Catalytic system

Abstract

The present invention relates to an improved silica-supported catalyst system comprising a specific class of metallocene complexes in combination with a boron-containing co-catalyst and an aluminoxane co-catalyst, and preferably to the use thereof for the production of propylene homopolymers, particularly propylene copolymers with ethylene, and heterophase propylene copolymers in a multi-step method comprising a gas phase polymerization step.

Description

Technology Field

[0001] The present invention relates to a novel, improved silica-supported catalyst system comprising a specific class of metallocene complexes in combination with a boron-containing co-catalyst and an aluminoxane co-catalyst. Furthermore, the present invention relates to the use of the novel, improved catalyst system for producing propylene homopolymers, particularly propylene copolymers with ethylene, and heterophasic propylene copolymers in a multi-stage process preferably comprising a gas phase polymerization step. The catalyst system is particularly useful for the production of propylene-ethylene copolymers because it exhibits significant catalytic activity in such polymerization. Background Technology

[0002] Metallocene catalysts have been used for many years in the production of polyolefins. Numerous academic and patent publications describe the use of said catalysts in olefin polymerization. Currently, metallocenes are used industrially, and typically, polyethylene and polypropylene are produced using cyclopentadienyl based on catalyst systems having particularly different substitution patterns.

[0003] Metallocene catalysts are used in propylene polymerization to achieve specific polymerization characteristics.

[0004] However, there are some problems with using metallocene catalysts on an industrial scale, particularly in multi-stage polymerization structures.

[0005] Therefore, there is room to improve the process and the catalytic behavior for said process. Some multi-stage polymerizations utilize two or more consecutive reactors in which a first reactor (typically a loop reactor) is operated in a liquid monomer slurry (also referred to as bulk polymerization), and second and subsequent reactors are operated in the gas phase. Generally, one of the possible limitations of polymerization catalysts, and particularly metallocene-based catalysts, is that when the catalyst has high activity in the liquid monomer reactor (bulk phase), the activity in the gas phase reactor is too low to achieve the desired bulk:gas phase ratio of the material being produced (so-called bulk / GP split), particularly when said ratio must be less than 2.

[0006] To be suitable for industrial polypropylene production, metallocene catalysts must have excellent performance in all substantial polymerization reactors of multi-stage processes, including both liquid (ideally bulk slurry) and gas phase reactors, under all polymerization conditions, especially when the polymerization temperature is 60°C or higher.

[0007] One problem with copolymerization of propylene and comonomers, such as ethylene, is that faster catalyst decay and an increase in MFR occur compared to propylene homopolymerization.

[0008] In particular, in the industrial production of heterophase copolymers via 3-step polymerization, the catalyst must have a sufficiently long lifespan to maintain acceptable activity, especially in the third reactor where the rubber phase is produced. One problem here is that when the catalyst has high bulk activity in the first gas phase reactor (GPR1), its activity in the second gas phase reactor (GPR2) is frequently low, which does not allow for the achievement of a high GPR2:bulk+GPR1 ratio (so-called rubber split) of the resulting material. This means that strong (initial) activity in the bulk phase can lead to faster catalyst deactivation, which consequently results in a catalyst with low activity in the second gas phase reactor.

[0009] Therefore, there is a need to explore catalytic systems that provide high and stable activity, particularly when propylene copolymers are produced by copolymerization between propylene and α-olefins and / or ethylene having 4 to 8 carbon atoms. Stable catalytic activity means that the decline of catalytic activity over residence time in the reactor must be limited in order to ensure high gas phase activity. Various prior art references aim for one or more of these features.

[0010] C2-symmetric metallocenes are disclosed, for example, in WO 2007 / 116034. In particular, the document reports the synthesis and characterization of the metallocene rac-Me2Si(2-Me-4-Ph-5-OMe-6-tBuInd)2ZrCl2, and its use as a polymerization catalyst after activation with methylaluminoxane (MAO) for the homopolymerization of propylene in solution polymerization and the copolymerization of propylene with ethylene and higher alpha-olefins.

[0011] WO 02 / 02576 and WO 2014 / 096171 specifically cover rac-Me2Si[2-Me-4-(3,5-Me2Ph)Ind]2ZrCl2 and high M w Its use in the manufacture of high melting point polypropylene and other materials has been disclosed.

[0012] A metallocene catalyst of WO 02 / 02576 activated by MAO or borate is supported on a silica support. At a polymerization temperature of 60°C or 70°C, this corresponds to T 156°C to 159°C. m It provides i-PP, but the catalytic activity is very poor.

[0013] The metallocene catalyst of WO 2014 / 096171 is prepared by an emulsification / coagulation technique involving subsequent off-line prepolymerization of the said catalyst, which has a higher T compared to the metallocene catalyst of WO 02 / 02576. m At the same time, it enables the production of i-PP with higher activity.

[0014] WO 06 / 097497 describes, in particular, rac-Me2Si(2-Me-4-Ph-1,5,6,7-tetrahydro-s-indacene-1-yl)2ZrCl2 supported on silica and its use in homopolymerization and copolymerization of propylene and ethylene.

[0015] WO 2013 / 007650 describes a specific asymmetric catalyst comprising an alkoxy group at one 5-position of a ring, such as dimethylsilylene(6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-indene-1-yl)-(6-tert-butyl-2-methyl-4-phenyl-1H-indene-1-yl)zirconium dichloride. Despite its excellent performance, the catalyst based on the above reference has limitations in the melting point of polypropylene homopolymers and productivity at low MFRs. Furthermore, the overall productivity of the catalyst still needs to be improved.

[0016] WO 2015 / 158790 specifically discloses the complex [dimethylsilandyl [6-tert-butyl-4-(3,5-di-tert-butylphenyl)-5-methoxy-2-methylindene-1-yl]-[4-(3,5-di-tert-butylphenyl)-2-methyl-5,6,7-trihydro-s-indacene-1-yl]zirconium dichloride] and the use of said complex in the formation of an ethylene / 1-octene copolymer in a solution process.

[0017] WO 2018 / 122134 specifically describes the complex rac-anti-dimethylsilandyl[2-methyl-4-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, which is activated by MAO and supported on silica.

[0018] Although there have been many achievements in the field of metallocene catalysts, particularly regarding low melt index (MI) (i.e., high molecular weight, M w When polymers of ) are manufactured, it has been found that productivity or activity is relatively low, and in particular, in multi-stage polymerization processes, some problems mainly related to the productivity or activity of the catalyst still exist.

[0019] The inventors have achieved improved polymerization behavior, higher catalyst productivity, and enhanced performance in the production of propylene homopolymers, propylene random copolymers, and heterophase propylene copolymers compared to systems known in the art, thereby providing high M wA supported catalyst system composed of a specific class of metallocene catalysts in combination with a boron-containing co-catalyst and an aluminoxane co-catalyst, which is ideal for the production of propylene random copolymers, particularly propylene-ethylene random copolymers, and suitably heterophase propylene copolymers, by enabling the production of propylene-ethylene copolymers, was identified. The specific catalyst system provides greater flexibility / degree of freedom in the design of propylene polymers than the catalyst system of the prior art.

[0020] In one aspect, the present invention

[0021] (i) Metallocene complex of the following chemical formula (I);

[0022] (ii) a co-catalyst system comprising a boron-containing co-catalyst and an aluminoxan co-catalyst; and

[0023] (iii) porous inorganic support

[0024] A supported catalyst system comprising:

[0025]

[0026] In the above formula,

[0027] Each X is independently a sigma-donor ligand;

[0028] L is a carbon, silicon, or germanium-based divalent bridge connecting one or two skeletal valence ligands;

[0029] 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 group;

[0030] Each R 1 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10- It is a hydrocarbyl group, and arbitrarily, 2 adjacent R 1 The gi may be part of a ring containing the carbon to which they bond;

[0031] Each R 2 can be independently identical or different, and CHR 8 ' -R 8 Gigo, R 8 H, linear or branched C1-C6 alkyl groups, C3-C8 cycloalkyl groups, C6-C 10 -aryl group, or 1 to 3 R 11 It is a heteroaryl group having 3 to 20 carbon atoms arbitrarily substituted with a group, and R 8' is H or C1-C6-alkyl;

[0032] R 3 It is a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 -Aril Giigo;

[0033] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group;

[0034] R 5 is H or aliphatic C1-C 20 - A hydrocarbyl group, optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table, and

[0035] R 6 H or aliphatic C1-C 20 - A hydrocarbyl group, optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table,

[0036] R 5 and R 6 together with n R 10It can form a five-membered saturated carbon ring arbitrarily substituted with a gi, where n is 0 to 4;

[0037] Each R 10 is identical or different, and C1-C 20 - A C1-C group optionally containing a hydrocarbyl group, or one or more heteroatoms belonging to groups 14 to 16 of the periodic table. 20 - It can be a hydrocarbyl radical;

[0038] R 7 H, a linear or branched C1-C6-alkyl group, or 1 to 3 R 11 An aryl or heteroaryl group having 3 to 20 carbon atoms arbitrarily substituted with a group, such as a phenyl ring or a 5 or 6-membered heteroaryl group;

[0039] Each R 11 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group.

[0040] In one aspect, the present invention

[0041] (i) Metallocene complex of the following chemical formula (II);

[0042] (ii) a co-catalyst system comprising a boron-containing co-catalyst and an aluminoxan co-catalyst; and

[0043] (iii) silica support

[0044] A supported catalyst system comprising:

[0045]

[0046] In the above formula,

[0047] Each X is independently a sigma-donor ligand;

[0048] L is a divalent crosslink selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, and -R'2Ge-, and each R' is a C1-C that independently optionally contains a hydrogen atom, or one or more heteroatoms of groups 14 to 16 of the periodic table, or a fluorine atom. 20 - It is a hydrocarbyl group, or optionally, two R' groups can form a ring together;

[0049] Each R 1 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group, and arbitrarily, 2 adjacent R 1 The group may be part of a ring containing a phenyl carbon to which they are bonded;

[0050] Each R 2 It may be independently the same or different, and CH2-R 8 Gigo, R 8 H, linear or branched C1-C6 alkyl groups, C3-C8 cycloalkyl groups, or C6-C 10 -Aril Giigo;

[0051] R 3 It is a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 -Aril Giigo;

[0052] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group;

[0053] R 5 is H or aliphatic C1-C 20- A hydrocarbyl group, optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table, and

[0054] R 6 H or aliphatic C1-C 20 - A hydrocarbyl group, optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table,

[0055] R 5 and R 6 together with n R 10 It can form a five-membered saturated carbon ring arbitrarily substituted with a gi, where n is 0 to 4;

[0056] Each R 10 is identical or different, and C1-C 20 - A C1-C group optionally containing a hydrocarbyl group, or one or more heteroatoms belonging to groups 14 to 16 of the periodic table. 20 - It can be a hydrocarbyl radical;

[0057] R 7 H, a linear or branched C1-C6-alkyl group, or 1 to 3 R 11 It is an aryl or heteroaryl group having 6 to 20 carbon atoms arbitrarily substituted with a group;

[0058] Each R 11 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group.

[0059] In a further aspect, the present invention relates to a method for producing a propylene homopolymer, a propylene random copolymer, or a heterophase propylene copolymer using the specific catalyst system defined above.

[0060] The catalyst system according to the present invention is particularly suitable for a multi-stage process comprising two or more reactors connected in series, each comprising one or more gas phase polymerization steps.

[0061] In another aspect, the present invention provides for the use of the defined catalyst system in olefin polymerization for the production of a propylene homopolymer, a propylene random copolymer, or a heterophase propylene copolymer comprising a matrix polypropylene homopolymer and an amorphous propylene copolymer (A) dispersed in the matrix (M).

[0062] By using the catalyst system of the present invention, very high activity can be obtained, for example, in a multi-stage polymerization process, particularly where a gas phase polymerization step and even a second gas phase polymerization step are present, which is much higher than the activity of different catalysts having different substitution patterns. The advantage of having high activity in the first and optional second gas phases lies not only in the overall productivity of the process but also in the polymer-specific achievable range, for example, where a higher gas phase split enables the production of polypropylene having a wider molecular weight distribution. In the context of heterophase propylene copolymers, control of the gas phase split allows for the control of the xylene-soluble content of the polymer, i.e., its physical and mechanical properties.

[0063] Furthermore, the catalyst system of the present invention, particularly having MAO and borate as co-catalysts, exhibits higher productivity, particularly in the production of polypropylene copolymers with ethylene, compared to a catalyst system without a boron-containing co-catalyst. Surprisingly, this effect is increased by the amount of ethylene added and can be expressed by the following Equation I:

[0064] [Mathematical Formula I]

[0065] ΔProductivity [kg PP / g 촉매 ] > 10 x C2[weight%]

[0066] In the above equation, Δ productivity is the difference between the productivity of the metallocene-MAO-borate catalyst and the productivity of the metallocene-MAO catalyst at a predetermined ethylene concentration in the monomer feed for propylene-ethylene copolymerization performed under strict comparison conditions.

[0067] definition

[0068] Throughout this institution, the following definitions are used.

[0069] Term "C1-C 20 - The hydrocarbyl group is C1-C 20 -alkyl, C2-C 20 -Alkenyl, C2-C 20 -Alkinil, C3-C 20 -cycloalkyl, C3-C 20 -Cycloalkenyl, C6-C 20 -Aryl Gi, C7-C 20 -alkylaryl group or C7-C 20 - It includes an arylalkyl group, or a mixture of the above groups, such as an alkyl-substituted cycloalkyl. Linear and branched hydrocarbyl groups cannot contain cyclic units. Aliphatic hydrocarbyl groups cannot contain an aryl ring.

[0070] Unless otherwise noted, the desirable C1-C 20 - The hydrocarbyl group is C1-C 20 -alkyl, C4-C 20 -cycloalkyl, C5-C 20 -cycloalkyl-alkyl group, C7-C 20 -alkylaryl group, C7-C 20 -arylalkyl group or C6-C 20 -Aryl groups, especially C1-C 10 -alkyl group, C6-C 10 -Aryl group, or C7-C 12 - It is an arylalkyl group, e.g., a C1-C8-alkyl group. The most particularly preferred hydrocarbyl group is methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl, or benzyl.

[0071] The term "halo" includes fluoro, chloro, bromo, and iodo groups, particularly chloro or fluoro groups, when in relation to the definition of a complex.

[0072] Any group, including "one or more heteroatoms belonging to groups 14 to 16 of the periodic table," preferably means O, S, or N. The N group may exist as -NH- or -NR"-, wherein R" is C1-C 10 - It is an alkyl. This can be, for example, 1 to 4 heteroatoms. A group containing one or more heteroatoms belonging to Groups 14 to 16 of the periodic table is an alkoxy group, for example, C1-C 10 - It could be an alkoxy group.

[0073] The oxidation state of a metal ion is primarily determined by the properties of the target metal ion and the stability of the individual oxidation state of each metal ion. In the complex of the present invention, it will be understood that the metal ion M can be coordinated by a ligand X such that the valence of the metal ion is satisfied and it fills its available coordination sites. The properties of such a σ-ligand can vary significantly.

[0074] The term “heteroaryl” defines an aromatic cyclic or polycyclic group in which one or more heteroatoms belonging to groups 14 to 16 of the periodic table are present in one or more of the rings. Such a group may comprise 3 to 20 carbon atoms and one or more heteroatoms selected from O, S and N.

[0075] Catalytic activity is defined herein as the amount of polymer produced per gram of catalyst per hour. Metallocene catalytic activity is defined herein as the amount of polymer produced per gram of metallocene per hour. The term "productivity" is often used to denote catalytic activity, but herein it refers to the amount of polymer produced per unit weight of catalyst.

[0076] Unless otherwise noted herein, the term "molecular weight" refers to the weight-average molecular weight M w It is used to refer to.

[0077] Detailed description of the present invention

[0078] The present invention relates to a novel, enhanced, supported catalyst system comprising a specific class of metallocene complexes in combination with a boron-containing co-catalyst and an aluminoxane co-catalyst, and thereby being an ideal catalyst system for the polymerization of propylene. The metallocene catalyst complex of the present invention is symmetric or asymmetric. An asymmetric type simply means that the two indenyl ligands coordinated to the transition metal center of the metallocene are different, that is, each ligand possesses a chemically different set of substituents. In this context, the definition of an indenyl ligand also includes indasenyl.

[0079] The metallocene catalyst complex of the present invention may be a chiral, racemically cross-linked bis-indeneyl metallocene of its anti-configuration. The metallocene of the present invention may be C2-symmetric or C1-symmetric. It is maintained as pseudo-C2-symmetric due to being maintained as C2-symmetric proximal to the metal center, but not at the ligand terminals. Due to the nature of its chemistry, both the meso form and racemic enantiomer pairs (in the case of C2-symmetric complexes) or anti and syn enantiomer pairs (in the case of C1-symmetric complexes) are formed during the synthesis of the complex. For the purposes of the present invention, racemi-anti means that two indenyl ligands are oriented in opposite directions with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, and racemi-syn means that two indenyl ligands are oriented in the same direction with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, as presented below.

[0080]

[0081] Chemical formula I, and any sub-chemical formulas thereof, are intended to encompass both syn- and anti-configurations. The preferred metallocene catalyst complex is the anti-configuration.

[0082] The metallocene catalyst complex of the present invention can be used as a racemic-anti-isomer. Ideally, therefore, 95 mol%, e.g. 98 mol% or more, particularly 99 mol% or more of the metallocene catalyst complex is in the racemic-anti-isomer form.

[0083] In the metallocene catalyst complex of the present invention, the following preferences apply. The metallocene catalyst complex according to the present invention is a compound of the following formula (I), preferably a compound of the following formula (II):

[0084]

[0085]

[0086] In any formula of the present invention, the following preferred features are applied.

[0087] Each X is independently a sigma-donor ligand. Therefore, each X may be the same or different, and preferably a hydrogen atom, a halogen atom, a linear or branched, cyclic or acyclic C1-C 20 -alkyl or C1-C 20 - Alkoxy group, C6-C 20 -Aryl Gi, C7-C 20 -alkylaryl group or C7-C 20 - It is an arylalkyl group, optionally containing one or more heteroatoms of groups 14 to 16 of the periodic table.

[0088] The term "halogen" includes fluoro, chloro, bromo, and iodo groups, preferably chloro groups. The term "heteroatom belonging to groups 14 to 16 of the periodic table" includes, for example, Si, N, O, or S.

[0089] More preferably, each X is independently a hydrogen atom, a halogen atom, a linear or branched C1-C6-alkyl or C1-C6-alkoxy group, a phenyl or benzyl group.

[0090] More preferably, each X is independently a halogen atom, a linear or branched C1-C4-alkyl or C1-C4-alkoxy group, a phenyl or benzyl group.

[0091] Most preferably, each X is independently a chlorine, benzyl, or methyl group.

[0092] Preferably, both X and X are the same.

[0093] The most desirable options for both X groups are two chloride, two methyl, or two benzyl groups.

[0094] L is a divalent bridge based on carbon, silicon, or germanium. One or two skeletons connecting atoms, such as a ligand-C-ligand (one skeleton atom) or a ligand-Si-Si-ligand (two skeleton atoms), exist between the two ligands.

[0095] The crosslinking atoms may possess other groups. For example, a suitable crosslinking ligand L is selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, and -R'2Ge-, where each R' independently contains a hydrogen atom, or optionally a C1-C group having one or more heteroatoms of groups 14 to 16 of the periodic table or a fluorine atom. 20 - It may be a hydrocarbyl group, or optionally, two R' groups may form a ring together. In one embodiment, R' may be an alkyl having 1 to 10 carbon atoms substituted with an alkoxy having 1 to 10 carbon atoms.

[0096] The term "heteroatoms belonging to groups 14 to 16 of the periodic table" includes, for example, Si, N, O, or S.

[0097] Preferably, L is -R'2Si-, ethylene or methylene.

[0098] In the chemical formula -R'2Si-, each R' is preferably independently C1-C 20 - It is a hydrocarbyl group. The term "C1-C 20 - The "hydrocarbyl group" is therefore C1-C 20 -alkyl, C2-C 20 -Alkenyl, C2-C 20 -Alkinil, C3-C 20 -cycloalkyl, C3-C 20 -Cycloalkenyl, C6-C 20 -Aryl Gi, C7-C 20 -alkylaryl group or C7-C 20 - It comprises an arylalkyl group, or a mixture of said groups, e.g., a cycloalkyl group substituted with an alkyl. Unless otherwise noted, a preferred C1-C 20 - The hydrocarbyl group is C1-C 20 -alkyl, C4-C 20 -cycloalkyl, C5-C 20 -cycloalkyl-alkyl group, C7-C 20 -alkylaryl group, C7-C 20 -arylalkyl group or C6-C 20 - It is Aril Gi.

[0099] In one embodiment, the chemical formula -R'2Si- represents a silacycloalkanedyl, such as silacyclobutane, silacyclopentane, or 9-silafluorene.

[0100] Preferably, both R' groups are identical. R' is C1-C 10 - Hydrocarbyl or C6-C 10- The aryl group is, for example, methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C3-C8-cycloalkyl, cyclohexylmethyl, phenyl, or benzyl, and more preferably both R' are C1-C6-alkyl, C5-C6-cycloalkyl, or C6-aryl groups, and most preferably both R' are methyl, or one is methyl and the other is cyclohexyl. Most preferably, the crosslink is -Si(CH3)2-.

[0101] 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, thiophenyl, or pyridyl ring. However, it is preferable that the Ar group is a phenyl group.

[0102] When the Ar group is a phenyl group, it is preferable that the R1 substituent be located at the 3,4,5-position of the ring (the 1-position is attached to the indenyl ring).

[0103] Each R 1 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group, and arbitrarily, 2 adjacent R 1 The group may be part of a ring containing a phenyl carbon to which they are bonded.

[0104] Preferably, each R 1 It may be independently the same or different and is H, a linear or branched C1-C6-alkyl group, e.g., methyl or tert-butyl.

[0105] For example, an Ar ring, such as a phenyl ring, is unsubstituted (i.e., all three R's 1(This is hydrogen), can be substituted only at the para position (e.g., 4'-tert-butylphenyl), or can be disubstituted at the 3' and 5' positions (e.g., 3',5'-dimethylphenyl or 3',5'-di-tert-butylphenyl).

[0106] In addition, both phenyl rings may have the same substitution pattern, or the two phenyl rings may have different substitution patterns.

[0107] Therefore, 1 or 2 R 1 It is preferable for the gigabyte to be H. Two Rs 1 If gigabytes are H, the remainder R 1 The group is preferably in the para position. 1 R 1 If gigabytes are H, the remainder R 1 The gi is preferably in the meta position.

[0108] Each R 2 can be independently identical or different, and CHR 8 ' -R 8 Gigo, R 8 H, linear or branched C1-C6 alkyl groups, C3-C8 cycloalkyl groups, C6-C 10 -aryl group, or 1 to 3 R 11 It is a heteroaryl group having 3 to 20 carbon atoms arbitrarily substituted with a group, and R 8' It is H or C1-C6-alkyl.

[0109] Preferably R 8' It is H or methyl, especially H.

[0110] Preferably each R 2 It may be independently the same or different, and CH2-R 8 Gigo, R 8 H, linear or branched C1-C6 alkyl groups, C3-C8 cycloalkyl groups, or C6-C 10 - It is Aril Gi.

[0111] Preferably, R 2Both are identical, and CH2-R 8 Gigo, R 8 H, a linear or branched C1-C4-alkyl group, more preferably, R 2 Both are identical, and CH2-R 8 Gigo, R 8 is H, a linear or branched C1-C3-alkyl group. Most preferably, R 2 Both are methyl.

[0112] R 3 It is a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is Aril Gi.

[0113] R 3 is preferably a linear or branched C1-C6-alkyl group or C6-C 20 - An aryl group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or tert-butyl, preferably a linear C1-C4-alkyl group, more preferably a C1-C2-alkyl group, most preferably methyl.

[0114] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group.

[0115] Preferably each R 9 is identical or different, but R 9 is a linear or branched C1-C4-alkyl group, more preferably R 9 is identical and is a C1-C2-alkyl group. Most preferably, R 4 is a tert-butyl group, and therefore R 9 The git is methyl.

[0116] In one aspect of the present invention, R 5 and R 6It may be independently identical or different, and is an aliphatic C1-C that optionally contains H, or one or more heteroatoms from groups 14 to 16 of the periodic table. 20 - Hydrocarbyl group, e.g., alkoxy group, e.g., C1-C 10 - It is an alkoxy group.

[0117] Preferably, R 5 and R 6 It may be independently the same or different and is H, a linear or branched C1-C6-alkyl group or a C1-C6-alkoxy group.

[0118] More preferably, R 5 and R 6 It may be independently the same or different and is H, a linear or branched C1-C4-alkyl group or a C1-C4-alkoxy group.

[0119] In another mode, R 5 and R 6 They can form a 5-membered saturated carbon ring together, but n R 10 It is arbitrarily substituted with a gi, and n is 0 to 4, preferably 0 or 2, more preferably 0;

[0120] Each R 10 It may be the same or different, and C1-C 20 - A C1-C group optionally containing a hydrocarbyl group, or one or more heteroatoms belonging to groups 14 to 16 of the periodic table. 20 - It is a hydrocarbyl radical, preferably a linear or branched C1-C6 alkyl group.

[0121] R 7 H, a linear or branched C1-C6-alkyl group, or 1 to 3 R 11 It is an aryl or heteroaryl group having 3 to 20 carbon atoms arbitrarily substituted with a group.

[0122] Preferably, R 7 H, or 1 to 3 R11 It is an aryl group having 6 to 10 carbon atoms optionally substituted with a group, and more preferably R 7 It is H or phenyl, with 1 to 3 R 11 It is arbitrarily replaced with gi.

[0123] R 7 In the case of this optionally substituted aryl group having 6 to 10 carbon atoms, e.g., phenyl, each R 11 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group. R 7 The case where this H is not the most desirable is.

[0124] R 7 These 1 to 3 R 11 It is a phenyl group optionally substituted with a group, and more preferably R 7 is 1 or 2 R 11 It is most desirable when the phenyl group is substituted.

[0125] R 7 This is not H, and especially R 7 These 1 to 3 R 11 In the case of an aryl or heteroaryl group having 3 to 20 carbon atoms arbitrarily substituted with a group, the metallocene complex is novel and itself forms an additional aspect of the present invention.

[0126] Preferably, each R 11 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups or C6-C 20 - It is an aryl group or an OY group, where Y is a C1-C4-hydrocarbyl group. More preferably, each R 11may be independently the same or different, and is H, a linear or branched C1-C4-alkyl group or an OY group, and Y is a C1-C4-hydrocarbyl group. More preferably, each R 11 may be independently the same or different, and is H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, in particular H, methyl, or tert-butyl. More preferably, each R 11 It may be independently the same or different, and is methyl, ethyl, isopropyl, tert-butyl or methoxy, in particular, methyl or tert-butyl.

[0127] When an aryl group, such as a phenyl group, is substituted, this preferably has one or two Rs. 11 Gi, for example, R rather than H 11 It is replaced by gi.

[0128] The group at the 4-position in the above ligand and R in the above ligand 7 It is most desirable when the qi is identical. Accordingly, R 7 In the case of this 3,5-dimethylphenyl group, the group at the 4-position of the ligand must be a 3,5-dimethylphenyl group. This is especially the case when the ring is an indacenyl ring.

[0129] In a more preferred embodiment, the metallocene complex may be a compound of the following formula (III):

[0130]

[0131] In the above formula,

[0132] Each X is independently a sigma-donor ligand;

[0133] L is a carbon, silicon, or germanium-based divalent bridge connecting one or two skeletal valence ligands;

[0134] 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;

[0135] Each R 1 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group, and arbitrarily, 2 adjacent R 1 The gi may be part of a ring containing the carbon to which they bond;

[0136] Each R 2 can be independently identical or different, and CHR 8 ' -R 8 Gigo, R 8 H, linear or branched C1-C6 alkyl groups, C3-C8 cycloalkyl groups, C6-C 10 - An aryl group, or a heteroaryl group having 3 to 20 carbon atoms, wherein 1 to 3 R 11 Arbitrarily substituted with gi, and R 8' is H or C1-C6-alkyl;

[0137] R 3 It is a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 -Aril Giigo;

[0138] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group;

[0139] R 5 is H or aliphatic C1-C 20 - A hydrocarbyl group, optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table, and

[0140] R 6H or aliphatic C1-C 20 - A hydrocarbyl group, optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table,

[0141] R 5 and R 6 together with n R 10 It can form a five-membered saturated carbon ring arbitrarily substituted with a gi, where n is 0 to 4;

[0142] Each R 10 is identical or different, and C1-C 20 - A C1-C group optionally containing a hydrocarbyl group, or one or more heteroatoms belonging to groups 14 to 16 of the periodic table. 20 - It can be a hydrocarbyl radical;

[0143] R 7 It is a linear or branched C1-C6-alkyl group, or 1 to 3 R groups. 11 An aryl or heteroaryl group having 3 to 20 carbon atoms optionally substituted with a group, such as a phenyl ring or a 5 or 6-membered heteroaryl ring;

[0144] Each R 11 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group.

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

[0146]

[0147] In the above formula,

[0148] Each X is independently a sigma-donor ligand;

[0149] L is a divalent crosslink selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, and -R'2Ge-, and each R' is a C1-C that independently optionally contains a hydrogen atom, or one or more heteroatoms of groups 14 to 16 of the periodic table, or a fluorine atom. 20 - It is a hydrocarbyl group, or optionally, two R' groups can form a ring together;

[0150] Each R 1 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group, and arbitrarily, 2 adjacent R 1 The group may be part of a ring containing a phenyl carbon to which they are bonded;

[0151] Each R 2 It may be independently the same or different, and CH2-R 8 Gigo, R 8 H, linear or branched C1-C6 alkyl groups, C3-C8 cycloalkyl groups, or C6-C 10 -Aril Giigo;

[0152] R 3 It is a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 -Aril Giigo;

[0153] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group;

[0154] R 5 is H or aliphatic C1-C 20- It is a hydrocarbyl group, which may contain one or more heteroatoms from groups 14 to 16 of the periodic table, and

[0155] R 6 H or aliphatic C1-C 20 - A hydrocarbyl group, optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table,

[0156] R 5 and R 6 together with n R 10 It can form a five-membered saturated carbon ring arbitrarily substituted with a gi, where n is 0 to 4;

[0157] Each R 10 is identical or different, and C1-C 20 - A C1-C group optionally containing a hydrocarbyl group, or one or more heteroatoms belonging to groups 14 to 16 of the periodic table. 20 - It can be a hydrocarbyl radical;

[0158] R 7 It is a linear or branched C1-C6-alkyl group, or 1 to 3 R groups. 11 It is an aryl or heteroaryl group having 6 to 20 carbon atoms arbitrarily substituted with a group;

[0159] Each R 11 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group.

[0160] In a more preferred embodiment, the metallocene complex may be a compound of the following formula (V):

[0161]

[0162] In the above formula,

[0163] Each X is independently a sigma-donor ligand;

[0164] L is a divalent bridge selected from -R'2C- and -R'2Si-, and each R' independently contains a hydrogen atom, or one or more heteroatoms of groups 14 to 16 of the periodic table, or a fluorine atom optionally, in a C1-C 20 - It is a hydrocarbyl group, or optionally, two R' groups can form a ring together;

[0165] Each R 1 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group, and arbitrarily, 2 adjacent R 1 The group may be part of a ring containing a phenyl carbon to which they are bonded;

[0166] Each R 2 It may be independently the same or different, and CH2-R 8 Gigo, R 8 H, linear or branched C1-C6 alkyl groups, C3-C8 cycloalkyl groups, or C6-C 10 -Aril Giigo;

[0167] R 3 It is a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 -Aril Giigo;

[0168] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group;

[0169] R 5 is H,

[0170] R 6 is H or,

[0171] R 5 and R 6 together with n R 10 It can form a five-membered saturated carbon ring arbitrarily substituted with a gi, where n is 0 to 4;

[0172] Each R 10 is identical or different, and C1-C 20 - A C1-C group optionally containing a hydrocarbyl group, or one or more heteroatoms belonging to groups 14 to 16 of the periodic table. 20 - It can be a hydrocarbyl radical;

[0173] R 7 1 to 3 R 11 A linear or branched C1-C6-alkyl group or aryl optionally substituted with a group;

[0174] Each R 11 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group.

[0175] In a more preferred embodiment, the metallocene complex may be a compound of the following formula (VI):

[0176]

[0177] In the above formula,

[0178] Each X is independently a sigma-donor ligand;

[0179] L is a divalent crosslink selected from -R'2C- and -R'2Si-, and each R' is independently C1-C6-alkyl, C5-C6-cycloalkyl, C1-C 10 -alkyl-O-C1-C 10- It is an alkyl or C6-aryl group;

[0180] Each Ar is a phenyl ring or a 5- or 6-membered heteroaryl ring;

[0181] Each R 1 can be independently the same or different, and is H, a linear or branched C1-C6-alkyl group;

[0182] Each R 2 can be independently identical or different, and CHR 8 ' -R 8 Gigo, R 8 is H, a linear or branched C1-C6-alkyl group, and R 8' is H or C1-C6-alkyl;

[0183] R 3 It is a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 -Aril Giigo;

[0184] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group;

[0185] R 5 is H,

[0186] R 6 is H or,

[0187] R 5 and R 6 They can form a five-membered saturated carbon ring together;

[0188] R 7 It is a linear or branched C1-C6-alkyl group, or 1 to 3 R groups. 11 An aryl or heteroaryl group having 3 to 20 carbon atoms optionally substituted with a group, e.g., 1 to 3 R 11 It is a phenyl ring or a 5- or 6-membered heteroaryl ring arbitrarily substituted with a group;

[0189] Each R 11 It can be independently the same or different and is H, a linear or branched C1-C6-alkyl group.

[0190] In a more preferred embodiment, the metallocene complex may be a compound of the following formula (VII):

[0191]

[0192] In the above formula,

[0193] Each X is independently a sigma-donor ligand;

[0194] L is a divalent crosslink selected from -R'2C- and -R'2Si-, and each R' is independently C1-C6-alkyl, C5-C6-cycloalkyl, C1-C 10 -alkyl-O-C1-C 10 - It is an alkyl or C6-aryl group;

[0195] Each Ar is a phenyl ring or a 5- or 6-membered heteroaryl ring;

[0196] Each R 1 can be independently the same or different, and is H, a linear or branched C1-C6-alkyl group;

[0197] Each R 2 can be independently identical or different, and CHR 8 ' -R 8 Gigo, R 8 is H, a linear or branched C1-C6-alkyl group, and R 8' is H or C1-C6-alkyl;

[0198] R 3 is a linear or branched C1-C6-alkyl group;

[0199] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group;

[0200] R5 and R 6 They can form a five-membered saturated carbon ring together;

[0201] R 7 It is a phenyl ring or a 5- or 6-membered heteroaryl ring, wherein 1 to 3 R 11 Arbitrarily substituted with gi;

[0202] Each R 11 It can be independently the same or different and is H, a linear or branched C1-C6-alkyl group.

[0203] In a more preferred embodiment, the metallocene complex may be a compound of the following formula (VIII):

[0204]

[0205] In the above formula,

[0206] Each X is independently a sigma-donor ligand;

[0207] L is a divalent crosslink selected from -R'2C- and -R'2Si-, and each R' is independently C1-C6-alkyl, C5-C6-cycloalkyl, C1-C 10 -alkyl-O-C1-C 10 - It is an alkyl or C6-aryl group;

[0208] Each R 1 can be independently the same or different, and is H, a linear or branched C1-C6-alkyl group;

[0209] Each R 2 It may be independently the same or different, and CH2-R 8 Gigo, R 8 is H, a linear or branched C1-C6-alkyl group;

[0210] R 3 is a linear or branched C1-C6-alkyl group;

[0211] R 4 is C(R 9 It is the 3rd stage, and R 9is a linear or branched C1-C6-alkyl group;

[0212] R 5 is H,

[0213] R 6 is H or,

[0214] R 5 and R 6 They can form a five-membered saturated carbon ring together;

[0215] R 7 1 to 3 R 11 It is a phenyl group arbitrarily substituted with a group;

[0216] Each R 11 It can be independently the same or different and is H, a linear or branched C1-C6-alkyl group.

[0217] In a more preferred embodiment, the metallocene complex may be a compound of the following formula (IX):

[0218]

[0219] In the above formula,

[0220] Each X is independently a sigma-donor ligand;

[0221] L is -R'2Si-, and each R' is independently C1-C6-alkyl, C5-C6-cycloalkyl, C1-C 10 -alkyl-O-C1-C 10 - It is an alkyl or C6-aryl group;

[0222] Each R 1 can be independently the same or different, and is H, a linear or branched C1-C6-alkyl group;

[0223] Each R 2 is methyl;

[0224] R 3 is a linear or branched C1-C6-alkyl group;

[0225] R 4 is C(R 9 It is the 3rd stage, and R 9is a linear or branched C1-C6-alkyl group;

[0226] R 5 is H,

[0227] R 6 is H or,

[0228] R 5 and R 6 They can form a five-membered saturated carbon ring together;

[0229] R 7 1 to 3 R 11 It is a phenyl group arbitrarily substituted with a group;

[0230] Each R 11 It can be independently the same or different and is H, a linear or branched C1-C6-alkyl group.

[0231] In a more preferred embodiment, the metallocene complex may be a compound of the following chemical formula (X):

[0232]

[0233] In the above formula,

[0234] Each X is independently a sigma-donor ligand;

[0235] L is -R'2Si-, and each R' is independently C1-C6-alkyl, C5-C6-cycloalkyl, C1-C 10 -alkyl-O-C1-C 10 - It is an alkyl or C6-aryl group;

[0236] Each R 1 can be independently the same or different, and is H, a linear or branched C1-C6-alkyl group;

[0237] Each R 2 It may be independently the same or different, and CH2-R 8 Gigo, R 8 is H, a linear or branched C1-C6-alkyl group;

[0238] R 3is a linear or branched C1-C6-alkyl group;

[0239] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group;

[0240] R 7 1 to 3 R 11 It is a phenyl group arbitrarily substituted with a group;

[0241] Each R 11 It can be independently the same or different and is H, a linear or branched C1-C6-alkyl group.

[0242] In a more preferred embodiment, the metallocene complex may be a compound of the following chemical formula (XI):

[0243]

[0244] In the above formula,

[0245] Each X is independently a sigma-donor ligand, e.g., a halogen atom, a linear or branched C1-C4-alkyl or C1-C4-alkoxy group, a phenyl or benzyl group;

[0246] L is -R'2Si-, and each R' is independently C1-C6-alkyl, C5-C6-cycloalkyl, C1-C 10 -alkyl-O-C1-C 10 - It is an alkyl or C6-aryl group;

[0247] Each R 1 can be independently the same or different, and is H, a linear or branched C1-C6-alkyl group;

[0248] R 3 is a linear or branched C1-C6-alkyl group;

[0249] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group;

[0250] R 71 to 3 R 11 It is a phenyl group arbitrarily substituted with a group;

[0251] Each R 11 It can be independently the same or different and is H, a linear or branched C1-C6-alkyl group.

[0252] In a more preferred embodiment, the metallocene complex may be a compound of the following formula (XII):

[0253]

[0254] In the above formula,

[0255] Each X is independently a sigma-donor ligand, e.g., a halogen atom, a linear or branched C1-C4-alkyl or C1-C4-alkoxy group, a phenyl or benzyl group;

[0256] L is -Me2Si- and;

[0257] Each R 1 can be independently the same or different, and is H, a linear or branched C1-C6-alkyl group;

[0258] R 3 is a linear or branched C1-C6-alkyl group;

[0259] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group;

[0260] R 7 1 to 3 R 11 It is a phenyl group arbitrarily substituted with a group;

[0261] Each R 11 It can be independently the same or different and is H, a linear or branched C1-C6-alkyl group.

[0262] In one embodiment, the metallocene complex may be a compound of the following formula (XIII):

[0263]

[0264] In the above formula,

[0265] Each X is independently a sigma-donor ligand;

[0266] L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, and -R'2Ge-, and each R' is a C1-C that independently contains an H atom, or one or more heteroatoms of groups 14 to 16 of the periodic table, or a fluorine atom. 20 - It is a hydrocarbyl group, or optionally, two R' groups can form a ring together;

[0267] Each R 1 may independently be the same or different, and H, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or OY group, and Y is C1-C 10 - It is a hydrocarbyl group, and arbitrarily, 2 adjacent R 1 The group may be part of a ring containing a phenyl carbon to which they are bonded;

[0268] Each R 2 It may be independently the same or different, and CH2-R 8 Gigo, R 8 H, linear or branched C1-C6 alkyl groups, C3-C8 cycloalkyl groups, or C6-C 10 -Aril Giigo;

[0269] R 3 It is a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl, C7-C 20 -alkylaryl group or C6-C 20 -Aril Giigo;

[0270] R 4 is C(R 9 It is the 3rd stage, and R 9is a linear or branched C1-C6-alkyl group;

[0271] R 5 and R 6 together with n R 10 It can form a five-membered saturated carbon ring arbitrarily substituted with a gi, where n is 0 to 4;

[0272] Each R 10 is identical or different, and C1-C 20 - A C1-C group optionally containing a hydrocarbyl group, or one or more heteroatoms belonging to groups 14 to 16 of the periodic table. 20 - It can be a hydrocarbyl radical;

[0273] R 7 is H;

[0274] In particular, here, each X is independently a sigma-donor ligand, e.g., a halogen atom, a linear or branched C1-C4-alkyl or C1-C4-alkoxy group, a phenyl or benzyl group;

[0275] L is -Me2Si- and;

[0276] Each R 1 can be independently the same or different, and is H, a linear or branched C1-C6-alkyl group;

[0277] R 3 is a linear or branched C1-C6-alkyl group;

[0278] R 4 is C(R 9 It is the 3rd stage, and R 9 is a linear or branched C1-C6-alkyl group;

[0279] R 7 is H.

[0280] In particular, the complex of the present invention comprises the following:

[0281] rac-dimethylsilandiylbis[2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride,

[0282] rac-anti-dimethylsilandyl[2-methyl-4-(4'-tert-butylphenyl)-indene-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride,

[0283] rac-anti-dimethylsilandyl[2-methyl-4-(4'-tert-butylphenyl)-indene-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride,

[0284] rac-anti-dimethylsilandyl[2-methyl-4-(3',5'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride,

[0285] rac-anti-dimethylsilandyl[2-methyl-4,8-bis-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride,

[0286] rac-anti-dimethylsilandyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, and

[0287] rac-anti-dimethylsilandyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3',5'-di-tert-butyl-phenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride.

[0288] To avoid doubt, any narrower definition of the substituent presented above may be combined with any other broad or narrow definition of any other substituent.

[0289] Throughout the foregoing of this invention, where a narrower definition of a substituent is presented, said narrower definition is deemed to be disclosed in conjunction with all other broader and narrower definitions of substituents in this invention.

[0290] The ligands required to produce the complexes of the present invention and the catalysts thereof can be synthesized by any method, and a skilled organic chemist may devise various synthesis protocols for the preparation of the necessary ligand materials. For example, WO 2007 / 116034 discloses the necessary chemistry. Additionally, synthesis protocols can generally be found 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 those skilled in the art.

[0291] Co-catalyst

[0292] In order to produce an active catalyst species, it is typically necessary to use a co-catalyst known in the art.

[0293] According to the present invention, a co-catalyst system comprising a boron-containing co-catalyst and an aluminoxan co-catalyst is used in combination with the metallocene catalyst complex defined above.

[0294] The aluminoxan co-catalyst may be a compound of the following chemical formula (A):

[0295]

[0296] In the above formula, n is 6 to 20, and R has the following meaning.

[0297] Aluminoxan is an organoaluminum compound, such as the chemical formulas AlR3, AlR2Y, and Al2R3Y3 (where R is, for example, C1-C 10 -alkyl, preferably C1-C5-alkyl or C3-C 10 -cycloalkyl, C7-C 12-arylalkyl or C7-C 12 - May be an alkylaryl and / or phenyl or naphthyl, and Y is H, a halogen, preferably chlorine or bromine, or C1-C 10 It is produced from the partial hydrolysis of a compound of -alkoxy, preferably methoxy or ethoxy). The resulting oxygen-containing aluminoxane is generally not a pure compound, but a mixture of oligomers of formula (II).

[0298] A preferred aluminoxan is methylaluminoxan (MAO). The aluminoxan used as a co-catalyst according to the present invention is not a pure compound due to its method of preparation, and the molar concentration of the aluminoxan solution is based on its aluminum content.

[0299] According to the present invention, a boron-containing co-catalyst is also used in combination with an aluminoxan co-catalyst.

[0300] The boron-containing co-catalyst in question is a compound of the following chemical formula (B):

[0301] BY3(B)

[0302] In the above formula, Y is the same or different hydrogen atom, an alkyl group having 1 to about 20 carbon atoms, an aryl group having 6 to about 15 carbon atoms, or an alkylaryl, arylalkyl, haloalkyl or haloaryl having 1 to 10 carbon atoms in an alkyl radical and 6 to 20 carbon atoms in an aryl radical, or fluorine. Preferred examples for Y are fluorine, trifluoromethyl, aromatic fluoride groups, such as p-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl, and 3,5-di(trifluoromethyl)phenyl. Preferred options for BY3 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, tris(3,5-di(trifluoromethyl)phenyl)borane and / or tris(3,4,5-trifluorophenyl)borane.

[0303] Tris(pentafluorophenyl)borane is particularly desirable.

[0304] However, it is preferable to use a borate. Generally, the above compound contains an anion of the following chemical formula (C):

[0305] (Z)4B - (C)

[0306] In the above formula, Z is an optionally substituted phenyl derivative, and the substituent is a halo-C1-C6-alkyl or halo group. A preferred option is fluoro or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0307] These ionic co-catalysts preferably contain weakly coordinating anions, such as tetrakis(pentafluorophenyl) borate or tetrakis(3,5-di(trifluoromethyl)phenyl) borate.

[0308] Suitable cationic counterions include triphenylcarbenium and 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.

[0309] Preferred ionic compounds that can be used according to the present invention include the following:

[0310] Tributylammonium tetrakis(pentafluorophenyl) borate,

[0311] Tributylammonium tetrakis(trifluoromethylphenyl) borate,

[0312] Tributylammonium tetrakis(4-fluorophenyl) borate,

[0313] N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl) borate,

[0314] N,N-DimethylbenzylammoniumTetrakis(Pentafluorophenyl)Borate,

[0315] N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,

[0316] N,N-Di(propyl)AmmoniumTetrakis(Pentafluorophenyl)Borate,

[0317] Di(cyclohexyl)ammonium tetrakis(pentafluorophenyl) borate,

[0318] Triphenylcarbenium tetrakis(pentafluorophenyl) borate, or

[0319] Ferrosenium tetrakis(pentafluorophenyl) borate.

[0320] Triphenylcarbenium tetrakis(pentafluorophenyl) borate,

[0321] N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,

[0322] N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl) borate or

[0323] N,N-DimethylbenzylammoniumTetrakis(Pentafluorophenyl)Borate

[0324] It is desirable.

[0325] Surprisingly, a specific boron-containing co-catalyst was found to be particularly desirable. The preferred borate used in the present invention accordingly contains trityl, i.e., triphenylcarbenium ions. Accordingly, the use of Ph3CB(PhF5)4 and analogs thereof is therefore particularly desirable.

[0326] The appropriate amount of co-catalyst will be known to those skilled in the art.

[0327] The molar ratio of the supply amount of zirconium ions of the metallocene to boron may be 0.1:1 to 10:1 mol / mol, preferably 0.3:1 to 7:1 mol / mol, particularly 0.3:1 to 5:1 mol / mol.

[0328] More preferably, the molar ratio of the supply amount of zirconium ions of the boron:metallocene B / Zr is 0.3:1 to 3:1.

[0329] The catalyst may contain 10 to 100 μmol of zirconium per gram of silica / support and 5 to 10 mmol of Al per gram of silica / support.

[0330] The molar ratio of Al to zirconium ions of metallocene in aluminoxane may be 1:1 to 2000:1 mol / mol, preferably 10:1 to 1000:1 mol / mol, more preferably 50:1 to 600:1 mol / mol.

[0331] Catalytic system

[0332] The aforementioned metallocene complex is used as a catalyst in combination with the aforementioned suitable co-catalyst combination.

[0333] The catalyst system of the present invention is used in a supported form. The particulate support material used is a porous inorganic support, such as silica, alumina, or a mixed oxide, such as silica-alumina, particularly silica.

[0334] The use of a silica support is preferred. Those skilled in the art know the procedures required to support a metallocene catalyst.

[0335] Particularly preferably, the support is a porous material so that a complex can be loaded into the pores of the support, and a method similar to that described in, for example, WO 94 / 14856, WO 95 / 12622, WO 2006 / 097497 and EP 1828266 is used.

[0336] The average particle size of a support, such as a silica support, can typically be 10 to 100 μm. However, it has been found that special advantages can be obtained when the support has an average particle size of 15 to 80 μm, preferably 18 to 50 μm.

[0337] The average pore size of a support, such as a silica support, may be 10 to 100 nm and the pore volume may be 1 to 3 mL / g.

[0338] 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.

[0339] The support may be optionally calcined before use in catalyst preparation to achieve an optimal silanol group content. The use of such a support is common in the art.

[0340] Manufacturing of catalytic systems

[0341] There are several methods for manufacturing a catalyst system according to the present invention.

[0342] In one embodiment, the manufacture of a catalyst system according to the present invention comprises the following steps:

[0343] (a) a step of reacting a support, e.g., a silica support, with an aluminoxan co-catalyst in a suitable hydrocarbon solvent, e.g., toluene, and then optionally drying to obtain an aluminoxan co-catalyst-treated support;

[0344] (b) a step of reacting a metallocene complex of formula (I) with an aluminoxane co-catalyst in a suitable hydrocarbon solvent, such as toluene;

[0345] (c) adding a borate co-catalyst to the solution obtained in step (b) to obtain a solution of a metallocene complex of formula (I), a borate co-catalyst, and an aluminoxane co-catalyst (wherein the borate co-catalyst is added in an amount such that the molar ratio of the boron / zirconium supply reaches 0.1:1 to 10:1);

[0346] (d) adding the solution obtained in step (c) to the aluminoxan co-catalyst-treated support obtained in step (a) (wherein the amount of aluminoxan co-catalyst added in step (a) is 75.0 to 97.0 weight% of the total amount of aluminoxan co-catalyst, and the amount of aluminoxan co-catalyst added in step (b) is 3.0 to 25.0 weight% of the total amount of aluminoxan co-catalyst); and

[0347] (e) A step of drying the supported catalyst system obtained above.

[0348] polymerization

[0349] In a further aspect, the present invention relates to a method for producing a propylene homopolymer, a propylene random copolymer, or a heterophase propylene copolymer using the specific catalyst system defined above.

[0350] The method for producing propylene homopolymers and propylene random copolymers may be a one-step polymerization method, for example, in bulk, for example, in a loop reactor. Propylene homopolymers, propylene random copolymers, or heterophase propylene copolymers may be further produced by a multi-step polymerization method. Preferably, particularly in the case of heterophase propylene copolymers, the method is a multi-step polymerization method comprising a gas phase polymerization step.

[0351] The polymerization of the method of the present invention may preferably be carried out in one or more, or two or more, e.g., two, three, or four liquid slurry reactors, and among the one or more reactors, the polymerization reactor is a gas phase reactor. Additionally, the method may include a prepolymerization step. Such a prepolymerization step is a conventional step typically used in polymer synthesis.

[0352] In one embodiment, a polymerization method for producing a propylene homopolymer or a propylene random copolymer uses a single liquid slurry reactor combined with a prepolymerization reactor.

[0353] In another embodiment, particularly for the production of heterophase propylene copolymers and propylene random copolymers, the method of the present invention preferably uses two or three main reactors, wherein one or more reactors are gas phase reactors. Ideally, the multi-stage method of the present invention comprises a first reactor operated in a liquid slurry and a second and optional third reactor that are gas phase reactors. Additionally, the method may utilize a prepolymerization step. The liquid slurry reaction may be carried out in a cyclic reactor.

[0354] The method using the catalytic system of the present invention is ideally suitable for the production of propylene homopolymers, propylene random copolymers, or heterophase propylene copolymers, which will be defined in more detail below. In the heterophase propylene copolymer, the homopolymer or random copolymer matrix (M) is combined with a copolymerizable amorphous fraction, namely an amorphous propylene-ethylene copolymer (A), to produce the heterophase copolymer of the present invention.

[0355] According to the present invention, an amorphous propylene-ethylene copolymer (A) is produced in a gas phase reactor. For the purposes of the present invention, the amorphous propylene-ethylene copolymer (A) is also referred to as ethylene-propylene rubber or EPR.

[0356] When two gas phase reactors are used, the first gas phase reactor can produce a homopolymer or copolymer component, ideally a homopolymer component, and thereby the polymer component from the first gas phase reactor forms part of the matrix (M) of the polymer.

[0357] For liquid slurry and gas phase copolymerization reactions, the reaction temperature used will generally be 60 to 115°C (e.g., 70 to 90°C), and the reactor pressure will generally be 10 to 25 bar for the gas phase reaction, and the liquid slurry polymerization will be operated at a higher pressure, e.g., 30 to 60 bar. The residence time will generally be 0.25 to 8 hours (e.g., 0.5 to 4 hours). The gas used will optionally be the monomer as a mixture with a non-reactive gas, e.g., nitrogen or propane. It is a specific feature of the present invention that the polymerization is carried out at a temperature of 60°C or higher. For the purposes of the present invention, the liquid monomer slurry polymerization is also referred to as the bulk phase.

[0358] Generally, the amount of catalyst used will depend on the properties of the catalyst, the type and conditions of the reactor, and the desired characteristics of the polymer product. As is known to those skilled in the art, hydrogen can be used to control the molecular weight of the polymer.

[0359] The manufacturing split between the various reactors may vary. When two reactors are used, the split is generally 30 to 70 wt% : 70 to 30 wt%, preferably 40 to 60 wt% : 60 to 40 wt%, in the bulk:gaseous phase. When three reactors are used, it is desirable for each reactor to produce at least 20 wt%, for example, at least 25 wt% of the polymer. The total amount of polymer produced in the gaseous phase reactors should preferably exceed the amount produced in the bulk stage. The values ​​may be 30 to 45% in the bulk and 70 to 55 wt% in the gaseous phase reactors.

[0360] The metallocene catalyst system of the present invention possesses excellent catalytic activity and superior comonomer reaction.

[0361] In addition, the above catalyst system has an average molecular weight M w It can provide a polymer of.

[0362] Furthermore, the catalyst system of the present invention, in particular the catalyst system containing MAO and a borate co-catalyst, exhibits higher productivity compared to a catalyst system without a borate co-catalyst, particularly in the production of polypropylene copolymers with ethylene. Surprisingly, this effect increases with the amount of ethylene added and can be expressed by the following inequality (Equation I):

[0363] [Mathematical Formula I]

[0364] ΔProductivity [kg PP / g 촉매 ] > 10 x C2[weight%].

[0365] Δ productivity is the difference between the productivity of the metallocene-MAO-borate catalyst and the metallocene-MAO catalyst at a given ethylene concentration in the monomer feed in propylene-ethylene copolymerization performed under strictly equivalent, that is, identical conditions. C2 weight% is the amount of ethylene in the polymer.

[0366] It is also preferable that the catalyst system of the present invention be used in the production of heterophase PP / EPR formulations. Such reactor formulations can be produced in two steps (bulk homopolypropylene (hPP) + gaseous ethylene-propylene rubber) or three steps (bulk hPP + gaseous hPP + gaseous EPR).

[0367] Accordingly, in this aspect, the present invention provides a method for manufacturing a heterophase polypropylene copolymer comprising the following:

[0368] (I) a step of polymerizing bulk propylene in the presence of a catalyst system defined herein to produce a polypropylene homopolymer matrix; and

[0369] (II) A step of polymerizing propylene and ethylene in the gaseous phase in the presence of the matrix and the catalyst system to produce a heteropolymer of polypropylene comprising a homopolymer matrix and ethylene-propylene rubber, and an amorphous propylene copolymer (A).

[0370] In another aspect, the present invention provides a method for manufacturing a heterophase polypropylene copolymer comprising the following:

[0371] (I) a step of polymerizing bulk propylene in the presence of a catalyst system defined herein to produce a polypropylene homopolymer;

[0372] (II) a step of polymerizing propylene in the gaseous phase in the presence of the homopolymer and the catalyst system to produce a polypropylene homopolymer matrix; and

[0373] (III) a step of polymerizing propylene and ethylene in the gaseous phase in the presence of the matrix and the catalyst system to produce a heteropolymer or amorphous propylene copolymer (A) comprising a homopolymer matrix and ethylene propylene rubber (EPR).

[0374] polymer

[0375] It is a feature of the present invention that the claimed catalyst system enables the production of propylene random copolymers with higher productivity.

[0376] M of a random polymer prepared using the catalyst of the present invention w can be greater than 200,000, preferably 220,000 or more, e.g. 240,000 or more. Values ​​exceeding 320,000 have also been achieved. M of the copolymer produced in a single reactor w / M n The value is generally low, for example less than 4, for example less than 3.5, or even less than 3.3.

[0377] The propylene random copolymer produced by the catalyst system of the present invention can be produced to have an MFR2 value of 0.1 to 100 g / 10 min depending on the amount of comonomer and / or the use and amount of hydrogen used as an MFR regulator (MFR2 is measured at 230°C / 2.16 kg load according to ISO 1133). Due to the very high molecular weight capability of the catalyst of the present invention, the MFR2 of the copolymer, M w and M w / M n The value can be widened as needed by using multiple reactors, where temperature, pressure, and H2 concentration can vary within the process window.

[0378] An additional feature of the present invention is that the claimed catalyst system enables the production of a heterophase copolymer having a rubber phase having a high molecular weight.

[0379] Accordingly, in another aspect, the present invention provides for the use of the catalyst system defined above in the olefin polymerization for the production of a heterophase propylene copolymer comprising a matrix polypropylene homopolymer and an amorphous propylene copolymer (A), or ethylene-propylene rubber dispersed in said matrix (M), and

[0380] Here, the heterophase polypropylene copolymer is

[0381] (a1) 30.0 to 85.0 weight% of crystalline fraction (CF); and

[0382] (a2) 15.0 to 70.0 wt% of soluble fraction (SF) having an ethylene content of 15.0 to 80.0 wt% and an intrinsic viscosity of 2.0 to 5.0 dl / g (at 135°C in decalin)

[0383] It is characterized by, and the crystalline fraction (CF) and soluble fraction (SF) are measured at 40°C in 1,2,4-trichlorobenzene.

[0384] These heterophase propylene copolymers (HECOs) comprise a semicrystalline polymer matrix (M) (propylene homopolymer (hPP) or semicrystalline random propylene-ethylene or propylene-butene copolymer (rPP), or a combination of the two), wherein a largely amorphous copolymer (A), e.g., propylene-ethylene copolymer (EP), is dispersed (rubber phase or EPR).

[0385] Accordingly, the polypropylene matrix (M) contains (fine) dispersed inclusions that are not part of the matrix, and said inclusions contain an amorphous copolymer (A).

[0386] The term "heterophase polypropylene copolymer" as used herein is a copolymer composed of a matrix resin (which is a polypropylene homopolymer or a propylene copolymer) defined more specifically below and a copolymer (A) that is mostly amorphous and dispersed in said matrix resin.

[0387] In the present invention, the term "matrix" is understood in its commonly recognized sense, namely, to refer to a continuous phase (the continuous polymer phase of the present invention) in which isolated or individual particles, such as rubber particles, can be dispersed. The propylene polymer is present in an amount that forms a continuous phase capable of acting as a matrix.

[0388] Also, the terms "amorphous copolymer," "dispersed phase," "copolymer that is mostly amorphous," and "rubber phase" refer to the same thing, that is, they are interchangeable in the present invention. Amorphous means that the copolymer has a heat of fusion of less than 20 J / g when analyzed by DSC as a pure component (after extraction from the matrix by xylene extraction).

[0389] Matrix (M):

[0390] The matrix (M) of a particular heterophase polypropylene copolymer is a propylene homopolymer, or a semicrystalline propylene-ethylene or propylene-butene copolymer, or a combination of the two. The term “semicrystalline” indicates that the copolymer has a well-limited melting point and a heat of fusion greater than 50 J / g.

[0391] The expression "copolymer" as used in the present invention relates to polypropylene composed substantially, i.e., 97.0 wt% or more, preferably 98.0 wt% or more, more preferably 99.0 wt% or more, and even more preferably 99.8 wt% or more of propylene units. In a preferred embodiment, only propylene units are detectable in the propylene homopolymer.

[0392] In one embodiment, the matrix (M) comprises a homopolymer of propylene defined above or below, and preferably consists of a homopolymer of propylene defined above or below.

[0393] The polypropylene homopolymer may comprise or consist of a single polypropylene homopolymer fraction (= unipolar), but may also comprise different polypropylene homopolymer fractions.

[0394] When a polypropylene homopolymer contains different fractions, the polypropylene homopolymer is understood to be bipolar or polypolar.

[0395] The above fractions may have different average molecular weights or different molecular weight distributions.

[0396] In terms of molecular weight or molecular weight distribution, it is preferable that the polypropylene homopolymer be bipolar or polypolar.

[0397] It is also desirable that the polypropylene homopolymer be monocrystalline in terms of average molecular weight and / or molecular weight distribution.

[0398] Accordingly, in one embodiment of the present invention, the matrix (M) is monopolar, and in another embodiment, the matrix (M) is monopolar and consists of two propylene homopolymer fractions hPP-1 and hPP-2.

[0399] In an additional embodiment, the matrix (M) is bipolar and consists of one homopolymer fraction and one semicrystalline copolymer fraction.

[0400] Amorphous propylene copolymer (A):

[0401] The second component of a specific heterophase polypropylene copolymer is a propylene copolymer (A), which is an amorphous copolymer of propylene and ethylene.

[0402] Therefore, the second component is an elastomeric copolymer dispersed (i.e., dispersed phase) in the matrix (M).

[0403] The aforementioned terms "amorphous (propylene-ethylene) copolymer," "dispersed phase," and "rubber phase" refer to the same thing, that is, they are interchangeable in the present invention. The amorphous propylene-ethylene copolymer (A) is completely soluble in xylene at room temperature.

[0404] As with a propylene polymer matrix, the dispersed phase may be monopolar or polypolar, e.g., bipolar.

[0405] In one embodiment, the dispersed phase may be monostatic. More particularly, the dispersed phase is preferably monostatic with respect to intrinsic viscosity and / or comonomer distribution.

[0406] Regarding the definitions of 1-verticeness and multiverticeness, e.g. 2-verticeness, refer to the above definitions.

[0407] Preferably, a unidirectional dispersed phase is prepared in one reaction step, and more preferably, the gas phase reactor comprises or consists of a propylene-ethylene copolymer fraction.

[0408] Final heterophase propylene copolymer

[0409] The heterophase propylene copolymer according to the present invention described above is prepared by sequential polymerization, wherein, in one or more steps, a propylene homopolymer matrix is ​​produced, and in a subsequent step, an amorphous propylene-ethylene copolymer (A) is produced in the presence of the propylene homopolymer.

[0410] Several methods are known for characterizing the matrix phase and amorphous phase of heterophase propylene copolymers.

[0411] One method is to extract the xylene cold-soluble (XCS) fraction, thereby separating the xylene cold-soluble (XCS) fraction from the xylene cold-insoluble (XCI) fraction. It is known that the xylene cold-soluble (XCS) fraction of a heterophase propylene copolymer largely corresponds to an amorphous phase. However, it may contain a small amount of matrix phase, for example, about 1.0 weight%. Xylene extraction is particularly suitable for heterophase polypropylene compositions having a highly crystalline matrix phase, for example, a propylene homopolymer matrix phase.

[0412] The heterophase propylene copolymer has a total xylene-soluble (XCS) fraction of 15.0 to 70.0 weight%, preferably 20.0 to 60.0 weight% (measured at 25°C according to ISO 16152).

[0413] Another method is the separation of the crystalline fraction and the soluble fraction by the CRYSTEX QC method using 1,2,4-trichlorobenzene (TCB) as the solvent. This method is described later in the measurement method section. In this method, the crystalline fraction (CF) and the soluble fraction (SF) are separated from each other. The crystalline fraction (CF) largely corresponds to the matrix phase and contains only a small portion of the elastomeric phase, and the soluble fraction (SF) largely corresponds to the elastomeric phase and contains only a small portion of the matrix phase.

[0414] Due to differences in separation methods using extraction with xylene and 1,2,4-trichlorobenzene, the characteristics of the XCS / XCI fraction on one hand and the soluble / crystalline (SF / CF) fraction on the other are not exactly the same but similar.

[0415] As indicated above, the heterophase propylene copolymer according to the present invention is characterized by a soluble fraction (SF) of 15.0 to 70.0 weight% based on the total weight of the heterophase propylene copolymer measured at 40°C in 1,2,4-trichlorobenzene, and the soluble fraction (SF) has an ethylene content C2 (SF) of 15.0 to 80.0 weight% and an intrinsic viscosity of 2.0 to 5.0 dl / g.

[0416] Preferably, the amount of the soluble fraction (SF) of the heterophase propylene copolymer is 20.0 weight% to 50.0 weight%.

[0417] Preferably, the soluble fraction (SF) has an ethylene content C2 (SF) of 18.0 to 60 weight%, more preferably 20.0 to 50 weight%.

[0418] Preferably, the soluble fraction (SF) has an intrinsic viscosity of 2.0 to 4.0 dl / g.

[0419] The heterophase polypropylene composition preferably has a melt flow rate MFR2 of 0.2 to 100 g / 10 min, more preferably 1 to 40 g / 10 min.

[0420] The propylene propylene homopolymer, propylene propylene random copolymer, or heterophase propylene copolymer according to the present invention may include conventional additives, which are selected based on the requirements of the final application and are well known in the art.

[0421] Propylenepropylene homopolymers, propylenepropylene random copolymers, or heteropropylene copolymers produced by the catalyst of the present invention are useful for all kinds of end articles, such as pipes, films (cast, blown, or BOPP films), fibers, molded articles (e.g., injection-molded, blown, or rotationally molded articles), and extrusion coatings, etc.

[0422] Hereinafter, the present invention will be described with reference to the following non-limiting embodiments and drawings. Brief explanation of the drawing

[0423] FIG. 1A shows a schematic diagram of a CRISTIX QC instrument. FIG. 1B shows an elution diagram of an exemplary ethylene-propylene copolymer sample and the obtained soluble and crystalline fractions in a TREF column (a column packed with an inert material, e.g., glass beads). Figure 2 illustrates, for example, the productivity of the IV fraction in the XCS versus gas phase in the present invention. Figure 3 illustrates the ethylene content of the XCS fraction versus the IV of the XCS fraction for, for example, an embodiment of the present invention. Figure 4 illustrates the ethylene content of the XCS fraction versus the IV of the XCS fraction for, for example, an embodiment of the present invention. Figure 5 illustrates the ethylene content versus productivity of a polymer for, for example, an embodiment of the present invention. Figure 6 illustrates the ethylene content versus Δproductivity of a polymer for, for example, an embodiment of the present invention. Figure 7 illustrates the ethylene content versus MFR of a polymer for, for example, an embodiment of the present invention. Specific details for implementing the invention

[0424] measurement method

[0425] (a) Melting flow rate ( MFR )

[0426] The melt flow rate for polypropylene is measured as MFR2 according to ISO 1133 15 (at 230°C, with a 2.16 kg load). MFR is an indicator of the polymer's fluidity and, consequently, its processability, and the polymer M w It is also a measure of. The higher the melt flow rate, the lower the viscosity of the polymer and its consequent molecular weight.

[0427] (b) Number average molecular weight (M n ), weight-average molecular weight (M w ) and polyvariance (M w / M n )

[0428] Average molecular weight (M z , M w and M n ), molecular weight distribution (MWD) and its width (polydispersity index, PDI = M w / M n Explained by)(here M n is the number average molecular weight, and M w (where is the weight-average molecular weight) is measured by gel permeation chromatography (GPC) according to ISO 16014-1:2003, ISO 16014-2:2003, ISO 16014-4:2003 and ASTM D 6474-12 using the following mathematical formulas (1), (2), and (3):

[0429]

[0430] Constant elution volume interval ΔV i In the case of, A i is the chromatographic peak slice area, and M i is the molecular weight of the polyolefin (M w ) and, respectively, the elution volume V i It is associated with, and N is the number of data points obtained from the chromatogram between the integration limits.

[0431] Equipped with an infrared (IR) detector (IR4 or IR5 from PolymerChar (Valencia, Spain)), and 3 x Agilent-PLgel Olexis )A high-temperature GPC instrument equipped with a 1 x Agilent-PL gel Olexis Guard column was used. 250 mg / L of 2,6-ditert-butyl-4-methylphenol-stabilized 1,2,4-trichlorobenzene (TCB) was used as the solvent and mobile phase. The chromatography system was operated at 160°C at a constant flow rate of 1 mL / min. 200 μL of sample solution was injected for each analysis. Data acquisition was performed using Agilent Cirrus software version 3.3 or polymerase chain GP control software.

[0432] The column set was calibrated (according to ISO 16014-2:2003) using a common correction based on 19 narrow MWD polystyrene (PS) standards ranging from 0.5 kg / mol to 11,500 kg / mol. The PS standards were dissolved at room temperature over several hours. The conversion of polystyrene peak molecular weights to polyolefin molecular weights was achieved using the Mark Houwink equation and the following Mark Houwink constants:

[0433] K PS = 19 x 10 -3 mL / g, α PS = 0.655

[0434] K PE = 39 x 10 -3 mL / g, α PE = 0.725

[0435] K PP = 19 x 10 -3 mL / g, α PP = 0.725

[0436] The correction data was fitted using a third-order polynomial fit.

[0437] All samples were prepared at a concentration of 0.5 to 1 mg / mL and dissolved in PP for 2.5 hours and in PE for 3 hours at 160°C under continuous mild shaking.

[0438] (c) DSC Analysis, peak melting temperature ( T m ), fusion heat ( H m ), and peak crystallization temperature ( T c )

[0439] DSC analysis was performed on 5 to 7 mg samples using a Mettler TA Q2000 differential scanning calorimeter (DSC). DSC was performed according to ISO 11357 / part 3 / method C2 in a heating / cooling / heating cycle at a scan rate of 10°C / min from -30 to +225°C. Crystallization temperature (T c ) is measured from the cooling stage, and the peak melting temperature (T m ) and heat of fusion (H m ) was measured from the second heating step.

[0440] (d) intrinsic viscosity

[0441] Intrinsic viscosity (IV) was measured (at 135°C in decalin) according to DIN ISO 1628 / 1 of October 1999.

[0442] (e) Xylene cold Available fraction

[0443] Xylene cold solubles (XCS, wt%) were measured at 25°C according to ISO 16152; 2005.

[0444] (f) Al and Zr Measurement (ICP-method)

[0445] Elemental analysis of the catalyst was performed by taking a solid sample of mass (M) cooled with dry ice. The sample was diluted by dissolving it in nitric acid (HNO3, 65%, 5% V) and fresh deionized water (deionized water, DI) (5% V) to a known volume (V). Subsequently, the solution was added to hydrofluoric acid (HF, 40%, 3% V), diluted with deionized water to a final volume V, and stabilized by leaving it for 2 hours.

[0446] Analysis was performed at room temperature using a Thermo Elemental iCAP 6300 Inductively Coupled Plasma - Optical Emission Spectrometer (ICP-OES) (blank (5% HNO3, 3% HF solution in deionized water), and corrected using six standards of Al at 0.5 ppm, 1 ppm, 10 ppm, 50 ppm, 100 ppm, and 300 ppm, and Hf and Zr at 0.5 ppm, 1 ppm, 5 ppm, 20 ppm, 50 ppm, and 100 ppm in 5% HNO3, 3% HF solution in deionized water).

[0447] Immediately before analysis, the correction was re-grafted using untreated samples and 100 ppm Al, 50 ppm Hf, and Zr standards, and the re-grafting was verified by performing the test on quality control samples (20 ppm Al, 5 ppm Hf, and Zr in 5% HNO3 and 3% HF solutions in deionized water). QC samples were also tested after every 5th sample and at the end of the planned analysis set.

[0448] Hafnium content was monitored using the 282.022 nm and 339.980 nm lines, and zirconium content was monitored using the 339.198 nm line. Aluminum content was monitored through the 167.079 nm line, at which time the Al concentration in the ICP samples was 0 to 10 ppm (corrected only to 100 ppm), and the Al concentration through the 396.152 nm line was greater than 10 ppm.

[0449] The reported value is the average of three consecutive fractions taken from the same sample and is inversely related to the original catalyst by inputting the original mass and dilution volume of the sample into the software.

[0450] (g) Critex analyze

[0451] Crystalline and soluble fractionation method

[0452] The crystalline fraction (CF) and soluble fraction (SF) of the polypropylene (PP) composition, as well as the comonomer content and intrinsic viscosity of each fraction, were analyzed by Critex QC (Polymercha (Valencia, Spain)).

[0453] A schematic diagram of the Critex QC instrument is shown in Fig. 1A. The crystalline fraction and the amorphous fraction were separated through a temperature cycle of dissolution at 160°C, crystallization at 40°C, and redissolution in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160°C (shown in Fig. 1B). Quantitative analysis of SF and CF of the ethylene content (C2) was achieved by an infrared detector (IR4) and an online 2-capillary viscometer used for measuring intrinsic viscosity (IV).

[0454] The IR4 detector is a detector that detects IR absorption in two different bands (CH3 and CH2) for measuring the ethylene concentration and content in ethylene-propylene copolymers. To use the IR4 detector for each EP copolymer used for calibration, calibration was performed on a series of eight EP copolymers having known ethylene content of 2 wt% to 69 wt% (measured by 13C-NMR) and various concentrations of 2 to 13 mg / mL.

[0455] The amounts of the soluble fraction (SF) and the crystalline fraction (CF) were correlated with the amount of "xylene cold soluble" (XCS) measured according to the standard gravimetric method according to ISO 16152 and the XCS correction for each xylene cold insoluble (XCI) fraction. XCS correction was achieved by testing various EP copolymers having an XCS content of 2 to 31 wt%.

[0456] The intrinsic viscosity (IV) of the mother EP copolymer and its soluble and crystalline fractions was measured using an online 2-capillary viscometer and correlated with the corresponding IV measured by the standard method in decalin according to ISO 1628. Correction was achieved with various EP and PP polymers having an IV of 2 to 4 dL / g.

[0457] Samples of the PP composition to be analyzed were weighed at a concentration of 10 to 20 mg / mL. After automatically filling the vial with 1,2,4-TCB containing 250 mg / L of 2,6-tert-butyl-4-methyl-phenol (BHT) as an antioxidant, the samples were dissolved for typically 60 minutes at 160°C with constant stirring at 800 rpm until complete dissolution was achieved.

[0458] As illustrated in FIGS. 1A and 1B, a limited volume of the sample solution was injected into a column filled with an inert support, where crystallization of the sample and separation of the soluble fraction from the crystalline portion occurred. This process was repeated twice. During the first injection, the entire sample was measured at high temperature to determine the IV [dL / g] of the PP composition and the C2 [weight%] of the PP composition. During the second injection, the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) resulting from the crystallization cycle were measured (weight% SF, weight% C2, IV).

[0459] EP stands for ethylene propylene copolymer.

[0460] PP stands for polypropylene.

[0461] Figure 1A illustrates a schematic diagram of the Critex QC instrument.

[0462] FIG. 1B illustrates the elution diagram of an exemplary ethylene-propylene copolymer sample and the obtained soluble and crystalline fractions in a TREF column (a column packed with inert material, e.g., glass beads) (see reference [Del Hierro, P.; Ortin, A.; Monrabal, B.; 'Soluble Fraction Analysis in Polypropylene, The Column Advanstar Publications, February 2014. Pages 18-23]).

[0463] (h) NMR spectroscopy to Quantitative analysis of microstructure by

[0464] The comonomer content and comonomer sequence distribution of the polymer were quantitatively analyzed using additional quantitative nuclear magnetic resonance (NMR) spectroscopy. 13 C{ 1 H} NMR spectrum 1 H and 13For C, respectively, the solution state was recorded using a Bruker Advance III 400 NMR spectrometer running at 400.15 and 100.62 MHz. All spectra were recorded at 125°C using nitrogen gas for all aerodynamics. 13 C was recorded using an optimized 10 mm extended temperature probehead. Approximately 200 mg of substance was in 3 mL of 1 ,2 -Tetrachloroethane- d 2(TCE- d 2 A 65 mM solution of the relaxation agent in the solvent was prepared by dissolving it in chromium(III)-acetylacetonate (Cr(acac)3) (reference [Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475]). To obtain a homogeneous solution, after preparing the initial sample in a heating block, the NMR tube was further heated in a rotary oven for more than 1 hour. After inserting it into a magnet, the tube was rotated at 10 Hz. The above setup was essentially selected for high resolution and was quantitatively necessary for accurate quantitative analysis of ethylene content. Standard single-pulse excitation without NOE was used with an optimized tip angle, a 1-second recycle delay, and a 2-level WALTZ16 decoupling method (references [Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225]; and [Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128]). A total of 6144 (6k) transitions per spectrum were obtained.

[0465] Quantitative 13 C{ 1 The H} NMR spectra were processed and integrated, and the associated quantitative characteristics were determined from the integrated values ​​using our proprietary computer program. All chemical shifts indirectly referenced the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed for a comparable reference even in the absence of the structural unit. Characteristic signals corresponding to the incorporation of ethylene were observed (reference [Cheng, HN, Macromolecules 17 (1984), 1950]).

[0466] A characteristic signal corresponding to a 2,1-erythro region defect was observed (as described in [L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253], [Cheng, HN, Macromolecules 1984, 17, 1950], and [WJ. Wang and S. Zhu, Macromolecules 2000, 33 1157]), so it was necessary to correct for the effect of the region defect on the determined characteristics. No characteristic signals corresponding to other types of region defects were observed.

[0467] The comonomer fraction was prepared using the method of the literature [Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157], 13 C{ 1 Quantitative analysis was performed through the integration of multiple signals across the entire spectral region of the H} spectrum. This method was selected due to its strong properties and ability to explain the presence of region defects when necessary. The integration region was slightly adjusted to increase applicability across the entire range of the target comonomer content.

[0468] For systems in which only ethylene isolated from the PPPEP sequence is observed, the method of the aforementioned literature [Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157] was modified to reduce the influence of non-zero integral values ​​at positions known not to exist. This approach reduced the overestimation of ethylene content for the system and was achieved by reducing the number of positions used to measure absolute ethylene content as follows:

[0469] E = 0.5(Sββ + Sβγ + Sβδ + 0.5(Sαβ + Sαγ)).

[0470] By using the above set of positions, the corresponding integral formula is derived as follows using the same notation as used in the literature by Wang et al. (Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157):

[0471] E = 0.5(I H +I G + 0.5( I C + I D )).

[0472] The formula used for the absolute propylene content was not modified.

[0473] mol% comonomer incorporation was calculated from the molar fraction as follows:

[0474] E [mol%] = 100 * fE.

[0475] The weight % comonomer incorporation was calculated from the molar fraction as follows:

[0476] E [weight%] = 100 * (fE * 28.06) / ((fE * 28.06) + ((1-fE) * 42.08)).

[0477] Comonomer content by IR spectroscopy

[0478] The ethylene content of the copolymer was quantitatively analyzed using quantitative infrared (IR) spectroscopy with corrections to the original method.

[0479] Quantitative 13 Calibration was facilitated by using a set of in-house, non-commercial calibration standards for known ethylene content measured by C solution-state NMR spectroscopy. The calibration procedure was performed in a conventional manner well-documented in the literature. The calibration set consisted of 38 calibration standards with ethylene content ranging from 0.2 to 75.0 wt%, prepared on a small scale (pilot) or full scale under various conditions. The calibration set was selected to reflect various typical copolymers targeted by the final quantitative IR spectroscopy method.

[0480] Quantitative IR spectra were recorded in the solid-state using a Bruker Vertex 70 FTIR spectrometer. Spectra were recorded on 300 μm thick 25 x 25 mm square films prepared by compression molding at 180 to 210°C and 4 to 6 mPa. For samples with very high ethylene content (greater than 50 mol%), 100 μm thick films were used. 500 to 5000 cm⁻¹ -1 Spectral range of, 6 mm gap, 2 cm -1 Standard transmission FTIR spectroscopy was used with spectral resolution, 16 background scans, 16 spectral scans, an interferogram zero filling factor of 64, and Blackmann-Harris 3-term apodization.

[0481] Quantitative analysis is (CH2) >2 Structural units (integration method G, limit values ​​762 and 694 cm⁻¹) - 1 730 and 720 cm corresponding to ) -1 (A QIt was performed using the total area of ​​CH2 rocking deformation in ). The quantitative band was defined in CH structural units (integration method G, limit values ​​4650 and 4007 cm). - 1 4323 cm corresponding to ) -1 (A R It was normalized with respect to the area of ​​the CH band at ). Subsequently, the normalized absorption (A) was calculated using a quadratic calibration curve. Q / A R The ethylene content was predicted in weight% from ). The correction curve previously constructed by ordinary least squares (OLS) regression of the normalized absorption and original comonomer content was measured in the correction set.

[0482] The present invention will be explained by examples thereafter.

[0483] The complex C1 presented below was used to prepare catalysts for comparative examples (CE1 to CE4) and examples of the present invention (IE1 to IE4).

[0484]

[0485] C1(rac-anti-dimethylsilandyl(2-methyl-4-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl)(2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl) zirconium dichloride) was synthesized according to the procedure described in WO 2019 / 007655 (pp 49ff).

[0486] Preparation of MAO-silica support

[0487] A glass reactor equipped with a mechanical stirrer was filled with AGC Sea-Tech Company's silica grade DM-L-303, pre-calcined at 600°C (10.0 g). Then, dry toluene (50 mL) was added. Subsequently, the mixture was heated to 35°C and stirred at 35°C (40 rpm) for 15 minutes. Next, a 30 wt% solution of MAO in toluene (25 mL) from Lanxess was added through a cannula over 25 minutes, followed by stirring at 35°C for 2 more hours. The solid was allowed to settle, and the mother liquor was removed by siphon and discarded. Toluene (50 mL) was added, and the mixture was heated to 80°C and stirred at this temperature for 1 hour. The solid was allowed to settle, and the liquid was removed by siphon and discarded. After repeating the toluene wash two more times, a heptane (50 mL) wash was performed at 60°C. Next, the cake was dried under vacuum at 60°C for several hours to obtain 13.7 g of support as a white powder.

[0488] ICS 1 (Catalytic System 1 of the present invention): Catalyst preparation

[0489] ​In a nitrogen-filled glove box, a solution of 0.5 mL of MAO (30 wt% in toluene, AXION 1330 CA Langes) in 2 mL of dry toluene was added to an aliquot of metallocene C1 (63.0 mg, 78 μmol). After stirring at room temperature for 60 minutes, 72.0 mg of trityltetrakis(pentafluorophenyl) borate was added. The mixture was stirred at room temperature for 60 minutes. Next, 2.0 g of the MAO-treated silica prepared as above was placed in a glass vial. The solution of metallocene, MAO, and borate in toluene was slowly added to the support over 10 minutes while gently mixing. The resulting mixture was shaken well and left overnight. Subsequently, 10 mL of dry toluene was added, and the slurry was thoroughly mixed at 60°C for 30 minutes. The solid was precipitated, and the liquid was removed by siphon and discarded. Washing was repeated twice with 10 mL of toluene and once with 10 mL of heptane at room temperature. The resulting cake was dried in an Ar flow at 60°C for 3 hours to produce 2.3 g of pink free-flowing catalyst powder.

[0490] ICS 2 (Catalytic System 2 of the present invention): Catalyst preparation

[0491] ​In a nitrogen-filled glove box, a solution of 0.5 mL of MAO (30 wt% in toluene, Axion 1330 CA Langes) in 2 mL of dry toluene was added to an aliquot of metallocene C1 (63.0 mg, 78 μmol). After stirring at room temperature for 60 minutes, 36.0 mg of trityltetrakis(pentafluorophenyl) borate was added. The mixture was stirred at room temperature for 60 minutes. Next, 2.0 g of the MAO-treated silica (support B) prepared as above was placed in a glass vial. The solution of metallocene, MAO, and borate in toluene was slowly added to the support over 10 minutes while gently mixing. The resulting mixture was shaken well and left overnight. Subsequently, 10 mL of dry toluene was added, and the slurry was thoroughly mixed at 60°C for 30 minutes. The solid was precipitated, and the liquid was removed by siphon and discarded. Washing was repeated twice with 10 mL of toluene and once with 10 mL of heptane at room temperature. The resulting cake was dried in an Ar flow at 60°C for 3 hours to produce 2.2 g of pink free-flowing catalyst powder.

[0492] CCS 1 (Comparative Catalytic System 1): Catalytic Preparation

[0493] In a nitrogen-filled glove box, a solution of 0.25 mL of MAO (30 wt% in toluene, Axion 1330 CA Langes) in dry toluene (1 mL) was added to an aliquot of metallocene C1 (31.5 mg, 38 μmol). The mixture was stirred at room temperature for 60 minutes. Next, 1.0 g of the MAO-treated silica (support B) prepared as above was placed in a glass vial. Subsequently, the solution of metallocene and MAO in toluene was slowly added to the support over 5 minutes while gently mixing. The resulting mixture was shaken well and left overnight. Then, dry toluene (5 mL) was added, and the slurry was thoroughly mixed at 60°C for 30 minutes. The solid was precipitated, and the liquid was removed by siphon and discarded. Washing was repeated twice with 5 mL of toluene and once with 5 mL of heptane at room temperature. The generated cake was dried in an Ar flow at 60°C for 3 hours to obtain 1.0 g of catalyst as a pink free-flowing powder.

[0494] CCS 2 (Comparative Catalytic System 2): Catalyst Preparation

[0495] 86.8 mg of dried and degassed surfactant S2 was mixed with 2 mL of MAO in a diaphragm bottle inside a glove box and left to react overnight. The next day, 41.1 mg of C1 (0.051 mmol, 1 equivalent) was dissolved in 4 mL of MAO solution in another diaphragm bottle and left to be stirred inside a glove box.

[0496] After 60 minutes, 1 mL of surfactant solution and 4 mL of MAO-metallocene solution were sequentially added to a 50 mL glass emulsion reactor equipped with an overhead stirrer (stirring speed = 600 rpm) containing 40 mL of PFC (perfluoro-1,3-dimethylcyclohexane) at -10°C. A red emulsion was immediately formed and stirred for 15 minutes at -10°C / 600 rpm. Subsequently, the emulsion was transferred through a 2 / 4 Teflon tube to 100 mL of PFC hot at 90°C, stirred at 600 rpm until the transfer was complete, and 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 allowed to settle at the top of the PFC, and after 35 minutes, the solvent was removed by a siphon. The remaining red catalyst was dried under an argon flow at 50°C for 2 hours. 0.54 g of red free-flowing powder was obtained (Al 36.9 wt%, Zr 0.26 wt% Al / Zr (mol) 480).

[0497] S2: 1H,1H-perfluoro(2-methyl-3-oxahexane-1-ol) (CAS 26537-88-2) was purchased from Unimatec, dried on an activated molecular sieve (twice), and degassed by argon foaming before use.

[0498] The catalyst prepolymerization step (offline prepolymerization) was carried out in a 125 mL pressure reactor equipped with a gas supply line and an overhead stirrer. Dryed and degassed perfluoro-1,3-dimethylcyclohexane (15 cm 3The desired amount of the catalyst to be prepolymerized and the propylene were loaded into the reactor inside the glove box, and the reactor was sealed. Subsequently, the reactor was removed from the glove box and placed in a water-cooled bath maintained at 25°C. An overhead stirrer and feed line were connected, and the stirring speed was set to 450 rpm. The experiment began by opening the propylene feed to the reactor. The total pressure in the reactor was raised to approximately 5 barg and maintained constant by the propylene feed through a mass flow controller until the target degree of polymerization was reached. The reaction was stopped by flashing the volatile components. The reactor was opened inside the glove box, and the contents were poured into a glass container. Perfluoro-1,3-dimethylcyclohexane was evaporated until a constant weight was obtained to acquire the prepolymerized catalyst.

[0499] CC3 (Comparative Catalytic System 3): Catalytic Preparation

[0500] The same catalyst complex as CC2 was used, but a borate co-catalyst was added in addition to MAO.

[0501] 234.3 mg of dried and degassed surfactant S2 (in 0.2 mL of toluene) was added dropwise to 5 mL of MAO inside a glove box. The solution was stirred for 30 minutes. Then, 95.6 mg of C1 was added to the MAO / surfactant solution. After stirring for 60 minutes, 104.9 mg of trityltetrakis(pentafluorophenyl)borate was added.

[0502] After stirring for 60 minutes, 5 mL of a surfactant-MAO-metallocene-borate solution was sequentially added to a 50 mL glass emulsion reactor containing 40 mL of PFC at -10°C and equipped with an overhead stirrer (stirring speed = 600 rpm). A red emulsion was immediately formed and stirred for 15 minutes at -10°C / 600 rpm. Subsequently, the emulsion was transferred through a 2 / 4 Teflon tube to 100 mL of PFC hot at 90°C, stirred at 600 rpm until the transfer was complete, and 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 allowed to settle on top of the PFC, and after 35 minutes, the solvent was removed by a siphon. The remaining catalyst was dried at 50°C for 2 hours under argon flow. 0.70 g of red free-flowing powder was obtained (Al 31.9 wt%, Zr 0.56 wt%, Al / Zr (mol) 193, B / Zr (mol) 0.98).

[0503] The catalyst was prepolymerized with respect to CC2 as described above.

[0504] [Table 1]

[0505] catalyst (*)

[0506]

[0507] polymerization:

[0508] 2-step bulk (C3 homo) + gas phase (C2 / C3) polymerization

[0509] Step 1: Pre-polymerization and bulk homopolymerization

[0510] An autoclave containing 0.4 bar g of propylene was filled with approximately 4400 g of propylene. Triethylaluminum (0.80 mL of a 0.62 mol / L solution in heptane) was injected into the reactor with an additional x g of propylene. The solution was stirred at 20°C and 250 rpm for at least 20 minutes. The prepared catalyst system was injected as described below. After placing the desired amount of solid catalyst into a 5 mL stainless steel vial inside a glove box, a second 5 mL vial containing 4 mL of n-heptane and pressurized with 7 bar nitrogen was added on top of it. The dual feeder system was mounted on a port on the autoclave lid. The desired amount of H2 was injected directly via a mass flow controller. Subsequently, the valve between the two vials was opened, and the solid catalyst was brought into contact with heptane under nitrogen pressure for 2 seconds, followed by flushing into the reactor with x g of propylene. Prepolymerization was carried out for 10 minutes. After the prepolymerization step was completed, the temperature was raised to 75°C and maintained constant throughout the polymerization. The polymerization time was measured starting when the internal reactor temperature reached a temperature 2°C lower than the set polymerization temperature.

[0511] Step 2: Gaseous phase C3C2 copolymerization

[0512] After the bulk phase was completed, the stirrer speed was reduced to 50 rpm and the pressure was reduced to 0.3 barg by discharging the monomer. The stirrer speed was set to 180 rpm and the reactor temperature was set to 70°C. Subsequently, the reactor pressure was increased to the set value by supplying a defined C3 / C2 gas mixture (see table). The pressure and temperature were maintained constant by supplying a C3 / C2 gas mixture with a composition corresponding to the target polymer composition via a mass flow controller and a temperature controller, respectively, until the set time of this phase expired.

[0513] ​Next, the reactor was cooled (to about 30°C) and the volatile components were flashed out. After purging the reactor three times with N2 and one vacuum / N2 cycle, the product was removed and dried overnight in a fume hood. 0.5 wt% of Irganox B225 (solution in acetone) was added to 100 g of polymer and dried overnight in the hood, then dried in a vacuum drying oven at 60°C for 2 hours.

[0514] [Table 2]

[0515] Polymerization procedure

[0516]

[0517] Tables 3a and 3b below show the polymerization results.

[0518] [Table 3a]

[0519] Total polymer

[0520]

[0521] [Table 3b]

[0522] Available fraction

[0523]

[0524] From FIGS. 2 to 4, it is clear that by adding borate to a silica / MAO / metallocene catalyst, a catalyst system having higher gas phase activity is obtained (Fig. 2), and also a heterophase propylene copolymer having a higher molecular weight than a heterophase propylene copolymer produced with a self-supported catalyst (prepared according to the Borealis Sirius catalyst technology) is produced (Figs. 3 and 4).

[0525] To prepare the catalysts for comparative examples (CE5 to CE9) and examples of the present invention (IE5 to IE9), the following complex C2 as described below was used.

[0526]

[0527] 4,8- die (3,5- dimethylphenyl )-6- methyl -1,2,3,5- Tetrahydro -s- Indasen

[0528]

[0529] 2.0 g (2.56 mmol) of NiCl2 (PPh 3　To a mixture of 4,8-dibromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacen and 36.3 g (100.8 mmol) of 4,8-dibromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacen, 500 mL of 0.5 M 3,5-dimethylphenylmagnesium bromide (250 mmol, 2.5 equivalents) in THF was added at a rate maintaining gentle reflux (for about 15 minutes). After refluxing the resulting solution for an additional 1 hour, it was cooled to room temperature, and 1200 mL of 0.5 M HCl and 500 mL of dichloromethane were added. The organic layer was separated, dried with K2CO3, passed through a short pad of silica gel 60 (40 to 63 μm, approx. 30 mL), and then evaporated to obtain an unpurified mixture of the diastereomer of 4,8-di(3,5-dimethylphenyl)-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene as a brown oil. Subsequently, 315 mg of TsOH was added to a solution of the crude product in 420 mL of toluene, and the resulting mixture was refluxed for 10 minutes using a Dean-Stark head. Then, 220 mg of TsOH was added in one or more fractions, and the resulting mixture was refluxed for 10 minutes. Finally, the last operation was repeated with 50 mg of TsOH. After cooling to room temperature, the reaction mixture was washed with 200 mL of 10% K2CO3. The organic layer was separated, and the aqueous layer was further extracted with 200 mL of dichloromethane. The combined organic extract was dried with anhydrous K2CO3 (the organic layer turned crimson at this stage), passed through a short pad of silica gel 60 (40 to 63 μm, 30 mL), and the resulting pale yellow solution was evaporated to about 30 mL to obtain a solution containing a significant amount of white precipitate. 300 mL of n-hexane was added to the mixture. The precipitated solid was filtered (G3), washed with n-hexane, and dried under vacuum. By the above procedure, 29.33 g (77.48 mmol, 76.4,8-di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacen (9%) was obtained as a white microcrystalline solid. The mother liquor was evaporated to obtain a yellow solid mass. This mass was ground with 40 mL of warm n-hexane, cooled to room temperature, and filtered (G3). The obtained solid was washed with n-hexane and vacuum dried. Through this procedure, an additional 4.55 g (12.02 mmol, 11.9%) of 4,8-di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacen was obtained as a white powder. Thus, the total yield of the title product was 33.88 g (89.5 mmol, 88.8%).

[0530] 1 H NMR (CDCl3): δ 7.04 (s, 2H), 7.03 (s, 2H), 6.98 (s, 2H), 6.43 (m, 1H), 3.23 (s, 2H), 2.89 (t, J = 7.3 Hz, 2H), 2.83 (t, J = 7.3 Hz, 2H), 2.38 (s, 6H), 2.37 (s, 6H), 2.04 (s, 3H), 1.99 (quint, J = 7.3 Hz, 2H). 13 C{ 1 H} NMR (CDCl3): δ 145.38, 142.84, 140.85, 140.43, 140.21, 139.80, 138.37, 137.55, 137.39, 133.44, 129.64, 128.39, 128.19, 127.31, 126.61, 126.34, 42.49, 32.76, 32.51, 26.08, 21.43, 16.81

[0531] [4,8- Bis (3,5- dimethylphenyl )-2- methyl -1,5,6,7- Tetrahydro -s- Indasen -1-day]Chlorodimethylsilane

[0532]

[0533] To a suspension cooled to -30°C in 11.96 g (31.59 mmol) of 4,8-di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in a mixture of 250 mL of ether and 40 mL of THF, 13.0 mL (31.59 mmol) of 2.43 M hexane n BuLi was added all at once. The resulting mixture was stirred overnight at room temperature, and the resulting yellowish-orange solution containing a large amount of orange precipitate was cooled to -50°C, and 19.0 mL (20.33 g, 157.5 mmol, 4.99 equivalents) of dichlorodimethylsilane was added all at once. The mixture was stirred overnight at room temperature, filtered through a glass frit (G3), and the flask and filter cake were rinsed with 50 mL of toluene. The filtrate was evaporated to obtain 14.9 g (about 100%) of the title compound as a white solid mass, which was used further without further purification.

[0534] 1 H NMR (CDCl3): δ 7.09 (s, 2H), 7.02-6.94 (m, 4H), 6.51 (m, 1H), 4.07 (s, 1H), 3.26-3.14 (m, 1H), 2.95-2.79 (m, 2H), 2.60 (ddd, J = 12.4 Hz, J = 8.4 Hz, J = 4.1 Hz, 1H), 2.38 and 2.37 (2s, sum 12H), 2.24 (s, 3H), 2.12-1.99 (m, 1H), 1.95-1.80 (m, 1H), -0.16 (s, 3H), -0.20 (s, 3H). 13 C{ 1 H} NMR (CDCl3): δ146.19, 143.17, 140.68, 140.29, 139.94, 139.92, 138.37, 137.59, 137.42, 132.60, 129.86, 128.52, 128.24, 127.85, 127.28, 126.32, 49.67, 33.33, 32.73, 26.15, 21.45, 21.42, 18.10, 3.92, -1.45.

[0535] [4,8- Bis (3,5- dimethylphenyl )-2- methyl -1,5,6,7- Tetrahydro -s- Indasen -1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-1H-indene-1-yl]dimethylsilane

[0536]

[0537] In a -30°C cooled solution of 10.13 g (31.59 mmol) of 5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-2-methyl-1H-indene (prepared as previously described for MC-1) in 250 mL of ether, 13.0 mL (31.59 mmol) of 2.43 M in hexane nBuLi was added all at once. After stirring the mixture overnight at room temperature, the resulting yellowish-orange solution containing a small amount of precipitate was cooled to -45°C and 200 mg of CuCN was added. The obtained mixture was stirred at -25°C for 0.5 hours, after which a solution of 14.9 g (31.59 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane (prepared above) in 200 mL of THF was added all at once. After stirring the mixture overnight at room temperature, it was filtered through a silica gel 60 (40 to 63 μm) pad and further washed with 2 x 50 mL of dichloromethane. The combined organic eluent was evaporated and dried, and the residue was dried at high temperature under vacuum to obtain 24.0 g (about 100% of about 90% purity) of the title product (about 55:45 mixture of stereoisomers) as a slightly yellowish solid foam, which was used further without further purification.

[0538] 1 H NMR (CDCl3): δ 7.27 and 7.25 (2s, sum 2H), 7.04 (s, 4H), 6.98, 6.95 and 6.93 (3s, sum 3H), 6.90 and 6.85 (2s, sum 1H), 6.46 (s, 1H), 6.23 and 6.20 (2s, sum 1H), 4.41 and 4.16 (2s, sum 1H), 3.30-2.62 (m, 1H), 3.22 and 3.20 (2s, sum 3H), 3.04-2.79 (m, 2H), 2.68-2.56 (m, 1H), 2.39 (s, 6H), 2.35 (s, 9H), 2.32 (s, 3H), 2.18-1.80 (6s and 2m, sum 9H), 1.44 and 1.38 (2s, sum 9H), -0.52, -0.58, -0.62 and -0.73 (4s, sum 6H).

[0539] anti- Dimethylsilanediyl [2- methyl -4,8- die (3,5- dimethylphenyl )-1,5,6,7- Tetrahydro -s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride

[0540]

[0541] In a slightly cloudy yellowish solution of 23.06 g (30.54 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5-dimethyl-phenyl)-5-methoxy-2-methyl-1H-indene-1-yl]-dimethyl cooled to -30°C in 250 mL of ether, 25.1 mL (60.99 mmol) of 2.43 M in hexane nBuLi was added all at once. After stirring the mixture at room temperature for 5.5 hours, the resulting red solution was cooled to -50°C, and 7.12 g (30.55 mmol) of ZrCl4 was added. The reaction mixture was stirred at room temperature for 24 hours to obtain a dark red solution with precipitated LiCl. As confirmed by NMR spectroscopy, the solution contained a mixture of approximately 85 / 15 anti- and syn-zirconocene dichlorides contaminated with some other impurities. The mixture was evaporated dry (to a red foamed state), and the residue was treated with 100 mL of warm toluene. The obtained suspension was filtered through a glass frit (G4), and the filter cake was treated with 2 x 50 mL of warm toluene. The filtrate was evaporated dry, and the residue was dissolved in 70 mL of hot n-hexane. The yellowish-orange precipitate that settled from the solution overnight at room temperature was collected and dried under vacuum. By the above procedure, 7.8 g of anti-dimethylsilandiyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride containing about 1.0 mol of n-hexane per mol of complex was obtained, and the adjusted net weight of the isolated anti-complex was 7.13 g (26%). The mother liquor was evaporated to about 60 mL. A yellowish-orange powder precipitated overnight at -25°C was collected from the solution and dried under vacuum. By the above procedure, 8.6 g of anti-dimethylsilandiyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride was obtained containing about 0.75 mol of n-hexane per mole of complex (or 0.57 g of n-hexane in 8.6 g of product), and the adjusted net weight of the isolated anti-complex was 8.03 g (29%).

[0542] anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride x 1.0 n Hexane.

[0543] C 54 H 60 Cl2OSiZr x C6H 14 Calculated values ​​for: C, 71.96; H, 7.45. Measured values: C, 72.30; H, 7.69.

[0544] 1 H NMR (CDCl3): δ 7.55-6.90 (very br.s., 4H), 7.39 (s, 1H), 7.10 (s, 1H), 7.03 (s, 1H), 6.98 (s, 1H), 6.95 (s, 1H), 6.94 (s, 1H), 6.81 (s, 1H), 6.58 (s, 1H), 3.41 (s, 3H), 3.15-3.01 (m, 2H), 2.93 (ddd, J = 16.0 Hz, 8.1 Hz, 3.3 Hz, 1H), 2.51-2.41 (m, 1H), 2.39 (s, 3H), 2.36 (s, 3H), 2.34 (s, 12H), 2.30 (s, 3H), 2.04 (s, 3H), 2.07-1.95 (m, 1H), 1.85-1.68 (m, 1H), 1.35 (s, 9H), 1.14 (s, 3H), -0.13 (s, 3H). 13 C{ 1 H} NMR (CDCl3): δ159.87, 144.73, 144.10, 143.25, 141.39, 138.39, 138.08, 137.81, 137.47, 136.90, 134.61, 134.39, 134.26, 132.05, 131.96, 131.74, 131.11, 128.96, 128.91, 128.82, 128.74, 127.74, 127.44, 127.01 (br.s), 126.76, 123.42, 123.12, 121.60, 121.08, 82.55, 81.91, 62.67, 35.68, 33.87, 32.39, 30.39, 26.04, 21.53, 21.47, 21.41, 21.24, 19.78, 18.60, 3.62, 1.70.

[0545] Preparation of MAO-silica support

[0546] A steel reactor equipped with a mechanical stirrer and filter mesh was flushed with nitrogen, and the reactor temperature was set to 20°C. Subsequently, pre-calcined AGC Sea-Tech Company silica grade DM-L-303 at 600°C (5.0 kg) was added from the feed drum, and then the pressure was carefully increased and decreased with nitrogen using a manual valve. Then, toluene (22 kg) was added. The mixture was stirred for 15 minutes. Next, a 30 wt% solution of MAO in Langes toluene (9.0 kg) was added through the feed line at the top of the reactor within 70 minutes. Subsequently, the reaction mixture was heated to 90°C and stirred for an additional 2 hours at 90°C. The slurry was settled, and the mother liquor was filtered. The catalyst was washed twice with toluene (22 kg) at 90°C, then settled and filtered. The reactor was cooled to 60°C, and the solid was washed with heptane (22.2 kg). Finally, the MAO-treated SiO2 was dried at 60°C for 2 hours under nitrogen flow, and then dried under vacuum (-0.5 barg) for 5 hours while stirring. The MAO-treated support was collected as a free-flowing white powder found to contain 12.2 wt% Al.

[0547] Catalyst system 3 of the present invention ( ICS3 ) Catalyst manufacturing

[0548] 30 wt% MAO in 0.7 kg of toluene was added to a steel nitrogen-blanked reactor via a burette at 20°C. Subsequently, 5.4 kg of toluene was added under stirring. Metallocene C2 (93 g) was added from a metal cylinder and flushed with 1 kg of toluene. The mixture was stirred at 20°C for 60 minutes. Subsequently, trityl tetrakis(pentafluorophenyl) borate (91 g) was added from a metal cylinder and flushed with 1 kg of toluene. The mixture was stirred at room temperature for 1 hour. The resulting dilution was added to the stirred cake of the MAO-silica support prepared as described above over a period of 1 hour. After leaving the cake for 12 hours, it was dried under a vacuum (about 0.5 barg) under an N2 flow at 60°C for 2 hours under stirring and for an additional 5 hours.

[0549] The dried catalyst was sampled in the form of a pink free-flowing powder containing 13.9% Al and 0.11% Zr.

[0550] Comparative Catalytic System 4 ( CCS4 )

[0551] 30 wt% MAO in 0.7 kg of toluene was added to a steel nitrogen blanking reactor via a burette at 20°C. Subsequently, 6.4 kg of toluene was added under stirring. After adding 93 g of metallocene C2 from a metal cylinder, the mixture was flushed with 1 kg of toluene. The mixture was stirred at 20°C for 60 minutes. The resulting dilution was added to the stirred cake of the MAO-silica support prepared as described above over a period of 1 hour. After leaving the cake for 12 hours, it was dried under a vacuum (about 0.5 barg) under an N2 flow at 60°C for 2 hours under stirring and for an additional 5 hours.

[0552] The dried catalyst was sampled in the form of a pink free-flowing powder containing 12.8% Al and 0.084% Zr.

[0553] polymerization:

[0554] Pre-polymerization and bulk polymerization

[0555] A 21.2 L autoclave containing 0.4 bar g of propylene was filled with 3950 g of propylene. Triethylaluminum (0.80 mL of a 0.62 mol / L solution in heptane) was injected into the reactor along with an additional 240 g of propylene. The solution was stirred at 20°C and 250 rpm for at least 20 minutes. The desired amount of H2 was supplied to the reactor via a mass flow controller. The catalyst was injected as follows: The desired amount of solid catalyst was placed in a 5 mL stainless steel vial inside a glove box, and a second 5 mL vial containing 4 mL of n-heptane and pressurized with 7 bar nitrogen was added on top of it. The dual feeder system was mounted on a port on the autoclave lid. Subsequently, the valve between the two vials was opened, and the solid catalyst was brought into contact with heptane under nitrogen pressure for 2 seconds, after which it was flushed into the reactor with 240 g of propylene. Prepolymerization was carried out for 10 minutes. After the prepolymerization step was completed, the temperature was raised to 75°C and maintained constant throughout the polymerization. For the ethylene-propylene copolymerization experiment, ethylene was added starting at 55°C. The amounts and feed rates can be found in Table 4 below. The polymerization time was measured from the moment the internal reactor temperature reached a temperature 2°C lower than the set polymerization temperature. After the desired polymerization time had elapsed, 5 mL of ETOH was added to the reactor to stop the polymerization. Subsequently, the reactor was cooled to approximately 30°C to flush out volatile components. After purging the reactor three times with N2 and one vacuum / N2 cycle, the product was removed and dried overnight in a fume hood. 0.5 wt% of Irganox B225 (solution in acetone) was added to 100 g of polymer, dried overnight in the hood, and then dried in a vacuum drying oven at 60°C for 2 hours.

[0556] The exact amounts of catalyst H2 and C2 can be seen in Table 4 below.

[0557] [Table 4]

[0558]

[0559] Table 5 below shows the polymerization results.

[0560] [Table 5]

[0561]

[0562] From Figures 5 and 6, it can be easily seen that the more ethylene is added, the greater the difference in productivity using the catalyst system according to the present invention compared to a catalyst system without a boron-containing co-catalyst.

[0563] The silica-MAO catalyst containing a tritilborate co-activator also has slightly better MFR control (lower MFR at the same H2 concentration) at any given C2 content compared to the non-borate catalyst. This effect is illustrated in Fig. 7.

Claims

Claim 1 (i) a metallocene complex of the following chemical formula (III); (ii) a co-catalyst system comprising a boron-containing co-catalyst and a methylaluminoxane co-catalyst; and (ii) a supported catalyst system comprising an inorganic porous support: In the above formula, each X is independently a sigma-donor ligand; L is a carbon, silicon, or germanium-based divalent bridge connecting one or two skeletal atoms to the ligand; each Ar is an aryl or heteroaryl group having 3 to 20 carbon atoms; and each R1 may independently be the same or different, and may be hydrogen, a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl group, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or an OY group, where Y is C1-C 10 - It is a hydrocarbyl group, and optionally two adjacent R1 groups may be part of a ring containing a phenyl carbon to which they are bonded; and each R 2 may be independently identical or different, and CHR 8' -R 8 It is, and at this time R 8 H, or linear or branched C1-C6 alkyl groups, C3-C8 cycloalkyl groups, C6-C 10 -aryl group, or 1 to 3 R 11 It is a heteroaryl group having 3 to 20 carbon atoms that are optionally substituted with a group, wherein R 8' is an H or C1-C6-alkyl group; R 3 It is a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl group, C7-C 20 -alkylaryl group or C6-C 20 -Aril Giigo;R 4 is C(R 9 It is stage 3, and at this time R 9 is a linear or branched C1-C6-alkyl group; R 5 It is an aliphatic C1-C element optionally containing hydrogen or one or more heteroatoms from groups 14 to 16 of the periodic table. 20 - Hydrocarbyl group, R 6 Aliphatic C1-C elements optionally containing one or more heteroatoms from silver, hydrogen, or groups 14 to 16 of the periodic table. 20 - Hydrocarbyl group or, R 5 and R 6 together with n R 10 A five-membered saturated carbon ring can be formed arbitrarily substituted with a group, wherein n is 0 to 4; and each R 10 is identical or different, and C1-C 20 - A C1-C group optionally containing a hydrocarbyl group, or one or more heteroatoms belonging to groups 14 to 16 of the periodic table. 20 - It can be a hydrocarbyl radical; R 7 It is a linear or branched C1-C6-alkyl group, or 1 to 3 R groups. 11 An aryl or heteroaryl group having 3 to 20 carbon atoms that is optionally substituted with a group; and each R 11 may independently be the same or different, and hydrogen, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl group, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or an OY group, where Y is C1-C 10 - It is a hydrocarbyl group. Claim 2 (i) a metallocene complex of the following chemical formula (II); (ii) a co-catalyst system comprising a boron-containing co-catalyst and a methylaluminoxane co-catalyst; and (ii) a supported catalyst system comprising an inorganic porous support: In the above formula, each X is independently a sigma-donor ligand; L is -R'2Si-, ethylene, or methylene, where each R' is independently C1-C 20 - It is a hydrocarbyl group; each R1 may independently be the same or different, and may be hydrogen, a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl group, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or an OY group, where Y is C1-C 10 - It is a hydrocarbyl group, and optionally two adjacent R1 groups may be part of a ring containing a phenyl carbon to which they are bonded; and each R 2 It may be independently the same or different, and CH2-R 8 It is, and at this time R 8 It is hydrogen, or a linear or branched C1-C6 alkyl group, C3-C8 cycloalkyl group, or C6-C 10 -Aril Giigo;R 3 It is a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl group, C7-C 20 -alkylaryl group or C6-C 20 -Aril Giigo;R 4 is C(R 9 It is stage 3, and at this time R 9 is a linear or branched C1-C6-alkyl group; R 5 is hydrogen, or aliphatic C1-C 20 - Hydrocarbyl group, R 6 It is hydrogen, or aliphatic C1-C 20 - Hydrocarbyl group or, R 5 and R 6 ... can form a five-membered saturated carbon ring having two carbons of a phenyl ring together, wherein n R 10 It can be arbitrarily substituted with a gi, where n is 0 to 4; and each R 10 C1-C that are identical or different and optionally contain one or more heteroatoms belonging to groups 14 to 16 of the periodic table. 20 -Hydrocarbyl giigo;R 7 H, or a linear or branched C1-C6-alkyl group, or 1 to 3 R 11 An aryl or heteroaryl group having 6 to 20 carbon atoms that is optionally substituted with a group; and each R 11 may independently be the same or different, and hydrogen, linear or branched C1-C6-alkyl groups, C7-C 20 -arylalkyl group, C7-C 20 -alkylaryl group or C6-C 20 - It is an aryl group, or an OY group, where Y is C1-C 10 - It is a hydrocarbyl group. Claim 3 delete Claim 4 In paragraph 1, each Ar and / or R 7 A supported catalyst system that is a phenyl ring or a 5- or 6-membered heteroaryl ring. Claim 5 A supported catalyst system according to claim 1, wherein the metallocene complex is a metallocene complex of the following chemical formula (VI): In the above formula, each X is independently a sigma-donating ligand; L is a divalent crosslink selected from -R'2C- and -R'2Si-, where each R' is independently a C1-C6-alkyl group, a C5-C6-cycloalkyl group, a C1-C 10 -alkyl-O-C1-C 10 - is an alkyl group or a C6-aryl group; each Ar is a phenyl ring or a 5- or 6-membered heteroaryl ring; each R1 may independently be the same or different, hydrogen, or a linear or branched C1-C6-alkyl group; and each R 2 can be independently identical or different, and CHR 8' -R 8 It is, and at this time R 8 is H, or a linear or branched C1-C6-alkyl group, and R 8' is an H or C1-C6-alkyl group; R 3 It is a linear or branched C1-C6-alkyl group, C7-C 20 -arylalkyl group, C7-C 20 -alkylaryl group or C6-C 20 -Aril Giigo;R 4 is C(R 9 It is stage 3, and at this time R 9 is a linear or branched C1-C6-alkyl group; R 5 is hydrogen, and R 6 is hydrogen, or R 5 and R 6 It can form a five-membered saturated carbon ring together;R 7 It is a linear or branched C1-C6-alkyl group, or 1 to 3 R groups. 11 An aryl or heteroaryl group having 3 to 20 carbon atoms that is optionally substituted with a group; and each R 11 It can be independently the same or different and is hydrogen, or a linear or branched C1-C6-alkyl group. Claim 6 A supported catalyst system according to claim 1, wherein the metallocene complex is a metallocene complex of the following formula (VII): In the above formula, each X is independently a sigma-donating ligand; L is a divalent crosslink selected from -R'2C- and -R'2Si-, where each R' is independently a C1-C6-alkyl group, a C5-C6-cycloalkyl group, a C1-C 10 -alkyl-O-C1-C 10 - is an alkyl group or a C6-aryl group; each Ar is a phenyl ring or a 5- or 6-membered heteroaryl ring; each R1 may independently be the same or different, hydrogen, or a linear or branched C1-C6-alkyl group; and each R 2 can be independently identical or different, and CHR 8' -R 8 It is, and at this time R 8 is H, or a linear or branched C1-C6-alkyl group, and R 8' is an H or C1-C6-alkyl group; R 3 is a linear or branched C1-C6-alkyl group; R 4 is C(R 9 It is stage 3, and at this time R 9 is a linear or branched C1-C6-alkyl group; R 5 and R 6 It can form a five-membered saturated carbon ring together;R 7 1 to 3 R 11 A phenyl ring or a 5- or 6-membered heteroaryl ring optionally substituted with a group; and each R 11 It can be independently the same or different and is hydrogen, or a linear or branched C1-C6-alkyl group. Claim 7 A supported catalyst system according to claim 1, wherein the metallocene complex is a metallocene complex of the following formula (VIII): In the above formula, each X is independently a sigma-donating ligand; L is a divalent crosslink selected from -R'2C- and -R'2Si-, where each R' is independently a C1-C6-alkyl group, a C5-C6-cycloalkyl group, a C1-C 10 -alkyl-O-C1-C 10 - an alkyl group or a C6-aryl group; each R1 may independently be the same or different, hydrogen, or a linear or branched C1-C6-alkyl group; and each R 2 It may be independently the same or different, and CH2-R 8 It is, and at this time R 8 is H, or a linear or branched C1-C6-alkyl group; R 3 is a linear or branched C1-C6-alkyl group; R 4 is C(R 9 It is stage 3, and at this time R 9 is a linear or branched C1-C6-alkyl group; R 5 is H and R 6 is H or R 5 and R 6 It can form a five-membered saturated carbon ring together;R 7 1 to 3 R 11 A phenyl group arbitrarily substituted with a group; and each R 11 It can be independently the same or different and is hydrogen, or a linear or branched C1-C6-alkyl group. Claim 8 A supported catalyst system according to claim 1, wherein the metallocene complex is a metallocene complex of the following chemical formula (IX): In the above formula, each X is independently a sigma-donating ligand; L is -R'2Si-, where each R' is independently a C1-C6-alkyl group, a C5-C6-cycloalkyl group, a C1-C 10 -alkyl-O-C1-C 10 - an alkyl group or a C6-aryl group; each R1 may independently be the same or different, hydrogen, or a linear or branched C1-C6-alkyl group; and each R 2 is methyl and;R 3 is a linear or branched C1-C6-alkyl group; R 4 is C(R 9 It is stage 3, and at this time R 9 is a linear or branched C1-C6-alkyl group; R 5 is H and R 6 is H or R 5 and R 6 It can form a five-membered saturated carbon ring together;R 7 1 to 3 R 11 A phenyl group arbitrarily substituted with a group; and each R 11 It can be independently the same or different and is hydrogen, or a linear or branched C1-C6-alkyl group. Claim 9 A supported catalyst system according to claim 1, wherein the metallocene complex is a metallocene complex of the following chemical formula (X): In the above formula, each X is independently a sigma-donating ligand; L is -R'2Si-, where each R' is independently a C1-C6-alkyl group, a C5-C6-cycloalkyl group, a C1-C 10 -alkyl-O-C1-C 10 - an alkyl group or a C6-aryl group; each R1 may independently be the same or different, hydrogen, or a linear or branched C1-C6-alkyl group; and each R 2 It may be independently the same or different, and CH2-R 8 It is, and at this time R 8 is H, a linear or branched C1-C6-alkyl group; R 3 is a linear or branched C1-C6-alkyl group; R 4 is C(R 9 It is stage 3, and at this time R 9 is a linear or branched C1-C6-alkyl group; R 7 1 to 3 R 11 A phenyl group arbitrarily substituted with a group; and each R 11 It can be independently the same or different and is hydrogen, or a linear or branched C1-C6-alkyl group. Claim 10 A supported catalyst system according to claim 1, wherein the metallocene complex is a metallocene complex of the following chemical formula (XI): In the above formula, each X is independently a sigma-donating ligand; L is -R'2Si-, where each R' is independently a C1-C6-alkyl group, a C5-C6-cycloalkyl group, a C1-C 10 -alkyl-O-C1-C 10 - an alkyl group or a C6-aryl group; each R1 may independently be the same or different, hydrogen, or a linear or branched C1-C6-alkyl group; R 3 is a linear or branched C1-C6-alkyl group; R 4 is C(R 9 It is stage 3, and at this time R 9 is a linear or branched C1-C6-alkyl group; R 7 1 to 3 R 11 A phenyl group arbitrarily substituted with a group; and each R 11 It can be independently the same or different and is hydrogen, or a linear or branched C1-C6-alkyl group. Claim 11 A supported catalyst system according to claim 1, wherein the metallocene complex is a metallocene complex of the following chemical formula (XII): In the above formula, each X is independently a sigma-donor ligand; L is -Me2Si-; each R1 may independently be the same or different, hydrogen, or a linear or branched C1-C6-alkyl group; and R 3 is a linear or branched C1-C6-alkyl group; R 4 is C(R 9 It is stage 3, and at this time R 9 is a linear or branched C1-C6-alkyl group; R 7 1 to 3 R 11 A phenyl group arbitrarily substituted with a group; and each R 11 It can be independently the same or different and is hydrogen, or a linear or branched C1-C6-alkyl group. Claim 12 (i) rac-anti-dimethylsilandyl[2-methyl-4-(4'-tert-butylphenyl)-indene-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; rac-anti-dimethylsilandyl[2-methyl-4-(4'-tert-butylphenyl)-indene-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylindene-1-yl]zirconium Dichloride; rac-anti-dimethylsilandyl[2-methyl-4-(3',5'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; rac-anti-dimethylsilandyl[2-methyl-4,8-bis-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium Dichloride; rac-anti-dimethylsilandyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; (ii) a metallocene complex selected from rac-anti-dimethylsilandiyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacene-1-yl][2-methyl-4-(3',5'-di-tert-butyl-phenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride; (ii) a co-catalyst system comprising a boron-containing co-catalyst and a methylaluminoxane co-catalyst; and (ii) a supported catalyst system comprising an inorganic porous support. Claim 13 delete Claim 14 The supported catalyst system of claim 1, wherein the boron-containing co-catalyst is a compound of the following formula (B); or a borate containing anion of the following formula (C): BY3(B)(Z)4B - (C) In the above formula, Y may be independently the same or different, and is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an alkylaryl group having 1 to 10 carbon atoms in an alkyl radical and 6 to 20 carbon atoms in an aryl radical, an arylalkyl group, a haloalkyl group or a haloaryl group, or fluorine; Z is an optionally substituted phenyl derivative, the substituent of the substituted phenyl derivative is a halo-C1-C6-alkyl group or a halo group, and the counterion is a protonated amine or aniline derivative. Claim 15 A supported catalyst system according to claim 1, wherein the boron-containing co-catalyst is triphenylcarbenium tetrakis(pentafluorophenyl) borate; N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate; N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl) borate; or N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl) borate. Claim 16 A supported catalyst system according to claim 1, wherein the molar ratio of the supply amount of boron in the boron-containing co-catalyst to zirconium in the complex of formula (III) is 0.1:1 to 10:1 mol / mol; and the molar ratio of aluminum in the methylaluminoxane co-catalyst to zirconium in the complex of formula (III) is 1:1 to 2000:1 mol / mol. Claim 17 A supported catalyst system according to claim 1, wherein the average particle size of the support is 10 to 100 μm. Claim 18 A supported catalyst system according to claim 1, wherein the average pore size of the support may be 10 to 100 nm and the pore volume may be 1 to 3 mL / g. Claim 19 A supported catalyst system according to claim 1, comprising 10 to 100 μmol of zirconium per 1 g of support and 5 to 10 mmol of Al per 1 g of support. Claim 20 The supported catalyst system according to claim 1, comprising a metallocene complex (i), methylaluminoxane (MAO), a borate co-catalyst, and a support; and a supported catalyst system that exhibits higher productivity in the polymerization of propylene and ethylene than the same catalyst system without a borate co-catalyst, according to the inequality of Formula I below: [Formula I] Δ productivity [kg PP / g 촉매 ] > 10 x C2 [weight%] In the above formula, Δ productivity is the difference between the productivity of the metallocene-MAO-borate catalyst and the productivity of the metallocene-MAO catalyst at a predetermined ethylene concentration in the monomer feed for propylene-ethylene copolymerization. Claim 21 A supported catalyst system according to claim 1, wherein the inorganic porous support is a silica support. Claim 22 A method for manufacturing a supported catalyst system according to any one of claims 1, 2, 4 to 12 and 14 to 21, comprising: (a) reacting a support with a methylaluminoxane co-catalyst in a hydrocarbon solvent and optionally drying the support to obtain a methylaluminoxane co-catalyst-treated support; (b) reacting a metallocene complex defined in any one of claims 1, 2 and 4 to 12 with a methylaluminoxane co-catalyst in a hydrocarbon solvent; (c) adding a borate co-catalyst to the solution obtained in step (b) to obtain a solution of a metallocene complex of formula (III) according to claim 1 or formula (II) according to claim 2, a borate co-catalyst, and a methylaluminoxane co-catalyst, wherein the borate is added in an amount such that the molar ratio of boron to zirconium in the supplied amount reaches 0.1:1 to 10:

1. A method for manufacturing comprising: a step of adding a co-catalyst; (d) a step of adding the solution obtained in step (c) to a methylaluminoxane co-catalyst-treated support obtained in step (a), wherein the amount of methylaluminoxane co-catalyst added in step (a) is 75.0 to 97.0 weight% of the total amount of methylaluminoxane co-catalyst, and the amount of methylaluminoxane co-catalyst added in step (b) is 3.0 to 25.0 weight% of the total amount of methylaluminoxane co-catalyst; and (e) a step of drying the obtained supported catalyst system. Claim 23 (I) a step of polymerizing propylene in bulk in the presence of a supported catalyst system according to any one of claims 1, 2, 4 to 12 and 14 to 21 to produce a polypropylene homopolymer matrix; and (II) a step of polymerizing propylene and ethylene in the gaseous phase in the presence of the matrix and the catalyst system to produce a heteropolymer comprising the homopolymer matrix and ethylene-propylene rubber, a method for producing a heteropolymer. Claim 24 (I) a step of producing a polypropylene homopolymer by polymerizing propylene in bulk in the presence of a supported catalyst system according to any one of claims 1, 2, 4 to 12 and 14 to 21; (II) a step of producing a polypropylene homopolymer matrix by polymerizing propylene in a gaseous phase in the presence of the homopolymer and the catalyst system; and (III) a step of producing a heteropolymer polypropylene copolymer comprising a homopolymer matrix and ethylene propylene rubber (EPR) by polymerizing propylene and ethylene in a gaseous phase in the presence of the matrix and the catalyst system. Claim 25 delete Claim 26 delete

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