Improved Preparation of Catalyst Systems

Abstract

The present invention relates to an improved method of preparation for supported catalyst systems comprising a particular class of metallocene complexes that combine a boron-containing cocatalyst and an aluminoxane cocatalyst, and to uses of the new and improved catalyst systems.

Description

[Technical field]

[0001] The present invention relates to an improved method of preparation for silica supported catalyst systems comprising a specific class of metallocene complexes combining a boron-containing cocatalyst and an aluminoxane cocatalyst. The present invention also relates to the use of the novel and improved catalyst systems. [Background technology]

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

[0003] Metallocene catalysts are used in propylene polymerization to achieve several desired polymer properties. Suitable metallocene catalysts should have high activity and high productivity.

[0004] Several attempts have been described in the patent literature.

[0005] WO 2002 / 040549 discloses an olefin polymerization catalyst comprising a metallocene compound, a supported activator, such as MAO, an ionizing activator, such as dimethylanilinium tetra(pentafluorophenyl)borate and triphenylcarbenium tetra(pentafluorophenyl)borate, and a support.

[0006] US 2006 / 0116490 discloses metallocene catalysts for olefin polymerization, which comprise a combination of a support 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.

[0007] As an improvement, EP 2545084 suggests providing a highly active supported metallocene catalyst, in which a metallocene compound having an alkoxide or aryloxide substituted ligand is incorporated into a conventional supported metallocene catalyst, and a borate compound is incorporated as a second cocatalyst, to show significantly better catalytic activity.

[0008] The catalyst system includes a support, a first cocatalyst (e.g., MAO) layer disposed on the support, a first metallocene compound layer disposed on the first cocatalyst layer, and a second cocatalyst layer disposed on the first metallocene compound layer, where the second cocatalyst layer is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0009] Although such catalytic systems show improved catalytic activity compared to the catalysts described in WO 2002 / 040549 and US 2006 / 0116490, and can produce polyolefins, especially polyethylenes, with high molecular weight, narrow molecular weight distribution, and prevent fouling in the preparation process, there is still room to improve the behavior of the catalysts in terms of higher activity and productivity.In addition, it would be desirable to simplify the preparation process in view of EP 2545084, for example to reduce the number of preparation steps.

[0010] It is therefore desirable to find a catalyst system that provides high activity and productivity to form propylene copolymers, especially in the case of copolymerization between propylene and α-olefins with 4-8C atoms and / or ethylene. The desired catalyst should also have improved performance in producing high molecular weight polypropylene polymers, especially homopolymers with high melting point temperatures. Various prior art references are directed to one or more of these features.

[0011] WO 02 / 02576, inter alia, discloses rac-Me 2 Si[2-Me-4-(3,5-Me 2 Ph)Ind] 2 ZrCl 2 and its use in the production of high Mw and high melting point polypropylene are described.

[0012] The metallocene catalysts of WO 02 / 02576 are activated with either MAO or borate, which are supported on a silica support. At polymerization temperatures of 60° C. or 70° C., they give iPP with a Tm of 156° C.-159° C., but with very poor catalytic activity.

[0013] WO 2013 / 007650 describes certain asymmetric catalysts that contain an alkoxy group at 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 by a specific emulsion / solidification technique and is activated only with MAO.

[0014] Despite its excellent performance, the catalyst based on this reference is limited in terms of productivity at low MFR, melting temperature of polypropylene homopolymer.In addition, the overall productivity of the catalyst needs to be improved.Moreover, it would be desirable to simplify the manufacture of the catalyst system.According to WO2013 / 007650, an additional prepolymerization step is required before using the catalyst system.

[0015] WO 2018 / 122134 describes, inter alia, the complex rac-anti-dimethylsilanediyl[2-methyl-4-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, which is activated with MAO only and supported on silica.

[0016] WO 2014 / 060540 describes, inter alia, 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 by a special emulsion / solidification technique, which, as mentioned above, includes an offline prepolymerization step of the catalyst system before use. In addition, the activity of the prepolymerized catalyst system is very low. Summary of the Invention [Problem to be solved by the invention]

[0017] Although much research has been done in the field of metallocene catalysts, some problems still remain, mainly related to the productivity or activity of the catalysts. In addition, a simple and cost-effective catalyst preparation procedure is desired.

[0018] The present inventors have identified an improved preparation process for the supported catalyst system, which is composed of a metallocene complex in combination with a boron-containing cocatalyst and an aluminoxane cocatalyst, and which leads to 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 preferably heterophase propylene copolymers.In addition, the enhanced melting temperature of propylene homopolymers can be achieved.The particular catalyst system provides greater flexibility / freedom in the design of propylene polymers than the catalyst systems of the prior art.

[0019] In addition, the new preparation procedure is more robust and requires fewer steps compared to the prior art. [Means for solving the problem]

[0020] In one aspect, the present invention provides a method for preparing a supported catalyst system, the method comprising: (i) metallocene complexes; (ii) a cocatalyst system comprising a boron-containing cocatalyst and an aluminoxane cocatalyst; and (iii) Porous inorganic support Including, The method comprises: a) treating a porous inorganic support with an aluminoxane cocatalyst in a hydrocarbon solvent, optionally followed by heat treatment of the aluminoxane treated support; b) combining the metallocene complex with a boron-containing cocatalyst and, optionally, with an aluminoxane cocatalyst in a hydrocarbon solvent; c) applying the solution of step b) onto the treated support of step a); The process includes the steps of: wherein the amount of the aluminoxane co-catalyst added in step a) is 75.0 to 100.0% by weight of the total amount of the aluminoxane co-catalyst, and the amount of the aluminoxane co-catalyst added in step b) is 0.0 to 25.0% by weight of the total amount of the aluminoxane co-catalyst. The above method is provided.

[0021] In step b) of the process, the components can be mixed in any order. mixed with the metallocene complex followed by addition of the hydrocarbon and optional alumoxane, or The metallocene complex can be mixed with any alumoxane and hydrocarbon, followed by the addition of the boron-containing cocatalyst. In some embodiments, all components can be mixed simultaneously. According to the method of the present invention, only one impregnation step is used, i.e., the treated support of step a) is impregnated with the metallocene and one or more cocatalysts in only one step.

[0022] By preparing the catalyst system according to the present invention, very high activity and productivity of the catalyst system and preferably also an increased melting temperature of the propylene homopolymer can be obtained.

[0023] In a further aspect, the present invention provides a catalyst system obtained according to the process defined herein.

[0024] In a further aspect, the present invention provides a process for preparing a polyethylene homopolymer or a polyethylene copolymer using one or more C3-C8 alpha-olefin comonomers, which process comprises polymerizing ethylene, and optionally one or more C3-C8 alpha-olefin comonomers, in the presence of the catalyst system.

[0025] In a further aspect, the present invention provides a process for the preparation of a polypropylene homopolymer or a polypropylene copolymer with one or more C2-C12 alpha-olefin comonomers, comprising polymerizing propylene and, optionally, one or more C2-C12 alpha-olefin comonomers in the presence of a catalyst system according to claim 20, in particular wherein the polypropylene is a propylene homopolymer, a propylene random copolymer or a heterophasic propylene copolymer, preferably a propylene homopolymer.

[0026] 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 olefins comprise olefins of 2 to 12 C atoms, preferably 2 to 8 C atoms, or mixtures thereof, typically ethylene olefins or propylene olefins with monomers selected from monomers of 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.

[0027] In one embodiment, the metallocene complex is an optionally bridged biscyclopentadienyl type metallocene complex or a constrained geometry metallocene complex. Preferred metallocene complexes are of the following formulae (I) to (III):

[0028] [ka]

[0029] each X is independently a sigma donor ligand; M is Ti, Zr, Hf, Y, Sc, La or an element from the lanthanides, preferably Ti, Zr or Hf; each Cp is independently an unsubstituted or substituted cyclopentadienyl-containing ligand or an unsubstituted or substituted fused cyclopentadienyl-containing ligand; Q is -O or -NW or -PW; W is an organic group or H; L is a carbon, silicon or germanium based bridge in which 1 to 4 backbone atoms link multiple said ligands; and r is an integer such that the oxidation state of the metal is satisfied.

[0030] Any Cp ligand is preferably a substituted or unsubstituted cyclopentadienyl, a substituted or unsubstituted indenyl, a substituted or unsubstituted indacenyl ligand, or a substituted or unsubstituted fluorenyl ligand.

[0031] L is preferably a carbon, silicon or germanium based divalent bridge in which one or two backbone atoms link multiple of the ligands. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] definition

[0033] The following definitions are used throughout the detailed description of the invention.

[0034] The word “C” 1~20 -hydrocarbyl group" is 1~20 -Alkyl, C 2~20 -Alkenyl, C 2~20 -Alkynyl, C 3~20 -Cycloalkyl, C 3~20 -Cycloalkenyl, C 6~20 -aryl group, C 7~20 -alkylaryl group or C 7~20-arylalkyl groups, or combinations of these groups, such as cycloalkyl substituted with alkyl. Linear and branched hydrocarbyl groups cannot contain ring units. Aliphatic hydrocarbyl groups cannot contain aryl rings.

[0035] Unless otherwise stated, preferred C 1~20 The hydrocarbyl group is C 1~20 -Alkyl, C 4~20 -Cycloalkyl, C 5~20 -Cycloalkyl-alkyl group, C 7~20 -alkylaryl group, C 7~20 -arylalkyl group or C 6~20 -aryl groups, especially C 1~10 -Alkyl group, C 6~10 -aryl group or C 7~12 -arylalkyl groups, such as C 1~8 -alkyl groups. Most particularly preferred hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C 5~6 -cycloalkyl, cyclohexylmethyl, phenyl or benzyl.

[0036] The term "halo", when referring to the definition of the complex, includes fluoro, chloro, bromo and iodo groups, especially chloro or fluoro groups.

[0037] Any group containing "one or more heteroatoms belonging to groups 14 to 16 of the Periodic Table of the Elements" preferably means O, S or N. The N group can be present as -NH- or -NR"-, where R" is C 1 ~C 10 -alkyl. For example, there may be 1 to 4 heteroatoms. The groups containing one or more heteroatoms belonging to groups 14 to 16 of the Periodic Table of the Elements may also be alkoxy groups, e.g. C 1 ~C 10 -alkoxy group.

[0038] The term "heteroaryl" defines an aromatic monocyclic or polycyclic group in which one or more heteroatoms from groups 14 to 16 of the periodic table are present in one or more rings. Such groups may contain 3 to 20 carbon atoms and one or more heteroatoms selected from O, S and N.

[0039] The oxidation states of metal ions are governed primarily by the nature of the metal ion in question and the stability of each metal ion's respective oxidation state.

[0040] It will be understood that in the complexes of the invention, the metal ion M is coordinated by ligands X so as to satisfy the valence of the metal ion and fill its available coordination sites. The nature of these σ-ligands can vary widely.

[0041] Catalyst activity is defined in this application as the amount of polymer produced / g catalyst / hour. Catalyst metal activity is defined herein as the amount of polymer produced / g metal / hour. The term productivity is sometimes also used to indicate catalyst activity, but in this specification the term productivity indicates the amount of polymer produced per unit weight of catalyst.

[0042] The term "molecular weight" is used herein, unless otherwise specified, to refer to the weight average molecular weight, Mw.

[0043] The present invention relates to an improved method for the preparation of supported catalyst systems which comprise a metallocene complex in combination with a boron-containing cocatalyst and an aluminoxane cocatalyst and are therefore ideal for the polymerization of olefins, such as propylene and ethylene.

[0044] The metallocene catalyst complexes of the present invention can be either symmetrical or asymmetrical, where asymmetrical simply means that the two ligands forming the metallocene are different, i.e., each ligand has a chemically different set of substituents.

[0045] The metallocene catalyst complexes of the present invention may be chiral racemic bridged bis-indenyl metallocenes in their anti configuration. The metallocenes of the present invention are either C2 or C1 symmetric. When the metallocenes of the present invention are C1 symmetric, they maintain pseudo-C2 symmetry since they maintain C2 symmetry in the immediate vicinity of the metal center, and not around the ligands. Due to their chemical nature, during the synthesis of the complexes, both meso and racemic enantiomeric pairs (in the case of C2 symmetric complexes) or anti and syn enantiomeric pairs (in the case of C1 symmetric complexes) are formed. For the purposes of the present invention, the racemic anti form means that the two indenyl ligands are positioned in the opposite direction with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, while the racemic syn form means that the two indenyl ligands are positioned in the same direction with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the diagram below.

[0046] [ka]

[0047] The formulae herein are intended to cover both the cis and anti configurations. Preferred metallocene catalyst complexes are in the anti configuration.

[0048] The metallocene catalyst complex of the present invention may be used as the rac-anti isomer. Therefore, ideally, at least 95 mol%, such as at least 98 mol%, especially at least 99 mol%, of the metallocene catalyst complex is in the rac-anti isomer form.

[0049] In the metallocene catalyst complexes of the present invention, the following preferences apply:

[0050] The metallocene complex can be any biscyclopentadienyl type complex, especially a bridged biscyclopentadienyl type complex, or it can be a constrained geometry metallocene catalyst.

[0051] In any formula of the present invention the following preferred features apply.

[0052] M can be any Group 3 or 4 metal, or a metal from the lanthanide series. M is preferably Zr or Hf, preferably Zr.

[0053] Each X is independently a sigma donor ligand, i.e., each X is independently 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 group, C 6~20 -aryl group, C 7~20 -alkylaryl group or C 7~20 -arylalkyl groups; these groups may contain one or more heteroatoms from groups 14 to 16 of the periodic table.

[0054] In one embodiment, the X group is trihydrocarbylsilyl, C 1~10 -Alkoxy, C 1~10 Alkoxy-C 1~10- It can be an alkyl-group or an amide group.

[0055] The term "halogen" includes fluoro, chloro, bromo and iodo groups, preferably chloro groups.

[0056] The term "heteroatom belonging to Groups 14 to 16 of the Periodic Table" includes, for example, Si, N, O or S.

[0057] More preferably, each X is independently a hydrogen atom, a halogen atom, a linear or branched C 1~6 -Alkyl or C 1~6- an alkoxy group, a phenyl group or a benzyl group.

[0058] Even more preferably, each X is independently a halogen atom, a linear or branched C 1~4 -Alkyl or C 1~4 - an alkoxy group, a phenyl group or a benzyl group.

[0059] Most preferably, each X is independently a chlorine atom, a benzyl group or a methyl group.

[0060] Preferably, both X groups are the same.

[0061] The most preferred choices for both X groups are two chlorides, two methyl groups, or two benzyl groups.

[0062] W is preferably C 1~20 Hydrocarbyl groups, especially C 1~10 An alkyl group.

[0063] L is a carbon, silicon atom or germanium based bridge. Between the two ligands there are 1-4, e.g. 1 or 2, backbone bonding atoms, e.g. structures such as Ligand-C-Ligand (one backbone atom) or Ligand-Si-Si-Ligand (two backbone atoms).

[0064] The bridging atoms may carry other groups. For example, a suitable bridging ligand L is -R' 2 C-, -R' 2 C-CR' 2 -,-R' 2 Si-, -R' 2 Si-SiR' 2 -,-R' 2 Ge-, where each R' is independently selected from hydrogen atoms or C which may contain one or more heteroatoms of Groups 14 to 16 of the Periodic Table or fluorine atoms. 1 ~C 20-hydrocarbyl group, or two R' groups together may form a ring. In one embodiment, R' may be an alkyl having 1 to 10 carbon atoms substituted with an alkoxy having 1 to 10 carbon atoms.

[0065] The term "heteroatom belonging to Groups 14 to 16 of the Periodic Table" includes, for example, Si, N, O or S.

[0066] Preferably, L is -R' 2 Si-, ethylene or methylene.

[0067] Expression-R' 2 In Si-, each R' is independently preferably C 1 ~C 20 -hydrocarbyl radical. Hence the term C 1~20 The hydrocarbyl group is C 1~20 -Alkyl, C 2~20 -Alkenyl, C 2~20 -Alkynyl, C 3~20 -Cycloalkyl, C 3~20 -Cycloalkenyl, C 6~20 -aryl group, C 7~20 -alkylaryl group or C 7~20 -arylalkyl groups, or of course combinations of these groups, such as cycloalkyl substituted with alkyl. Unless otherwise specified, preferred C 1~20 The hydrocarbyl group is C 1~20 -Alkyl, C 4~20 -Cycloalkyl, C 5~20 -Cycloalkyl-alkyl group, C 7~20 -alkylaryl group, C 7~20 -arylalkyl group, or C 6~20 -aryl group.

[0068] In one embodiment, the formula -R' 2 Si- represents a silacycloalkanediyl, such as silacyclobutane, silacyclopentane or 9-silafluorene.

[0069] Preferably, both R' groups are the same. 1 ~C 10 -hydrocarbyl or C 6 ~C 10 -aryl groups, such as methyl, ethyl, propyl, isopropyl, tertbutyl, isobutyl, C 3~8 -cycloalkyl, cyclohexylmethyl, phenyl or benzyl, more preferably both R' are C 1 ~C 6 -Alkyl, C 5~6- Cycloalkyl or C 6 -aryl group, most preferably both R' are methyl or one is methyl and the other is cyclohexyl. Most preferably, the bridge is -Si(CH 3 ) 2 -It is.

[0070] 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 ring, a thiophenyl ring or a pyridyl ring. However, it is preferred if the Ar group is a phenyl group.

[0071] When Ar is a phenyl group, R 1 Preferably the substituents are at the 3, 4 and 5 ring positions (wherein the 1 position is attached to the indenyl ring).

[0072] Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 -arylalkyl group, C 7~20 -alkylaryl group or C 6~20 -aryl group or OY group, where Y is C 1~10 -hydrocarbyl group, and two adjacent R 1 The groups may be part of a ring that includes the phenyl carbon to which they are attached.

[0073] Preferably, each R 1 are independently the same or different and are a hydrogen atom or a linear or branched C alkyl group, such as methyl or tert-butyl. 1 ~C 6 -alkyl group.

[0074] For example, the Ar ring, e.g., a phenyl ring, is unsubstituted (i.e., R 1 is a hydrogen atom), it can be substituted only at the para position, such as 4'-tert.-butylphenyl, or it can be substituted at the 3' and 5' positions, such as 3',5'-dimethylphenyl or 3',5'-ditert.-butylphenyl. Moreover, both phenyl rings can have the same substitution pattern, or the two phenyl rings can have different substitution patterns.

[0075] Therefore, one or two R 1 It is preferred if the group is H. Two R 1 If the group is H, the remaining R 1 The group is preferably in the para position. 1 If the group is H, the remaining R 1 The group is preferably in the meta position.

[0076] Each R 2 may be independently the same or different, and CHR 8’ -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group, C 3~8 -Cycloalkyl group, C 6~10 -aryl group, 1 to 3 R 11 R is a heteroaryl group having 3 to 20 carbon atoms, optionally substituted by a group; 8’ is H or C 1~6 It is an alkyl.

[0077] Preferably, R8’ is H or, in particular, H.

[0078] Preferably, each R 2 may be independently the same or different, and CH 2 -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group, C 3~8 -Cycloalkyl group, C 6~10 -aryl group.

[0079] Preferably, R 2 are the same, and CH 2 -R 8 group, where R 8 is H or linear or branched C 1 ~C 4 -alkyl group, more preferably R 2 are the same, and CH 2 -R 8 is a group, where R 8 is H or linear or branched C 1 ~C 3 -alkyl groups. Most preferably, both R 2 is methyl.

[0080] R 3 is a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 -arylalkyl group, C 7~20 -alkylaryl group or C 6 ~C 20 -aryl group.

[0081] R 3 is preferably a linear or branched, C 1 ~C 6 -Alkyl group or C 6~20 -aryl groups, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl and tert.-butyl, preferably linear C1 ~C 4 -alkyl group, more preferably C 1 ~C 2 -alkyl group, most preferably methyl.

[0082] R 4 is preferably C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 -alkyl group.

[0083] Preferably, each R 9 may be the same or different, where R 9 is a linear or branched C 1 ~C 4 -alkyl group, more preferably R 9 is the same and C 1 ~C 2 -alkyl group. Most preferably, R 4 is a tert.-butyl group, and therefore all R 9 The group is methyl.

[0084] In one embodiment of the present invention, R 5 and R 6 are independently the same or different and may contain a hydrogen atom or one or more heteroatoms from groups 14 to 16 of the periodic table of the elements; 1 ~C 20 - a hydrocarbyl group, for example an alkyl or alkoxy group, for example C 1 ~C 10 - an alkyl or alkoxy group.

[0085] Preferably, R 5 and R 6 may be independently the same or different, and each independently represents a hydrogen atom or a linear or branched C 1 ~C 6 Alkyl group or C 1 ~C 6-alkoxy group.

[0086] More preferably, R 5 and R 6 may be independently the same or different, and each independently represents a hydrogen atom or a linear or branched C 1 ~C 4 -Alkyl group or C 1 ~C 4 -alkoxy group.

[0087] In other embodiments, R 5 and R 6 may be fused to indenyl to form a part of a five-membered ring, and the five-membered ring may include n R 10 group, where n is 0 to 4, preferably 0 or 2, more preferably 0; where each R 10 may be the same or different, and C 1 ~C 20 - a hydrocarbyl group or a C group which may contain one or more heteroatoms belonging to groups 14 to 16 of the periodic table of the elements 1 ~C 20 -hydrocarbyl group; preferably linear or branched C 1 ~C 6 -alkyl group; preferably a linear or branched C 1 ~C 6 -alkyl group.

[0088] R 7 is H or linear or branched C 1 ~C 6 - an alkyl group or 1 to 3 R 11 It is an aryl or heteroaryl group, optionally substituted by a group.

[0089] Preferably, R 7 is H or 1 to 3 R 11 R is an aryl group having 6 to 10 carbon atoms, which may be substituted by a group. 7 is H or 1 to 3 R11 It is a phenyl group which may be substituted by a group.

[0090] R 7 is an optionally substituted aryl group having 6 to 10 carbon atoms, e.g., phenyl, then each R 11 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 -arylalkyl group, C 7~20 -alkylaryl group or C 6~20 -aryl group or OY group, where Y is C 1~10 -hydrocarbyl groups.

[0091] More preferably, R 7 But 1 to 3 R 11 R is a phenyl group optionally substituted by a group, and more preferably 7 1 to 2 R 11 It is a phenyl group which may be substituted by a group.

[0092] Preferably, each R 11 may be independently the same or different and are a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group or C 6~20 -aryl group or OY group, where Y is C 1~4 -hydrocarbyl group, more preferably each R 11 may be independently the same or different, and each independently represents a hydrogen atom or a linear or branched C 1 ~C 4 -alkyl group or OY group, where Y is C 1~4 Even more preferably, each R 11 are independently the same or different and are a hydrogen atom, methyl, ethyl, isopropyl, tert.-butyl or methoxy, in particular a hydrogen atom, methyl or tert.-butyl.

[0093] Even more preferably, each R 11 are independently the same or different and are methyl, ethyl, isopropyl, tert.-butyl or methoxy, in particular methyl or tert.-butyl.

[0094] When an aryl group, such as a phenyl group, is substituted, it preferably has one or two R 11 Groups, e.g. R other than H 11 Group, substituted by.

[0095] Group at 4th position and R 7 It is most preferred when the groups R 7 is a 3,5-dimethylphenyl group, then the group on the 4-position of the ligand should be a 3,5-dimethylphenyl group. This is particularly true when the ring is an indacenyl ring.

[0096] In a preferred embodiment, the metallocene complex has one of the following formulas (I) to (III):

[0097] [ka]

[0098] each X is independently a sigma donor ligand; M is Ti, Zr, Hf, Y, Sc, La or an element from the lanthanides, preferably Ti, Zr or Hf; each Cp is independently an unsubstituted or substituted cyclopentadienyl-containing ligand and / or an unsubstituted or substituted fused cyclopentadienyl-containing ligand; Q is -O or -NW or -PW; W is an organic group or H; L is a carbon, silicon or germanium based bridge in which 1 to 4 backbone atoms link multiple said ligands; and r is an integer such that the oxidation state of the metal is satisfied. When M is Ti, Zr or Hf, r is 2.

[0099] The term cyclopentadienyl-containing ligand means any ligand in which a cyclopentadienyl ring is present, which may be cyclopentadienyl itself, or it may be cyclopentadienyl fused to another ring, making such as indenyl.

[0100] In a more preferred embodiment, the metallocene complex is of formula (VI):

[0101] [ka]

[0102] each X is independently a sigma donor ligand; M is a Group 4 metal, such as Zr or Hf; L is a carbon, silicon or germanium based bridge in which 1 to 4 backbone atoms link multiple said ligands; and Each Ind is a substituted or unsubstituted indenyl, or a substituted or unsubstituted fused indenyl, such as a substituted or unsubstituted indacenyl ligand, or a substituted or unsubstituted fluorenyl ligand.

[0103] More preferred metallocenes are of formula (VII):

[0104] [ka]

[0105] each X is independently a sigma donor ligand; M is a Group 4 metal, such as Zr or Hf; L is a carbon, silicon or germanium based divalent bridge in which one or two backbone atoms link multiple of said ligands; R 2 and R 2’ are independently H, -OSi(C 1~10 -hydrocarbyl) 3 , C.H.R. 8’ -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group, C 3~8 -Cycloalkyl group, C 6~10 - an aryl group or an optionally substituted heteroaryl group having 3 to 20 carbon atoms; and R 8’ is H or C 1~6 is alkyl; R 4~6 are independently hydrogen atoms or C which may contain one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - a hydrocarbyl group; R 4’~6’ are independently hydrogen atoms or C which may contain one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - is a hydrocarbyl group; or R 5 and R 6 may be taken together to form an optionally substituted 5- or 6-membered carbocyclic ring; and / or R 5’ and R 6’ may be taken together to form an optionally substituted 5- or 6-membered carbocyclic ring; R 7 may contain hydrogen atoms or up to two silicon atoms or heteroatoms, C 1~20 is a hydrocarbyl group; and R 7’ is a hydrogen atom, C 1~3 Hydrocarbyl group or C 1~10 It is an alkoxy group.

[0106] More preferred metallocenes are those of formula (VIII) below:

[0107] [ka]

[0108] each X is independently a sigma donor ligand; M is a Group 4 metal, such as Zr or Hf; L is a carbon, silicon or germanium based divalent bridge in which one or two backbone atoms link multiple of said ligands; R 2 and R 2’ are independently H, -OSi(C 1~10 -hydrocarbyl) 3 , C.H.R. 8’ -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group, C 3~8 -Cycloalkyl group, C 6~10 - an aryl group or an optionally substituted heteroaryl group having 3 to 20 carbon atoms, and R 8’ is H or C 1~6 is alkyl; R 5~6 are independently hydrogen atoms or C which may contain one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - a hydrocarbyl group; R 5’~6’ are independently hydrogen atoms or C which may contain one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - is a hydrocarbyl group; or R 5 and R 6 Taken together, n R 10 where n is 0 to 4; or R 5’and R 6’ Taken together, n R 10 wherein n is 0 to 4; Each R 10 may be the same or different, and C 1 ~C 20 - a hydrocarbyl group or a C group which may contain one or more heteroatoms belonging to groups 14 to 16 of the periodic table of the elements 1 ~C 20 - may be a hydrocarbyl group; R 7 may contain hydrogen atoms or up to two silicon atoms or heteroatoms, C 1~20 is a hydrocarbyl group; R 7’ is a hydrogen atom, C 1-3 Hydrocarbyl group, or C 1~10 is an alkoxy group; Ar and Ar′ are independently 5 or less R 1 C 6 ~C 22 Aryl group or C 3 ~C 20 is a heteroaryl group; and R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 -arylalkyl group, C 7~20 -alkylaryl group or C 6~20 -aryl group or OY group, where Y is C 1~10 -hydrocarbyl groups.

[0109] More preferred metallocenes are those of formula (IX) below:

[0110] [ka]

[0111] each X is independently a sigma donor ligand; M is a Group 4 metal, such as Zr or Hf; L is a carbon, silicon or germanium based divalent bridge in which one or two backbone atoms link multiple of said ligands; R 2 and R 2’ are independently H, -OSi(C 1~10 -hydrocarbyl) 3 , C.H.R. 8’ -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group, C 3~8 -Cycloalkyl group, C 6~10 - an aryl group or an optionally substituted heteroaryl group having 3 to 20 carbon atoms; and R 8’ is H or C 1~6 is alkyl; R 5~6 are independently hydrogen atoms or C which may contain one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - a hydrocarbyl group; R 5’~6’ are independently hydrogen atoms or C which may contain one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - is a hydrocarbyl group; or R 5 and R 6 Taken together, n R 10 where n is 0 to 4; or R 5’ and R 6’ Taken together, n R 10 wherein n is 0 to 4; Each R 10 may be the same or different, and C 1 ~C20 - a hydrocarbyl group or a C group which may contain one or more heteroatoms belonging to groups 14 to 16 of the periodic table of the elements 1 ~C 20 - may be a hydrocarbyl group; Ar and Ar' are R of 5 or less. 1 phenyl, naphthyl, anthracenyl, pyridyl, thiophenyl, 2-alkylthiophenyl, benzothiophenyl, pyrrolyl, furanyl, 2-alkylfuranyl, optionally substituted by groups; and R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 -arylalkyl group, C 7~20 -alkylaryl group or C 6~20 -aryl group or OY group, where Y is C 1~10 -hydrocarbyl groups.

[0112] More preferred metallocenes are of formula (X):

[0113] [ka]

[0114] each X is independently a sigma donor ligand; M is a Group 4 metal, such as Zr or Hf; L is a carbon, silicon or germanium based divalent bridge in which one or two backbone atoms link multiple of said ligands; R 2 and R 2’ are independently H, -OSi(C 1~10 -hydrocarbyl) 3 , C.H.R. 8’ -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group, C 3~8-Cycloalkyl group, C 6~10 - an aryl group or an optionally substituted heteroaryl group having 3 to 20 carbon atoms; and R 8’ is H or C 1~6 is alkyl; R 5~6 is a hydrogen atom or a C which may contain one or more heteroatoms from groups 14 to 16 of the periodic table of the elements 1 ~C 20 - a hydrocarbyl group; R 5’~6’ is a hydrogen atom or a C which may contain one or more heteroatoms from groups 14 to 16 of the periodic table of the elements 1 ~C 20 - is a hydrocarbyl group; or R 5 and R 6 Taken together, n R 10 where n is 0 to 4; or R 5’ and R 6’ Taken together, n R 10 wherein n is 0 to 4; Each R 10 may be the same or different, and C 1 ~C 20 - a hydrocarbyl group or a C group which may contain one or more heteroatoms belonging to groups 14 to 16 of the periodic table of the elements 1 ~C 20 - may be a hydrocarbyl group; Ar is R less than 5 1 phenyl optionally substituted by a group; Ar' is R less than 5 1 phenyl, naphthyl, anthracenyl, pyridyl, thiophenyl, 2-alkylthiophenyl, benzothiophenyl, pyrrolyl, furanyl, 2-alkylfuranyl, optionally substituted by groups; and R 1may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 -arylalkyl group, C 7~20 -alkylaryl group or C 6~20 -aryl group or OY group, where Y is C 1~10 -hydrocarbyl groups.

[0115] More preferred metallocenes are those of formula (XI) below:

[0116] [ka]

[0117] each X is independently a sigma donor ligand; L is a carbon, silicon or germanium based divalent bridge in which one or two backbone atoms link multiple of said ligands; Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 -arylalkyl group, C 7~20 -alkylaryl group or C 6~20 -aryl group or OY group, where Y is C 1~10 -hydrocarbyl group, and two adjacent R 1 The groups may be part of a ring that includes the phenyl carbon to which they are attached; Each R 2 may be independently the same or different, and CHR 8’ -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group, C 3~8 -Cycloalkyl group, C 6~10 -aryl group or 1 to 3 R 11a heteroaryl group having 3 to 20 carbon atoms, optionally substituted by a group; and R 8’ is H or C 1~6 is alkyl; R 5 is an aliphatic C which may contain a hydrogen atom or one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - a hydrocarbyl group; R 6 is an aliphatic C which may contain a hydrogen atom or one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - is a hydrocarbyl group; or R 5 and R 6 Taken together, n R 10 wherein n is 0 to 4; R 5' is an aliphatic C which may contain a hydrogen atom or one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - a hydrocarbyl group; R 6' is an aliphatic C which may contain a hydrogen atom or one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - is a hydrocarbyl group; or R 5’ and R 6’ Taken together, n R 10 where n is 0 to 4; and Each R 10 may be the same or different, and C 1 ~C 20 - a hydrocarbyl group or a C group which may contain one or more heteroatoms belonging to groups 14 to 16 of the periodic table of the elements 1 ~C 20 -hydrocarbyl groups.

[0118] In a more preferred embodiment, the metallocene complex may be of formula (XII):

[0119] [ka]

[0120] each X is independently a sigma donor ligand; M is Zr or Hf; L is a carbon, silicon or germanium based divalent bridge in which one or two backbone atoms link multiple of said ligands; each 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; Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 -arylalkyl group, C 7~20 -alkylaryl group or C 6~20 -aryl group or OY group, where Y is C 1~10 -hydrocarbyl group, and two adjacent R 1 The groups may be part of a ring that includes the phenyl carbon to which they are attached; Each R 2 may be independently the same or different, and CHR 8’ -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group, C 3~8 -Cycloalkyl group, C 6~10 -aryl group or 1 to 3 R 11 R is a heteroaryl group having 3 to 20 carbon atoms, optionally substituted by a group; 8’ is H or C 1~6 is alkyl; R 3is a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 -arylalkyl group, C 7~20 -alkylaryl group or C 6 ~C 20 - an aryl group; R 4 is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 - is an alkyl group; R 5 is an aliphatic C which may contain a hydrogen atom or one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - a hydrocarbyl group; R 6 is an aliphatic C which may contain a hydrogen atom or one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - is a hydrocarbyl group; or R 5 and R 6 Taken together, n R 10 wherein n is 0 to 4; Each R 10 may be the same or different, and C 1 ~C 20 - a hydrocarbyl group or a C group which may contain one or more heteroatoms belonging to groups 14 to 16 of the periodic table of the elements 1 ~C 20 - may be a hydrocarbyl group; R 7 is a linear or branched C 1 ~C 6 - an alkyl group or 1 to 3 R 11 an aryl or heteroaryl group, such as a phenyl ring or a 5- or 6-membered heteroaryl ring, optionally substituted by a group; Each R 11may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 -arylalkyl group, C 7~20 -alkylaryl group or C 6~20 -aryl group or OY group, where Y is C 1~10 -hydrocarbyl groups.

[0121] In a more preferred embodiment, the metallocene complex may be of formula (XIII):

[0122] [ka]

[0123] each X is independently a sigma donor ligand; M is Zr or Hf; L is -R' 2 C-, -R' 2 C-CR' 2 -,-R' 2 Si-, -R' 2 Si-SiR' 2 -,-R' 2 Ge-, where each R' is independently a hydrogen atom or one or more heteroatoms of Groups 14-16 of the Periodic Table or fluorine atoms, 1 ~C 20 - a hydrocarbyl group, or two R' groups may be joined together to form a ring; Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 Arylalkyl groups, C 7~20 Alkylaryl group or C 6~20 an aryl group or an OY group, where Y is C 1~10 -hydrocarbyl group, and two adjacent R 1The groups may be part of a ring that includes the phenyl carbon to which they are attached; Each R 2 may be independently the same or different, and CH 2 -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group, C 3~8 Cycloalkyl groups, C 6~10 is an aryl group; R 3 is a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 Arylalkyl groups, C 7~20 Alkylaryl group or C 6 ~C 20 - an aryl group; R 4 is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; R 5 is an aliphatic C which may contain a hydrogen atom or one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - a hydrocarbyl group; R 6 is an aliphatic C which may contain a hydrogen atom or one or more heteroatoms from groups 14 to 16 of the periodic table of the elements. 1 ~C 20 - is a hydrocarbyl group; or R 5 and R 6 Taken together, n R 10 wherein n is 0 to 4; Each R 10 may be the same or different, and C 1 ~C 20- a hydrocarbyl group or a C group which may contain one or more heteroatoms belonging to groups 14 to 16 of the periodic table of the elements 1 ~C 20 - may be a hydrocarbyl group; R 7 is a linear or branched C 1 ~C 6 -Alkyl group or 1 to 3 R 11 an aryl or heteroaryl group having 6 to 20 carbon atoms, optionally substituted by a group; Each R 11 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 Arylalkyl groups, C 7~20 Alkylaryl group or C 6~20 an aryl group or an OY group, where Y is C 1~10 -hydrocarbyl groups.

[0124] In a more preferred embodiment, the metallocene complex may be of formula (XIV):

[0125] [ka]

[0126] each X is independently a sigma donor ligand; M is Zr or Hf; L is -R' 2 C- or -R' 2 where each R' is independently a hydrogen atom or a C which may contain one or more heteroatoms of Groups 14-16 of the Periodic Table or fluorine atoms. 1 ~C 20 - a hydrocarbyl group, or two R' groups may be joined together to form a ring; Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C1 ~C 6 -Alkyl group, C 7~20 Arylalkyl groups, C 7~20 Alkylaryl group or C 6~20 an aryl group or an OY group, where Y is C 1~10 -hydrocarbyl group, and two adjacent R 1 The groups may be part of a ring that includes the phenyl carbon to which they are attached; Each R 2 may be independently the same or different, and CH 2 -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group, C 3~8 Cycloalkyl groups, C 6~10 is an aryl group; R 3 is a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 Arylalkyl groups, C 7~20 Alkylaryl group or C 6 ~C 20 - an aryl group; R 4 is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; R 5 is a hydrogen atom; R 6 is a hydrogen atom; or R 5 and R 6 Taken together, n R 10 wherein n is 0 to 4; Each R 10 may be the same or different, and C 1 ~C 20- a hydrocarbyl group or a C group which may contain one or more heteroatoms belonging to groups 14 to 16 of the periodic table of the elements 1 ~C 20 - may be a hydrocarbyl group; R 7 is a linear or branched C 1 ~C 6 -Alkyl group or 1 to 3 R 11 is an aryl optionally substituted by a group; Each R 11 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 Arylalkyl groups, C 7~20 Alkylaryl group or C 6~20 an aryl group or an OY group, where Y is C 1~10 -hydrocarbyl groups.

[0127] In a more preferred embodiment, the metallocene complex may be of formula (XV):

[0128] [ka]

[0129] each X is independently a sigma donor ligand; M is Zr or Hf; L is -R' 2 C- or -R' 2 Si-, where each R' is independently selected from 1 ~C 6 -Alkyl, C 5~6- Cycloalkyl, C 1~10 -Alkyl-OC 1~10 Alkyl or C 6 - an aryl group; each Ar is a phenyl ring or a 5- or 6-membered heteroaryl ring; Each R 1may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 - is an alkyl group; Each R 2 may be independently the same or different, and CHR 8’ -R 8 group, where R 8 is H or linear or branched C 1~6 -alkyl group, and R 8’ is H or C 1~6 is alkyl; R 3 is a linear or branched C 1 ~C 6 -Alkyl group, C 7~20 -arylalkyl group, C 7~20 -alkylaryl group or C 6 ~C 20 - an aryl group; R 4 is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 - is an alkyl group; R 5 is a hydrogen atom; R 6 is a hydrogen atom; or R 5 and R 6 may be taken together to form a five-membered saturated carbocyclic ring; R 7 is a linear or branched C 1 ~C 6 - an alkyl group or 1 to 3 R 11 an aryl or heteroaryl group, for example 1 to 3 R 11 a phenyl ring or a 5- or 6-membered heteroaryl ring, optionally substituted by a group; and Each R 11may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -alkyl group.

[0130] In a more preferred embodiment, the metallocene complex may be of formula (XVI):

[0131] [ka]

[0132] each X is independently a sigma donor ligand; M is Zr or Hf; L is -R' 2 C- or -R' 2 Si-; where each R' is independently selected from 1 ~C 6 -Alkyl, C 5~6- Cycloalkyl, C 1~10 -Alkyl-OC 1~10 Alkyl or C 6 - an aryl group; each Ar is a phenyl ring or a 5- or 6-membered heteroaryl ring; Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 - is an alkyl group; Each R 2 may be independently the same or different, and CHR 8’ -R 8 group, where R 8 is H or linear or branched C 1~6 -alkyl group, and R 8’ is H or C 1~6 is alkyl; R 3 is a linear or branched C 1 ~C 6 - is an alkyl group; R4 is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 - is an alkyl group; R 5 and R 6 may be taken together to form a five-membered saturated carbocyclic ring; R 7 1 to 3 R 11 a phenyl ring or a 5- or 6-membered heteroaryl ring, optionally substituted by a group; and Each R 11 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -alkyl group.

[0133] In a more preferred embodiment, the metallocene complex may be of formula (XVII):

[0134] [ka]

[0135] each X is independently a sigma donor ligand; M is Zr or Hf; L is -R' 2 C- or -R' 2 Si-, where each R' is independently selected from 1 ~C 6 -Alkyl, C 5~6- Cycloalkyl, C 1~10 -Alkyl-OC 1~10 Alkyl or C 6 - an aryl group; Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 - is an alkyl group; Each R 2may be independently the same or different, and CH 2 -R 8 group, where R 8 is H or linear or branched C 1~6 - is an alkyl group; R 3 is a linear or branched C 1 ~C 6 - is an alkyl group; R 4 is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; R 5 is a hydrogen atom; R 6 is a hydrogen atom; or R 5 and R 6 may be taken together to form a five-membered saturated carbocyclic ring; R 7 1 to 3 R 11 a phenyl group optionally substituted by a group; Each R 11 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -alkyl group.

[0136] In a more preferred embodiment, the metallocene complex may be of formula (XVIII):

[0137] [ka]

[0138] each X is independently a sigma donor ligand; M is Zr or Hf; L is -R' 2 Si-; where each R' is independently C 1 ~C6 -Alkyl, C 5~6- Cycloalkyl, C 1~10 -Alkyl-OC 1~10 Alkyl or C 6 - an aryl group; Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 - is an alkyl group; Each R 2 may be independently the same or different, and CH 2 -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group R 2 , for example methyl; R 3 is a linear or branched C 1 ~C 6 -alkyl group, R 4 is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; R 6 is O.C. 1 ~C 6 - is an alkyl group; R 5 is C(R 9 ) groups, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; or R 5 and R 6 may be taken together to form a five-membered saturated carbocyclic ring; R 7 is H or 1 to 3 R 11 a phenyl group optionally substituted by a group; Each R 11may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -alkyl group.

[0139] In a more preferred embodiment, the metallocene complex may be of formula (XIX):

[0140] [ka]

[0141] each X is independently a sigma donor ligand; M is Zr or Hf; L is -R' 2 Si-; where each R' is independently C 1 ~C 6 -Alkyl, C 5~6- Cycloalkyl, C 1~10 -Alkyl-OC 1~10 Alkyl or C 6 - an aryl group; Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 - is an alkyl group; Each R 2 may be independently the same or different, and CH 2 -R 8 group, where R 8 is H or linear or branched C 1~6 -Alkyl group R 2 , for example methyl; R 6 is O.C. 1 ~C 6 - is an alkyl group; R 5 is C(R 9 ) groups, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; R 5’ OC 1 ~C 6 - is an alkyl group; R 6’ is C(R 9 ) groups, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; or R 5 and R 6 may be taken together to form a five-membered saturated carbocyclic ring; R 5’ and R 6' may be taken together to form a five-membered saturated carbocyclic ring; R 7 is H or 1 to 3 R 11 a phenyl group optionally substituted by a group; Each R 11 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -alkyl group.

[0142] In a more preferred embodiment, the metallocene complex may be of formula (XX):

[0143] [ka]

[0144] each X is independently a sigma donor ligand; M is Zr or Hf; L is -R' 2 Si-; where each R' is independently C 1 ~C 6 -Alkyl, C 5~6- Cycloalkyl, C 1~10 -Alkyl-OC 1~10 Alkyl or C 6 - an aryl group; Each R 1may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 - is an alkyl group; Each R 2 may be independently the same or different, and CH 2 -R 8 group, where R 8 is H or linear or branched C 1~6 - is an alkyl group; R 3 is a linear or branched C 1 ~C 6 -alkyl group, R 4 is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; R 7 1 to 3 R 11 a phenyl group optionally substituted by a group; Each R 11 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -alkyl group.

[0145] In a more preferred embodiment, the metallocene complex may be of formula (XXI):

[0146] [ka]

[0147] Each X is independently a sigma donor ligand, e.g., a halogen atom, a linear or branched C 1~4 -Alkyl or C 1~4 - an alkoxy group, a phenyl group or a benzyl group; M is Zr or Hf; L is -R' 2Si-; where each R' is independently C 1 ~C 6 -Alkyl, C 5~6- Cycloalkyl, C 1~10 -Alkyl-OC 1~10 Alkyl or C 6 - an aryl group; Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 - is an alkyl group; R 3 is a linear or branched C 1 ~C 6 - is an alkyl group; R 4 is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; R 7 1 to 3 R 11 a phenyl group optionally substituted by a group; Each R 11 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -alkyl group.

[0148] In a more preferred embodiment, the metallocene complex may be of formula (XXII):

[0149] [ka]

[0150] Each X is independently a sigma donor ligand, e.g., a halogen atom, a linear or branched C 1~4 -Alkyl or C 1~4 - an alkoxy group, a phenyl group or a benzyl group; L is -Me 2Si- and; Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 - is an alkyl group; R 3 is a linear or branched C 1 ~C 6 -alkyl group, R 4 is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; R 7 1 to 3 R 11 a phenyl group optionally substituted by a group; Each R 11 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -alkyl group.

[0151] Particularly preferred complexes of the present invention include: rac-Dimethylsilanediyl-bis-[2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-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, rac-anti-dimethylsilanediyl[2-methyl-4-(4'-tert.-butylphenyl)-inden-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(3',5'-ditert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-ditert-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-Dimethylsilanediylbis[2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, rac-Dimethylsilanediylbis(2-methyl-4-(3',5'-ditertbutylphenyl)-5-methoxy-6-tert-butylinden-1-yl)zirconium dichloride, rac-Dimethylsilanediylbis[2-methyl-4-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, or their Hf analoguesHf analogues.

[0152] For the avoidance of doubt, any narrower definition of a substituent provided above can be combined with any other broader or narrower definition of any other substituent. Throughout the above description, wherever a narrower definition of a substituent is given, the narrower definition will be deemed to be disclosed in conjunction with all broader and narrower definitions of other substituents in this application.

[0153] The ligands required to form the complex, and therefore the catalyst of the present invention, can be synthesized by any process, and an organic chemist skilled in the art will be able to devise various synthetic protocols for the preparation of the required ligand materials. By way of example, WO 2007 / 116034 discloses the necessary chemistry. Synthetic protocols are also generally disclosed in WO 2002 / 02576, WO 2011 / 135004, WO 2012 / 084961, WO 2012 / 001052, WO 2011 / 076780, WO 2015 / 158790, and WO 2018 / 122134. The Examples section also provides sufficient guidance to the skilled artisan.

[0154] Cocatalyst

[0155] In order to form an active catalytic species, it is usually necessary to use a promoter, as is well known in the art.

[0156] In accordance with 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.

[0157] The aluminoxane cocatalyst may be of formula (A):

[0158] [ka]

[0159] Here, n is 6 to 20, and R has the following meaning:

[0160] Aluminoxanes can be prepared by the partial hydrolysis of organoaluminum compounds, e.g., those of the formula AlR 3 , AlR 2 Y and Al 2 R 3 Y 3 where R is, for example, C 1 ~C 10 -alkyl, preferably C 1 ~C 5 -Alkyl or C 3 ~C 10 -Cycloalkyl, C 7 ~C 12 -arylalkyl or alkylaryl, and / or phenyl or naphthyl, and where Y is a hydrogen atom, a halogen, preferably a chlorine or bromine atom, or C 1 ~C 10 -alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing aluminoxanes are generally not pure compounds, but are mixtures of oligomers of formula (A).

[0161] A preferred aluminoxane is methylaluminoxane (MAO). The aluminoxanes used according to the invention as cocatalysts are not pure compounds due to their mode of preparation, so that hereinafter the molar concentrations of the aluminoxane solutions are based on their aluminum content.

[0162] In accordance with the present invention, a boron-containing cocatalyst is also used in combination with the aluminoxane cocatalyst. Boron-containing cocatalysts of interest include those of formula (B) below: BY 3 (B) wherein Y may be 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 alkylaryl, an arylalkyl, a haloalkyl or a haloaryl, wherein each of the alkyl radicals has 1 to 10 carbon atoms and each of the aryl radicals has 6 to 20 carbon atoms, or a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Preferred examples for Y are a fluorine atom, trifluoromethyl, an aromatic fluorinated group, such as p-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl, and 3,5-di(trifluoromethyl)phenyl. Preferred choices are trifluoroborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(penta-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, and / or tris(3,4,5-trifluorophenyl)borane.

[0163] Tris(pentafluorophenyl)borane is particularly preferred.

[0164] However, it is preferred that borates, ie compounds containing borate, are used.

[0165] These compounds generally include an anion of formula (C): (Z) 4 B - (C) wherein Z is an optionally substituted phenyl derivative, wherein the substituent is haloC 1~6 -alkyl or halo groups. Preferred choices are fluoro or trifluoromethyl. Most preferably, the phenyl group is fluorinated.

[0166] Such ionic cocatalysts are preferably weakly-coordinating anions, such as tetrakis(pentafluorophenyl)borate or tetrakis(3,5-di(trifluoromethyl)phenyl)borate.

[0167] Suitable cationic counterions include triphenylcarbenium or protonated amine or aniline derivatives, such as methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylanilinium, or p-nitro-N,N-dimethylanilinium.

[0168] Preferred ionizing compounds that may be used in accordance with the present invention include: tributylammonium tetrakis(pentafluorophenyl)borate, tributylammonium tetrakis(trifluoromethylphenyl)borate, tributylammonium tetrakis(4-fluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-di(propyl)ammonium tetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammonium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, or Ferrocenium tetrakis(pentafluorophenyl)borate.

[0169] Preferably, the following is provided: triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, or N,N-Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate.

[0170] It has surprisingly been found that certain boron-containing cocatalysts are particularly preferred. Thus, the preferred borates for use in the present invention contain the trityl, i.e., triphenylcarbenium ion. Thus, Ph 3 CB(PhF 5 ) 4 and their analogues are particularly preferred.

[0171] Suitable amounts of promoter will be known to those skilled in the art.

[0172] Preferably, the amount of promoter is selected to reach less than the defined molar ratio.

[0173] The molar ratio of the supply amount of boron (B) to the metal ion M (preferably zirconium) of the metallocene, boron / M, is in the range of 0.1:1 to 10:1 mol / mol, preferably 0.3:1 to 7:1, particularly 0.3:1 to 5:1 mol / mol.

[0174] Even more preferably, the molar ratio of the supply amount of boron (B) to the metal ion M (preferably zirconium) of the metallocene, boron / M, is 0:3:1 to 3:1.

[0175] The molar ratio Al / M of aluminum from the aluminoxane to the metal ion M (preferably zirconium) of the metallocene is in the range of 1:1 to 2000:1 mol / mol, preferably 10:1 to 1000:1 mol / mol, more preferably 50:1 to 600:1 mol / mol.

[0176] Catalyst system

[0177] The metallocene complexes described above are used together with suitable cocatalyst combinations as described above.

[0178] The catalyst system of the present invention is used in supported form. The particulate support material used is silica, an inorganic porous support such as silica, alumina or a mixed oxide such as silica-alumina, in particular silica.

[0179] The use of a silica support is preferred.

[0180] Particularly preferably, the particulate support is a porous material such that the complex can be applied within the pores of the support using methods similar to those described in WO 94 / 14856, WO 95 / 12622, WO 2006 / 097497 and European Patent Application EP 18282666.

[0181] The support, for example a silica support, may have an average particle size of 10 to 100 μm. However, it has been found that particular advantages can be obtained when the support has an average particle size of 15 to 80 μm, preferably 18 to 50 μm.

[0182] The support, for example a silica support, may have an average pore size in the range of 10-100 nm and a pore volume in the range of 1-3 mL / g.

[0183] Examples of suitable support materials are, for example, ES757 manufactured and sold by PQ Corporation, Sylopol 948 manufactured and sold by Grace, or SUNSPERA DM-L-303 silica manufactured by AGC Si-Tech Co. The support can optionally be calcined prior to use in the catalyst preparation to reach an optimum silanol group content.

[0184] The use of these supports is routine in the art.

[0185] The catalyst may contain 5 to 500 micromoles of transition metal per gram of silica, for example 10 to 100 micromoles, and 3 to 15 millimoles of Al per gram of silica.

[0186] Preparation process:

[0187] Process a) In step a), the porous inorganic support is treated with an aluminoxane cocatalyst.

[0188] Preferably, the support is silica. Preferably, the reaction is carried out with a synthesis stoichiometry of Al in the aluminoxane to support in the range of 3 to 12 mmol Al / g support.

[0189] The support is preferably calcined prior to step a) in order to remove moisture from its surface. The calcination temperature is usually in the range of 200-800°C, preferably in the range of 400-650°C.

[0190] The porous inorganic support, preferably a silica support, is then suspended in a suitable hydrocarbon solvent, such as toluene, for example, at a temperature between 15° C. and 25° C. under an inert gas atmosphere, for example nitrogen.

[0191] The support / solvent, preferably silica / toluene, suspension is stirred for a few minutes, preferably 5 to 60 minutes, more preferably 10 to 30 minutes.

[0192] An aluminoxane cocatalyst, preferably MAO (e.g., as a 30 wt % solution in toluene), is then added, preferably SiO 2 A stoichiometry of 3-12 mmol of Al per gram of silica is added to the support / silica / toluene suspension.

[0193] According to the present invention, all or most of the aluminoxane cocatalyst is added in step a), so that 75.0 to 100.0% by weight, preferably 77.0 to 95.0% by weight, more preferably 85.0 to 92.0% by weight of the total amount of the aluminoxane cocatalyst is added in step a).

[0194] In one embodiment, 97.1 to 100% of the aluminoxane cocatalyst is added in step a).

[0195] After addition of the aluminoxane cocatalyst, support / solvent / aluminoxane, the mixture may optionally be heated to a temperature in the range, for example, of 60° C. to 120° C., preferably 70° C. to 120° C., more preferably 80° C. to 120° C., even more preferably 80° C. to 100° C. The support is preferably silica and the solvent is preferably toluene.

[0196] The mixture can be stirred at this temperature for a few minutes to a few hours, preferably 60 minutes to 5 hours, more preferably 90 minutes to 3 hours.

[0197] Thereafter, stirring is stopped, the slurry so obtained is allowed to settle, and the mother liquor is removed, for example by filtering or decanting.

[0198] Subsequently, the remaining aluminoxane cocatalyst treated support is preferably washed one or more times, such as once or twice, more preferably twice, with toluene and, optionally, one or more times with heptane at elevated temperatures in the range of from 70° C. to 115° C., preferably from 80° C. to 110° C., more preferably from 90° C. to 100° C., to obtain a solid activated support.

[0199] Preferably subsequently, the aluminoxane co-catalyst treated support, preferably an aluminoxane co-catalyst treated silica support, is first dried at a suitable temperature, for example 40-80° C., preferably 50-70° C., more preferably 58-62° C., under a nitrogen atmosphere and then under vacuum.

[0200] Step b) In step b), the metallocene complex is combined with a boron-containing cocatalyst, and optionally an aluminoxane cocatalyst, in a suitable hydrocarbon solvent, such as toluene. Preferably, the same hydrocarbon solvent as in step a) is used.

[0201] Any mixing order is possible. The boron-containing cocatalyst, preferably a borate cocatalyst, can be added to obtain a solution of the metallocene complex. The solution can then be optionally combined with an alumoxane cocatalyst.

[0202] However, any other mixing order is possible. Alternatively, the metallocene complex is first mixed with any alumoxane and hydrocarbon, followed by addition of the boron-containing cocatalyst.

[0203] All ingredients may be combined at the same time.

[0204] The boron containing promoter, preferably a borate promoter, is preferably added in an amount to achieve a molar ratio of boron / M in the range of 0.1:1 to 10:1. Preferably, the molar ratio of boron / M in the feed 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.

[0205] The solution thus obtained is stirred for an appropriate time, preferably 10 to 180 minutes, more preferably 20 to 100 minutes, and even more preferably 40 to 80 minutes, at a temperature of 10°C to 30°C, preferably 15°C to 25°C.

[0206] In this step, the amount of aluminoxane cocatalyst, preferably MAO, added (e.g., as a 30 wt % solution in toluene) is 0.0-25.0 wt %, preferably 5.0-23.0 wt %, more preferably 8.0-13.0 wt % of the total amount of aluminoxane cocatalyst. In one embodiment, 0-2.9 wt % of aluminoxane is added in step b).

[0207] In one embodiment, the boron-containing cocatalyst, the aluminoxane and the metallocene are combined simultaneously. In one embodiment, the aluminoxane is added to the combination of the metallocene and the boron-containing cocatalyst. In one embodiment, the aluminoxane and the boron-containing cocatalyst are combined and then added to the metallocene. According to another embodiment, the aluminoxane is not combined, but only the boron-containing cocatalyst and the metallocene are combined in step b).

[0208] Process c) The solution obtained in step b) is then added to the aluminoxane cocatalyst treated support obtained in step a) to obtain a supported catalyst system.

[0209] Step d) In an optional final step, the supported catalyst system so obtained may be washed with a suitable hydrocarbon solvent, such as toluene or heptane, and then dried, preferably in vacuum, to obtain a free-flowing powder.

[0210] If desired, the resulting supported catalyst system can be provided as an oil slurry having a desired solids content, for example, the solid catalyst content in the slurry can be 30% by weight or less, such as 25% by weight or less.

[0211] The amounts of support, aluminoxane, preferably MAO, boron-containing cocatalyst and metallocene depend on the desired ratios defined above (boron / M, Al / M, Al / SiO2, M / SiO2).

[0212] Viewed from another aspect, the present invention provides a method for preparing a supported catalyst system, the method comprising: (i) metallocene complexes; (ii) a cocatalyst system comprising a boron-containing cocatalyst and an aluminoxane cocatalyst; and (iii) Porous inorganic support Including, wherein the method comprises: a) treating a porous inorganic support with an aluminoxane cocatalyst in a hydrocarbon solvent, followed by heat treating the aluminoxane treated support; b) combining the metallocene complex with a boron-containing cocatalyst and, optionally, with an aluminoxane cocatalyst in a hydrocarbon solvent; c) applying the solution of step b) onto the treated support of step a); The process includes the steps of: wherein the amount of the aluminoxane co-catalyst added in step a) is 75.0 to 100.0% by weight of the total amount of the aluminoxane co-catalyst, and the amount of the aluminoxane co-catalyst added in step b) is 0.0 to 25.0% by weight of the total amount of the aluminoxane co-catalyst. The method includes the steps of:

[0213] polymerization

[0214] The catalyst system prepared according to the present invention is particularly suitable for the formation of propylene homopolymers or copolymers, especially copolymers with ethylene, having high activity levels, high molecular weights and therefore low MFR, and having ideal melting points, and preferably enhanced melting points of propylene homopolymers.

[0215] The polymerization in the process of the present invention may be carried out in one or more, e.g., 1, 2 or 3, polymerization reactors using conventional polymerization techniques, such as gas phase, liquid phase, slurry or bulk polymerization, or a combination thereof, e.g., a combination of a slurry and at least one gas phase reactor.

[0216] The method may also include a prepolymerization step, which is a conventional step routinely used in polymer synthesis and should be distinguished from the catalyst off-line prepolymerization step used for catalysts prepared by emulsion / solidification techniques, as discussed in the art.

[0217] Generally, the amount of catalyst used will depend on the nature of the catalyst, the type and conditions of the reactor, and the properties desired in the polymer product. As is well known in the art, hydrogen can be used to control the molecular weight of the polymer.

[0218] The catalyst system prepared according to the present invention in particular has excellent catalytic activity and is also capable of providing polymers with high weight average molecular weights Mw.

[0219] In the case of bulk and gas phase copolymerization reactions, the reaction temperatures used are generally in the range of 60-115°C (e.g. 70-90°C), while in the case of gas phase reactions, where the bulk polymerization is operated at slightly higher pressures, the reactor pressure is generally in the range of 10-25 bar. The residence time is generally 0.25-8 hours (e.g. 0.5-4 hours). The gas used is the monomer, optionally in a mixture with a non-reactive gas, such as nitrogen or propane. It is a particular feature of the present invention that the polymerization takes place at a temperature of at least 60°C.

[0220] polymer It is a feature of the present invention that the claimed catalysts allow the formation of polymers with high molecular weight. These features can be achieved at commercially interesting polymerization temperatures, e.g., 60° C. or higher. It is a preferred feature of the present invention that the catalysts of the present invention are used to polymerize propylene at temperatures of at least 60° C., preferably at least 70° C., e.g., at least 80° C. In a particular embodiment, the propylene polymers obtained using the catalysts of the present invention have a polydispersity index (Mw / Mn) of 2.0 or higher, e.g., from 2.2 to 4.5.

[0221] Polypropylene Homopolymer Polypropylene homopolymers produced by the catalyst system prepared according to the present invention can be produced with Mw (weight average molecular weight) values ​​in the range of 50-2000 kg / mol, preferably in the range of 100-1500 kg / mol, more preferably in the range of 150-1000 kg / mol, even more preferably in the range of 200-800 kg / mol, depending on the use and amount of hydrogen used as Mw regulator. The catalyst of the present invention allows the formation of polypropylene homopolymers with high melting points. In a preferred embodiment, the propylene homopolymers formed by the process of the present invention have a melting point of more than 149.0°C, preferably more than 149.5°C, especially more than 150.0°C. Propylene homopolymers with melting points of 158.0°C or less, or 160.0°C or less are possible.

[0222] The polymers produced by the catalysts of the present invention are useful for all kinds of end products, such as pipes, films (cast, blown or BOPP films, such as BOPP for capacitor films), fibers, molded articles (e.g., injection molded, blown, rotomolded articles), extrusion coatings, etc.

[0223] The invention will now be illustrated by reference to the following non-limiting examples and figures.

[0224] Measurement method

[0225] (a) Melt flow rate (MFR) The melt flow rate is calculated for polypropylene according to ISO 133 15 (230°C, 2.16 kg load) as MFR 2 The MFR is an indication of the flowability of a polymer and therefore its processability. The higher the melt flow rate, the lower the viscosity of the polymer.

[0226] (b) Number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw / Mn) The average molecular weights (Mz, Mw and Mn), molecular weight distribution (MWD) and its breadth, described by the polydispersity index, PDI=Mw / Mn, where Mn is the number average molecular weight and Mw is the weight average molecular weight, were determined by Gel Permeation Chromatography (GPC) according to ISO16014-1:2003, ISO16014-2:2003, ISO16014-4:2003 and ASTM D6474-12 using the following formulas:

[0227]

number

[0228] Constant elution volume interval ΔVi , where A i and M i are the chromatographic peak slice area and polyolefin molecular weight (MW) associated with the elution volume Vi, respectively, where N is equal to the number of data points obtained from the chromatogram between the integration limits.

[0229] A high temperature GPC instrument equipped with either an infrared (IR) detector (IR4 or IR5 from PolymerChar, Valencia, Spain, or a differential refractometer (RI) from Agilent Technologies equipped with 3x Agilent-PLgel Olexis and 1x Agilent-PLgel Olexis Guard columns) was used. As solvent and mobile phase, 1,2,4-trichlorobenzene (TCB) stabilized with 250 mg / L of 2,6-ditertbutyl-4-methyl-phenol) was used. The chromatographic system was operated at 160°C with a constant flow rate of 1 mL / min. 200 μL of sample solution was injected per analysis. Data collection was performed using either Agilent Cirrus software version 3.3 or PolymerChar GPC-IR control software.

[0230] The column set was calibrated using 12 narrow MWD polystyrene (PS) standards ranging from 0.37 kg / mol to 13,200 kg / mol using universal calibration (according to ISO 16014-2:2003). The PS standards were dissolved at room temperature for several hours or alternatively at 160° C. for 30 minutes. Conversion of polystyrene peak molecular weights to polyolefin molecular weights is accomplished by using the Mark Houwink equation and the Mark Houwink constants below:

[0231]

number

[0232] A third order polynomial fit was used to fit the calibration data.

[0233] All samples were prepared in the concentration range of 0.5-1 mg / ml and dissolved at 160°C under gentle continuous shaking for 2.5 h for PP and 3 h for PE.

[0234] (c) DSC analysis, main peak melting temperature (T m ) Differential scanning calorimetry (DSC) experiments were carried out on a Mettler Toledo DSC2 device calibrated with indium, zinc, and tin according to ISO 11357 / 1. The measurements were carried out under a nitrogen atmosphere (50 mL min -1 ) was performed on 6 ± 1 mg samples in a heat / cool / heat cycle from 30 °C to 225 °C at a scan rate of 10 °C / min according to ISO 11357 / 3. The crystallization temperature (Tc) and melting temperature (Tm) were taken as the endothermic and exothermic peaks in the cooling cycle and the second heating cycle, respectively.

[0235] (d) Catalytic activity The catalytic activity was calculated based on the following formula:

[0236]

number

[0237] (e) Metal activity The metal activity (M activity) was calculated based on the following formula:

[0238]

number

[0239] Here, the catalyst loading refers to grams of transition metal (M) present in the catalyst.

[0240] (f) Al, B and Zr determination (ICP method) In a glove box, an aliquot of the catalyst (approximately 40 mg) was weighed into a glass weighing 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. 5 mL of concentrated (65%) nitric acid was then used to pour the contents of the boat into an Xpress microwave container (20 mL). The sample was then subjected to microwave-assisted digestion at 150° C. for 35 minutes using a MARS 6 laboratory microwave unit. The digested sample was allowed to cool for at least 4 hours and then transferred to a 100 mL glass volumetric flask. A standard solution containing 1000 mg / LY and Rh (0.4 mL) was added. The flask was then filled with distilled water and shaken thoroughly. The solution was filtered through a 0.45 μm nylon syringe filter and then subjected to analysis using a Thermo iCAP 6300 ICP-OES and iTEVA software.

[0241] The instrument was run with a blank (5% HNO 3 (solution) and 0.005mg / L, 0.01mg / L, 0.1mg / L, 1mg / L, 10m / L and 100mg / L of 5% HNO 3The instrument was calibrated for Al, B, Hf, Mg, Ti, and Zr using six standards of Al, B, Hf, Mg, Ti, and Zr in a solution of distilled water. However, not all calibration points were used for each wavelength. Each calibration solution contained 4 mg / L 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. Al 167.079 nm was calibrated as Al 394.401 nm using blank, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L standards, except for 100 mg / L and Zr 339.198 nm. Curvilinear fitting and 1 / concentration weighting were used for the calibration curves.

[0242] Just prior to analysis, the calibration was verified and adjusted using blanks and standards of 10 mg / L Al, B, Hf, Mg, Ti, and Zr with 4 mg / L LY and Rh (instrument reslope function). Quality control samples (QC: 1 mg / L Al, Au, Be, Hg, and Se; 2 mg / L Hf and Zr; 2.5 mg / L As, B, Cd, Co, Cr, Mo, Ni, P, Sb, Sn, and V; 4 mg / L Rh and Y; 5 mg / L Ca, K, Mg, Mn, Na, and Ti; 10 mg / L Cu, Pb, and Zn; 25 mg / L Fe and 37.5 mg / L Ca, 5% HNO in distilled water. 3 solution) were performed to check for regrading for Al, B, Hf, Mg, Ti and Zr. The QC samples were also run at the end of the scheduled analytical set.

[0243] The content for Zr was monitored using the Zr 339.198 nm {99} line. The aluminum content was monitored via the 167.079 nm {502} line when the Al concentration in the test part was less than or equal to 2 wt.% and via the 394.401 nm {85} line when the Al concentration was greater than 2 wt.%. Y 371.030 nm {91} was used as an internal standard for Zr 339.198 nm and Al 394.401 nm, and Y 224.306 nm {450} was used as an internal standard for Al 167.079 nm. The B content was monitored using the B 249 nm line.

[0244] The B content was monitored using the B 249 nm line. The reported values ​​were back-calculated to the original catalyst sample using the original mass of the catalyst aliquot and the dilution amount.

[0245] Catalyst Complex

[0246] The catalyst complex MC1 used in the polymerization process of the propylene homopolymer used for the inventive examples IE1 and IE2 and for the comparative examples CE1 to CE5 was as follows:

[0247] [ka]

[0248] The metallocene (MC1) (rac-anti-dimethylsilanediyl(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride) was synthesized as described in WO 2013 / 007650, E2.

[0249] The catalyst system was prepared using metallocene MC1 and a cocatalyst system of MAO and trityltetrakis(pentafluorophenyl)borate. The catalyst was supported on silica.

[0250] The catalyst complex MC2 used in the polymerization process of propylene homopolymer for the inventive example IE3 and for the comparative examples CE6 to CE7 was (rac-anti-dimethylsilanediyl(2-methyl-4-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-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 WO 2019 / 007655, pp 49ff.

[0251] [ka]

[0252] The catalyst system was prepared using metallocene MC2 and a cocatalyst system of MAO and trityltetrakis(pentafluorophenyl)borate. The catalyst was supported on silica for IE3.

[0253] The catalyst complex MC3 used in the polymerization process of propylene homopolymer for the inventive examples IE4, IE5 as well as for the comparative example CE8 was the following rac-anti-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-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 International Patent Application PCT / EP2019 / 056737 (synthesis of MC-3).

[0254] [ka]

[0255] The catalyst complex MC4 is rac-dimethylsilanediylbis[2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride shown below.

[0256] [ka]

[0257] The catalyst complex MC5 is rac-dimethylsilanediylbis(2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl)zirconium dichloride shown below.

[0258] [ka]

[0259] Cocatalyst: Trityl borate = trityl tetrakis(pentafluorophenyl)borate provided by Bolder Corp

[0260] Preparation of MAO-silica support (Option A)

[0261] A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set to 20°C. Silica grade DM-L-303 (AGC Si-Tech Co) (7.4 kg), pre-calcined at 600°C, was then added from a feed drum and carefully pressurized and depressurized with nitrogen using a manual valve. Toluene (32.2 kg) was then added. The mixture was stirred (40 rpm) for 15 minutes. A 30 wt% solution of MAO in toluene (Lanxess) (17.5 kg) was then added via a 12 mm line at the top of the reactor within 70 minutes. The reaction mixture was then heated to 90°C and stirred at 90°C for an additional 2 hours. The slurry was settled and the mother liquor was filtered off. The MAO-treated silica support was washed twice with toluene (32.2 kg) at 90°C, followed by settling and filtration. 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 hours under nitrogen flow at 2 kg / hour and 0.3 bar g pressure, and then dried under vacuum (−0.5 bar g) with stirring at 5 rpm for 5 hours. The MAO-treated support was collected as a free-flowing white powder and found to contain 12.7 wt. % Al.

[0262] This support is used for inventive examples 1 to 4 (ICS1, ICS2, ICS3 and ICS4) and all comparative examples 1 to 5 (CCS1 to CCS5). In comparative examples CE6 and CE7, no silica was used.

[0263] Preparation of MAO-silica support (Option B) A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set to 20°C. Then, silica grade DM-L-303 (5.0 kg) from AGC Si-Tech Co, pre-calcined at 600°C, was added from a feed drum and carefully pressurized and depressurized with nitrogen using a manual valve. Then, toluene (21.8 kg) was added. The mixture was stirred (40 rpm) for 15 minutes. Then, a 30 wt% solution of MAO in toluene (Lanxess) (9.0 kg) was added through a 12 mm line at the top of the reactor within 70 minutes. Then, the reaction mixture was heated to 90°C and stirred at 90°C for an additional 2 hours. The slurry was settled and the mother liquor was filtered off. The catalyst was washed twice with toluene (21.8 kg) at 90°C, followed by settling and filtration. The reactor was cooled to 60° C. and the solids were washed with heptane (21.8 kg). Finally, the MAO-treated SiO 2 The MAO-treated support was collected as a free-flowing white powder and found to contain 13.0 wt. % Al.

[0264] This support B is used for the examples of the present invention (ICS5 to ICS12) as well as the comparative examples (CCS8 to CCS13).

[0265] ICS1 (catalytic system 1 of the invention): Preparation of the catalyst In a nitrogen filled glove box, a solution of 0.25 mL of MAO (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. Trityl borate (35.6 mg, 38 μmol) was then added to the mixture, and the mixture was stirred for an additional hour at room temperature. 1.0 g of MAO treated silica (option A), prepared as described above, was placed in a glass flask. The solution of metallocene, borate and MAO in toluene was then slowly added to the support over a period of 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and left overnight. The resulting cake was dried in vacuum for 1 hour to give 1.1 g of catalyst as a pink free-flowing powder containing 13.4 wt % Al and 0.27 wt % Zr according to ICP analysis.

[0266] ICS2 (catalytic system 2 of the invention): Preparation of the catalyst ICS2 was prepared as described for ICS1, except that 36.0 mg of trityl tetrakis(pentafluorophenyl)borate was added and the catalyst was washed with 5 mL of toluene after standing overnight and then dried.

[0267] CCS1 (Comparative Catalyst System 1): Preparation of the Catalyst In a nitrogen-filled glove box, a solution of 0.25 mL of MAO (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 micromoles). The mixture was stirred at room temperature for 60 minutes. The solution was then slowly added to 1.0 g of MAO-treated silica (option A), prepared as described above, which was placed in a glass flask. The mixture was left overnight and then subjected to vacuum drying for 1 hour to obtain a pink, free-flowing powder. Next, a solution of trityl borate (35.6 mg, 38 micromoles) in 1 ml of toluene was slowly added to the metallocene-MAO impregnated support. The mixture was shaken thoroughly and left overnight. The resulting cake was dried in vacuum for 1 hour to obtain 1.1 g of catalyst as a pink, free-flowing powder.

[0268] CCS2 (Comparative Catalyst System 2): Catalyst preparation: In a nitrogen-filled glove box, a solution of trityl borate (35.6 mg, 38 micromoles) in 1 ml of toluene was slowly added to 1.0 g of MAO-treated silica (option A), prepared as described above, which was placed in a glass flask. The mixture was left overnight and then subjected to vacuum drying for 1 hour to obtain a white free-flowing powder. In a separate flask, a solution of 0.25 mL of MAO (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 micromoles). The mixture was stirred at room temperature for 60 minutes. The solution of metallocene and MAO in toluene was then slowly added to the borate-treated support over 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and left overnight. The resulting cake was dried in vacuum for 1 hour to obtain 1.2 g of catalyst as a pink free-flowing powder.

[0269] CCS3 (Comparative Catalyst System 3): Preparation of catalyst: In a nitrogen-filled glove box, a solution of 0.25 mL of MAO (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. The solution was then slowly added to 1.0 g of MAO-treated silica (option A), prepared as described above, which was placed in a glass flask. The mixture was left overnight, washed with 5 mL of toluene, and then subjected to vacuum drying for 1 hour to obtain a pink free-flowing powder. A solution of trityl borate (35.6 mg, 38 μmol) in 1 mL of toluene was then slowly added to the metallocene-MAO impregnated support. The mixture was shaken thoroughly and left overnight, and then washed with 5 mL of toluene. The resulting cake was dried in vacuum for 1 hour to give 1.0 g of catalyst as a pink, free-flowing powder.

[0270] CCS4 (Comparative Catalyst System 4): Preparation of catalyst: In a nitrogen-filled glove box, a solution of trityl borate (35.6 mg, 38 μmol) in 1 mL of toluene was slowly added to 1.0 g of MAO-treated silica (option A) prepared as described above, which was placed in a glass flask. The mixture was left overnight, washed with 5 mL of toluene, and then subjected to vacuum drying for 1 hour to obtain a white free-flowing powder. In a separate flask, a solution of 0.25 mL of MAO (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. The solution of metallocene and MAO in toluene was then slowly added to the borate-treated support over 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and left overnight. The resulting cake was washed with 5 mL of toluene and then dried in vacuum for 1 h to give 1.1 g of catalyst as a pink, free-flowing powder.

[0271] CCS5 (Comparative Catalyst System 5): Preparation of catalyst: In a nitrogen-filled glove box, a solution of 0.25 mL of MAO (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. The solution was then slowly added to 1.0 g of MAO-treated silica (option A), prepared as described above, which was placed in a glass flask. The mixture was left overnight, washed with 5 mL of toluene, and then subjected to vacuum drying for 1 hour to obtain a pink, free-flowing powder, yielding 1.1 g of catalyst as a pink, free-flowing powder.

[0272] ICS3 (catalytic system 3 of the invention): Preparation of the catalyst In a nitrogen filled glove box, a solution of 0.2 mL of MAO (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. Trityl borate (25.6 mg, 28 μmol) was then added to the mixture, and the mixture was stirred for an additional hour at room temperature. 2.0 g of MAO treated silica (option A), prepared as described above, was placed in a glass flask. The solution of metallocene, borate and MAO in toluene was then slowly added to the support over a period of 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and allowed to stand for 1 hour. The resulting cake was dried in vacuum for 1 hour to give 2.1 g of catalyst as a pink free-flowing powder containing 12.9 wt % Al and 0.095 wt % Zr according to ICP analysis. B / Zr mole / mol=1; 17 mmol Zr / g SiO 2

[0273] ICS4 (catalytic system 4 of the invention): Preparation of the catalyst In a nitrogen filled glove box, a solution of 0.12 mL of MAO (30 wt % in toluene, AXION 1330 CA Lanxess) 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. Trityl borate (18.0 mg, 20 μmol) was then added to the mixture, and the mixture was stirred for an additional hour at room temperature. 1.0 g of MAO treated silica (option A) was placed in a glass flask. The solution of metallocene, borate, and MAO in toluene was then slowly added to the support over a period of 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and left overnight. The resulting cake was washed with 5 mL of toluene at room temperature and then dried in vacuum for 1 h to give 1.2 g of catalyst as a pink, free-flowing powder containing 11.3 wt. % Al and 0.089 wt. % Zr according to ICP analysis.

[0274] CCS6 (Comparative Catalyst System 6) The same catalyst complex (i.e., MC2) was used as in ICS3, but without the silica support.

[0275] In a glove box, 234.3 mg of dried and degassed surfactant S2 (in 0.2 mL toluene) was added dropwise to 5 mL of MAO. The solution was left 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.

[0276] After stirring for 60 minutes, 5 mL of the surfactant-MAO-metallocene-borate solution was added continuously at -10°C into a 50 mL emulsifying glass reactor containing 40 mL of PFC (perfluoro-1,3-dimethylcyclohexane) and equipped with an overhead stirrer (stirring speed = 600 rpm). A red emulsion was immediately formed and stirred at -10°C / 600 rpm for 15 minutes. The emulsion was then transferred via a 2 / 4 Teflon tube into 100 mL of hot PFC at 90°C and stirred at 600 rpm until the transfer was complete, then the speed was reduced to 300 rpm. After stirring for 15 minutes, the oil bath was removed and the stirrer was turned off. The catalyst was precipitated on top of the PFC and the solvent was siphoned off after 35 minutes. The catalyst was precipitated on top of the PFC and the solvent was siphoned off after 35 minutes. The remaining catalyst was dried at 50° C. for 2 hours under a flow of argon. 0.70 g of a red free-flowing powder was obtained. (Al 28.7 wt %, Zr 0.53 wt %, Al / Zr (molar) 182; B / Zr (molar) 0.98).

[0277] S2: 1H,1H-perfluoro(2-methyl-3-oxahexan-1-ol) (CAS 26537-88-2) was purchased from Unimatec, dried over activated molecular sieves (twice) and degassed by argon bubbling before use.

[0278] CCS7 (Comparative Catalyst System 7) (Offline Prepolymerization) Comparative catalyst system 7 (CCS7) was prepared as described for CCS6 above, but with a subsequent off-line prepolymerization step.

[0279] The offline prepolymerization step was carried out in a 125 mL pressure reactor equipped with a gas supply line and an overhead stirrer. Dry and degassed perfluoro-1,3-dimethylcyclohexane (15 cm 3 ) and the desired amount of catalyst to be prepolymerized were loaded into the reactor in the glove box and the reactor was sealed. The reactor was then removed from the glove box and placed in a water cooling bath maintained at 25°C. An overhead stirrer and a feed line were connected and the stirring speed was set at 450 rpm. The experiment was started by opening the propylene feed into the reactor. The total pressure in the reactor was raised to about 5 bar g and kept constant by propylene feed via a mass flow controller until the targeted degree of polymerization was reached. The reaction was stopped by flushing out the volatile components. In the glove box, the reactor was opened and the contents were poured into a glass vessel. Perfluoro-1,3-dimethylcyclohexane was evaporated until a constant weight was obtained to obtain the prepolymerized catalyst. (Al 4.4 wt%, Zr 0.082 wt%, Al / Zr (molar) 182; B / Zr (molar) 0.98)

[0280] The degree of prepolymerization (weight of polymer / weight of solid catalyst before prepolymerization step) was 5.47.

[0281] CCS8 (Comparative Catalyst System 8) 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.

[0282] ICS5 (catalytic system 5 of the invention) In a nitrogen filled glove box, a solution of 0.2 mL of MAO (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. An aliquot of trityl borate (26.5 mg, 28 μmol) was then added and the mixture was stirred for an additional 30 minutes. Next, 2.0 g of MAO treated silica (option B) prepared as described above was placed in a glass vial. Next, a solution of metallocene, trityl tetrakis(pentafluorophenyl)borate and MAO in toluene was slowly added to the support over a period of 5 minutes with gentle 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 give 2.0 g of catalyst as a pink free-flowing powder.

[0283] ICS6 (catalytic system 6 of the invention): Preparation of the catalyst In a nitrogen filled glove box, dry toluene (2.5 mL) was added to an aliquot of metallocene MC3 (17.6 mg, 19 μmol). The mixture was stirred at room temperature for 30 minutes. An aliquot of trityl borate (27.0 mg, 29 μmol) was then added and the mixture was stirred for an additional 30 minutes. Then, 2.0 g of MAO treated silica (option B) prepared as described above was placed in a glass vial.

[0284] The metallocene and trityl borate in toluene were then slowly added to the support over a period of 5 minutes with gentle 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 give 2.6 g of catalyst as a pink, free-flowing powder.

[0285] ICS7 - (catalytic system 7 of the invention) In a nitrogen filled glove box, an aliquot of MC3 (17.7 mg, 19 μmol) and an aliquot of trityl borate (27.0 mg, 29 μmol) were placed in a glass vial equipped with a stir bar. Toluene (2.3 mL) was added to the vial under stirring, followed by MAO (0.20 mL, 30 wt % in toluene). The mixture was stirred at room temperature for 60 minutes. 2.0 g of MAO treated silica (option B) prepared as described above was placed in a glass flask. Then, a solution of metallocene, trityl borate and MAO in toluene was slowly added to the support over a period of 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and allowed to stand for 1 hour. The resulting cake was dried in vacuum for 1 hour to give 2.0 g of catalyst as a pink free-flowing powder.

[0286] ICS8- (catalytic system 8 of the invention) In a nitrogen filled glove box, a solution of 0.2 mL of MAO (30 wt % in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3 mL) was added to an aliquot of tributylborate (26.5 mg, 28 μmol). The mixture was stirred at room temperature for 30 minutes. An aliquot of metallocene MC3 (17.6 mg, 19 μmol) was then added and the mixture was stirred for an additional 30 minutes. Next, 2.0 g of MAO treated silica (option B) prepared as described above was placed in a glass vial. Next, the solution of metallocene, MAO and tributylborate in toluene was slowly added to the support over a period of 5 minutes with gentle 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 give 2.0 g of catalyst as a pink free-flowing powder.

[0287] CCS9 (Comparative Catalyst System 9) In a nitrogen filled glove box, a solution of 0.2 mL of MAO (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 for 30 minutes at room temperature. Then, 2.0 g of MAO treated silica (option B) prepared as described above was placed in a glass vial. Then, the solution of metallocene and MAO in toluene was slowly added to the support over 5 minutes with gentle mixing. The resulting mixture was shaken well and left for 1 hour. The resulting solid was dried in vacuum for 1 hour to give a pink powder. Then, an aliquot of tributylborate (26.5 mg, 28 μmol) was added to a new vial and dissolved in toluene (2 mL). The solution of tributylborate in toluene was added to the previously obtained solid over 5 minutes with gentle 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 give 2.0 g of catalyst as a pink, free-flowing powder.

[0288] ICS10 (catalytic system 10 of the present invention) In a nitrogen filled glove box, a solution of 0.20 mL of MAO (30 wt % in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3 mL) was added to an aliquot of metallocene MC4 (40.5 mg, 53 μmol). The mixture was stirred at room temperature for 30 minutes. Trityl borate (48.9 mg, 53 μmol) was then added to the mixture, and the mixture was stirred at room temperature for 30 minutes. 2.0 g of MAO treated silica (option B) was placed in a glass flask. The solution of metallocene, borate and MAO in toluene was then slowly added to the support over a period of 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and allowed to stand for 1 hour. The resulting cake was dried in vacuum for 1 hour to give 2.0 g of catalyst as a pink free-flowing powder.

[0289] ICS11 - (catalytic system 11 of the invention) In a nitrogen filled glove box, an aliquot of MC4 (40.0 mg, 52 μmol) and an aliquot of trityl borate (48.9 mg, 53 μmol) were placed in a glass vial equipped with a stir bar. Toluene (2.3 mL) was added to the vial under stirring, followed by MAO (0.20 mL, 30 wt % in toluene). The mixture was stirred at room temperature for 60 minutes. 2.0 g of MAO treated silica (option B) was placed in a glass flask. Then, a solution of metallocene, borate and MAO in toluene was slowly added to the support over 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and allowed to stand for 1 hour. The resulting cake was dried in vacuum for 1 hour to give 2.0 g of catalyst as a pink free-flowing powder.

[0290] CCS10 (Comparative Catalyst System 10) In a nitrogen filled glove box, a solution of 0.20 mL of MAO (30 wt % in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3 mL) was added to an aliquot of metallocene MC4 (40.4 mg, 53 μmol). The mixture was stirred at room temperature for 60 minutes. 2.0 g of MAO treated silica (option B) was placed in a glass flask. Then, the solution of metallocene and MAO in toluene was slowly added to the support over a period of 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and allowed to stand for 1 hour. The resulting cake was dried in vacuum for 1 hour to give 2.0 g of catalyst as a pink free-flowing powder.

[0291] CCS11 (Comparative Catalyst System 11) In a nitrogen filled glove box, a solution of 0.20 mL of MAO (30 wt % in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3 mL) was added to an aliquot of metallocene MC4 (40.0 mg, 52 micromoles). The mixture was stirred at room temperature for 60 minutes. Then, 2.0 g of MAO treated silica (option B) was placed in a glass flask. The solution was slowly added to the support over 5 minutes with gentle mixing. The mixture was left for 1 hour and then vacuum dried for 1 hour to obtain a pink free-flowing powder. Next, a solution of 2 ml of trityl borate (48.8 mg, 53 micromoles) in toluene was slowly added to the metallocene-MAO impregnated support. The mixture was shaken thoroughly and left for 1 hour. The resulting cake was dried in vacuum for 1 hour to obtain 2.0 g of catalyst as a pink free-flowing powder.

[0292] ICS12 - (catalytic system 12 of the invention) In a nitrogen filled glove box, a solution of 0.20 mL of MAO (30 wt % in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3 mL) was added to an aliquot of metallocene MC5 (44.3 mg, 52 μmol). The mixture was stirred at room temperature for 30 minutes. Trityl borate (48.9 mg, 53 μmol) was then added to the mixture, and the mixture was stirred at room temperature for 30 minutes. 2.0 g of treated silica (option B) was placed in a glass flask. The solution of metallocene, borate, and MAO in toluene was then slowly added to the support over a period of 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and allowed to stand for 1 hour. The resulting cake was dried in vacuum for 1 hour to give 2.0 g of catalyst as a pink free-flowing powder.

[0293] ICS13 - (catalytic system 13 of the invention) In a nitrogen filled glove box, an aliquot of MC5 (44.6 mg, 52 μmol) and an aliquot of trityl borate (48.9 mg, 53 μmol) were placed in a glass vial equipped with a stir bar. Toluene (2.3 mL) was added to the vial under stirring, followed by MAO (0.20 mL, 30 wt % in toluene). The mixture was stirred at room temperature for 60 minutes. 2.0 g of MAO treated silica (option B) was placed in a glass flask. Then, a solution of metallocene, borate and MAO in toluene was slowly added to the support over 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and allowed to stand for 1 hour. The resulting cake was dried in vacuum for 1 hour to give 2.0 g of catalyst as a pink free-flowing powder.

[0294] CCS12 (Comparative Catalyst System 12) In a nitrogen filled glove box, a solution of 0.20 mL of MAO (30 wt % in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3 mL) was added to an aliquot of metallocene MC5 (45.0 mg, 53 μmol). The mixture was stirred at room temperature for 60 minutes. 2.0 g of MAO treated silica (option B) was placed in a glass flask. Then, the solution of metallocene and MAO in toluene was slowly added to the support over a period of 5 minutes with gentle mixing. The resulting mixture was shaken thoroughly and allowed to stand for 1 hour. The resulting cake was dried in vacuum for 1 hour to give 2.0 g of catalyst as a pink free-flowing powder.

[0295] CCS13 (Comparative Catalyst System 13) In a nitrogen filled glove box, a solution of 0.20 mL of MAO (30 wt % in toluene, AXION 1330 CA Lanxess) in dry toluene (2.3 mL) was added to an aliquot of metallocene MC5 (44.8 mg, 52 micromoles). The mixture was stirred at room temperature for 60 minutes. Then, MAO treated silica (option B) was placed in a glass flask. The solution was slowly added to the support over 5 minutes with gentle mixing. The mixture was left for 1 hour and then dried under vacuum for 1 hour to obtain a pink free-flowing powder. Next, a solution of 2 ml of trityl borate (48.8 mg, 53 micromoles) in toluene was slowly added to the metallocene-MAO impregnated support. The mixture was shaken thoroughly and left for 1 hour. The resulting cake was dried in vacuum for 1 hour to obtain 2.1 g of catalyst as a pink free-flowing powder.

[0296] [Table 1] [Table 2]

[0297] Polymerization procedure for propylene homopolymerization in bulk.

[0298] The polymerizations were carried out in a 5 liter jacketed stainless steel reactor equipped with an agitator, lines for monomer and hydrogen, an exhaust line, and feeding systems for catalyst and scavengers.

[0299] The catalyst feeder is equipped with two stainless steel cylinders in series. In the glove box, the desired amount of catalyst, as shown in Tables 3 and 4, was loaded into the lower steel cylinder of the feeder, and a second cylinder containing 5 ml of dry pentane was attached to the top. The steel cylinder of the scavenger feeder was filled with 250 μl of triethylaluminum (purchased from Lanxess; trade name TEA-S) and 5 ml of dry pentane (purchased from Scharlau; reagent grade, ≧99%). Outside the glove box, the feed cylinder was attached to the reactor, and the connections were flushed with nitrogen. The temperature of the reactor was controlled at 20° C. The contents of the scavenger feeder were flushed into the reactor with nitrogen overpressure.

[0300] The desired amount of hydrogen (25 mmol, Table 3; 15 mmol, Table 4; 6 mmol, Table 5) was then fed into the reactor, followed by 1400 g of liquid propylene. The stirring speed was set at 400 rpm. The reactor temperature was stabilized at 20° C., and after a minimum of 5 minutes, polymerization was started by injecting the catalyst into the reactor, as described below. The valve between the two cylinders of the catalyst feeder was opened, and then the catalyst was immediately flushed into the reactor with nitrogen overpressure. The feeder was pressurized with nitrogen three times and flushed into the reactor.

[0301] After 5 min prepolymerization at 20° C., the reactor temperature was raised to 70° C. over 15-18 min. The polymerization was continued at 70° C. for 60 min and then stopped by flushing the reactor to atmospheric pressure. After flushing the reactor with nitrogen several times, the polymer was collected, dried overnight, and then weighed to record the yield.

[0302] The catalytic activity was calculated based on 60 minutes according to the following formula:

[0303]

number

[0304] [Table 3]

[0305] The above table discloses catalytic systems ICS1, ICS2 and CCS1 to CCS5 prepared from the same MAO-silica support using metallocene MC1 and two catalysts (IE4, CE8) prepared with metallocene MC3 at the same loading.

[0306] Comparative Example CE5 shows a catalyst prepared without trityl borate, which has low metal activity. Inventive Examples 1 and 2 using catalyst systems ICS1 and ICS2 were prepared using one equivalent of trityl borate added simultaneously with MC1, resulting in the highest improvement in activity. Comparative catalyst systems CCS3 (CE3) and CC8 (CE8) are prepared according to the teachings of the prior art documents, i.e., using a reverse impregnation sequence, such that the borate is added in a second impregnation step after the metallocene is added to the activated support. As can be seen in the table above, the addition sequence of the present invention results in the highest improvement in metal activity.

[0307] Inventive Example 4, using catalyst ICS4 containing metallocene MC3, is prepared with trityl borate added simultaneously with MC3. As can be seen in the table above, the addition order of the present invention results in significantly higher metal activity compared to CE8.

[0308] Polymerization procedure for propylene homopolymerization in bulk. The polymerization procedure was the same as above with the only difference being that 15.0 mmol of hydrogen was used.

[0309] [Table 4]

[0310] From the above table, it can be seen that the catalytic system prepared according to the present invention has obviously higher metal activity than the catalytic system prepared by emulsion / solidification process technology.In addition, the preparation method according to the present invention is much simpler, that is, only one impregnation step is used in the preparation.

[0311] We also observe a higher melting point after applying MAO / metallocene to the substrate than the polymer obtained using boron doped CCS9.

[0312] Polymerization procedure for propylene homopolymerization in bulk. The polymerization procedure was the same as above with the only difference being that 6.0 mmol of hydrogen was used.

[0313] [Table 5]

[0314] The above table discloses catalytic systems ICS10, ICS12 and CCS10 to CCS13 prepared from the same MAO-silica support using the same loading of metallocene MC4 / .

[0315] Examples 10 and 12 of the invention using catalyst systems ICS10 and ICS12 give the highest improvement in activity. Comparative catalyst systems CCS10 and CCS12 have no boron atoms. CCS11 and CCS13 are prepared according to the teachings of the prior art documents such that borate is added in a second impregnation step after the addition of MC to the activated support. According to the method of the invention, only one impregnation step is used in the preparation of the catalyst system. As can be seen in the table above, the addition order of the invention results in the highest improvement in metal activity and the highest melting point.

Claims

1. A method for preparing a supported catalyst system, the catalyst system comprising: (i) metallocene complexes; (ii) a cocatalyst system comprising a boron-containing cocatalyst and an aluminoxane cocatalyst; and (iii) Porous inorganic support Including, The method further comprising: a) mixing a porous inorganic support with an aluminoxane cocatalyst in a hydrocarbon solvent, followed by heat treatment of the support, and then drying the support, wherein the support / solvent / aluminoxane mixture is heated at a temperature in the range of 60° C. to 120° C.; b) combining the metallocene complex with a boron-containing cocatalyst and, optionally, with an aluminoxane cocatalyst in a hydrocarbon solvent; c) applying the solution of step b) onto the heat-treated support of step a); The process includes the steps of: wherein the amount of aluminoxane co-catalyst added in step a) is 75.0-100.0 wt % of the total amount of aluminoxane co-catalyst, and the amount of aluminoxane co-catalyst added in step b) is 0.0-25.0 wt % of the total amount of aluminoxane co-catalyst; The metallocene complex is of the formula (VI): 【Chemistry 1】 each X is independently a sigma donor ligand; M is a Group 4 metal; L is -R' 2 Si-, ethylene or methylene, where each R' is independently a C 1 -C 20 -hydrocarbyl group; and each Ind is a substituted or unsubstituted indenyl, or a substituted or unsubstituted fused indenyl, or a substituted or unsubstituted fluorenyl ligand; The method.

2. The method of claim 1 , wherein the metallocene complex has C2 symmetry.

3. The metallocene complex is of the following formula (XIX): 【Chemistry 2】 each X is independently a sigma donor ligand; M is Zr or Hf; L is -R' 2 Si-, where each R' is independently 1 ~C 6 -Alkyl, C 5～6 -Cycloalkyl, C 1～10 -Alkyl-OC 1～10 Alkyl or C 6 - an aryl group; Each R 1 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 -alkyl group; Each R 2 may be independently the same or different, and CH 2 -R 8 group, where R 8 is H or linear or branched C 1～6 -alkyl group; R 6 is O.C. 1 ~C 6 -alkyl group; R 5 is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; R 5’ OC 1 ~C 6 -alkyl group; R 6’ is C(R 9 ) 3 group, where R 9 is a linear or branched C 1 ~C 6 is an alkyl group; or R 5 and R 6 may be taken together to form a five-membered saturated carbocyclic ring; or R 5’ and R 6' may be taken together to form a 5-membered saturated carbocyclic ring; R 7 is H or 1 to 3 R 11 a phenyl group optionally substituted by a group; Each R 11 may be independently the same or different, and may be a hydrogen atom, a linear or branched C 1 ~C 6 is an alkyl group, The method of claim 1.

4. The process according to any one of claims 1 to 3, wherein the metallocene (i) is selected from rac-Dimethylsilanediyl-bis-[2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-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, rac-anti-dimethylsilanediyl[2-methyl-4-(4'-tert.-butylphenyl)-inden-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(3',5'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-ditert-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-Dimethylsilanediylbis[2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, rac-Dimethylsilanediylbis[2-methyl-4-(3,5-ditertbutylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, rac-Dimethylsilanediylbis[2-methyl-4-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride or their hafnium analogues.

5. The process according to any one of claims 1 to 4, wherein the aluminoxane cocatalyst is of formula (A): 【Chemistry 3】 where n is 6 to 20 and R is C 1 ~C 10 -Alkyl or C 3 ~C 10 -Cycloalkyl, C 7 ~C 12 It may be -arylalkyl or -alkylaryl, and / or phenyl or naphthyl.

6. The method of any one of claims 1 to 5, wherein the aluminoxane cocatalyst is MAO.

7. The boron-containing cocatalyst is represented by the following formula (B): BY 3 (B) wherein Y are independently the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkylaryl, an arylalkyl, a haloalkyl or a haloaryl, wherein each of the alkyl radicals has 1 to 10 carbon atoms and each of the aryl radicals has 6 to 20 carbon atoms, or a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; Or a borate containing an anion of the formula: (Z) 4 B - (C) where Z is an optionally substituted phenyl derivative, where the substituent is halo-C 1～6 - an alkyl or halo group and, as counterion, a protonated amine or aniline derivative; The method according to any one of claims 1 to 6, wherein

8. 8. The method of claim 7, wherein the counterion is a methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylanilinium, p-nitro-N,N-dimethylanilinium, or triphenylcarbenium ion.

9. The boron-containing cocatalyst is triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, or N,N-Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate The method according to claim 7 or 8,

10. 10. The process of any one of claims 1 to 9, wherein the molar ratio of boron feed to metal ion M in the metallocene complex is in the range of 0.1:1 to 10:1 mol / mol, and the molar ratio of aluminum in the aluminoxane cocatalyst to metal ion M in the complex is in the range of 1:1 to 2000:1 mol / mol.

11. The method according to any one of claims 1 to 10, wherein the support has an average particle size of from 10 to 100 µm.

12. 12. The method according to any one of claims 1 to 11, wherein the support has an average pore size in the range of 10 to 100 nm and a pore volume in the range of 1 to 3 mL / g.

13. 13. The process according to any one of claims 1 to 12, wherein 97.1 to 100% of the aluminoxane cocatalyst is added in step a).

14. The process according to any one of claims 1 to 13, wherein an aluminoxane is added in step b).

15. In step b), the boron-containing cocatalyst, the aluminoxane and the metallocene are combined simultaneously; or The aluminoxane is added to the combination of the metallocene and the boron-containing cocatalyst; or The aluminoxane and the boron-containing cocatalyst are combined and added to the metallocene; The method according to any one of claims 1 to 14.

16. 16. The method according to any one of claims 1 to 15, wherein in step a), the dried support is washed one or more times with toluene and optionally one or more times with heptane at elevated temperatures in the range of 70°C to 115°C, followed by a drying step.

17. 17. The method of any one of claims 1 to 12 or 14 to 16, wherein in step a) 77.0 to 95.0 wt. % of the total amount of aluminoxane cocatalyst is added, and in step b) 5.0 to 23.0 wt. % of the total amount of aluminoxane cocatalyst is added.

18. The method according to any one of claims 1 to 17, wherein the porous inorganic support is a silica support.

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