-20 Alkyl or C 6-20 Aryl or OY group, where Y is C 1-10 Hydrocarbon.

[0273] In a more preferred embodiment, the metallocene complex may have the formula (XIV)

[0274]

[0275] Each X is independently a σ donor ligand;

[0276] M is Zr or Hf;

[0277] L is a divalent bridge selected from -R'2C- or -R'2Si-, wherein each R' is independently a hydrogen atom or a C1-C2-alkyl group optionally containing one or more heteroatoms of Groups 14 to 16 of the Periodic Table or fluorine atoms. 20 - a hydrocarbon group, or, optionally, two R' groups together may form a ring;

[0278] Each R 1 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 Aralkyl, C 7-20 Alkyl or C 6-20 Aryl or OY group, where Y is C 1-10 A hydrocarbon group, and optionally, two adjacent R 1 The groups may be part of a ring including the phenyl carbon to which they are bonded;

[0279] Each R 2 are independently the same or may be different and are CH2-R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C3-8 cycloalkyl, C 6-10 Aryl;

[0280] R 3 It is a straight chain or branched C1-C6-alkyl, C 7-20 Aralkyl, C 7-20 Alkyl or C6-C 20 - aryl;

[0281] R 4 is C(R 9 )3 groups, wherein R 9 is a straight chain or branched C1-C6 alkyl group;

[0282] R 5 It is hydrogen;

[0283] R 6 is hydrogen; or

[0284] R 5 and R 6 can be formed together optionally by n R 10 A 5-membered saturated carbon ring substituted with a radical, wherein n is 0 to 4;

[0285] Each R 10 Same or different, and can be C1-C 20 A hydrocarbon group, or a C1-C ... 20 Hydrocarbon;

[0286] R7 is a linear or branched C1-C6-alkyl group or optionally substituted by 1 to 3 R 11 substituted aryl groups,

[0287] Each R 11 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 Aralkyl, C 7-20 Alkyl or C 6-20 Aryl or OY group, where Y is C 1-10 Hydrocarbon.

[0288] In a more preferred embodiment, the metallocene complex may have the formula (XV)

[0289]

[0290] Each X is independently a σ donor ligand,

[0291] M is Zr or Hf;

[0292] L is a divalent bridge selected from -R'2C- or -R'2Si-; wherein each R' is independently C1-C6-alkyl, C 5-6 -cycloalkyl, C 1-10 -Alkyl-OC 1-10 Alkyl or C6-aryl;

[0293] Each Ar is a phenyl ring or a 5-membered or 6-membered heteroaryl ring;

[0294] Each R 1 are independently identical or may be different and are hydrogen, linear or branched C1-C6-alkyl,

[0295] Each R 2 are independently the same or may be different and are CHR 8 '-R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, and R 8’ Is H or C 1-6 alkyl;

[0296] R 3 It is a straight chain or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -Alkaryl or C6-C 20 - aryl;

[0297] R 4 is C(R 9 )3 groups, wherein R 9 is a straight-chain or branched C1-C6-alkyl group;

[0298] R 5 It is hydrogen;

[0299] R 6 is hydrogen; or

[0300] R 5 and R 6 They can form a 5-membered saturated carbon ring together;

[0301] R 7 is a linear or branched C1-C6-alkyl group or optionally substituted by one to three R 11 A substituted aryl or heteroaryl group having 3 to 20 carbon atoms, for example optionally substituted by one to three R 11 A phenyl ring or a 5-membered or 6-membered heteroaryl ring substituted with a radical; and

[0302] Each R 11 are independently identical or may be different and are hydrogen, straight-chain or branched C1-C6-alkyl.

[0303] In a more preferred embodiment, the metallocene complex may have the formula (XVI)

[0304]

[0305] Each X is independently a σ donor ligand;

[0306] M is Zr or Hf;

[0307] L is a divalent bridge selected from -R'2C- or -R'2Si-; wherein each R' is independently C1-C6-alkyl, C 5-6 -cycloalkyl, C 1-10 -Alkyl-OC 1-10 Alkyl or C6-aryl;

[0308] Each Ar is a phenyl ring or a 5-membered or 6-membered heteroaryl ring;

[0309] Each R 1 are independently identical or different and are hydrogen, linear or branched C1-C6-alkyl,

[0310] Each R 2 are independently the same or may be different and are CHR 8 '-R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, and R 8’ Is H or C 1-6 alkyl;

[0311] R 3is a straight-chain or branched C1-C6-alkyl group;

[0312] R 4 is C(R 9 )3 groups, wherein R 9 is a straight-chain or branched C1-C6-alkyl group;

[0313] R 5 and R 6 They can form a 5-membered saturated carbon ring together;

[0314] R 7 is a phenyl ring or optionally substituted by one to three R 11 A 5-membered or 6-membered heteroaryl ring substituted with a group; and

[0315] Each R 11 are independently identical or may be different and are hydrogen, linear or branched C1-C6-alkyl.

[0316] In a more preferred embodiment, the metallocene complex may have the formula (XVII)

[0317]

[0318] Each X is independently a σ donor ligand,

[0319] M is Zr or Hf;

[0320] L is a divalent bridge selected from -R'2C- or -R'2Si-; wherein each R' is independently C1-C6-alkyl, C 5-6 -cycloalkyl, C 1-10 -Alkyl-OC 1-10 Alkyl or C6-aryl;

[0321] Each R 1 are independently identical or may be different and are hydrogen, linear or branched C1-C6-alkyl;

[0322] Each R 2 are independently the same or may be different and are CH2-R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl,

[0323] R 3 is a straight-chain or branched C1-C6-alkyl group,

[0324] R 4 is C(R 9 )3 groups, wherein R 9 is a straight chain or branched C1-C6 alkyl group,

[0325] R5 It is hydrogen;

[0326] R 6 is hydrogen; or

[0327] R 5 and R 6 They can form a 5-membered saturated carbon ring together;

[0328] R 7 is optionally replaced by 1 to 3 R 11 phenyl substituted with a radical,

[0329] Each R 11 are independently identical or may be different and are hydrogen, linear or branched C1-C6-alkyl.

[0330] In a more preferred embodiment, the metallocene complex may have the formula (XVIII)

[0331]

[0332] Each X is independently a σ donor ligand,

[0333] M is Zr or Hf;

[0334] L is -R'2Si-; wherein each R' is independently C1-C6-alkyl, C 5-6 -cycloalkyl, C 1-10 -Alkyl-OC 1-10 Alkyl or C6-aryl;

[0335] Each R 1 are independently identical or may be different and are hydrogen, linear or branched C1-C6-alkyl;

[0336] Each R 2 It is methyl;

[0337] R 3 is a straight-chain or branched C1-C6-alkyl group,

[0338] R 4 is C(R 9 )3 groups, wherein R 9 is a straight chain or branched C1-C6 alkyl group,

[0339] R 5 It is hydrogen;

[0340] R 6 is hydrogen; or

[0341] R 5 and R 6 They can form a 5-membered saturated carbon ring together;

[0342] R 7 is optionally replaced by 1 to 3 R 11 phenyl substituted with a radical,

[0343] Each R 11 are independently identical or may be different and are hydrogen, straight-chain or branched C1-C6-alkyl.

[0344] In a more preferred embodiment, the metallocene complex may have the formula (XIX)

[0345]

[0346] Each X is independently a σ donor ligand,

[0347] M is Zr or Hf;

[0348] L is -R'2Si-; wherein each R' is independently C1-C6-alkyl, C 5-6 -cycloalkyl, C 1-10 -Alkyl-OC 1-10 Alkyl or C6-aryl;

[0349] Each R 1 are independently identical or may be different and are hydrogen, linear or branched C1-C6-alkyl;

[0350] Each R 2 are independently the same or may be different and are CH2-R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl;

[0351] R 3 is a straight-chain or branched C1-C6-alkyl group,

[0352] R 4 is C(R 9 )3 groups, wherein R 9 is a straight chain or branched C1-C6 alkyl group,

[0353] R 7 is optionally replaced by 1 to 3 R 11 phenyl substituted with a radical,

[0354] Each R 11 are independently identical or may be different and are hydrogen, straight-chain or branched C1-C6-alkyl.

[0355] In a more preferred embodiment, the metallocene complex may have the formula (XX)

[0356]

[0357] Each X is independently a sigma donor ligand, such as a halogen atom, a linear or branched C 1-4 -alkyl or C 1-4 -alkoxy, phenyl or benzyl, M is Zr or Hf;

[0358] L is -R'2Si-; wherein each R' is independently C1-C6-alkyl, C 5-6 -cycloalkyl, C 1-10 -Alkyl-OC 1-10 Alkyl or C6-aryl;

[0359] Each R 1 are independently identical or may be different and are hydrogen, linear or branched C1-C6-alkyl;

[0360] R 3 is a straight-chain or branched C1-C6-alkyl group,

[0361] R 4 is C(R 9 )3 groups, wherein R 9 is a straight chain or branched C1-C6 alkyl group,

[0362] R 7 is optionally replaced by 1 to 3 R 11 phenyl substituted with a radical,

[0363] Each R 11 are independently identical or may be different and are hydrogen, linear or branched C1-C6-alkyl.

[0364] In a more preferred embodiment, the metallocene complex may have the formula (XXI)

[0365]

[0366] Each X is independently a sigma donor ligand, such as a halogen atom, a linear or branched C 1-4 -alkyl or C 1-4 -alkoxy, phenyl or benzyl, L is -Me2Si-,

[0367] Each R 1 are independently identical or may be different and are hydrogen, linear or branched C1-C6-alkyl;

[0368] R 3 is a straight-chain or branched C1-C6-alkyl group,

[0369] R 4 is C(R 9 )3 groups, wherein R 9 is a straight chain or branched C1-C6 alkyl group,

[0370] R7 is optionally replaced by 1 to 3 R 11 phenyl substituted with a radical,

[0371] Each R 11 are independently identical or may be different and are hydrogen, straight-chain or branched C1-C6-alkyl.

[0372] Particularly preferred complexes of the present invention include:

[0373] rac-dimethylsilanediyl-bis-[2-methyl-4-(3'5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0374] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4′-tert-butylphenyl)-inden-1-yl][2-methyl-4-(4′-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0375] Racemic-trans-dimethylsilanediyl[2-methyl-4-(4′-tert-butylphenyl)-inden-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0376] Racemic-trans-dimethylsilanediyl[2-methyl-4-(3',5'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-dicyclopentadienylbenzo-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0377] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis-(4′-tert-butylphenyl)-1,5,6,7-tetrahydro-s-dicyclopentadienylbenzo-1-yl][2-methyl-4-(3′,5′-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0378] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-dicyclopentadienylbenzo-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0379] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-dicyclopentadienylbenzo-1-yl][2-methyl-4-(3',5'-di-tert-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0380] or their Hf analogs.

[0381] For the avoidance of doubt, any narrower definition of a substituent given above may be combined with any other broad or narrow definition of any other substituent. Throughout the above disclosure, where a narrower definition of a substituent is provided, that narrower definition is deemed to be disclosed together with all broader and narrower definitions of other substituents in the application.

[0382] The ligands required for forming the complexes of the present invention and the catalysts therefrom can be synthesized by any method, and a skilled organic chemist will be able to design various synthesis schemes to make the necessary ligand materials. For example, WO2007 / 116034 discloses the necessary chemical reactions. Synthesis schemes can also be found generally in WO2002 / 02576, WO2011 / 135004, WO2012 / 084961, WO2012 / 001052, WO2011 / 076780, WO2015 / 158790 and WO2018 / 122134. The embodiments also provide sufficient guidance for the technician.

[0383] Catalyst

[0384] In order to form an active catalytic substance, it is usually necessary to use a promoter known in the art

[0385] According to the present invention, a cocatalyst system comprising a boron-containing cocatalyst and an aluminoxane cocatalyst is used in combination with the metallocene catalyst complex defined above.

[0386] The aluminoxane cocatalyst may be one of formula (A):

[0387]

[0388] wherein n is 6 to 20, and R has the following meanings.

[0389] Aluminoxanes are formed by partial hydrolysis of organoaluminum compounds such as those having the formula AlR3, AlR2Y, and Al2R3Y3, wherein R can be, for example, C1-C 10 -alkyl, preferably C1-C5-alkyl; or C3-C 10 -Cycloalkyl, C7-C 12 -aralkyl or -alkaryl and / or phenyl or naphthyl, wherein Y can be hydrogen, halogen, preferably chlorine or bromine; or C1-C 10 - alkoxy, preferably methoxy or ethoxy. The oxygen-containing aluminoxane obtained is usually not a pure compound but a mixture of oligomers of formula (A).

[0390] The preferred aluminoxane is methylaluminoxane (MAO).Since the aluminoxanes used as cocatalysts according to the invention are not pure compounds due to the way they are prepared, the molar concentrations of the aluminoxane solutions hereinafter are based on their aluminum content.

[0391] According to the present invention, boron-containing cocatalysts are also used in combination with aluminoxane cocatalysts. Boron-containing cocatalysts of interest include those of formula (B)

[0392] BY3(B)

[0393] Wherein Y is the same or different and is a hydrogen atom, an alkyl group having 1 to about 20 carbon atoms, an aryl group having 6 to about 15 carbon atoms, an alkaryl group, an aralkyl group, a haloalkyl group or a haloaryl group, each of which has 1 to 10 carbon atoms in the alkyl group and 6-20 carbon atoms in the aryl group, or fluorine, chlorine, bromine or iodine. Preferred examples of Y are fluorine, trifluoromethyl, aromatic fluorinated groups such as p-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-bis(trifluoromethyl)phenyl. Preferred options are trifluoroborane, tri(4-fluorophenyl)borane, tri(3,5-difluorophenyl)borane, tri(4-fluoromethylphenyl)borane, tri(2,4,6-trifluorophenyl)borane, tri(penta-fluorophenyl)borane, tri(3,5-difluorophenyl)borane and / or tri(3,4,5-trifluorophenyl)borane.

[0394] Tris(pentafluorophenyl)borane is particularly preferred.

[0395] However, preference is given to using borates, ie compounds containing borate.

[0396] These compounds generally contain anions of formula (C):

[0397] (Z)4B- (C)

[0398] wherein Z is an optionally substituted phenyl derivative, the substituent being a halo-C 1-6 -alkyl or halo. Preferred options are fluoro or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0399] Such ionic promoters preferably contain a weakly coordinating anion, such as tetrakis(pentafluorophenyl)borate or tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

[0400] Suitable cationic counterions include triphenylcarbonium, and are protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylamine, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylamine, pyridinium, p-bromo-N,N-dimethylanilinium or p-nitro-N,N-dimethylanilinium.

[0401] Preferred ionic compounds that can be used according to the present invention include:

[0402] Tributylammonium tetrakis(pentafluorophenyl)borate,

[0403] Tributylammonium tetrakis(trifluoromethylphenyl)borate,

[0404] Tributylammonium tetrakis(4-fluorophenyl)borate,

[0405] N,N-Dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate,

[0406] N,N-Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate,

[0407] N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate,

[0408] N,N-Di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,

[0409] Di(cyclohexyl)ammonium tetrakis(pentafluorophenyl)borate,

[0410] Triphenylcarbonium tetrakis(pentafluorophenyl)borate,

[0411] Or ferrocenium tetrakis(pentafluorophenyl)borate.

[0412] Preferably triphenylcarbonium tetrakis(pentafluorophenyl)borate,

[0413] N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate,

[0414] N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate or

[0415] N,N-Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate.

[0416] Surprisingly, it has been found that certain boron-containing promoters are particularly preferred. Thus, preferred borates for use in the present invention contain trityl, i.e., triphenylcarbonium ions. Thus, the use of Ph3CB(PhF5)4 and its analogs is particularly advantageous.

[0417] Suitable amounts of promoters are known to those skilled in the art.

[0418] Preferably, the amount of cocatalyst is chosen so as to achieve a molar ratio below that defined.

[0419] The molar ratio of boron (B) to the metal ion (M) of the metallocene (preferably zirconium) may be in the range of 0.1:1 to 10:1 mol / mol, preferably 0.3:1 to 7:1, in particular 0.3:1 to 5:1 mol / mol.

[0420] Even more preferably, the molar ratio of the feed amount of boron (B) to the metal ion (M) of the metallocene, preferably zirconium, is from 0.3:1 to 3:1.

[0421] The molar ratio Al / M of Al of aluminoxane to the metal ion (M) of metallocene (preferably zirconium) may be in the range of 1:1 to 2000:1 mol / mol, preferably 10:1 to 1000:1, and more preferably 50:1 to 600:1 mol / mol.

[0422] Catalyst system

[0423] The metallocene complexes as described above are used in combination with a suitable cocatalyst combination as described above.

[0424] The catalyst system according to the invention is used in supported form. The particulate support material used is an inorganic porous support, for example silicon dioxide, aluminum oxide or mixed oxides such as silicon dioxide-alumina, in particular silicon dioxide.

[0425] Preference is given to using a silica support.

[0426] Particularly preferably, the support is a porous material so that the complex can be loaded into the pores of the particulate support, for example using methods similar to those described in WO94 / 14856, WO95 / 12622, WO2006 / 097497 and EP18282666.

[0427] The average particle size of the support, for example a silica support, can generally be in the range of 10 to 100 μm. However, it has been shown that particular advantages can be obtained if the support has an average particle size of 15 to 80 μm, preferably 18 to 50 μm.

[0428] The average pore size of the support, such as a silica support, may be in the range of 10 nm to 100 nm, and the pore volume may be in the range of 1 mL / g to 3 mL / g.

[0429] Examples of suitable support materials are, for example, ES757 produced and sold by PQ, Sylopol 948 produced and sold by Grace or SUNSPERA DM-L-303 silica produced by AGC Si-Tech. The support may optionally be calcined before use in the catalyst preparation in order to achieve an optimum silanol group content.

[0430] The use of these vectors is routine in the art.

[0431] The catalyst may contain 5 to 500 μmol, for example 10 to 100 μmol, of transition metal per gram of support (eg silica), and 3 to 15 mmol of Al per gram of support (eg silica).

[0432] Preparation steps:

[0433] Step a)

[0434] In step a), a support, for example a silica support, is reacted with an aluminoxane cocatalyst.

[0435] Preferably, the reaction is carried out with a synthesis stoichiometry of Al in the aluminoxane to the silica support in the range of 3-12 mmol Al / g SiO2.

[0436] Preferably, the support, such as a silica support, is calcined before step a) to remove moisture from its surface. The calcination temperature is generally in the range of 200°C to 800°C, preferably in the range of 400°C to 650°C.

[0437] The support, for example a silica support, is then suspended in a suitable hydrocarbon solvent, for example toluene. The suspension is carried out at a temperature of 15°C to 25°C under an inert gas atmosphere, for example nitrogen.

[0438] The carrier / solvent (preferably silica / toluene) suspension is stirred for several minutes, preferably 5 to 60 minutes, more preferably 10 to 30 minutes.

[0439] An aluminoxane cocatalyst, preferably MAO (eg, as a 30 wt% toluene solution) is then added to the support / solvent such as silica / toluene suspension, wherein the stoichiometry is preferably 3-12 mmol Al / g SiO2 or other support.

[0440] According to the present invention, not all of the aluminoxane cocatalyst is added in step a), but the major part of the total amount of aluminoxane cocatalyst. Thus, 75.0 wt% to 97.0 wt%, preferably 77.0 wt% to 95.0 wt%, more preferably 85.0 wt% to 92.0 wt% of the total amount of aluminoxane cocatalyst is added in step a).

[0441] After addition of the aluminoxane cocatalyst, the support / solvent / aluminoxane mixture is heated up to a temperature in the range of 80°C to 120°C, preferably 95°C to 115°C and more preferably 100°C to 110°C.

[0442] At this temperature, the mixture is stirred for several minutes to several hours, preferably 60 minutes to 5 hours, more preferably 90 minutes to 3 hours.

[0443] Stirring is then stopped, the slurry thus obtained is allowed to settle, and the mother liquor is removed, for example by filtration or decantation.

[0444] The remaining aluminoxane co-catalyst treated support, e.g., silica support, is then preferably washed one or more times, e.g., once or twice, more preferably twice, with toluene at an elevated temperature in the range of 70°C to 115°C, preferably in the range of 80°C to 110°C and more preferably in the range of 90°C to 100°C, and optionally washed once more with heptane.

[0445] Preferably, the aluminoxane cocatalyst treated support, such as a silica support, is then first preferably dried at a suitable temperature, such as at 40°C to 80°C, preferably at 50°C to 70°C, more preferably at 58°C to 62°C, under a nitrogen atmosphere and then under vacuum.

[0446] Step b)

[0447] In step b), the metallocene complex is reacted with an aluminoxane cocatalyst in a suitable hydrocarbon solvent such as toluene. Preferably, the same hydrocarbon solvent as in step a) is used.

[0448] In this step, the remainder of the aluminoxane cocatalyst, preferably MAO (e.g. as a 30 wt % toluene solution), i.e. 3.0 wt % to 25.0 wt %, preferably 5.0 wt % to 23.0 wt %, more preferably 8.0 wt % to 13.0 wt % of the total amount of aluminoxane cocatalyst in step b) is added to the metallocene complex and the solution thus obtained is stirred for several minutes, preferably 10 to 120 minutes, more preferably 20 to 100 minutes, and even more preferably 40 to 80 minutes. Stirring is carried out at room temperature, for example at a temperature of 15° C. to 25° C., preferably 18° C. to 22° C.

[0449] Step c)

[0450] The boron-containing cocatalyst (such as a borate cocatalyst) is added to the solution of the metallocene / aluminoxane cocatalyst in a suitable hydrocarbon solvent (preferably in toluene) (prepared in step b)) to obtain a solution of the metallocene complex, the boron-containing cocatalyst and the aluminoxane cocatalyst in a suitable hydrocarbon solvent (preferably in toluene).

[0451] The boron-containing promoter is added in an amount such that the boron / M molar ratio of the feed amount is in the range of 0.1:1 to 10:1. Preferably, the boron / M molar ratio of the feed amount is in the range of 0.3:1 to 7:1, more preferably 0.3:1 to 5.0:1, most preferably 0.3:1 to 3:1, for example 1:1. M is preferably Hf or Zr, more preferably Zr.

[0452] The solution thus obtained is further stirred for several minutes, preferably 10 to 120 minutes, more preferably 20 to 100 minutes, and even more preferably 40 to 80 minutes.Stirring is performed at a temperature of 15 to 25°C, preferably 18 to 22°C.

[0453] Step d)

[0454] The solution obtained in step c) is then added to the aluminoxane cocatalyst treated support obtained in step a) to produce the supported catalyst system.

[0455] Step e)

[0456] In a final step, the supported catalyst system thus obtained may optionally be washed with a suitable hydrocarbon solvent such as toluene or heptane and optionally preferably dried in vacuo to produce a free-flowing powder. If desired, the supported catalyst system obtained may be provided as an oil slurry with a desired solid content. The solid catalyst content in the slurry may be, for example, up to 30 wt-%, such as up to 25 wt-%.

[0457] The amounts of support, e.g. silica support, aluminoxane (preferably MAO), boron-containing cocatalyst and metallocene depend on the desired defined ratios above (boron / M, Al / M, Al / SiO2, M / SiO2; M is Hf or Zr, preferably Zr).

[0458] The method thus comprises

[0459] a) mixing the porous inorganic carrier with an aluminoxane co-catalyst in a hydrocarbon solvent to obtain a carrier treated with the aluminoxane co-catalyst;

[0460] b) mixing the metallocene complex with an aluminoxane cocatalyst in a hydrocarbon solvent, wherein the amount of the aluminoxane cocatalyst added in step a) is 75.0 wt % to 97.0 wt % of the total amount of the aluminoxane cocatalyst, and the amount of the aluminoxane cocatalyst added in step b) is 3.0 wt % to 25.0 wt % of the total amount of the aluminoxane cocatalyst;

[0461] c) adding the boron-containing cocatalyst to the solution obtained in step b) to obtain a solution of a metallocene complex, a boron-containing cocatalyst and an aluminoxane cocatalyst, wherein the boron-containing cocatalyst is added in an amount such that the boron / M molar ratio of the feed amount reaches a range of 0.1:1 to 10:1;

[0462] d) adding the solution obtained in step c) to the aluminoxane cocatalyst treated support obtained in step a) and optionally

[0463] e) drying the supported catalyst system thus obtained.

[0464] polymerization

[0465] The catalyst system prepared according to the present invention is particularly suitable for forming propylene homopolymers or copolymers, especially with ethylene, having a high activity level, a high molecular weight and therefore a low MFR and a desirable melting point.

[0466] The polymerization in the process of the present invention can be carried out in one or more, e.g. 1, 2 or 3 polymerization reactors using conventional polymerization techniques, e.g. gas phase, solution phase, slurry or bulk polymerization or combinations thereof, e.g. a combination of slurry and at least one gas phase reactor.

[0467] The process may also involve a prepolymerization step. This prepolymerization step is a conventional step conventionally used in polymer synthesis and is different from the off-line prepolymerization step of the catalyst used for catalysts prepared by the emulsion / solidification technology discussed in the prior art.

[0468] Generally, the amount of catalyst used depends on the nature of the catalyst, the reactor type and conditions, and the desired properties of the polymer product.As is well known in the art, hydrogen can be used to control the molecular weight of the polymer.

[0469] The catalyst system prepared according to the present invention has particularly excellent catalyst activity and can also provide a polymer with a high weight average molecular weight Mw.

[0470] For bulk and gas phase copolymerizations, the reaction temperatures used are generally in the range of 60°C to 115°C (e.g. 70°C to 90°C), and for gas phase reactions of bulk polymerizations operating at slightly higher pressures, the reactor pressure is generally in the range of 10 to 25 bar. The residence time is generally 0.25 to 8 hours (e.g. 0.5 to 4 hours). The gas used will be the monomer, optionally in a mixture with a non-reactive gas such as nitrogen or propane. A particular feature of the invention is that the polymerization is carried out at a temperature of at least 60°C.

[0471] polymer

[0472] The invention is characterized in that the claimed catalyst is capable of forming polymers with high molecular weight. These features can be achieved at commercially interesting polymerization temperatures (e.g., 60° C. or higher). A preferred feature of the invention is that the catalyst of the invention is used to polymerize propylene at a temperature of at least 60° C., preferably at least 70° C., such as at least 80° C. In a specific embodiment, the propylene polymer obtained using the catalyst of the invention has a polydispersity index (Mw / Mn) of 2.0 or greater, such as 2.2-4.5.

[0473] Polypropylene homopolymer

[0474] The polypropylene homopolymer prepared by the catalyst system prepared according to the present invention can be made to have a Mw (weight average molecular weight) in the range of 50 to 2000 kg / mol, preferably in the range of 100 to 1500 kg / mol, more preferably in the range of 150 to 1000 kg / mol, even more preferably 200 to 800 kg / mol, depending on the use and amount of hydrogen used as an Mw regulator. The catalyst of the present invention enables the formation of polypropylene homopolymers with high melting points. In a preferred embodiment, the propylene homopolymer formed by the process of the present invention has a melting point higher than 149.0°C, preferably higher than 149.5°C, in particular higher than 150.0°C. Propylene homopolymers with melting points as high as 158.0°C and even as high as 160.0°C are possible.

[0475] The polymers produced by the catalysts of the present invention can be used in various final products such as pipes, films (cast, blown or BOPP films, such as BOPP for capacitor films), fibers, molded articles (such as injection molded, blow molded, rotational molded articles), extrusion coatings, etc.

[0476] The invention will now be described with reference to the following non-limiting examples.

[0477] Measurement method

[0478] (a) Melt flow rate (MFR)

[0479] The melt flow rate is measured as MFR2 according to ISO 1133 15 for polypropylene (230° C., 2.16 kg load). The MFR is an indication of the flowability and therefore the processability of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.

[0480] (b) Number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (Mw / Mn)

[0481] The molecular weight averages (Mz, Mw and Mn), the molecular weight distribution (MWD) and their breadth are determined by gel permeation chromatography (GPC) according to ISO 16014-1:2003, ISO 16014-2:2003, ISO 16014-4:2003 and ASTM D 6474-12 and are described by the polydispersity index PDI=Mw / Mn (where Mn is the number average molecular weight and Mw is the weight average molecular weight) using the following formula:

[0482]

[0483]

[0484]

[0485] For a constant elution volume interval ΔV i , where A i and Mi are respectively related to the elution volume V i The associated chromatographic peak slice area and the polyolefin molecular weight (MW), where N equals the number of data points obtained from the chromatogram between the integration limits.

[0486] Use a high temperature GPC instrument equipped with an infrared (IR) detector (IR4 or IR5 from PolymerChar in Valencia, Spain), which is equipped with 3x Agilent-PLgel Olexis and 1x Agilent-PLgel Olexis Guard columns. 1,2,4-trichlorobenzene stabilized with 250mg / L 2,6-di-tert-butyl-4-methylphenol is used as solvent and mobile phase. The chromatographic system is run at a constant flow rate of 1mL / min at 160°C. 200 μL of sample solution is injected per analysis. Data collection is carried out using AgilentCirrus software version 3.3 or PolymerChar GPC-IR control software.

[0487] The column set was calibrated using a universal calibration (according to ISO 16014-2:2003) with a minimum of 12 narrow MWD polystyrene (PS) standards ranging from 0.37 kg / mol to 13 200 kg / mol. The PS standards were dissolved at room temperature for several hours or at 160°C for 30 minutes. The conversion of polystyrene peak molecular weight to polyolefin molecular weight was accomplished by using the Mark-Houwink equation and the following Mark-Houwink constant:

[0488] K PS =19x10 -3 mL / g,α PS =0.655

[0489] K PE =39x10 -3 mL / g,α PE =0.725

[0490] K PP =19x10 -3 mL / g,α PP =0.725

[0491] A third-order polynomial fit was used to fit the calibration data.

[0492] All samples were prepared in the concentration range of 0.5-1 mg / ml and dissolved at 160°C with constant gentle shaking for 2.5 hours for PP and 3 hours for PE.

[0493] (c)DSC analysis, peak melting temperature (Tm),

[0494] Differential Scanning Calorimetry (DSC) experiments were run on a Mettler Toledo DSC2 apparatus calibrated with indium, zinc and tin according to ISO 11357 / 1. Measurements were performed on 6±1 mg samples in a nitrogen atmosphere (50 mL min-1) between 30°C and 225°C at a scan rate of 10°C / min in a hot / cold / hot cycle according to ISO 11357 / 3. The crystallization (Tc) and melting (Tm) temperatures were taken as the peak values ​​of the endotherm and exotherm in the cooling cycle and the second heating cycle, respectively.

[0495] (d) Catalyst activity

[0496] The catalyst activity was calculated according to the following formula:

[0497]

[0498] (e) Metal activity

[0499] The metal activity (M activity) was calculated according to the following formula:

[0500]

[0501] The catalyst loading refers to the grams of transition metal (M) present in the catalyst.

[0502] (f) Determination of Al, B and Zr (ICP method)

[0503] In a glove box, an aliquot of catalyst (approximately 40 mg) was weighed into a glass weigh boat using an analytical balance. The sample was then exposed to air overnight while placed in a steel secondary container equipped with an air inlet. The contents of the boat were then rinsed into an Xpress microwave container (20 mL) using 5 mL of concentrated (65%) nitric acid. The sample was then subjected to microwave-assisted digestion for 35 minutes at 150°C using a MARS6 laboratory microwave unit. The digested sample was cooled for at least 4 hours and then transferred to a 100 mL capacity glass volumetric flask. A standard solution containing 1000 mg / LY and Rh (0.4 mL) was added. The bottle was then filled with distilled water and shaken thoroughly. The solution was filtered through a 0.45 μm nylon syringe filter and analyzed using a Thermo iCAP6300 ICP-OES and iTEVA software.

[0504] The instrument was calibrated for Al, B, Hf, Mg, Ti and Zr using a blank (5% HNO3 solution) and 6 standards of Al, B, Hf, Mg, Ti and Zr at 0.005 mg / L, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L and 100 mg / L in 5% HNO3 distilled water. However, not every calibration point was used for every wavelength. Each calibration solution contained 4 mg / L of Y and Rh standards. Al 394.401 nm was calibrated using the following calibration points: blank, 0.1 mg / L, 1 mg / L, 10 mg / L and 100 mg / L. Using blank, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L and 100 mg / L standards, Al 167.079 nm was calibrated to Al 394.401 nm, excluding 100 mg / L and Zr 339.198 nm. Curve fitting and 1 / concentration weighting were used for the calibration curve.

[0505] Calibration was verified and adjusted (instrument recalibration function) just prior to analysis using blanks and 10 mg / L Al, B, Hf, Mg, Ti, and Zr standards (containing 4 mg / L Y and Rh). Quality control samples (QC: 1 mg / L Al, Au, Be, Hg & Se; 2 mg / L Hf & Zr, 2.5 mg / L As, B, Cd, Co, Cr, Mo, Ni, P, Sb, Sn & V; 4 mg / L Rh & Y; 5 mg / L Ca, K, Mg, Mn, Na & Ti; 10 mg / L Cu, Pb, and Zn; 25 mg / L Fe and 37.5 mg / L Ca in 5% HNO3 solution in distilled water) were run to confirm the recalibration for Al, B, Hf, Mg, Ti, and Zr. QC samples were also run at the end of a scheduled analytical set.

[0506] The Zr 339.198nm{99} line was used to monitor the Zr content. When the Al concentration of the test portion was below 2wt%, the aluminum content was monitored by the 167.079nm{502} line, and when the Al concentration was above 2wt%, the aluminum content was monitored by the 394.401nm{85} line. Y 371.030nm{91} was used as an internal standard for Zr 339.198nm and Al 394.401nm, and Y 224.306nm{450} was used as an internal standard for Al 167.079nm. The B 249nm line was used to monitor the B content.

[0507] Using the original mass of the catalyst aliquot and the dilution volume, back-calculate the original catalyst sample to the reported value.

[0508] Catalyst complex

[0509] The catalyst complex used in the polymerization process for the propylene homopolymers of inventive examples IE1 and IE2 and comparative examples CE1 to CE5 is:

[0510]

[0511] Metallocene (MC1) (rac-trans-dimethylsilanediyl(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride) has been synthesized as described in E2 of WO 2013 / 007650.

[0512] The catalyst system was prepared using metallocene MC1 and a cocatalyst system of MAO and trityltetrakis(pentafluorophenyl)borate. The catalyst was supported on silica.

[0513] The catalyst complex MC2 used in the polymerization process for propylene homopolymers of inventive example IE3 and comparative examples CE6 to CE7 is

[0514]

[0515] (rac-trans-dimethylsilanediyl(2-methyl-4-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-dicyclopentadienol-1-yl)(2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl)zirconium dichloride) synthesized according to the procedure as described in pp 49ff of WO2019 / 007655.

[0516] The catalyst system was prepared using metallocene MC2 and a cocatalyst system of MAO and trityltetrakis(pentafluorophenyl)borate. For IE3, the catalyst was supported on silica.

[0517] The catalyst complex MC3 used in the polymerization process for propylene homopolymers of inventive example IE4 and comparative example CE8 is

[0518]

[0519] Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-dicyclopentadienylbenzo-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, synthesized as described in international application PCT / EP2019 / 056737 (Synthesis of MC-2)

[0520] Preparation of Metallocene-Silica Support (Option 1)

[0521] A steel reactor equipped with a mechanical stirrer and a filter screen was flushed with nitrogen, and the reactor temperature was set to 20°C. Next, silica grade DM-L-303 (7.4 kg) from AGC Si-Tech Co pre-calcined at 600°C was added from a feed barrel, and then carefully pressurized and decompressed with nitrogen using a manual valve. Toluene (32.2 kg) was then added. The mixture was stirred (40 rpm) for 15 min. Next, a 30 wt% MAO toluene solution (17.5 kg) from Lanxess was added through a 12 mm pipeline at the top of the reactor within 70 min. The reaction mixture was then heated to up to 90°C and stirred for another two hours at 90°C. The slurry was allowed to settle and the mother liquor was filtered out. The silica support treated with MAO was washed twice at 90°C with toluene (32.2 kg), followed by settling and filtering. The reactor was cooled to 60°C, and the solid was washed with heptane (32.2 kg). Finally, the MAO treated SiO2 was dried at 60°C for 2 h at a nitrogen flow rate of 2 kg / h and a pressure of 0.3 bar, and then dried for 5 h under vacuum (-0.5 bar) while stirring at 5 rpm. The MAO treated support was collected as a free flowing white powder and was found to contain 12.7% Al by weight.

[0522] This support was used in Inventive Examples ICS1-ICS4, ICS6, ICS7 and Comparative Examples CCS1 to CCS6 and CCS8. No silica was used in Comparative Examples CCS6 and CCS7.

[0523] ICS 1 (Catalyst System 1 of the Invention): Catalyst Preparation

[0524] In a nitrogen-filled glove box, a solution of MAO 0.25 mL (30% wt in toluene, AXION 1330 CALanxess) in dry toluene (1 mL) was added to an aliquot of metallocene MC1 (30.0 mg, 38 μmol). The mixture was stirred at room temperature for 60 minutes. Next, trityl tetrakis (pentafluorophenyl) borate (35.6 mg, 38 μmol) was added to the mixture, and the mixture was stirred for another hour at room temperature. 1.0 g of MAO-treated silica prepared as described above was placed in a glass flask. Then, while gently mixing, a solution of metallocene, borate and MAO in toluene was slowly added to the support over a 5-minute process. The resulting mixture was shaken thoroughly and left to stand overnight. The resulting filter cake was dried in a vacuum for 1 hour to produce 1.1 g of catalyst, a pink free-flowing powder, containing 13.4 wt% of Al and 0.27 wt% of Zr according to ICP analysis.

[0525] ICS 2 (Inventive Catalyst System 2): Catalyst Preparation

[0526] ICS 2 was prepared as described for ICS 1 except that 36.0 mg of trityltetrakis(pentafluorophenyl)borate was added and after standing overnight the catalyst was washed with 5 mL of toluene and then dried.

[0527] CCS 1 (Comparative Catalyst System 1): Catalyst Preparation

[0528] In a nitrogen-filled glove box, a solution of MAO 0.25 mL (30% wt in toluene, AXION 1330 CALanxess) in dry toluene (1 mL) was added to an aliquot of metallocene MC1 (30.0 mg, 38 μmol). The mixture was stirred at room temperature for 60 minutes. Next, the solution was slowly added to 1.0 g of MAO-treated silica prepared as described above and placed in a glass flask. The mixture was left to stand overnight and then vacuum dried for 1 hour to produce a pink free-flowing powder. A solution of trityl tetrakis (pentafluorophenyl) borate (35.6 mg, 38 μmol) in 1 ml of toluene was then slowly added to the metallocene-MAO impregnated support. The mixture was fully shaken and left to stand overnight. The resulting filter cake was dried in a vacuum for 1 hour to produce 1.1 g of catalyst as a pink free-flowing powder.

[0529] CCS 2 (Comparative Catalyst System 2): Catalyst Preparation:

[0530] In a nitrogen-filled glove box, a solution of trityl tetrakis (pentafluorophenyl) borate (35.6 mg, 38 μmol) in 1 ml toluene was slowly added to 1.0 g of MAO-treated silica prepared as described above and placed in a glass flask. The mixture was left to stand overnight and then vacuum dried for 1 hour to produce a white free-flowing powder. In a separate flask, a solution of MAO 0.25 mL (30% wt, in toluene, AXION 1330 CA Lanxess) in dry toluene (1 mL) was added to an aliquot of metallocene MC1 (30.0 mg, 38 μmol). The mixture was stirred at room temperature for 60 minutes. Next, while gently mixing, the MAO in toluene was slowly added to the borate-treated support over a 5-minute process. The resulting mixture was fully shaken and left to stand overnight. The resulting filter cake was dried in a vacuum for 1 hour to produce 1.2 g of catalyst, which was a pink free-flowing powder.

[0531] CCS3 (Comparative Catalyst System 3) Catalyst Preparation:

[0532] In a nitrogen-filled glove box, a solution of MAO 0.25mL (30%wt in toluene, AXION 1330 CALanxess) in dry toluene (1mL) was added to an aliquot of metallocene MC1 (30.0mg, 38μmol). The mixture was stirred at room temperature for 60 minutes. Next, the solution was slowly added to 1.0g of MAO-treated silica prepared as described above and placed in a glass flask. The mixture was left to stand overnight, washed with 5mL toluene, and then vacuum dried for 1 hour to produce a pink free-flowing powder. Then a solution of trityl tetrakis (pentafluorophenyl) borate (35.6mg, 38μmol) in 1ml toluene was slowly added to the metallocene-MAO impregnated support. The mixture was fully shaken and left to stand overnight, then washed with 5mL toluene. The resulting filter cake was dried in a vacuum for 1 hour to produce 1.0g of catalyst, which was a pink free-flowing powder.

[0533] CCS 4 (Comparative Catalyst System 4): Catalyst Preparation:

[0534] In a nitrogen-filled glove box, a solution of trityl tetrakis (pentafluorophenyl) borate (35.6 mg, 38 μmol) in 1 ml toluene was slowly added to 1.0 g of MAO-treated silica prepared as described above and placed in a glass flask. The mixture was left to stand overnight, washed with 5 mL toluene, and then vacuum dried for 1 hour to produce a white free-flowing powder. In a separate flask, a solution of MAO 0.25 mL (30% wt, in toluene, AXION 1330 CA Lanxess) in dry toluene (1 mL) was added to an aliquot of metallocene MC1 (30.0 mg, 38 μmol). The mixture was stirred at room temperature for 60 minutes. Next, while gently mixing, MAO in toluene was slowly added to the borate-treated support over a 5-minute process. The resulting mixture was fully shaken and left to stand overnight. The resulting filter cake was washed with 5 mL toluene, and then vacuum dried for 1 hour to obtain 1.1 g of catalyst, which was a pink free-flowing powder.

[0535] CCS 5 (Comparative Catalyst System 5): Catalyst Preparation:

[0536] In a nitrogen-filled glove box, a solution of MAO 0.25 mL (30% wt in toluene, AXION 1330 CALanxess) in dry toluene (1 mL) was added to an aliquot of metallocene MC1 (30.0 mg, 38 μmol). The mixture was stirred at room temperature for 60 minutes. Next, the solution was slowly added to 1.0 g of MAO-treated silica prepared as described above and placed in a glass flask. The mixture was left to stand overnight, washed with 5 mL of toluene, and then vacuum dried for 1 hour to produce a pink free-flowing powder, thereby obtaining 1.1 g of catalyst, which was a pink free-flowing powder.

[0537] ICS 3 (Inventive Catalyst System 3): Catalyst Preparation

[0538] In a nitrogen-filled glove box, a solution of MAO 0.2 mL (30% wt in toluene, AXION 1330 CA Lanxess) in dry toluene (2.5 mL) was added to an aliquot of metallocene MC2 (2.5 mg, 28 μmol). The mixture was stirred at room temperature for 60 minutes. Next, trityl tetrakis (pentafluorophenyl) borate (25.6 mg, 28 μmol) was added to the mixture, and the mixture was stirred for another hour at room temperature. 2.0 g of MAO-treated silica prepared as described above was placed in a glass flask. Then, while gently mixing, a solution of metallocene, borate and MAO in toluene was slowly added to the support over a 5-minute process. The resulting mixture was shaken thoroughly and allowed to stand for 1 hour. The resulting filter cake was dried in a vacuum for 1 hour to produce 2.1 g of catalyst, a pink free-flowing powder, containing 12.9 wt% of Al and 0.095 wt% of Zr according to ICP analysis. B / Zr mol / mol=1; 17mmol Zr / g SiO2

[0539] ICS 4 (Catalyst System 4 of the Invention): Catalyst Preparation

[0540] In a nitrogen-filled glove box, a solution of MAO 0.12 mL (30% wt, in toluene, AXION 1330 CALanxess) in dry toluene (1 mL) was added to an aliquot of metallocene MC3 (17.6 mg, 19 μmol). The mixture was stirred at room temperature for 60 minutes. Next, trityl tetrakis (pentafluorophenyl) borate (18.0 mg, 20 μmol) was added to the mixture, and the mixture was stirred for another hour at room temperature. 1.0 g of MAO-treated silica prepared as described above was placed in a glass flask. Then, while gently mixing, a solution of metallocene, borate and MAO in toluene was slowly added to the support over a 5-minute process. The resulting mixture was shaken thoroughly and left to stand overnight. The resulting filter cake was washed with 5 mL of toluene at room temperature and then dried in a vacuum for 1 hour to produce 1.2 g of catalyst, which was a pink free-flowing powder containing 11.3 wt% of Al and 0.089 wt% of Zr according to ICP analysis.

[0541] CCS6 (Comparative Catalyst System 6)

[0542] The same catalyst complex as ICS3 (ie MC2) was used, but without the silica support.

[0543] In a glove box, 234.3 mg of dry and degassed surfactant S2 (in 0.2 mL toluene) was added dropwise to 5 mL of MAO. The solution was placed under stirring for 30 minutes. Then, 95.6 mg of MC2 was added to the MAO / surfactant solution. After stirring for 60 minutes, 104.9 mg of trityl tetrakis (pentafluorophenyl) borate was added.

[0544] After stirring for 60 minutes, 5mL of surfactant-MAO-metallocene-borate solution was continuously added to a 50mL emulsified glass reactor containing 40mL of PFC (perfluoro-1.3-dimethylcyclohexane) at -10°C and equipped with an overhead stirrer (stirring speed = 600rpm). A red emulsion was formed immediately, which was stirred for 15 minutes at -10°C / 600rpm. The emulsion was then transferred to 100mL of hot PFC at 90°C through a 2 / 4 Teflon tube, stirred at 600rpm until the transfer was complete, and then the speed was reduced to 300rpm. After stirring for 15 minutes, the oil bath was removed and the agitator was turned off. The catalyst was placed on the top of the PFC and the solvent was pumped away after 35 minutes. The catalyst was placed on the top of the PFC and the solvent was pumped away after 35 minutes. The remaining catalyst was dried at 50°C under an argon stream for 2 hours. 0.70g of red free-flowing powder was obtained. (Al 28.7wt%, Zr 0.53wt%, Al / Zr (mol) 182; B / Zr (mol) 0.98)

[0545] S2: 1H,1H-Perfluoro(2-methyl-3-oxahexan-1-ol) (CAS 26537-88-2) purchased from Unimatec was dried over activated molecular sieves (2 times) and degassed by argon bubbling before use.

[0546] CCS7 (Comparative Catalyst System 7) (Offline Prepolymerization)

[0547] Comparative catalyst system 7 (CCS7) was prepared as described above for CCS6, but with a subsequent off-line prepolymerization step.

[0548] The off-line prepolymerization step was carried out in a 125 mL pressure reactor equipped with a gas feed line and an overhead stirrer. Dry and degassed perfluoro-1,3-dimethylcyclohexane (15 cm 3) and the desired amount of catalyst to be prepolymerized are loaded into a reactor in a glove box, and the reactor is sealed. The reactor is then taken out of the glove box and placed in a water-cooled bath maintained at 25°C. An overhead stirrer and feed line are connected, and the stirring speed is set to 450rpm. The experiment is started by opening the propylene feed into the reactor. The total pressure in the reactor is raised to about 5 bar and kept constant via a mass flow controller with the propylene feed until the target degree of polymerization is reached. The reaction is stopped by flashing the volatile components. Inside the glove box, the reactor is opened and the contents are poured into a glass container. Perfluoro-1,3-dimethylcyclohexane is evaporated until constant weight is obtained, thereby producing a prepolymerized catalyst.

[0549] (Al 4.4wt%, Zr 0.082wt%, Al / Zr (mol) 182; B / Zr (mol) 0.98)

[0550] The degree of prepolymerization (weight of polymer / weight of solid catalyst before the prepolymerization step) was 5.47.

[0551] CCS8 (Comparative Catalyst System 8)

[0552] Comparative catalyst system CCS8 was prepared according to the preparation of CCS3, except that metallocene MC3 (17.6 mg, 19 μmol) and trityl tetrakis(pentafluorophenyl)borate (18 mg, 19 μmol) were used. 1.1 g of catalyst was isolated in the form of a pink free-flowing powder.

[0553] Vectors used in Examples ICS5 to CCS9 and CCS10

[0554] Preparation of MAO-silica support (Option 2)

[0555] A steel reactor equipped with a mechanical stirrer and a filter screen was flushed with nitrogen, and the reactor temperature was set to 20°C. Next, the silica grade DM-L-303 (5.0 kg) from AGC Si-Tech Co pre-calcined at 600°C was added from the feed barrel, and then carefully pressurized and decompressed with nitrogen using a manual valve. Toluene (21.8 kg) was then added. The mixture was stirred (40 rpm) for 15 min. Next, within 70 min, a 30 wt% MAO toluene solution (9.0 kg) from Lanxess was added through a 12 mm pipeline at the top of the reactor. The reaction mixture was then heated to up to 90°C and stirred for another two hours at 90°C. The slurry was settled and the mother liquor was filtered out. The catalyst was washed twice at 90°C with toluene (21.8 kg), followed by settling and filtering. The reactor was cooled to 60°C, and the solid was washed with heptane (21.8 kg). Finally, the MAO treated SiO2 was dried at 60°C for 2 h at a nitrogen flow rate of 2 kg / h and a pressure of 0.3 bar, and then dried for 5 h under vacuum (-0.5 bar) while stirring at 5 rpm. The MAO treated support was collected as a free flowing white powder and was found to contain 13.0% Al by weight.

[0556] ICS 5 (Catalyst System 5 of the Invention): Catalyst Preparation

[0557] In a nitrogen-filled glove box, a solution of MAO 0.2 mL (30% wt in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3 mL) was added to an aliquot of metallocene MC3 (17.6 mg, 19 μmol). The mixture was stirred at room temperature for 30 minutes. Then, an aliquot of trityl tetrakis (pentafluorophenyl) borate (26.5 mg, 28 μmol) was added and the mixture was stirred for an additional 30 min. Next, 2.0 g of MAO-treated silica (option 2) prepared as described above was placed in a glass vial. The metallocene, trityl tetrakis (pentafluorophenyl) borate and MAO solution in toluene were then slowly added to the support over the course of 5 minutes while gently mixing. The resulting mixture was shaken thoroughly and allowed to stand for 1 hour. The resulting solid was dried in vacuum for 1 hour to produce 2.0 g of catalyst as a pink free-flowing powder.

[0558] ICS6 (Catalyst System 6 of the Invention): Catalyst Preparation

[0559] In a nitrogen-filled glove box, a solution of MAO 0.25 mL (30% wt in toluene, AXION 1330 CALanxess) in dry toluene (2.0 mL) was added to an aliquot of metallocene MC3 (35.1 mg, 38.3 μmol). The mixture was stirred at room temperature for 60 minutes. Next, trityl tetrakis (pentafluorophenyl) borate (54.8 mg, 59.4 μmol) was added to the mixture, and the mixture was stirred for another hour at room temperature. 2.0 g of MAO-treated silica (option 1) prepared as described above was placed in a glass flask. Then, while gently mixing, the metallocene, trityl tetrakis (pentafluorophenyl) borate and MAO solution in toluene were slowly added to the support over a 5-minute process. The resulting mixture was shaken thoroughly and left to stand overnight. The resulting filter cake was washed with 10 mL of toluene at room temperature and then vacuum dried for 1 hour to produce 2.1 g of catalyst, which was a pink free-flowing powder.

[0560] ICS 7 (Inventive Catalyst System 7): Catalyst Preparation

[0561] ICS7 was prepared in a similar manner to ICS6 except that 35.2 mg (38 μmol) of MC3 was used and 31.6 mg (38 μmol, 39 umol) of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate was used instead of trityltetrakis(pentafluorophenyl)borate (supplied by Boulder).

[0562] CCS 9 (Comparative Catalyst System 9): Catalyst Preparation:

[0563] In a nitrogen-filled glove box, a solution of MAO 0.2 mL (30% wt in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3 mL) was added to an aliquot of trityl tetrakis (pentafluorophenyl) borate (26.5 mg, 28 μmol). The mixture was stirred at room temperature for 30 minutes. Then, an aliquot of metallocene MC-3 (17.6 mg, 19 μmol) was added and the mixture was stirred for an additional 30 min. Next, 2.0 g of MAO-treated silica (option 2) prepared as described above was placed in a glass vial. The metallocene, MAO, and trityl tetrakis (pentafluorophenyl) borate solution in toluene were then slowly added to the support over the course of 5 minutes while gently mixing. The resulting mixture was shaken thoroughly and allowed to stand for 1 hour. The resulting solid was dried in vacuum for 1 hour to produce 2.0 g of catalyst as a pink free-flowing powder.

[0564] CCS10 (Comparative Catalyst System 10): Catalyst Preparation:

[0565] In a nitrogen-filled glove box, a solution of MAO 0.2 mL (30% wt in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3 mL) was added to an aliquot of metallocene MC-3 (17.6 mg, 19 μmol). The mixture was stirred at room temperature for 30 minutes. Next, 2.0 g of MAO-treated silica (Option 2) prepared as described above was placed in a glass vial. The solution of the metallocene and MAO in toluene was then slowly added to the support over the course of 5 minutes while gently mixing. The resulting mixture was shaken well and allowed to stand for 1 hour. The resulting solid was dried in vacuum for 1 hour to produce a pink powder. Then, an aliquot of trityltetrakis(pentafluorophenyl)borate (26.5 mg, 28 μmol) was added to a new vial and dissolved in toluene (2 mL). The solution of trityltetrakis(pentafluorophenyl)borate in toluene was added to the previously obtained solid over the course of 5 minutes while gently mixing. The resulting mixture was shaken well and allowed to stand for 1 hour. The resulting solid was dried in vacuo for 1 hour to yield 2.0 g of catalyst as a pink free-flowing powder.

[0566] Table 1. Catalysts

[0567] Al Zr Al / Zr B / Zr* Metallocene Catalyst system wt% wt% Moore Moore MC1 ICS 1 14.0 0.282 168 1 MC1 ICS 2 12.8 0.290 149 1 MC1 CCS 1 14.0 0.299 158 1 MC1 CCS 2 14.0 0.308 154 1 MC1 CCS 3 12.8 0.212 204 1 MC1 CCS 4 13.1 0.255 174 1 MC1 CCS 5 12.5 0.248 170 0 MC2 ICS3 12.8 0.095 457 1 MC2 CCS6 28.7 0.53 182 0.98 MC2 CCS7 4.4 0.82 182 0.98 MC3 ICS4 11.3 0.089 429 1 MC3 CCS8 13 0.091 483 1

[0568] *Based on feed composition

[0569] Table 2 Catalyst

[0570]

[0571]

[0572] Polymerization procedure for bulk homopolymerization of propylene

[0573] The polymerization was carried out in a 5 liter jacketed stainless steel reactor equipped with a stirrer, monomer and hydrogen lines, vent line, and catalyst and scavenger feed systems.

[0574] The catalyst feeder includes two stainless steel cylinders in series. In the glove box, the desired amount of catalyst is loaded into the lower steel cylinder of the feeder, and the second cylinder equipped with 5ml of dry pentane is attached to the top. The steel cylinder of the scavenger feeder is filled with 250μl triethylaluminum (purchased from Lanxess; trade name TEA-S) and 5ml of dry pentane (purchased from Scharlau; reagent grade, ≥99%). Outside the glove box, the feed cylinder is attached to the reactor and the connection is flushed with nitrogen. The reactor temperature is controlled at 20°C. The contents of the scavenger feeder are flushed into the reactor with overpressure nitrogen. Then, the desired amount of hydrogen (25 or 15mmol), followed by 1400g of liquid propylene, is sent to the reactor. The stirring speed is set to 400rpm. The reactor temperature is stabilized at 20°C, and after at least 5 minutes, polymerization is started by injecting the catalyst into the reactor, as described below. The valve between the two cylinders of the catalyst feeder is opened, and the catalyst is immediately flushed into the reactor with overpressure nitrogen. The feeder was pressurized three times with nitrogen and then flushed into the reactor.

[0575] After 5 minutes of prepolymerization at 20°C, the reactor temperature was raised to 70°C over a period of 15 to 18 minutes. The polymerization was continued at 70°C for 60 minutes, and then the polymerization was stopped by flashing the reactor to normal pressure. After flushing the reactor with nitrogen several times, the polymer was collected, left to dry overnight, and then weighed to record the yield.

[0576] The catalyst activity was calculated based on a time of 60 minutes according to the following formula:

[0577]

[0578] Table 3. Polymerization experiments and results

[0579]

[0580]

[0581] Catalyst system: Catalyst system used

[0582] ndUndetermined

[0583] The above table discloses catalyst systems ICS1, ICS2 and CCS1-CCS5, which are prepared from the same MAO-silica support using the same loading of metallocene MC1 and two catalysts (IE4, CE8) prepared with metallocene MC3. Comparative example CE5 shows a catalyst prepared without trityl tetrakis (pentafluorophenyl) borate, which has low metal activity. Inventive examples 1 and 2 use catalyst systems ICS 1 and ICS 2, which are prepared using 1 equivalent of trityl tetrakis (pentafluorophenyl) borate added simultaneously with MC1 to give the highest activity increase. Comparative catalyst system CCS 3 (CE3) is prepared according to the teachings of the prior art literature, so that the borate is added in the second impregnation step after MC1 is added to the activated support. Comparative catalyst CCS 3 (CE3) is thus prepared using a reverse impregnation sequence, in which the metallocene is added to the support after the borate addition. As can be seen in the table, the addition sequence of the present invention leads to the highest metal activity increase.

[0584] Comparative catalyst CCS 8 (CE8) was prepared using metallocene MC3 and a reverse impregnation sequence, where the metallocene was added to the support after the borate addition. Inventive Example 4 used catalyst ICS 4 with metallocene MC3, which was prepared with trityltetrakis(pentafluorophenyl)borate added simultaneously with MC3. As can be seen in the table, the inventive sequence of addition resulted in significantly higher metal activity compared to CE8.

[0585] Polymerization procedure for bulk homopolymerization of propylene

[0586] The polymerization procedure was the same as above, with the only difference being that 15.0 mmol of hydrogen was used.

[0587] Table 4. Polymerization experiments and results.

[0588]

[0589]

[0590] Catalyst: Catalyst system used

[0591] As can be seen from the above table, the catalyst system prepared according to the present invention has significantly higher metal activity than the catalyst system prepared by the emulsion / solidification process technology. In addition, the preparation method according to the present invention is much simpler.

Claims

1. A method for preparing a supported catalyst system, wherein the catalyst system comprises (i) metallocene complexes; (ii) a cocatalyst system comprising a boron-containing cocatalyst and a methylaluminoxane cocatalyst; and (iii) a porous silica support, The method comprises the following steps a) reacting the porous silica carrier with a methylaluminoxane co-catalyst in a hydrocarbon solvent to obtain methylaluminoxane A carrier treated with an alkane promoter; b) reacting the metallocene complex with a methylaluminoxane cocatalyst in a hydrocarbon solvent, wherein the The amount of methylaluminoxane cocatalyst is 75.0 wt % to 97.0 wt % of the total amount of methylaluminoxane cocatalyst, and the amount of methylaluminoxane cocatalyst added in step b) is 3.0 wt % to 25.0 wt % of the total amount of methylaluminoxane cocatalyst; c) adding the boron-containing co-catalyst to the solution obtained in step b) to obtain a metallocene complex, a boron-containing co-catalyst and a A solution of a catalyst and a methylaluminoxane cocatalyst, wherein the molar ratio of boron / M in the feed amount reaches 0.1:1 to The boron-containing promoter is added in an amount in the range of 10:1; d) adding the solution obtained in step c) to the methylaluminoxane cocatalyst treated support obtained in step a) body; and optionally e) drying the supported catalyst system thus obtained; The metallocene complex has the formula (IV): in Each X is independently a σ donor ligand, M is Zr or Hf; L is a divalent bridge based on carbon, silicon or germanium, wherein one or two backbone atoms connect the ligands; each Ar is an aryl or heteroaryl group having 3 to 20 carbon atoms; Each R 1 are independently identical or different and are hydrogen, straight or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6- 20 -aryl or OY group, where Y is C 1-10 - a hydrocarbon group, and optionally, two adjacent R 1 The group includes Bonded phenyl Part of a carbon ring, Each R 2 are independently the same or different and are CHR 8’ -R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 -aryl or optionally substituted by one to three R 11 A heteroaryl group having 3 to 20 carbon atoms substituted by a group, and R 8’ Is H or C 1-6 alkyl; R 3 It is a straight chain or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -Alkaryl or C6-C 20 - aryl; R 4 is C(R 9 )3 groups, wherein R 9 is a straight-chain or branched C1-C6-alkyl group; R 5 is hydrogen or an aliphatic C1-C ... 20 - hydrocarbon group; R 6 is hydrogen or an aliphatic C1-C ... 20 - a hydrocarbon group; or R 5 and R 6 together to form optionally n R 10 A 5-membered saturated carbon ring substituted with a radical, wherein n is 0 to 4; Each R 10 Same or different and C1-C 20 -hydrocarbon, or a C1-C ... 20 - hydrocarbon group; R 7 is H or linear or branched C1-C6-alkyl or optionally substituted by one to three R 11 A substituted aryl or heteroaryl group having 3 to 20 carbon atoms; and Each R 11 are independently identical or different and are hydrogen, straight or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - hydrocarbon group; The boron-containing co-catalyst is any one of formula (B) BY3(B) wherein Y is independently the same or different and is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkaryl group, an aralkyl group, a haloalkyl group or a haloaryl group, each of which has 1 to 10 carbon atoms in the alkyl group and 6-20 carbon atoms in the aryl group, or fluorine, chlorine, bromine or iodine, or a borate containing an anion of formula (C): (Z)4B-(C) wherein Z is an optionally substituted phenyl derivative, the substituent being a halo-C 1-6 -alkyl or halide, and a protonated amine or aniline derivative as a counterion.

2. The method according to claim 1, which satisfies one or both of the following conditions: (1) each Ar is a benzene ring or a 5-membered or 6-membered heteroaryl ring; (2) R 7 In the formula (a), the aryl or heteroaryl group having 3 to 20 carbon atoms is a benzene ring or a 5-membered or 6-membered heteroaryl ring.

3. A method for preparing a supported catalyst system, the catalyst system comprising (i) a metallocene complex having the formula (V): in M is Zr or Hf Each X is independently a σ donor ligand, L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C ... 20 - a hydrocarbon group, or, optionally, two R' groups together form a ring, Each R 1 are independently identical or different and are hydrogen, straight or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20- Aryl or OY group, where Y is C 1-10 - a hydrocarbon group, and optionally, two adjacent R 1 The groups are part of a ring including the phenyl carbon to which they are bonded, Each R 2 are independently the same or different and are CH2-R 8 Group, where R 8 Is H or straight or branched chain C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 - aryl, R 3 It is a straight chain or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -Alkaryl or C6-C 20 - aryl, R 4 is C(R 9 )3 groups, wherein R 9 is a straight-chain or branched C1-C6-alkyl group, R 5 is hydrogen or an aliphatic C1-C ... 20 - hydrocarbon group; R 6 is hydrogen or an aliphatic C1-C ... 20 - a hydrocarbon group; or R 5 and R 6 As optionally represented by n R 10 The indenyl group is substituted with a portion of a 5-membered ring fused to the indenyl group, and n is 0 to 4; Each R 10 Same or different and C1-C 20 -hydrocarbon, or a C1-C ... 20 - hydrocarbon group; R 7 is H or linear or branched C1-C6-alkyl or optionally substituted by one to three R 11 a radical-substituted aryl or heteroaryl group having 6 to 20 carbon atoms, Each R 11 are independently identical or different and are hydrogen, straight or branched C1-C6-alkyl, C 7-20 -Arylalkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - a hydrocarbon group, (ii) a cocatalyst system comprising a boron-containing cocatalyst and a methylaluminoxane cocatalyst, and (iii) a silica support, The method comprises the following steps a) reacting the silica carrier with a methylaluminoxane co-catalyst in a hydrocarbon solvent to obtain a carrier treated with the methylaluminoxane co-catalyst; b) reacting a metallocene complex having formula (V) with a methylaluminoxane cocatalyst in a hydrocarbon solvent, wherein the amount of the methylaluminoxane cocatalyst added in step a) is 75.0 wt % to 97.0 wt % of the total amount of the methylaluminoxane cocatalyst, and the amount of the methylaluminoxane cocatalyst added in step b) is 3.0 wt % to 25.0 wt % of the total amount of the methylaluminoxane cocatalyst; c) adding the boron-containing cocatalyst to the solution obtained in step b) to obtain a solution of a metallocene complex having formula (V), a boron-containing cocatalyst and a methylaluminoxane cocatalyst, wherein the boron-containing cocatalyst is added in an amount such that the boron / M molar ratio of the feed amount reaches a range of 0.1:1 to 10.0:1; d) adding the solution obtained in step c) to the methylaluminoxane cocatalyst treated support obtained in step a); and e) drying the supported catalyst system thus obtained; The boron-containing co-catalyst is any one of formula (B) BY3(B) wherein Y is independently the same or different and is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkaryl group, an aralkyl group, a haloalkyl group or a haloaryl group, each of which has 1 to 10 carbon atoms in the alkyl group and 6-20 carbon atoms in the aryl group, or fluorine, chlorine, bromine or iodine, or a borate containing an anion of formula (C): (Z)4B-(C) Wherein Z is a substituted phenyl derivative, the substituent is a halo-C 1-6 -alkyl or halide, and a protonated amine or aniline derivative as a counterion.

4. The method according to claim 3, wherein in the formula (V) of the metallocene complex (i), each X is the same or different; L is -R'2Si-, ethylene or methylene, wherein in the formula -R'2Si-, each R' is independently C1-C 20 - hydrocarbon group; Each R 1 are independently identical or different and are hydrogen, or straight-chain or branched C1-C6-alkyl; Two R's 2 Same and CH2-R 8 Group, where R 8 is H or straight-chain or branched C1-C4-alkyl; R 3 is a straight chain or branched C1-C6-alkyl or C 6-20 - aryl; R 4 is C(R 9 )3 groups, wherein each R 9 The same or different, where R 9 is a straight-chain or branched C1-C4-alkyl group; R 5 and R 6 are independently the same or different and are hydrogen or an aliphatic C1-C2 optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table of the Elements. 20 - a hydrocarbon group, or R 5 and R 6 As optionally represented by n R 10 The group is substituted with an indenyl fused 5-membered ring part, n is 0 to 4, wherein each R 10 Same or different and C1-C 20 -hydrocarbon, or a C1-C ... 20 - hydrocarbon group; R 7 is H or optionally 1 to 3 R 11 The aryl group has 6 to 10 carbon atoms and is substituted by a radical.

5. The method according to claim 4, which satisfies one or more of the following conditions: (1) Each X is independently a hydrogen atom, a halogen atom, a linear or branched, cyclic or non-cyclic C 1-20 -alkyl or -alkoxy, C 6-20 -Aryl, C 7-20 -alkylaryl or C 7-20 - aralkyl; optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table; (2)R 1 wherein the straight-chain or branched C1-C6-alkyl group is a methyl group or a tert-butyl group; (3) Two Rs 2 Same and CH2-R 8 Group, where R 8 is H or a linear or branched C1-C3-alkyl group; (4)R 3 is a straight-chain C1-C4-alkyl group; (5)R 9 are identical and are C1-C2-alkyl; (6) n is 0 or 2; (7)R 10 is a straight-chain or branched C1-C6-alkyl group; (8)R 7 is H or optionally 1 to 3 R 11 A phenyl group substituted with each R 11 are independently identical or different and are hydrogen, straight or branched C1-C6-alkyl or C 6-20 -aryl or OY group, where Y is C 1-4 - Hydrocarbyl.

6. The method according to claim 5, which satisfies one or both of the following conditions: (1) Each X is independently a hydrogen atom, a halogen atom, a linear or branched C 1-6 -alkyl or C 1-6 - alkoxy, phenyl or benzyl; (2)n is 0.

7. The method according to claim 1, wherein the metallocene (i) is selected from Racemic-dimethylsilanediyl-bis-[2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, Racemic-trans-dimethylsilanediyl[2-methyl-4-(4′-tert-butylphenyl)-inden-1-yl][2-methyl-4-(4′tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, Racemic-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-inden-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, Racemic-trans-dimethylsilanediyl[2-methyl-4-(3',5'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-dicyclopentadienylbenzo-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis-(4′-tert-butylphenyl)-1,5,6,7-tetrahydro-s-dicyclopentadienylbenzo-1-yl][2-methyl-4-(3′,5′-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-dicyclopentadienylbenzo-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, Racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-dicyclopentadienylbenzo-1-yl][2-methyl-4-(3',5'-di-tert-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, or their hafnium analogs.

8. The method according to claim 1, which satisfies one or both of the following conditions: (1) The boron-containing co-catalyst is Triphenylcarbonium tetrakis(pentafluorophenyl)borate N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate or N,N-Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate; (2) The protonated amine or aniline derivative as the counter ion in the borate containing the anion of formula (C) is methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylamine, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylamine, pyridinium, p-bromo-N,N-dimethylanilinium, p-nitro-N,N-dimethylanilinium or triphenylcarbonium ion.

9. The process of claim 8, wherein the boron-containing cocatalyst is triphenylcarbonium tetrakis(pentafluorophenyl)borate.

10. The process according to claim 1, wherein the molar ratio of the feed amount of boron to the metal ion M in the complex is in the range of 0.1:1 to 10:1 mol / mol, and / or the molar ratio of the aluminum in the methylaluminoxane cocatalyst to the metal ion M in the complex is in the range of 1:1 to 2000:1 mol / mol.

11. The method according to claim 10, which satisfies one or both of the following conditions: (1) the molar ratio of the feed amount of boron to the metal ion M in the complex is in the range of 0.3:1 to 7:1 mol / mol; (2) The molar ratio of aluminum in the methylaluminoxane cocatalyst to the metal ion M in the complex is in the range of 10:1 to 1000:1 mol / mol.

12. The method according to claim 11, which satisfies one or both of the following conditions: (1) the molar ratio of the feed amount of boron to the metal ion M in the complex is in the range of 0.3:1 to 5:1 mol / mol; (2) The molar ratio of aluminum in the methylaluminoxane cocatalyst to the metal ion M in the complex is in the range of 50:1 to 600:1 mol / mol.

13. The method according to claim 12, wherein the molar ratio of the feed amount of boron to the metal ion M in the complex is in the range of 0.3:1 to 3:1 mol / mol. The method according to claim 1 , wherein the average particle size of the carrier is 10 μm to 100 μm. The method according to claim 14 , wherein the average particle size of the carrier is 15 μm to 80 μm.

16. The method according to claim 1, wherein the average pore size of the carrier is in the range of 10 nm to 100 nm, and the pore volume is in the range of 1 mL / g to 3 mL / g.

17. The process of claim 1, wherein the catalyst system contains 5 to 500 μmol of zirconium or hafnium per gram of silica support and 5 to 10 mmol of Al per gram of support.

18. The process according to claim 17, wherein the catalyst system contains 10 to 100 μmol of zirconium or hafnium per gram of silica support and 5 to 10 mmol of Al per gram of support.

19. The method according to claim 1, wherein in step a) First, the carrier is suspended in a suitable hydrocarbon solvent. Then, a methylaluminoxane cocatalyst is added to the suspension, wherein the synthetic stoichiometry of Al in the methylaluminoxane and the carrier is in the range of 3-12 mmolAl / g SiO2; The carrier / solvent / methylaluminoxane mixture is then heated to a temperature in the range of 80°C to 120°C, Toluene was used as the hydrocarbon solvent.

20. The method according to claim 19, which satisfies one or more of the following conditions: (1) the support is calcined before step a); (2) The carrier / solvent / methylaluminoxane mixture is heated to a temperature in the range of 95°C to 115°C.

21. The process of claim 1, wherein in step a), the methylaluminoxane cocatalyst treated support is washed one or more times with toluene.

22. The method according to claim 21, In step a), the methylaluminoxane cocatalyst treated support is washed one or more times with toluene at an elevated temperature ranging from 70°C to 115°C, and optionally washed once more with heptane, followed by a drying step; Alternatively, in step a), the methylaluminoxane co-catalyst treated support is washed one or more times with toluene at an elevated temperature in the range of 80°C to 110°C, and optionally washed once more with heptane, followed by a drying step. Alternatively, in step a), the methylaluminoxane co-catalyst treated support is washed one or more times with toluene at an elevated temperature in the range of 90°C to 100°C, and optionally washed once more with heptane, followed by a drying step.

23. The method according to claim 1, which satisfies one or both of the following conditions: (1) In step a), 77.0 wt% to 95.0 wt% of the total amount of methylaluminoxane co-catalyst is added. (2) In step b), 5.0 wt% to 23.0 wt% of the total amount of methylaluminoxane co-catalyst is added.

24. The method according to claim 23, which satisfies one or both of the following conditions: (1) adding 85.0 wt% to 92.0 wt% of the total amount of methylaluminoxane co-catalyst in step a); (2) In step b), 8.0 wt% to 13.0 wt% of the total amount of methylaluminoxane co-catalyst is added.

25. Catalyst system obtainable according to the process according to any one of claims 1 to 24.

26. A process for preparing a polyethylene homopolymer or a polyethylene copolymer using one or more C3 to C8 alpha olefin comonomers, the process comprising polymerizing ethylene and optionally one or more C3 to C8 alpha olefin comonomers in the presence of the catalyst system according to claim 25.

27. A process for preparing a polypropylene homopolymer or a polypropylene copolymer using one or more C2 to C8 alpha olefin comonomers, the process comprising polymerizing propylene and optionally one or more C2 to C8 alpha olefin comonomers in the presence of the catalyst system according to claim 25.

28. The process according to claim 27, wherein the polypropylene is a propylene homopolymer, a propylene random copolymer or a heterophasic propylene copolymer.

29. The method of claim 28, wherein the polypropylene is a propylene homopolymer.

30. Use of the catalyst system obtainable according to the process of any one of claims 1 to 24 for the production of propylene polymers.

31. Use according to claim 30, wherein the propylene polymer is a propylene homopolymer, a propylene random copolymer or a heterophasic propylene copolymer.

32. Use according to claim 31, wherein the propylene polymer is a propylene homopolymer.

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