A process for the preparation of a heterophasic propylene resin

Abstract

This invention relates to a method for preparing heterogeneous polypropylene resin via a multi-stage polymerization process in the presence of a metallocene catalyst. The method comprises: (I) in a first polymerization step, polymerizing propylene and optionally at least one C2-10 α-olefin comonomer; and subsequently (II) in a second polymerization step, polymerizing propylene, ethylene, and optionally at least one C3-10 α-olefin comonomer in the presence of the metallocene catalyst and the polymer obtained in step (I); wherein step (II) is carried out in at least one gas-phase reactor at an operating pressure of at least 26 bar. The invention also relates to a heterogeneous polypropylene resin comprising a polypropylene matrix phase (A) and an ethylene-propylene copolymer phase (B) dispersed in the polypropylene matrix phase, wherein the ethylene-propylene copolymer phase (B) is an amorphous ethylene-propylene copolymer having an intrinsic viscosity (iV) of at least 3.5 dl / g measured in decahydronaphthalene at 135 °C, and an ethylene content of at least 15 wt% of the total weight of the ethylene-propylene copolymer, and each copolymer chain comprising at least four long branches (LCBs).

Description

Technical Field

[0001] This invention relates to a method for preparing heterogeneous propylene resin using a metallocene catalyst in a multi-stage polymerization process. Specifically, this invention relates to a method for controlling the chemical and physical properties of the rubber phase of the heterogeneous propylene resin. This is achieved by preparing the rubber phase using a gas-phase reactor under specific pressure. The invention also relates to a heterogeneous propylene resin comprising a non-crystalline ethylene-propylene copolymer with unique properties, and articles comprising this resin. Background Technology

[0002] Multistage polymerization processes are well known and widely used in the art for the preparation of polypropylene compositions. For example, US4740550 discloses a process configuration comprising at least one slurry polymerization reactor and at least one gas-phase polymerization reactor, and this process configuration is further disclosed in patents WO98 / 058975 and WO98 / 058976. This process configuration typically includes a prepolymerization reactor to maximize catalyst performance.

[0003] For many years, researchers have used single-site catalysts to prepare polyolefins. Numerous academic and patent publications describe the applications of single-site catalysts in olefin polymerization. A large class of single-site catalysts is metallocene, which is currently used industrially, particularly in the preparation of polyethylene and polypropylene using cyclopentadienyl catalyst systems with different substitution modes.

[0004] Single-center catalysts, such as metallocenes, can be used in propylene polymerization to achieve certain desired polymer properties. However, there are limitations to the use of metallocenes in industrial-scale multi-stage polymerization configurations, especially when preparing copolymers in the gas phase. Therefore, there is still room for improvement in this method and the behavior of the catalysts used in it.

[0005] As described above, the multi-stage polymerization of propylene is typically carried out in at least one slurry-phase polymerization reactor and at least one gas-phase polymerization reactor. In heterogeneous polypropylene resins, a propylene homopolymer matrix (or a propylene copolymer matrix with a low comonomer content, i.e., a random propylene copolymer) and a propylene-ethylene (or propylene-ethylene-α-olefin terpolymer) rubber component, typically dispersed in the matrix, are generated in one or more gas-phase reactors (GPR). Examples of this method are disclosed in patents WO2018 / 122134 and WO2019 / 179959. However, there are some limitations to using metallocene catalysts for the gas-phase preparation of ethylene-propylene copolymers (EPR).

[0006] One limitation is the low reactivity of ethylene relative to propylene in the gas phase (the so-called C2 / C3 reactivity ratio), typically below 0.5. This means that the C2 / C3 gas ratio fed into the reactor must be significantly higher than the desired copolymer composition. However, due to pressure limitations in the GPR, the C2 / C3 gas ratio input to the GPR is restricted to a low value. Therefore, under ambient temperature and pressure conditions, the upward C2 content of the rubber is limited when using a metallocene catalyst.

[0007] The second limitation is that rubbers prepared in the gas phase using metallocene catalysts typically have lower molecular weights, and the higher the ethylene content in the copolymer (up to 50 to 60 wt%), the lower the molecular weight of the rubber. In other words, the molecular weight obtained by copolymerization in the gas phase using most metallocene catalysts is lower than that obtained by homopolymerization or copolymerization in a condensed phase. The low intrinsic viscosity (IV) value of the rubber phase reflects the low molecular weight.

[0008] Patent WO2015 / 139875 discloses a method for preparing a heterogeneous propylene copolymer (RAHECO), which includes (i) a matrix (M) as a propylene copolymer (R-PP) and (ii) an elastic propylene copolymer (EC) dispersed in the matrix (M). The heterogeneous propylene copolymer obtained by the disclosed method has a low molecular weight rubber phase dispersed in it, with an intrinsic viscosity equal to or less than 2.2 dl / g.

[0009] Patent WO2011 / 050963 discloses a method for preparing heterogeneous polypropylene resin, which includes a propylene random copolymer matrix phase (A) and an ethylene-propylene copolymer rubber phase (B) dispersed in the matrix phase. The rubber phase dispersant in the heterogeneous copolymer obtained by the disclosed method has a low molecular weight and an intrinsic viscosity of 1.0 to 2.5 dl / g. It is also modified to have long-chain branching, resulting in a strain hardening factor (SHF) of 0.7 to 4.0 when the strain rate is 3.0 s⁻¹ and the Hencky strain is 3.0.

[0010] Furthermore, the chemical properties of amorphous ethylene-propylene rubber (straight chain, i.e., without long branches) limit its applications, especially when elastic recovery (good tensile and compression set), high damping (impact strength), and shape stability (low flowability under compression or tension) are required. These properties can be improved through a combination of extremely high molecular weight and the presence of long branches.

[0011] Patent WO2019 / 134951 discloses a method for preparing a heterogeneous propylene polymer (HECO), comprising a) a matrix component (M) selected from propylene homopolymers or random copolymers (PP); and b) an ethylene-propylene rubber (EPR) dispersed in propylene homopolymers or random copolymers (PP), wherein the xylene cold-soluble portion (XCS) of the heterogeneous propylene polymer (HECO) has an intrinsic viscosity (IV) between 1.1 and 3.4 dl / g; and the xylene cold-insoluble portion (XCI) of the heterogeneous propylene polymer (HECO) has 2,1-erythroide region defects, the amount of which is at least 0.4 mol% of the composition comprising the heterogeneous propylene polymer (HECO). The inventors have now found a specific set of operating conditions for a gas-phase reactor that can solve the problems disclosed above. Specifically, the present invention combines a specific class of metallocene catalysts with a gas-phase reactor operating under high pressure. Surprisingly, this combination improves both catalyst performance (such as a higher C2 / C3 reactivity ratio and higher molecular weight) and rubber properties through higher molecular weight and greater long-chain branching. This leads to the identification of ethylene-propylene rubbers with unique properties. Under a defined set of polymerization conditions, the catalyst of this invention can produce rubbers with long-chain branching in molecular weight ranges previously unattainable. Summary of the Invention

[0012] This invention provides a method for preparing heterogeneous polypropylene resin by a multi-stage polymerization process in the presence of a metallocene catalyst, the method comprising:

[0013] (I) In a first polymerization step carried out in one or more reactors, propylene and optionally at least one C2-10 α-olefin comonomer are polymerized; and subsequently

[0014] (II) In the second polymerization step, in the presence of a metallocene catalyst and the polymer obtained in step (I), propylene, ethylene and optionally at least one C4-10 α-olefin comonomer are polymerized.

[0015] The metallocene catalyst includes the metallocene complex shown in Formula I.

[0016]

[0017] Where Mt is Zr or Hf;

[0018] Each X is a σ (sigma) ligand;

[0019] E is a -CR chemically linked to two cyclopentadienyl ligands. 1 2-、-CR 1 2-CR 1 2-、-CR 1 2-SiR1 2-, -SiR 1 2- or -SiR 1 2-SiR 1 2-group; R 1 The functional groups can be the same or different, and can be hydrogen or optionally contain up to two C atoms of silicon, oxygen, sulfur or nitrogen. 1-20 Hydrocarbon group, and optionally both R 1 The group can be part of a C4-C8 ring.

[0020] R 2 and R 2 'Same or different from each other;'

[0021] R 2 It is a -CH2R group, where R is H or a straight-chain or branched C. 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl;

[0022] R 2 'For C 1-20 Hydrocarbon group; preferably, R 2 and R 2 'Identical, and either straight or branched C' 1-6 alkyl;

[0023] Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C 1-6 Alkyl, C 7-20 Aryl alkyl, C 7-20 Alkyl, C 6-20 Aryl and OY groups, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4 The group can be part of a ring, including those with R 3 and R 4 The phenyl carbon linked to the group;

[0024] Each R 5 R 5’ R 6 and R 6’ A C atom that is independently hydrogen or optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms. 1-20 Hydrocarbon group, or OY group, where Y is C 1-10 Hydrocarbon group, and may be -CH=, -CY=, -CH2-, -CHY- or -CY2- group, which is part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand;

[0025] R7 and R 7 'Whether they are the same or different from each other, they are H or OY groups or optionally contain up to two silicon, oxygen, sulfur or nitrogen atoms.' 1-20 Hydrocarbon group, condition is when R 7 When =H, then R 5 R 6 All ≠ H, and when R 7 When '=H, then R 5 '、R 6 'All ≠ H, and another condition is that only if R 7 Unlike hydrogen, R 5 and R 6 Only when R can it be hydrogen, and only when R 7 Unlike hydrogen, R 5 'and R 6 Only then can it be hydrogen; and

[0026] Step (II) is carried out in at least one gas-phase reactor at a pressure of at least 26 bar.

[0027] In another respect, the present invention provides a heterogeneous polypropylene resin, which can be obtained by the method described above.

[0028] In another respect, the present invention provides the use of heterogeneous polypropylene resin as described above in the manufacture of articles such as hoses, pipes, profiles, cable insulations, sheets or films. Attached Figure Description

[0029] The present invention will now be described in more detail with reference to the accompanying drawings and preferred embodiments, wherein...

[0030] Figure 1 The intrinsic viscosity of EPR as a function of pressure is shown in the presence of catalysts 1, 2 and 3, with a gas phase temperature of 70°C, a copolymer ethylene content of approximately 25 wt%, and the presence of catalysts 1, 2 and 3.

[0031] Figure 2 The intrinsic viscosity of EPR as a function of pressure is shown at gas phase temperatures of 70 and 90 °C, with a copolymer ethylene content of approximately 25 wt%, and in the presence of catalysts 1 and 3.

[0032] Figure 3 The intrinsic viscosity of EPR as a function of pressure is shown at a gas phase temperature of 90°C, with copolymer ethylene contents of approximately 25, 70, and 80 wt%, and in the presence of catalysts 1 and 2.

[0033] Figure 4The diagram shows the change of the C2 / C3 relative reactivity ratio with pressure in the presence of catalysts 1, 2 and 3, with a gas phase temperature of 70°C and a copolymer ethylene content of approximately 25 wt%.

[0034] Figure 5 The changes in the relative reactivity ratio of C2 / C3 with pressure are shown at gas phase temperatures of 70 and 90 °C, with an ethylene content of approximately 25 wt% in the copolymer, and in the presence of catalysts 1 and 3; and

[0035] Figure 6 The results show the variation of the C2 / C3 relative reactivity ratio with pressure at a gas phase temperature of 90°C, copolymer ethylene content of approximately 25, 70, and 80 wt%, and in the presence of catalysts 1 and 2.

[0036] Figure 7 The calculation of the linear reference line and g' are shown. (85-100) The calculation. Detailed Implementation

[0037] This invention provides a method for preparing heterogeneous polypropylene resin in a multi-stage polymerization process in the presence of a metallocene catalyst as discussed herein, the method comprising:

[0038] (I) In a first polymerization step carried out in one or more reactors, propylene and optionally at least one C2-10 α-olefin comonomer are polymerized to obtain a polypropylene matrix phase (A); and subsequently

[0039] (II) In the second polymerization step, in the presence of a metallocene catalyst and the polymer obtained in step (I), propylene, ethylene and at least one C4-10 α-olefin comonomer are polymerized to obtain an ethylene-propylene copolymer phase (B) dispersed in the matrix phase (A).

[0040] Step (II) is carried out in at least one gas-phase reactor at a pressure of at least 26 bar.

[0041] The present invention also relates to heterogeneous polypropylene resins containing amorphous ethylene-propylene copolymers having a specific range of intrinsic viscosity (iV) and a specific C2 content, and each copolymer chain comprising at least four long branches (LCBs).

[0042] polymerization

[0043] The present invention relates to a method for multi-stage polymerization using a metallocene catalyst, the method comprising an optional but preferred prepolymerization step, followed by first and second polymerization steps.

[0044] Preferably, the same catalyst is used in each step, and preferably the transfer from prepolymerization to subsequent polymerization steps is carried out sequentially in a known manner. A preferred process configuration is based on... Type cascade.

[0045] Therefore, the method of the present invention for preparing heterogeneous polypropylene resin in a multi-stage polymerization process in the presence of a metallocene catalyst as discussed herein includes:

[0046] (I) In a first polymerization step carried out in one or more (preferably continuous) reactors, propylene and optionally at least one C2-10 α-olefin comonomer are polymerized; and subsequently

[0047] (II) In the second polymerization step, in the presence of a metallocene catalyst and the polymer obtained in step (I), propylene, ethylene and optionally at least one C4-10 α-olefin comonomer are polymerized.

[0048] The metallocene catalyst comprises a metallocene complex and preferably one or more co-catalysts as discussed herein; and

[0049] Step (II) is carried out in at least one gas-phase reactor at a pressure of at least 26 bar, wherein the method typically produces heterogeneous polypropylene resin as discussed herein.

[0050] As a further example of the method, the first polymerization step (I) produces a polypropylene matrix phase (A) as discussed herein, and the second polymerization step (II) produces a rubber component (B) (i.e., an amorphous ethylene-propylene copolymer) as discussed herein.

[0051] Prepolymerization

[0052] The method of the present invention can utilize an online prepolymerization step. The online prepolymerization step occurs prior to the first polymerization step (I) and can be carried out in the presence of hydrogen, although if hydrogen is present, its concentration should be very low. The hydrogen concentration can be 0 to 1 mol (hydrogen) / kmol (propylene), preferably 0.001 to 0.1 mol (hydrogen) / kmol (propylene).

[0053] Ideally, the temperature conditions during the prepolymerization step should be kept low, for example, 0 to 50°C, preferably 5 to 40°C, and more preferably 10 to 30°C.

[0054] The prepolymerization stage preferably polymerizes only propylene monomers. The residence time of the prepolymerization reaction stage is very short, typically 5 to 30 minutes.

[0055] The prepolymerization stage preferably produces less than 5 wt% of the total polymer formed, for example, 3 wt% or less.

[0056] Prepolymerization is preferably carried out in a dedicated reactor, and more preferably in a liquid propylene slurry. The prepolymerization catalyst is then transferred to the first polymerization step. However, prepolymerization can also be carried out in the same reactor as the first polymerization step, especially in batch processes.

[0057] First polymerization step (I) - Preparation of polypropylene matrix phase

[0058] In this invention, the first polymerization step involves the polymerization of propylene and optionally at least one C2-10 α-olefin comonomer. The first polymerization step (I) produces a polypropylene polymer matrix, which, if further modified in a second polymerization step (II), yields a desired amorphous polymer with unique properties.

[0059] Therefore, in one embodiment, the first polymerization step involves only polymerizing propylene to produce a propylene homopolymer.

[0060] In another embodiment, the first polymerization step involves polymerizing propylene with at least one C2-10 α-olefin. In this embodiment, the comonomer polymerized with propylene may be ethylene or a C4-10 α-olefin, or a mixture of comonomers, such as a mixture of ethylene and a C4-10 α-olefin, may be used.

[0061] As comonomers for propylene, ethylene, 1-butene, 1-hexene, 1-octene, or any mixture thereof are preferred, with ethylene being the most preferred. When ethylene comonomers are present in the polymer produced in the first polymerization step (I), their content can be up to 5 mol% or 3.4 wt%, while when butene comonomers are present, their content can be up to 5 mol% or 6.6 wt%, but their total content relative to the entire polymer is at most 5 mol%.

[0062] The first polymerization step can be carried out in any suitable reactor or a series of reactors. The first polymerization step can be carried out in a slurry polymerization reactor (such as a loop reactor) or a gas-phase polymerization reactor, or a combination thereof.

[0063] When a slurry polymerization reactor is used, the reaction is typically carried out in at least one circulating reactor. Ideally, the polymerization reaction takes place in bulk, for example in a liquid propylene medium. For general slurry reactors, and especially for bulk reactors, the reaction temperature is typically between 60 and 100°C, preferably 70 to 85°C. The reactor pressure is typically between 5 and 80 bar (e.g., 20 to 60 bar), and the residence time is typically between 0.1 and 5 hours (e.g., 0.3 to 2 hours). When a gas-phase reactor is used, the reaction temperature is typically between 60 and 120°C, preferably 70 to 90°C. The reactor pressure is typically between 10 and 35 bar (e.g., 15 to 30 bar), and the residence time is typically between 0.5 and 5 hours (e.g., 1 to 2 hours).

[0064] In a preferred embodiment, the first polymerization step is carried out in a slurry circulation reactor that is cascaded with the gas-phase reactor. In this case, the polymer produced in the loop reactor is transferred to the first gas-phase reactor.

[0065] Hydrogen is preferably used in the first polymerization step. The amount of hydrogen used is typically much larger than that used in the prepolymerization stage.

[0066] Second polymerization step (II) - Preparation of the rubber phase

[0067] The second polymerization step (II) of the method of the present invention is a gas polymerization step, wherein propylene, ethylene, and optionally at least one C4-10 α-olefin comonomer are polymerized in the presence of a metallocene catalyst and the polymer obtained in step (I). This polymerization step is carried out in at least one gas-phase reactor, optionally in the presence of an inert gas such as propane. Therefore, the second polymerization step can be carried out in a single gas-phase reactor or in multiple gas-phase reactors connected in series or parallel. The second polymerization step (II) produces a rubber phase dispersed in the semi-crystalline polypropylene matrix produced by the first polymerization step (I), which is crucial for preparing amorphous polymers with unique properties.

[0068] The C4-10 α-olefin may be, for example, 1-butene, 1-hexene, 1-octene, or any mixture thereof. However, preferably, step (II) involves only the polymerization of propylene and ethylene.

[0069] A key feature of this invention is the reactor pressure in at least one gas-phase reactor during the second polymerization step (II). In the method of this invention, the reactor pressure is at least 26 bar, preferably at least 28 bar, more preferably at least 30 bar, and even more preferably at least 35 bar, typically between 26 and 60 bar, preferably between 28 and 50 bar, more preferably between 30 and 45 bar, and even more preferably between 30 and 38 bar. The maximum pressure achievable in the gas phase obviously also depends on the temperature and gas composition (C2 / C3 ratio and propane content). For the purposes of this invention, the gas-phase step is defined as when at least 80 wt%, preferably 90 wt%, of the monomer in the gas-phase reactor is actually in the gas phase, calculated by vapor-liquid equilibrium, for example, by Aspen plus.

[0070] Increasing the pressure of the gas-phase reactor while maintaining the same temperature and gas-phase composition leads to increased productivity, increased molecular weight of rubber, and, most importantly, increased reactivity of ethylene relative to propylene, resulting in the preparation of polymers with a wider range of compositions. It also expands the process window at a given reactor temperature, enabling preparation separation between the bulk and gas-phase steps.

[0071] In the method of the present invention, the temperature in the gas-phase reactor is typically between 60 and 120°C, preferably between 65 and 110°C, more preferably between 65 and 100°C, and even more preferably between 70 and 90°C. Higher gas-phase reactor temperatures will facilitate increased operating pressures, thus contributing to the inventive features of the method.

[0072] Residence time in any gas-phase reactor is typically 0.5 to 8 hours (e.g., 0.5 to 4 hours). The gas used will be a monomer mixture, optionally a mixture with a non-reactive gas such as propane.

[0073] The hydrogen content in the gas-phase reactor is important for controlling polymer properties, but it is independent of the hydrogen added in the prepolymerization and first polymerization steps. Hydrogen remaining in the reactor from step I can be partially removed before being transferred to the gas-phase reactor from step II, but it can also be transferred to the gas-phase reactor from step II along with the polymer / monomer mixture from step I, where more hydrogen can be added to control the molecular weight (Mw) of the rubber to the desired value.

[0074] In a particularly preferred embodiment of the invention, no hydrogen is added during gas-phase polymerization step II.

[0075] The yield or distribution (by weight) between the first and second polymerization steps is preferably 55:45 to 85:15, more preferably 60:40 to 80:20. Note that any small amount of polymer formed in the prepolymerization is counted as part of the polymer prepared in the first polymerization step.

[0076] Metallocene catalysts

[0077] The method of this invention employs a metallocene catalyst. The metallocene complex is preferably a trans-configured chiral, racemic, bridged bis-indenyl metallocene. The metallocene can be symmetrical or asymmetrical. In this invention, symmetry means that the two indenyl ligands forming the metallocene complex are chemically identical, i.e., they have the same number and type of substituents. Asymmetry means that one or more substituents of the two indenyl ligands differ, both in their chemical structure and their position on the indenyl group. In the case of asymmetrical metallocene complexes, although they are formally C1-symmetrical, they ideally maintain pseudo-C2-symmetry because they maintain C2-symmetry near the metal center but not at the periphery of the ligands. Depending on their chemical properties, trans-enantiomers and cis-enantiomer pairs (in the case of C1-symmetrical complexes) or racemic trans-enantiomers and meso-forms (in the case of C2-symmetrical complexes) may be generated during the synthesis of the complex. For the purposes of this invention, racemic trans refers to the two indenyl ligands having opposite orientations relative to the cyclopentadienyl-metal-cyclopentadienyl plane, while racemic cis (or meso) refers to the two indenyl ligands having the same orientation relative to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the example below.

[0078]

[0079] Therefore, the following formula represents the racemic trans isomer of metallocene complexes.

[0080] Metallocene complexes are preferably racemic trans isomers. Therefore, ideally, at least 90 mol%, such as at least 95 mol%, and especially at least 98 mol%, of metallocene catalyst complexes are racemic trans isomers.

[0081] For the purposes of this invention, the numbering scheme for indenyl and diindenyl ligands is as follows:

[0082]

[0083] It is understood that in the complexes of this invention, the metal ion Mt coordinates with ligand X to satisfy the valence of the metal ion and fill its available coordination sites. The properties of these σ ligands can vary widely.

[0084] Term "C" 1-20 "Hydrocarbon group" includes C 1-20 Alkyl, C 2-20 alkenyl, C 2-20 alkynyl group, C 3-20 cycloalkyl, C 3-20 Cycloalkenyl, C 6-20Aryl, C 7-20 alkylaryl or C 7-20 Aryl groups, or mixtures thereof, such as cycloalkyl groups substituted with alkyl groups, are permitted. Straight-chain and branched hydrocarbon groups cannot contain cyclic units. Aliphatic hydrocarbon groups cannot contain aromatic rings.

[0085] Unless otherwise stated, C is preferred. 1-20 The hydrocarbon group is C 1-20 Alkyl, C 4-20 cycloalkyl, C 5-20 cycloalkyl-alkyl, C 7-20 Alkyl, C 7-20 Aryl or C 6-20 Aryl, especially C 1-10 Alkyl, C 6-10 Aryl or C 7-12 Aryl alkyl groups, such as C 1-8 Alkyl groups. The most particularly preferred hydrocarbon groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, and C. 5-6 -Cycloalkyl, cyclohexylmethyl, phenyl or benzyl.

[0086] The term "halogen" includes fluorine, chlorine, bromine, and iodine groups, especially the chlorine group.

[0087] The metallocene used in this invention is a racemic, trans-configured bridged bis-indene metallocene, the structure of which is shown in Formula I:

[0088]

[0089] Where Mt is Zr or Hf;

[0090] Each X is a σ (sigma) ligand;

[0091] E is a -CR chemically linked to two cyclopentadienyl ligands. 1 2-、-CR 1 2-CR 1 2-、-CR 1 2-SiR 1 2-, -SiR 1 2- or -SiR 1 2-SiR 1 2-group; R 1 The functional groups can be the same or different, and can be hydrogen or optionally contain up to two C atoms of silicon, oxygen, sulfur or nitrogen. 1-20 Hydrocarbon group, and optionally both R 1 The group can be part of a C4-C8 ring.

[0092] R 2 and R 2 'Same or different from each other;'

[0093] R 2 It is a -CH2R group, where R is H or a straight-chain or branched C. 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl;

[0094] R 2 'For C 1-20 Hydrocarbon group; preferably, R 2 and R 2 'Identical, and either straight or branched C' 1-6 alkyl;

[0095] Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C 1-6 Alkyl, C 7-20 Aryl alkyl, C 7-20 Alkyl, C 6-20 Aryl and OY groups, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4 The group can be part of a ring, including those with R 3 Or R 4 The phenyl carbon linked to the group;

[0096] Each R 5 R 5 '、R 6 and R 6 'C atoms that are independently hydrogen or optionally contain up to two silicon, oxygen, sulfur, or nitrogen atoms' 1-20 Hydrocarbon group, or OY group, where Y is C 1-10 Hydrocarbon group, and may be -CH=, -CY=, -CH2-, -CHY- or -CY2- group, which is part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand;

[0097] R 7 and R 7 'Whether they are the same or different from each other, they are H or OY groups or optionally contain up to two silicon, oxygen, sulfur or nitrogen atoms.' 1-20 Hydrocarbon group, condition is when R 7 When =H, then R 5 R 6 Both are not equal to H, and when R7' = H, then R 5 '、R 6 'All ≠ H, and another condition is that only if R 7 Unlike hydrogen, R 5 and R 6 Only when R can it be hydrogen, and only when R7 Unlike hydrogen, R 5 'and R 6’ Only then can it be hydrogen.

[0098] For Equation I as defined above, the following represent preferred embodiments that can be selected individually or in combination:

[0099] E is preferably SiMe2;

[0100] X is preferably a halogen, more preferably Cl or a methyl group;

[0101] R 2 and R 2 'Preferred is C' 1-6 Alkyl, more preferably methyl;

[0102] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl;

[0103] Each R 5 R 5 '、R 6 and R 6 'Independently preferred C' 1-10 Hydrocarbon group, OY group, where Y is C 1-6 Alkyl groups, or -CH=, -CY=, -CH2-, -CHY- or -CY2- groups, which are part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand;

[0104] R 7 H and C are preferred. 1-20 Alkyl or C 6-20 aryl; and / or

[0105] R 7 H is preferred.

[0106] Preferably, the metallocene suitable for the present invention is a racemic inverse-configuration bridged bis-indene metallocene, the structure of which is shown in Formula II:

[0107]

[0108] Where Mt is Zr or Hf;

[0109] X may be the same as or different from each other, and X may be a halogen, hydrogen, or optionally a carbon atom containing at most two silicon, oxygen, sulfur, or nitrogen atoms. 1-20 A hydrocarbon group, or an OY or NY2 group, wherein Y is a C group optionally containing at most two silicon atoms. 1-10 hydrocarbon group;

[0110] Two Rs on silicon 1 The functional groups may be the same or different from each other, and may be hydrogen or optionally contain up to two silicon, oxygen, sulfur or nitrogen atoms. 1-20 Hydrocarbon group, and preferably C 1-8 Hydrocarbon group; most preferably, one R 1 It is hydrogen, methyl, ethyl, n-propyl, or isopropyl, and the other R is... 1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl and phenyl;

[0111] R 2 and R 2 'Same or different from each other;'

[0112] R 2 It is a -CH2R group, where R is H or a straight-chain or branched C. 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl group, which optionally contains up to two silicon, oxygen, sulfur or nitrogen atoms;

[0113] R 2 'A C that optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms 1-20 Hydrocarbon group; preferably, R 2 and R 2 'Identical and either straight or branched C' 1-6 alkyl;

[0114] Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C. 1-6 Alkyl, C 7-20 Araneyl, C 7-20 Alkyl, C 6-20 Aryl, where Y is C 1-10 The hydrocarbon group is an OY or NY2 group, and optionally two adjacent R groups. 3 Or R 4 The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 The phenyl carbon linked to the group;

[0115] Each R 5 R 5 '、R 6 and R 6 'C atoms that are independently hydrogen or optionally contain up to two silicon, oxygen, sulfur, or nitrogen atoms' 1-20 Hydrocarbon group, or OY or NY2 group, where Y is C 1-10Hydrocarbon group, and may be -CH=, -CY=, -CH2-, -CHY- or -CY2- group, which is part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand;

[0116] R 7 and R 7 'Whether they are the same or different from each other, they are H or OY groups or optionally contain up to two silicon, oxygen, sulfur or nitrogen atoms.' 1-20 Hydrocarbon group, condition is when R 7 When =H, then R 5 R 6 Both are not equal to H, and when R7' = H, then R 5 '、R 6 'All ≠ H, and another condition is that only if R 7 Unlike hydrogen, R 5 and R 6 Only when R can it be hydrogen, and only when R 7 Unlike hydrogen, R 5 'and R 6 Only then can it be hydrogen;

[0117] For Equation II as defined above, the following are preferred embodiments that can be used alone or in combination:

[0118] R 1 Preferably methyl;

[0119] X is preferably a halogen, more preferably Cl or a methyl group;

[0120] R 2 and R 2 'Preferred is C' 1-6 Alkyl, more preferably methyl;

[0121] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl;

[0122] Each R 5 R 5 '、R 6 and R 6 'Independently preferred C' 1-10 Hydrocarbon group, OY group, where Y is C 1-6 Alkyl groups, or -CH=, -CY=, -CH2-, -CHY- or -CY2- groups, which are part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand;

[0123] R 7H and C are preferred. 1-20 Alkyl or C 6-20 aryl; and / or

[0124] R 7 H is preferred.

[0125] Even more preferably, the metallocene suitable for the present invention is a racemic inverse-configuration bridged bis-indene metallocene, the structure of which is shown in Formula III:

[0126]

[0127] Where Mt is Zr or Hf;

[0128] X can be the same as or different from each other, and X can be halogen, hydrogen, or carbon. 1-6 Hydrocarbon group, or OY or NY2 group, wherein Y is a C group optionally containing one silicon atom. 1-6 hydrocarbon group;

[0129] Two Rs on silicon 1 The functional groups may be the same or different from each other, and may be hydrogen or optionally contain up to two silicon, oxygen, sulfur or nitrogen atoms. 1-8 Hydrocarbon group, and preferably C 1-8 Hydrocarbon group; most preferably, one R 1 It is hydrogen, methyl, ethyl, n-propyl, or isopropyl, and the other R is... 1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl and phenyl;

[0130] R 2 and R 2 'Whether they are the same or different, they are -CH2R groups, where R is H or a straight-chain or branched C.' 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl;

[0131] Preferably, R 2 and R 2 'Identical and either straight or branched C' 1-6 alkyl;

[0132] Each R 3 and R 4 Independently identical or may be different, and is hydrogen, straight-chain or branched C1-C6 alkyl, C 7-20 Aryl alkyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 The phenyl carbon linked to the group;

[0133] Each R 5 R 5 '、R 6 and R 6 'C atoms that are independently hydrogen or optionally contain up to two silicon, oxygen, sulfur, or nitrogen atoms' 1-20 Hydrocarbon group, or OY group, where Y is C 1-10 Hydrocarbon group, and may be -CH=, -CY=, -CH2-, -CHY- or -CY2- group, which is part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand;

[0134] R 7 The C group is an H or OY group or optionally contains up to two silicon, oxygen, sulfur or nitrogen atoms. 1-20 Hydrocarbon group, condition is when R 7 When =H, then R 5 R 6 All ≠ H, and another condition is that only when R 7 Unlike hydrogen, R 5 and R 6 Only then can it be hydrogen.

[0135] For Equation III as defined above, the following are preferred embodiments that can be used alone or in combination:

[0136] Mt is preferably Zr;

[0137] R 1 Preferably methyl;

[0138] X is preferably a halogen, more preferably Cl or a methyl group;

[0139] R 2 and R 2 'Preferred is C' 1-6 Alkyl, more preferably methyl;

[0140] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl;

[0141] Each R 5 R 5 '、R 6 and R 6 'Independently preferred C' 1-10 Hydrocarbon group, OY group, where Y is C 1-6Alkyl groups, or -CH=, -CY=, -CH2-, -CHY-, or -CY2- groups, which are part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand; and / or

[0142] R 7 H and C are preferred. 1-20 Alkyl or C 6-20 Aryl.

[0143] In one embodiment, the metallocene suitable for the present invention is a racemic inverse-configuration bridged bis-indene metallocene, the structure of which is shown in Formula IV:

[0144]

[0145] Where Mt is Zr or Hf;

[0146] X can be the same as or different from each other, X is a halogen, C 1-6 Hydrocarbon group, or OY or NY2 group, wherein Y is a C group optionally containing one silicon atom. 1-6 hydrocarbon group;

[0147] Two Rs on silicon 1 The functional groups can be the same or different, and can be hydrogen or optionally contain up to two silicon, oxygen, sulfur, or nitrogen atoms. 1-8 Hydrocarbon group, and preferably C 1-8 Hydrocarbon group; most preferably, one R 1 It is hydrogen, methyl, ethyl, n-propyl, or isopropyl, and the other R is... 1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, and phenyl; most preferably, R 1 They are the same and are methyl;

[0148] R 2 and R 2 'Whether they are the same or different, they are -CH2R groups, where R is H or a straight-chain or branched C.' 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl;

[0149] Preferably, R 2 and R 2 'Identical and either straight or branched C' 1-6 alkyl;

[0150] Each R 3 and R 4 Independently identical or may be different, and is hydrogen, straight-chain or branched C1-C6 alkyl, C 7-20 Aryl alkyl, C 7-20 Alkyl, C6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4 The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 The phenyl carbon linked to the group;

[0151] Each R 6 and R 6 Independently, it may optionally contain up to two silicon, oxygen, sulfur, or nitrogen atoms (C). 1-20 hydrocarbon groups; and

[0152] Y is C 1-10 Hydrocarbon group.

[0153] For formula IV as defined above, the following represent preferred embodiments that can be used alone or in combination:

[0154] R 1 Preferably methyl;

[0155] X is preferably a halogen, more preferably Cl or a methyl group;

[0156] R 2 and R 2 'Preferred is C' 1-6 Alkyl, more preferably methyl;

[0157] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl;

[0158] Y is preferably C 1-6 Alkyl, more preferably methyl; and / or

[0159] Each R 6 and R 6 'Independently preferred C' 1-10 Hydrocarbon group.

[0160] In the same embodiment, more preferably, the structure of the metallocene is as shown in Formula V:

[0161]

[0162] Where Mt is Zr or Hf;

[0163] X can be the same as or different from each other, X is a halogen, C 1-6 Hydrocarbon group, or OY or NY2 group, wherein Y is a C group optionally containing one silicon atom. 1-6 hydrocarbon group;

[0164] R 2 and R 2 'Whether they are the same or different, they are -CH2R groups, where R is H or a straight-chain or branched C.' 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl;

[0165] Preferably, R 2 and R 2 'Identical and either straight or branched C' 1-6 alkyl;

[0166] Each R 3 and R 4 Independently identical or may be different, and is hydrogen, straight-chain or branched C1-C6 alkyl, C 7-20 Aryl alkyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4 The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 The phenyl carbon linked to the group;

[0167] Each R 6 and R 6 'Independently is C' 1-10 hydrocarbon groups; and

[0168] Y is C 1-10 Hydrocarbon group.

[0169] For the formula V defined above, the following represent preferred embodiments that can be used alone or in combination:

[0170] X is preferably a halogen, more preferably Cl or a methyl group;

[0171] R 2 and R 2 'Preferred is C' 1-6 Alkyl, more preferably methyl;

[0172] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl;

[0173] Y is preferably C 1-6 Alkyl, more preferably methyl; and / or

[0174] Each R 6 and R 6'Independently preferred C' 1-10 Hydrocarbon group.

[0175] In the same embodiment, or even more preferably, the metallocene structure is as shown in Formula VI:

[0176]

[0177] Where Mt is Zr or Hf;

[0178] X can be the same as or different from each other, X is a halogen, C 1-6 Hydrocarbon group, or OY or NY2 group, wherein Y is a C group optionally containing one silicon atom. 1-6 hydrocarbon group;

[0179] Each R 3 and R 4 Independently identical or may be different, and is hydrogen, straight-chain or branched C1-C6 alkyl, C 7-20 Aryl alkyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4 The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 The phenyl carbon linked to the group;

[0180] R 5 and R 5 'Independently for C 1-10 hydrocarbon group;

[0181] R 8 and R 8 'Independently H or C 1-10 hydrocarbon groups; and

[0182] Y is C 1-10 Hydrocarbon group.

[0183] For formula VI as defined above, the following represent preferred embodiments that can be used alone or in combination:

[0184] X is preferably a halogen, more preferably Cl or a methyl group;

[0185] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl;

[0186] Y is preferably C 1-6 Alkyl, more preferably methyl; and / or

[0187] Each R 8 and R 8 'Independently preferred C' 1-10 Hydrocarbon group.

[0188] In this implementation scheme, metallocene is preferred:

[0189] Racemic dimethylsilanediylbis(2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl)zirconium dichloride;

[0190] Racemic dimethylsilanediylbis(2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl)zirconium dichloride;

[0191] Racemic dimethylsilanediylbis(2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl)zirconium dichloride;

[0192] Racemic dimethylsilanediylbis(2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl)zirconium dichloride;

[0193] And its dimethylzirconium and hafnium analogues.

[0194] In the second embodiment, the metallocene suitable for the present invention is a racemic inverse-configuration bridged bis-indene metallocene, the structure of which is shown in Formula VII:

[0195]

[0196] Where Mt is Zr or Hf;

[0197] X may be the same as or different from each other, X is a halogen, and optionally contains at most two silicon, oxygen, sulfur or nitrogen atoms in a C group. 1-6 A hydrocarbon group, or an OY or NY2 group, wherein Y is a C group optionally containing at most two silicon atoms. 1-10 hydrocarbon group;

[0198] Two Rs on silicon 1 The functional groups may be the same or different from each other, and may be hydrogen or optionally contain up to two silicon, oxygen, sulfur or nitrogen atoms. 1-20 Hydrocarbon group, and preferably C 1-8 Hydrocarbon group; most preferably, one R 1 It is hydrogen, methyl, ethyl, n-propyl, or isopropyl, and the other R is... 1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl and phenyl;

[0199] R 2 and R 2'Same or different from each other;'

[0200] R 2 It is a -CH2R group, where R is an H or a straight-chain or branched C. 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl group, which optionally contains up to two silicon, oxygen, sulfur or nitrogen atoms;

[0201] R 2 'A C that optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms 1-20 Hydrocarbon group; preferably, R 2 and R 2 'Identical and either straight or branched C' 1-6 alkyl;

[0202] Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C 1-6 Alkyl, C 7-20 Araneyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4 The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 The phenyl carbon linked to the group;

[0203] Each R 5 R 5 '、R 6 and R 6 'Independently, C contains at most two silicon, oxygen, sulfur, or nitrogen atoms' 1-20 A hydrocarbon group, which may be -CH=, -CY=, -CH2-, -CHY- or -CY2-, which is part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand.

[0204] For Equation VII as defined above, the following represent preferred embodiments that can be used alone or in combination:

[0205] R 1 Preferably methyl;

[0206] X is preferably a halogen, more preferably Cl or a methyl group;

[0207] R 2 and R 2 'Preferred is C' 1-6 Alkyl, more preferably methyl;

[0208] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl; and / or

[0209] Each R 5 R 5 '、R 6 and R 6 'Independently preferably -CH=, -CY=, -CH2-, -CHY- or -CY2- groups, which are part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand.

[0210] In this second embodiment, more preferably, the structure of the metallocene is as shown in Formula VIII:

[0211]

[0212] Where Mt is Zr or Hf;

[0213] X may be the same as or different from each other, X is a halogen, and optionally contains at most two silicon, oxygen, sulfur or nitrogen atoms in a C group. 1-6 A hydrocarbon group, or an OY or NY2 group, wherein Y is a C group optionally containing at most two silicon atoms. 1-10 hydrocarbon group;

[0214] Two Rs on silicon 1 The functional groups may be the same or different from each other, and may be hydrogen or optionally contain up to two silicon, oxygen, sulfur or nitrogen atoms. 1-20 Hydrocarbon group, and preferably C 1-8 Hydrocarbon group; most preferably, one R 1 It is hydrogen, methyl, ethyl, n-propyl, or isopropyl, and the other R is... 1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl and phenyl;

[0215] R 2 and R 2 'Same or different from each other;'

[0216] R 2 It is a -CH2R group, where R is an H or a straight-chain or branched C. 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl group, which optionally contains up to two silicon, oxygen, sulfur or nitrogen atoms;

[0217] R 2 'A C that optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms 1-20Hydrocarbon group; preferably, R 2 and R 2 'Identical and either straight or branched C' 1-6 alkyl;

[0218] Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C 1-6 Alkyl, C 7-20 Araneyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4 The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 The phenyl carbon linked to the group;

[0219] Y is C 1-10 Hydrocarbon group and n is an integer between 2 and 5.

[0220] For Equation VIII as defined above, the following represent preferred embodiments that can be used alone or in combination:

[0221] R 1 Preferably methyl;

[0222] X is preferably a halogen, more preferably Cl or a methyl group;

[0223] R 2 and R 2 'Preferred is C' 1-6 Alkyl, more preferably methyl;

[0224] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl; and / or

[0225] Y is C 1-10 Hydrocarbon group and n is an integer between 3 and 4;

[0226] In this second embodiment, more preferably, the structure of the metallocene is as shown in Formula IX:

[0227]

[0228] Where Mt is Zr or Hf;

[0229] X may be the same as or different from each other, X is a halogen, and optionally contains at most two silicon, oxygen, sulfur or nitrogen atoms in a C group. 1-6A hydrocarbon group, or an OY or NY2 group, wherein Y is a C group optionally containing at most two silicon atoms. 1-10 Hydrocarbon group; most preferably, X is chlorine or methyl;

[0230] Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C 1-6 Alkyl, C 7-20 Araneyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4 The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 The phenyl carbon linked to the group;

[0231] Y is C 1-10 Hydrocarbon group and n is an integer between 3 and 4.

[0232] For Equation IX as defined above, the following represent preferred embodiments that can be used alone or in combination:

[0233] Mt is preferably Zr;

[0234] X is preferably a halogen, more preferably Cl or a methyl group;

[0235] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl; and / or

[0236] Y is C 1-10 Hydrocarbon group and n is an integer between 3 and 4.

[0237] In this implementation scheme, metallocene is preferred:

[0238] Racemic dimethylsilane di-bis[2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indeno-1-yl]zirconium dichloride;

[0239] Racemic dimethylsilane di-bis[2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indeno-1-yl]zirconium dichloride;

[0240] Racemic dimethylsilane di-bis[2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indeno-1-yl]zirconium dichloride;

[0241] Racemic dimethylsilane di-bis[2-methyl-4-(3',5'-di-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indeno-1-yl]zirconium dichloride;

[0242] And its dimethylzirconium and hafnium analogues.

[0243] In the third embodiment, the metallocene suitable for the present invention is an asymmetric bridged bis-indene metallocene with a racemic inverse configuration, the structure of which is shown in Formula X:

[0244]

[0245] Where Mt is Zr or Hf;

[0246] X may be the same as or different from each other, and X may be a halogen, hydrogen, or optionally a carbon atom containing at most two silicon, oxygen, sulfur, or nitrogen atoms. 1-20 A hydrocarbon group, or an OY or NY2 group, wherein Y is a C group optionally containing at most two silicon atoms. 1-10 hydrocarbon group;

[0247] Two Rs on silicon 1 The functional groups may be the same or different from each other, and may be hydrogen or optionally contain up to two silicon, oxygen, sulfur or nitrogen atoms. 1-20 Hydrocarbon group, and preferably C 1-8 Hydrocarbon group; most preferably, one R 1 It is hydrogen, methyl, ethyl, n-propyl, or isopropyl, and the other R is... 1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl and phenyl;

[0248] R 2 and R 2 'Same or different from each other;'

[0249] R 2 It is a -CH2R group, where R is H or a straight-chain or branched C. 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl group, which optionally contains up to two silicon, oxygen, sulfur or nitrogen atoms;

[0250] R 2 'A C that optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms 1-20 Hydrocarbon group; preferably, R 2 and R 2 'Identical and either straight or branched C' 1-6 alkyl;

[0251] Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C1-6 Alkyl, C 7-20 Araneyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4 The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 The phenyl carbon linked to the group;

[0252] R 5 and R 6 Independently, a C that optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms 1-20 Hydrocarbon group, which may be -CH=, -CY=, -CH2-, -CHY- or -CY2- group, which is part of a cyclic structure of 4 to 7 atoms, including the carbon atoms at the 5 and 6 positions of the corresponding indenyl ligand;

[0253] R 5 'and R 6 'Independently, C contains at most two silicon, oxygen, sulfur, or nitrogen atoms' 1-20 Hydrocarbon group, or OY or NY2 group, where Y is C 1-10 hydrocarbon group;

[0254] R 7 C, optionally containing up to two silicon, oxygen, sulfur, or nitrogen atoms 1-20 Hydrocarbon group.

[0255] For the formula X defined above, the following represent preferred embodiments that can be used alone or in combination:

[0256] R 1 Preferably methyl;

[0257] X is preferably a halogen, more preferably Cl or a methyl group;

[0258] R 2 and R 2 'Preferred is C' 1-6 Alkyl, more preferably methyl;

[0259] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl;

[0260] Each R 5 R 5 '、R 6 and R 6 'Independently preferred C' 1-10Hydrocarbon group, OY group, where Y is C 1-6 Alkyl groups, or -CH=, -CY=, -CH2-, -CHY-, or -CY2- groups, which are part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand; and / or

[0261] R 7 C is preferred 6-20 Aryl.

[0262] More preferably, in this third embodiment, the metallocene is an asymmetric bridged bis-indene metallocene with a racemic inverse configuration, the structure of which is shown in Formula XI:

[0263]

[0264] Where Mt is Zr or Hf;

[0265] X may be the same as or different from each other, X is a halogen, and optionally contains at most two silicon, oxygen, sulfur or nitrogen atoms in a C group. 1-6 A hydrocarbon group, or an OY or NY2 group, wherein Y is a C group optionally containing at most two silicon atoms. 1-10 hydrocarbon group;

[0266] Two Rs on silicon 1 The functional groups may be the same or different from each other, and may be hydrogen or optionally contain up to two silicon, oxygen, sulfur or nitrogen atoms. 1-20 Hydrocarbon group, and preferably C 1-8 Hydrocarbon group; most preferably, one R 1 It is hydrogen, methyl, ethyl, n-propyl, or isopropyl, and the other R is... 1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl and phenyl;

[0267] R 2 and R 2 'Same or different from each other;'

[0268] R 2 It is a -CH2R group, where R is H or a straight-chain or branched C. 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl group, which optionally contains up to two silicon, oxygen, sulfur or nitrogen atoms;

[0269] R 2 'A C that optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms 1-20 Hydrocarbon group; preferably, R 2 and R 2 'Identical and either straight or branched C' 1-6 alkyl;

[0270] Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C 1-6 Alkyl, C 7-20 Araneyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4 The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 The phenyl carbon linked to the group;

[0271] R 5 and R 6 Independently, a C that optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms 1-20 Hydrocarbon group, which may be -CH=, -CY=, -CH2-, -CHY- or -CY2- group, which is part of a cyclic structure of 4 to 7 atoms, including the carbon atoms at the 5 and 6 positions of the corresponding indenyl ligand;

[0272] R 5 '、R 6 'For C 1-20 hydrocarbon group;

[0273] R 7 C, optionally containing at most two silicon, oxygen, sulfur, or nitrogen atoms 1-20 hydrocarbon groups; and

[0274] Y is C 1-10 Hydrocarbon group.

[0275] For formula XI as defined above, the following represent preferred embodiments that can be used alone or in combination:

[0276] R 1 Preferably methyl;

[0277] X is preferably a halogen, more preferably Cl or a methyl group;

[0278] R 2 and R 2 'Preferred is C' 1-6 Alkyl, more preferably methyl;

[0279] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl;

[0280] Each R5 and R 6 The preferred group is independently -CH=, -CY=, -CH2-, -CHY- or -CY2-, which is part of a cyclic structure of 4 to 7 atoms, including the carbon atoms at the 5 and 6 positions of the corresponding indenyl ligand;

[0281] R 6 'Preferred is C' 1-10 hydrocarbon group;

[0282] R 7 C is preferred 6-20 aryl; and / or

[0283] Y is C 1-6 Hydrocarbon group.

[0284] Even more preferably, in this third embodiment, the metallocene is an asymmetric bridged bis-indene metallocene with a racemic inverse configuration, the structure of which is shown in Formula XII:

[0285]

[0286] Where Mt is Zr or Hf;

[0287] X may be the same as or different from each other, X is a halogen, and optionally contains at most two silicon, oxygen, sulfur or nitrogen atoms in a C group. 1-6 A hydrocarbon group, or an OY or NY2 group, wherein Y is a C group optionally containing at most two silicon atoms. 1-10 hydrocarbon group;

[0288] Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C 1-6 Alkyl, C 7-20 Araneyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, optionally two adjacent R 3 Or R 4 The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 The phenyl carbon linked to the group;

[0289] R 5 '、R 6 'For C 1-20 hydrocarbon group;

[0290] Y is C 1-10 Hydrocarbon group and n is an integer between 3 and 4.

[0291] For formula XII as defined above, the following represent preferred embodiments that can be used alone or in combination:

[0292] X is preferably a halogen, more preferably Cl or a methyl group;

[0293] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl;

[0294] Y is C 1-6 Hydrocarbon group and n is 3;

[0295] R 6 'Preferred is C' 1-10 Hydrocarbon group; and / or

[0296] R 7 C is preferred 6-20 Aryl.

[0297] Most preferably, in this third embodiment, the metallocene is an asymmetric bridged bis-indene metallocene with a racemic inverse configuration, the structure of which is shown in Formula XIII:

[0298]

[0299] Where Mt is Zr or Hf;

[0300] X can be the same as or different from each other, X is a halogen, C 1-6 Hydrocarbon group, or OY or NY2 group, wherein Y is an optional C group containing at most 2 silicon atoms. 1-10 Hydrocarbon group; most preferably, X is chlorine or methyl;

[0301] Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C 1-6 Alkyl, C 7-20 Araneyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 Or R 4 The group can be part of a ring of 4 to 7 atoms, including those with R. 3 Or R 4 A phenyl carbon linked to a group.

[0302] For formula XIII as defined above, the following are preferred embodiments that can be used alone or in combination:

[0303] X is preferably a halogen, more preferably Cl or a methyl group; and / or

[0304] R 3 and R 4 Independently preferably H or straight-chain or branched-chain C 1-6 Alkyl, more preferably selected from the group consisting of H, tert-butyl and methyl.

[0305] In this implementation scheme, metallocene is preferred:

[0306] Racemic trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indeno-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindeno-1-yl]zirconium dichloride;

[0307] Racemic trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indenro-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindenro-1-yl]zirconium dichloride;

[0308] Racemic trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indeno-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindeno-1-yl]zirconium dichloride;

[0309] Racemic trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indeno-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindeno-1-yl]zirconium dichloride;

[0310] Racemic trans-dimethylsilanediyl[2-methyl-4,8-bis(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indeno-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylindeno-1-yl]zirconium dichloride;

[0311] And its dimethylzirconium and hafnium analogues.

[0312] To avoid any doubt, any narrow definition of substituents described above may be combined with any other broad or narrow definition of any other substituents.

[0313] Throughout the foregoing disclosure, when a narrower definition of a substituent is given, that narrower definition is considered to be disclosed together with all broader and narrower definitions of other substituents in this application.

[0314] co-catalyst

[0315] To form an active catalytic material, a co-catalyst well known in the art is typically required. Co-catalysts comprising one or more Group 13 metal compounds, such as organoaluminum, organoboron, or borate compounds used for activating metallocene catalysts, are suitable for this invention.

[0316] The catalyst system used in this invention may include (i) the complexes defined herein; and generally (ii) alkylaluminum compounds (or other suitable co-catalysts), or their reaction products. Therefore, the co-catalyst is preferably an aluminum oxane, such as methylaluminoxane (MAO).

[0317] Aluminoxane co-catalysts can be as shown in one of formulas (XX):

[0318]

[0319] Where n is typically between 6 and 20, and the meaning of R is as follows.

[0320] Aluminoxanes are formed, for example, by the partial hydrolysis of organoaluminum compounds, such as those shown in formula AlR3, where R can be, for example, H, C1-C10 alkyl, preferably C1-C5 alkyl, or C3-10-cycloalkyl, C7-C12-aralkyl or alkylaryl and / or phenyl or naphthyl. The resulting oxyaluminoxanes are usually not pure compounds, but mixtures of oligomers as shown in formula (XX).

[0321] The preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxane used as a cocatalyst in this invention is not a pure compound due to its preparation method, the molar concentration of the aluminoxane solution mentioned below is based on its aluminum content.

[0322] According to the present invention, a boron-containing co-catalyst can also be used instead of an aluminum oxane co-catalyst, or it can be used in combination with an aluminum oxane co-catalyst.

[0323] Those skilled in the art will understand that when using a boron-based cocatalyst in the absence of an aluminoxane, the complex complex is typically pre-alkylated by reacting it with an alkylaluminum compound, such as TIBA. This method is well known, and any suitable alkylaluminum, such as Al(C) 1-6 Alkyl groups (-alkyl)3 can all be used. Preferred alkylaluminum compounds are triethylaluminum, triisobutylaluminum, triisohexylaluminum, tri-n-octylaluminum, and triisooctylaluminum.

[0324] Alternatively, when using a borate cocatalyst in the absence of aluminoxane, the metallocene catalyst complex is its alkylated form, i.e., for example, a dimethyl or dibenzyl metallocene catalyst complex can be used.

[0325] The boron-based cocatalysts used include the cocatalyst shown in formula (Z).

[0326] BY3(Z)

[0327] Wherein Y may be the same or different, and may be a hydrogen atom, an alkyl group containing 1 to about 20 carbon atoms, an aryl group containing 6 to about 15 carbon atoms, an alkylaryl group, an aralkyl group, a haloalkyl group, or a haloaryl group (each alkyl group containing 1 to 10 carbon atoms, each aryl group containing 6 to 20 carbon atoms), or fluorine, chlorine, bromine, or iodine. Preferably, Y is a haloaryl group, such as p-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl, and 3,5-di(trifluoromethyl)phenyl. More preferably, it may be trifluoroborane, tri(4-fluorophenyl)borane, tri(3,5-difluorophenyl)borane, tri(4-fluoromethylphenyl)borane, tri(2,4,6-trifluorophenyl)borane, tri(pentafluorophenyl)borane, tri(3,5-difluorophenyl)borane, and / or tri(3,4,5-trifluorophenyl)borane.

[0328] Tris(pentafluorophenyl)borane is particularly preferred.

[0329] However, borates, i.e., compounds containing both borate anions and acidic cations, are preferred. Such ionic cocatalysts preferably contain noncoordinate anions, such as tetra(pentafluorophenyl)borate. Suitable cations are protonated amines or aniline derivatives, such as methylammonium, aniline, dimethylammonium, diethylammonium, N-methylaniline, diphenylammonium, N,N-dimethylaniline, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridine, p-bromo-N,N-dimethylaniline, or p-nitro-N,N-dimethylaniline.

[0330] According to the present invention, the ionic compound preferably comprises:

[0331] Tributylammonium tetra(pentafluorophenyl)borate;

[0332] Tributylammonium tetra(trifluoromethylphenyl)borate;

[0333] Tributylammonium tetra(4-fluorophenyl)borate;

[0334] N,N-Dimethylcyclohexylammonium tetra(pentafluorophenyl)borate;

[0335] N,N-Dimethylbenzylammonium tetra(pentafluorophenyl)borate;

[0336] N,N-Dimethylphenylammonium tetra(pentafluorophenyl)borate;

[0337] N,N-Di(propyl)ammonium tetra(pentafluorophenyl)borate;

[0338] Di(cyclohexyl)ammonium tetra(pentafluorophenyl)borate;

[0339] Triphenylcarbatotetra(pentafluorophenyl)borate; and

[0340] Ferrocene tetra(pentafluorophenyl)borate.

[0341] Triphenylcarbazo(pentafluorophenyl)borate is preferred.

[0342] N,N-Dimethylphenylammonium tetra(pentafluorophenyl)borate;

[0343] N,N-Dimethylcyclohexylammonium tetra(pentafluorophenyl)borate; and

[0344] N,N-Dimethylbenzylammonium tetra(pentafluorophenyl)borate.

[0345] In particular, triphenylcarbazo(pentafluorophenyl)borate and N,N-dimethylphenylaminetetra(pentafluorophenyl)borate are preferred.

[0346] Therefore, Ph3CB(PhF5)4 and similar compounds are particularly preferred.

[0347] According to the present invention, the cocatalyst is preferably an aluminum oxane, more preferably a combination of methylaluminoxane and a borate cocatalyst (e.g., N,N-dimethylammonium tetrapentafluorophenylborate and Ph3CB(PhF5)4). A combination of methylaluminoxane and tributyl borate is particularly preferred.

[0348] The appropriate amount of catalyst is known to those skilled in the art.

[0349] The molar ratio of boron to metal ions in the metallocene can be between 0.1:1 and 10:1 mol / mol, preferably between 0.3:1 and 7:1, and especially between 0.3:1 and 5:1 mol / mol.

[0350] The molar ratio of aluminum to metal ions in aluminoxane can be between 1:1 and 2000:1 mol / mol, preferably between 10:1 and 1000:1, and more preferably between 50:1 and 500:1 mol / mol.

[0351] The metallocene catalyst may contain 10 to 100 μmol of metallocene metal ions per gram of silicon dioxide, and 5 to 10 mmol of aluminum per gram of silicon dioxide.

[0352] Catalyst preparation

[0353] Metallocene catalysts can be used in supported or unsupported forms. The particulate support material used is preferably an organic or inorganic material, such as silica, alumina, or zirconium oxide, or a mixed oxide, such as silica-alumina, particularly silica, alumina, or silica-alumina. Silica support is preferred. Those skilled in the art understand the procedures required for supporting metallocene catalysts.

[0354] Particularly preferred is that the support is a porous material, allowing the complex to be loaded into the pores of the support, for example using methods similar to those described in WO94 / 14856 (Mobil), WO95 / 12622 (Borealis), and WO2006 / 097497. The particle size is not critical, but is preferably between 5 and 200 μm, more preferably between 20 and 80 μm. The use of such supports is conventional in the art. Particularly preferred is the procedure for preparing such supported catalysts as described in WO 2020 / 239598 and WO2020 / 239603.

[0355] In another embodiment, no external support is used, but the catalyst still exists in the form of solid particles. Therefore, no external support material, such as an inert organic or inorganic support, such as silica as described above, is used. Such catalysts can be prepared as described in WO 2003 / 051934, WO 2014 / 060540, and WO 2019 / 179959.

[0356] non-crystalline ethylene-propylene copolymer

[0357] The amorphous ethylene-propylene copolymer of the present invention is a copolymer comprising ethylene and propylene. The ethylene-propylene copolymer is soluble in 1,2,4-trichlorobenzene (TCB) and xylene at 23°C. The solubility of the ethylene-propylene copolymer in TCB and xylene can be determined as discussed in "Measurement Methods - Determination of the Soluble Component of Xylene".

[0358] Ethylene-propylene copolymers may contain comonomers other than ethylene and propylene, such as C... 4-20 Olefins, such as 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc. Therefore, in one embodiment, the EPR component can be an ethylene-propylene-α-olefin terpolymer, such as a propylene-ethylene-1-butene copolymer. However, it is preferable that no other comonomers are present.

[0359] In terms of molecular weight distribution and / or comonomer distribution, ethylene-propylene copolymers can be unimodal or multimodal (e.g., bimodal).

[0360] In one embodiment, the copolymer is unimodal. More specifically, the copolymer is preferably unimodal in terms of molecular weight distribution and / or comonomer distribution.

[0361] The ethylene-propylene copolymer is preferably an isotactic copolymer.

[0362] The ethylene content of the ethylene-propylene copolymer is preferably at least 15 wt%, more preferably at least 20 wt%, and even more preferably at least 21 wt%, for example at least 22 wt%, for example at least 24 wt%, relative to the total weight of the copolymer. Therefore, a suitable range for the ethylene content in the copolymer is 20 to 80 wt%, for example 22 to 75 wt%, relative to the total weight of the copolymer.

[0363] When measured at 135°C in decalin (DHN) according to DIN EN ISO 1628-1 and -3, the intrinsic viscosity (iV) of the ethylene-propylene copolymer is at least 3.5 dl / g, preferably at least 4.0 dl / g, and more preferably at least 4.5 dl / g. A suitable range for the intrinsic viscosity (iV) of the copolymer, when measured according to DIN EN ISO 1628-1 and -3, is 3.5 to 8.0 dl / g, preferably 4.0 to 7.5 dl / g, and more preferably 4.5 to 7.0 dl / g.

[0364] The weight-average molecular weight (Mw) of the ethylene-propylene copolymer is preferably at least 300,000 Da, more preferably at least 350,000 Da, and even more preferably at least 400,000 Da, as discussed in “Measurement Methods - GPC Analysis”.

[0365] The unique feature of the ethylene-propylene copolymer of the present invention is that it has an intrinsic viscosity (iV) of at least 3.5 dl / g and each ethylene-propylene copolymer chain contains at least 4 long branches (LCBs).

[0366] The number of LCBs in each copolymer chain can be determined as discussed in "Measurement Methods—Branch Calculation". Preferably, each copolymer chain of the ethylene-propylene copolymer contains at least 5 LCBs, and even more preferably, each copolymer chain contains at least 6 LCBs. In one aspect of the invention, each copolymer chain of the ethylene-propylene copolymer contains at least 8 LCBs, and even more preferably, each copolymer chain contains at least 9 LCBs, for example 5 to 30, preferably 6 to 25, more preferably 8 to 20, and even more preferably 9 to 15.

[0367] In a preferred aspect of the invention, the ethylene-propylene copolymer has a weight-average molecular weight (Mw) of at least 350,000 Da, preferably at least 400,000 Da, and an intrinsic viscosity (iV) of at least 4.0 dl / g, preferably at least 4.5, more preferably from 4.0 dl / g to 7.5 dl / g, and each copolymer chain contains at least 5 LCBs.

[0368] LCBs are typically composed of ethylene and propylene, and do not contain a crystallizable propylene sequence. This can be achieved through methods known in the art. 13 The determination was performed using C-NMR and DSC experiments.

[0369] Ethylene-propylene copolymers can be prepared by any suitable method. However, preferably, the ethylene-propylene copolymer is prepared in at least one gas-phase reactor at an operating pressure of at least 26 bar, particularly as discussed in the context of the method of the present invention.

[0370] heterogeneous polypropylene resin

[0371] The heterogeneous polypropylene resin (HECO) of the present invention comprises a crystalline or semi-crystalline propylene homopolymer or random propylene copolymer component, which is a polypropylene matrix phase (A), wherein an amorphous propylene-ethylene copolymer (B) (rubber phase, such as EPR) is dispersed therein.

[0372] Therefore, the polypropylene matrix phase (A) contains (finely) dispersed inclusions that are not part of the matrix, and the inclusions include amorphous copolymers (B).

[0373] In this invention, the term "heterogeneous polypropylene resin" refers to a copolymer composed of a matrix resin (polypropylene homopolymer or propylene copolymer) and a major non-crystalline copolymer (B) dispersed in the matrix resin, as defined below.

[0374] In this invention, the term "matrix" should be interpreted in its commonly accepted meaning, referring to a continuous phase (in this invention, a continuous polymer phase) in which isolated or discrete particles, such as rubber particles, may be dispersed. The presence of the propylene polymer results in it forming a continuous phase that can serve as the matrix.

[0375] The resin of the present invention preferably comprises an isotactic propylene matrix component (A). Component (A) may consist of a single propylene polymer, but (A) may also comprise a mixture of different propylene polymers. The same applies to component (B): it may consist of a single polymer, but may also comprise a mixture of different EPRs.

[0376] Therefore, in the preferred embodiment, the resin is essentially composed of components (A) and (B). The phrase "essentially composed of..." as used in this invention indicates the absence of other polyolefin components. It should be understood that the polymer contains additives, and these additives may be present.

[0377] The heterogeneous polypropylene resin of the present invention is typically prepared by sequential polymerization. Preferably, a polypropylene matrix phase (A) is prepared in at least one step, and an amorphous propylene-ethylene copolymer (B) is prepared in at least one subsequent step in the presence of the polypropylene matrix phase (A).

[0378] Several methods are known for characterizing the matrix phase and non-crystalline phase of heterogeneous acrylic resins.

[0379] 1,2,4-Trichlorobenzene (TCB) can be used as a solvent to separate the crystalline and soluble fractions using the CRYSTEX method. This method will be described in the Measurement Methods section below. In this method, the crystalline fraction (CF) and the soluble fraction (SF) are separated from each other. The crystalline fraction (CF) primarily corresponds to the matrix phase and contains only a small fraction of the amorphous phase, while the soluble fraction (SF) primarily corresponds to the amorphous phase and contains only a negligible (e.g., less than 0.5 wt%) fraction of the matrix phase. Therefore, in this invention, the term "crystalline fraction (CF)" refers to component (A), and "soluble fraction (SF)" refers to component (B).

[0380] The polypropylene matrix phase (A) is required to be at least partially crystalline, thereby ensuring that the resin as a whole includes both crystalline and non-crystalline phases.

[0381] Preferably, the melting point (Tm) of the heterogeneous polypropylene resin is 100°C to 165°C, more preferably 110°C to 165°C, and particularly 120°C to 165°C.

[0382] Preferably, the MFR2 (melt flow rate measured according to ISO 1133 at 230°C and 2.16 kg load) of the heterogeneous polypropylene resin is 0.1 to 200 g / 10 min, more preferably 1.0 to 100 g / 10 min, for example 2.0 to 50 g / 10 min.

[0383] Preferably, the Mw / Mn ratio of the heterogeneous polypropylene resin is 2.0 to 5.0, for example, 2.5 to 4.5.

[0384] Preferably, the heterogeneous polypropylene resin of the present invention contains at least 40 wt% of component (A), for example 45 to 90 wt%, more preferably 50 wt% to 85 wt%, relative to the total weight of the heterogeneous polypropylene resin.

[0385] In other words, ideally, at least 40 wt% of crystalline portion, for example 45 to 90 wt%, more preferably 50 wt% to 85 wt%, should be present in the heterogeneous polypropylene resin of the present invention relative to the total weight of the heterogeneous polypropylene resin.

[0386] Preferably, there is at least 10 wt% of EPR(B) and less than 60 wt% of component (B). The amount of component (B) relative to the total weight of the heterogeneous polypropylene resin is preferably between 10 and 55 wt%, most preferably between 15 and 50 wt%.

[0387] In other words, relative to the total weight of the heterogeneous polypropylene resin, the soluble fraction (SF) of the heterogeneous resin of the present invention is preferably 10 to less than 60 wt%, for example 10 to 55 wt%, ideally 15 to 50 wt%.

[0388] It should be understood that the amount of the soluble portion should be substantially the same as the amount of component (B), since component (A) should contain almost no soluble components. On the other hand, component (B) is completely soluble.

[0389] Another preferred feature of the present invention is that the intrinsic viscosity (iV) of the SF resin is greater than that of the CF resin. Intrinsic viscosity (iV) is a measure of molecular weight, therefore the Mw (weight-average molecular weight) of the SF resin can be considered higher than that of the CF resin.

[0390] The overall iV of the polymer can be from 0.9 to 7.0 dl / g, preferably between 1.0 and 6.0 dl / g.

[0391] Polypropylene matrix phase (A):

[0392] The polypropylene matrix phase (A) of the heterogeneous polypropylene resin is at least partially crystalline. Therefore, the matrix can be a crystalline or semi-crystalline propylene homopolymer or random propylene copolymer component, or a combination thereof. The term "semi-crystalline" means that the copolymer has a defined melting point and a heat of fusion greater than 50 J / g when analyzed as a pure component by DSC. Preferably, the matrix phase is at least partially crystalline, thereby ensuring that the polymer as a whole comprises both crystalline and amorphous phases.

[0393] In one embodiment, the polypropylene matrix phase (A) comprises, preferably, a propylene homopolymer as described below. As used in this invention, "homogeneous polymer" refers to polypropylene composed essentially of propylene units. In a preferred embodiment, only propylene units are detectable in the propylene homopolymer.

[0394] The propylene homopolymer is isotactic polypropylene, with an isotactic pentagonal content of more than 90%, more preferably more than 95%, and even more preferably more than 98%. The propylene homopolymer contains between 0.01% and 1.5% of regional defects (2,1-insertion units), more preferably between 0.01% and 1.0%.

[0395] Polypropylene homopolymers may contain a single polypropylene homopolymer moiety (= unimodal) or be composed of a single polypropylene homopolymer moiety (= unimodal), but may also contain a mixture of different polypropylene homopolymer moieties.

[0396] When a polypropylene homopolymer contains different fractions, it is understood to be bimodal or multimodal. These fractions may have different average molecular weights or different molecular weight distributions.

[0397] In terms of molecular weight or molecular weight distribution, polypropylene homopolymers are preferably bimodal or multimodal.

[0398] Alternatively, in terms of average molecular weight and / or molecular weight distribution, polypropylene homopolymers may preferably be unimodal.

[0399] Therefore, in one embodiment of the invention, the polypropylene matrix phase (A) is unimodal, while in another embodiment, the polypropylene matrix phase (A) is bimodal and consists of two propylene homopolymer portions (hPP-1) and (hPP-2).

[0400] In another embodiment, the polypropylene matrix phase (A) may be a random propylene copolymer, such as a propylene-ethylene random copolymer or a propylene-butene random copolymer or a combination thereof.

[0401] When ethylene comonomers are present in the polypropylene matrix phase (insoluble portion) component, their content can be as high as 5 mol% or 3.4 wt% relative to the total polypropylene matrix phase. When butene comonomers are present, their content can be as high as 5 mol% or 6.6 wt% relative to the total polypropylene matrix phase, provided that their combined content is at most 5 mol% relative to the total polypropylene matrix phase. Even more preferably, the ethylene content in the polypropylene matrix phase is less than 2 wt% relative to the total weight of the polypropylene matrix phase. Therefore, preferably, the ethylene content of the insoluble portion of the polymer of the present invention is 2 wt% or less, ideally 1.5 wt% or less, relative to the total weight of the polypropylene matrix phase (total weight of the insoluble portion). Even more preferably, the ethylene content of the insoluble portion is less than 1 wt% (C2(IF) < 1 wt%) relative to the total weight of the polypropylene matrix phase (total weight of the insoluble portion).

[0402] In another embodiment, the polypropylene matrix phase (A) is bimodal and consists of a homopolymer portion and a copolymer portion.

[0403] Preferably, the melting point (Tm) of the polypropylene matrix phase is 100 to 165°C, more preferably 110 to 165°C, and particularly 120 to 165°C.

[0404] The MFR2 of the polypropylene matrix phase (A) can be between 0.1 and 200 g / 10 min, for example 1 to 150 g / 10 min, preferably 2 to 100 g / 10 min.

[0405] The intrinsic viscosity (iV) of the polypropylene matrix phase (A) is ideally between 1 and 4 dl / g.

[0406] Rubber component (B)

[0407] The second component of the heterogeneous polypropylene resin is the rubber component (B), which is an ethylene-propylene copolymer phase, a non-crystalline copolymer of propylene and ethylene. Therefore, the second component is a non-crystalline copolymer dispersed in the polypropylene matrix phase (A).

[0408] As stated above, the terms "soluble portion", "non-crystalline (propylene-ethylene) copolymer", "dispersed phase" and "rubber phase" have the same meaning and are interchangeable in this invention.

[0409] The definition of the rubber phase of component (B) constituting the heterogeneous polypropylene resin of the present invention is as described in the above-described amorphous propylene-ethylene copolymer of the present invention.

[0410] application

[0411] The heterogeneous polypropylene resin of this invention can be used to manufacture articles such as flexible tubes / pipes, profiles, pads, cable insulation, sheets, or films. These articles can be used in the medical and general packaging fields, but also in technical applications such as power cables or geomembranes. Alternatively, the heterogeneous polypropylene resin can be used to modify the impact resistance of injection-molded compositions of articles, for example, for technical applications in the automotive field.

[0412] For impact modification, the heterogeneous polypropylene resin of the present invention can be blended with other polymers. Therefore, the present invention also relates to polymer blends comprising the amorphous ethylene-propylene copolymer or heterogeneous polypropylene resin of the present invention, particularly blends of any of them with other propylene polymers. The amorphous ethylene-propylene copolymer of the present invention may comprise 5 to 50 wt%, for example 10 to 40 wt%, particularly 15 to 30 wt%, relative to the total weight of the blend. Similarly, the heterogeneous polypropylene resin of the present invention may comprise 5 to 50 wt%, for example 10 to 40 wt%, particularly 15 to 30 wt%, relative to the total weight of the blend.

[0413] Heterogeneous polypropylene resins can be blended with polypropylenes having a high MFR2, for example, at a rate of at least 10 g / 10 min. In particular, it can be blended with polypropylenes used in automotive parts. This polypropylene can be a homopolymer. Preferably, it is not another amorphous polymer, like another EPR.

[0414] The polymers and resins of this invention can be used to manufacture a variety of final products, such as films (cast, blown, or BOPP films), molded products (e.g., injection molded, blow-molded, rotationally molded products), extruded coatings, etc. Preferably, products containing the films of this invention are used for packaging. Related packaging includes heavy-duty sacks, sanitary films, laminated films, and flexible packaging films.

[0415] The present invention will now be described with reference to the following non-limiting embodiments.

[0416] Example

[0417] Measurement methods

[0418] Determination of Al, B, and Zr (ICP method)

[0419] In a glove box, an equal volume of catalyst (approximately 40 mg) was weighed into a glass weighing dish using an analytical balance. The sample was then placed in a steel secondary container equipped with an air inlet and exposed to air overnight. The contents of the weighing dish were then rinsed into a 20 mL Xpress microwave oven container using 5 mL of concentrated nitric acid (65%). The sample was then microwave-assisted digested at 150 °C for 35 minutes using a MARS 6 laboratory microwave apparatus. The digested sample was cooled for at least 4 hours and then transferred to a 100 mL glass volumetric flask. A standard solution containing 1000 mg / L LY and 0.4 mL of Rh was added. The flask was then filled with distilled water and thoroughly mixed. The solution was filtered through a 0.45 μm nylon syringe filter and then analyzed using a Thermo iCAP6300 ICP-OES system and iTEVA software.

[0420] The instrument was calibrated using a blank (5% HNO3 solution) and six standards at concentrations of 0.005 mg / L, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L, prepared by dissolving Al, B, Hf, Mg, Ti, and Zr in a 5% HNO3 distilled aqueous solution. However, not every calibration point was used for every wavelength. Each calibration solution contained 4 mg / L of Y and Rh standards. Al at 394.401 nm was calibrated using the following calibration points: blank, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L. Al 167.079 nm was calibrated to Al 394.401 nm and Zr 339.198 nm excluding 100 mg / L using blank, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L, and 100 mg / L standards. Calibration curves were obtained using curve fitting and 1 / concentration weighting.

[0421] Immediately prior to analysis, calibration (instrument slope function) was validated and adjusted using blanks and 10 mg / L Al, B, Hf, Mg, Ti, and Zr standards containing 4 mg / L Y and Rh. Quality control samples (QC: 1 mg / L Al, Au, Be, Hg, and Se; 2 mg / L Hf and Zr; 2.5 mg / L As, B, Cd, Co, Cr, Mo, Ni, P, Sb, Sn, and V; 4 mg / L Rh and Y; 5 mg / L Ca, K, Mg, Mn, Na, and Ti; 10 mg / L Cu, Pb, and Zn; 25 mg / L Fe and 37.5 mg / L Ca in 5% HNO3 distilled aqueous solution) were used to confirm the slopes for Al, B, Hf, Mg, Ti, and Zr. QC samples were also run at the end of the predetermined analytical set.

[0422] Zr content was monitored using the Zr 339.198 nm {99} line. When the Al concentration in the test section was below 2 wt%, the Al content was monitored using the 167.079 nm {502} line; when the Al concentration was above 2 wt%, the Al content was monitored using the 394.401 nm {85} line. Y 371.030 nm {91} was used as an internal standard for Zr 339.198 nm and Al 394.401 nm, and Y 224.306 nm {450} was used as an internal standard for Al 167.079 nm. B content was monitored using the B 249 nm line.

[0423] The reported values ​​were back-calculated to the original catalyst sample using the original mass and dilution volume of the catalyst aliquots.

[0424] DSC analysis

[0425] Melting point (T) m ) and crystallization temperature (T) c The determination was performed on a DSC200 TA instrument. The method involved placing 5-7 mg of polymer sample into a sealed DSC aluminum dish, heating the sample from -10°C to 210°C at a rate of 10°C / min, holding it at 210°C for 5 minutes, cooling it from 210°C to -10°C, holding it at -10°C for 5 minutes, and then heating it back to 210°C at a rate of 10°C / min. The reported T... m T represents the maximum value of the second heating scan curve. c This represents the maximum value of the cooling scan curve.

[0426] melt flow rate

[0427] Melt flow rate (MFR) was determined according to ISO 1133 and expressed in g / 10 min. MFR indicates the flowability of a polymer and therefore its processability. A higher melt flow rate generally indicates a lower polymer viscosity. MFR was measured at 230°C and a load of 2.16 kg (MFR²).

[0428] Quantifying microstructure using nuclear magnetic resonance spectroscopy

[0429] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the ethylene content and isotactic regularity of the copolymer.

[0430] Quantitative recordings were performed in solution using a Bruker Avance III 400 NMR spectrometer. 13 C{ 1 ¹H NMR spectroscopy was performed using the spectrometer at 400.15 MHz and 100.62 MHz, respectively. 1 H and 13 C. All spectra are used. 13 A C-optimized 10mm extended temperature probe was used for recording at 125°C, and nitrogen was used for all pneumatic devices. Approximately 200 mg of material was dissolved together with chromium acetylacetone (III)-d2 (TCE-d2) in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) to obtain a 65 mM relaxant solvent solution as described in G. Singh, A. Kothari, V. Gupta, Polymer Testing 2009, 28(5), 475.

[0431] To ensure solution homogeneity, the NMR tubes were further heated in a rotary furnace for at least 1 hour after initial sample preparation in the heating block. The tubes were rotated at 10 Hz after the magnet was inserted. This setup was chosen primarily for its high resolution and quantitative capability required for accurate ethylene content determination. Standard single-pulse excitation was used without NOE, employing an optimized tip angle, a 1-second cycle delay, and a two-stage WALTZ16 decoupling scheme, as described in Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, J. Mag. Reson. 187 (2007) 225 and V. Busico, P. Carbonniere, R. Cipullo, C. Pellecchia, J. Severn, G. Talarico, Macromol. Rapid Commun. 2007, 28, 1128. A total of 6144 (6 k) transients were acquired for each spectrum.

[0432] Quantitative 13 C{ 1 The ¹H NMR spectra were processed, integrated, and the relevant quantitative characteristics were determined based on the integration. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This method allows for comparable references even if such a structural unit is not present.

[0433] Characteristic signals corresponding to the observed 2,1 Erythro type defects (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100(4), 1253, in Cheng, HN, Macromolecules 1984, 17, 1950, and WJ. Wang and S. Zhu, Macromolecules 2000, 33, 1157) require correction for the effect of regional defects on the performance of the measurements. No characteristic signals corresponding to other types of regional defects were observed.

[0434] Characteristic signals corresponding to ethylene incorporation were observed (as described in Cheng, HN, Macromolecules 1984, 17, 1950), and the comonomer fraction was calculated as the fraction of ethylene in the polymer relative to all monomers in the polymer:

[0435] fE = (E / (P+E))

[0436] The comonomer fraction was quantified using the method of W.J. Wang and S. Zhu, Macromolecules 2000, 33, 1157. 13 C{ 1 Multiple signals across the entire spectral region of the H spectrum are integrated. This method was chosen for its robustness and ability to account for regional defects when necessary. The integration region is slightly adjusted to increase applicability across the entire range of comonomer contents encountered.

[0437] The molar percentage of comonomer incorporation is calculated from the mole fraction:

[0438] E[mol%]=100*fE

[0439] The weight percentage of comonomer incorporation is calculated as a mole fraction:

[0440] E[wt%]=100*(fE*28.06) / ((fE*28.06)+((1-fE)*42.08))

[0441] The isotactic regularity of the copolymer was determined according to known methods, such as those described in Macromolecules 2005, vol.38, pp.3054-3059.

[0442] The isotactic regularity of the homopolymer matrix was determined by the following method:

[0443] Quantitative recordings were performed in solution using a Bruker Avance III 400 NMR spectrometer. 13 C{ 1 ¹H NMR spectroscopy was performed at 400.15 MHz and 100.62 MHz, respectively. 1 H and 13 C. All spectra are used. 13A C-optimized 10 mm selective excitation probe was used for recording at 125 °C, and nitrogen was used for all pneumatic devices. Approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d2 (TCE-d2). This setup was chosen primarily for the high resolution required for quantifying stereoregularity distribution (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 30 (1997) 6251). Standard single-pulse excitation was performed using a NOE and a two-stage WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 8192 (8k) transients were acquired for each spectrum. Quantitative analysis was performed... 13 C{ 1 The ¹H NMR spectra were processed and integrated, and the relevant quantitative characteristics were determined based on the integration using a proprietary computer program. All chemical shifts were internally referenced to the methyl signal at 21.85 ppm for the isosteretic pentagonal group mmmm.

[0444] Stereotactic regularity was quantified by integrating methyl regions between 23.6 and 19.7 ppm, with corrections made for any sites unrelated to the stereo sequence of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 30 (1997) 6251). Isosteretic regularity of the pentatonic units was determined by direct integration of the methyl regions and reported as the mole fraction or percentage of the isotactic pentatonic unit mmmm relative to all stereo pentatonic units, i.e., [mmmm] = mmmm / the sum of all stereo pentatonic units. This was corrected for the presence of sites not directly related to the stereo pentatonic unit when appropriate integration was performed.

[0445] Characteristic signals corresponding to regional irregular propylene insertions were observed (Resconi, L., Cavallo, L., Fait, A., Pietmontesi, F., Chem. Rev. 2000, 100, 1253). The presence of two methyl signals at 17.7 and 17.2 ppm indicated secondary propylene insertions in the form of 2,1-erythroid regional defects, which was confirmed by the presence of other characteristic signals. The amount of 2,1-erythroid regional defects was quantified using the average integral (e) of the e6 and e8 sites observed at 17.7 and 17.2 ppm, respectively, i.e., e = 0.5*(e6 + e8). No characteristic signals corresponding to other types of regional irregularities were observed. The amount of major propylene insertion (p) was quantified based on the integral of all signals from 23.6 to 19.7 ppm in the methyl region (CH3), noting the inclusion of other substances unrelated to the major insertion in the integral, as well as the major insertion signal excluded from this region, such that p = CH3 + 2*e. The relative content of specific types of regional defects is reported as the mole fraction or percentage of regional defects relative to all observed forms of propylene insertion, i.e., the sum of all primary (1,2), secondary (2,1), and tertiary (3,1) propylene insertion units, for example, [21e] = e / (p + e + t + i). The total amount of secondary propylene insertions present as 2,1-erythro or 2,1-threo-regional defects is quantified as the sum of all the aforementioned regional irregular units, i.e.,

[21] = [21e] + [21t].

[0446] Determination of xylene soluble fraction (XS)

[0447] The xylene-soluble fraction (XS) defined and described in this invention was determined according to ISO 16152 as follows: 2.5 ± 0.1 g of polymer was dissolved in 250 ml of o-xylene under reflux and continuous stirring in a nitrogen atmosphere. After 30 minutes, the solution was allowed to cool, first at ambient temperature for 15 minutes, and then maintained at a controlled temperature of 25 ± 0.5 °C for 30 minutes. The solution was filtered through filter paper. To determine the xylene-soluble content, an aliquot (100 ml) of the filtrate was taken. This aliquot was evaporated in a nitrogen stream, and the residue was dried under vacuum at 100 °C until constant weight was achieved.

[0448] The method for determining the soluble portion (by weight) of xylene is as follows:

[0449] XS%=(100 x m1 x v0) / (m0 x v1),

[0450] Where m0 represents the initial amount of polymer (grams), m1 represents the weight of the residue (grams), v0 represents the initial volume (milliliters), and v1 represents the volume of the analytical sample (milliliters).

[0451] To obtain the amorphous copolymer portion, further characterization was performed using GPC and NMR. The remaining xylene-soluble filtrate was precipitated with acetone. The precipitated polymer was filtered and dried to constant weight in a vacuum oven at 100°C.

[0452] Intrinsic viscosity

[0453] Intrinsic viscosity (iV) was measured according to DIN ISO 1628 / 1 (2009) and / 3 (2010) (at 135°C in decahydronaphthalene). The intrinsic viscosity (iV) value increases with increasing polymer molecular weight.

[0454] Crystex method

[0455] The crystalline and soluble fractions (CF and SF) of heterogeneous acrylic resins, along with the comonomer content and intrinsic viscosity of each fraction, were analyzed using the Crystex method. The crystalline and amorphous fractions were separated by temperature cycling in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160°C for dissolution, crystallization at 40°C, and redissolution at 160°C. Quantification of SF and CF, as well as determination of ethylene content (C2), were achieved using an infrared detector (IR4), and intrinsic viscosity (iV) was measured using an online dual-capillary viscometer.

[0456] The IR4 detector is a multi-wavelength detector that detects the IR absorbance in two different wavelength bands (CH3 and CH2) for determining the concentration and ethylene content of ethylene-propylene copolymers. The IR4 detector is calibrated using a range of EP copolymers with known ethylene contents ranging from 2 wt.% to 69 wt.% (via...). 13 (C-NMR determination).

[0457] The amounts of soluble fraction (SF) and crystalline fraction (CF) were determined by XS calibration, relating to the amount of xylene soluble (XS) and xylene insoluble (XI) fractions, according to the standard gravimetric analysis method of ISO 16152 (2005). XS calibration was achieved by testing various EP copolymers with XS contents between 2-31 wt%.

[0458] The intrinsic viscosity (iV) of the parent EP copolymer, as well as its soluble and crystalline portions, was determined using an online 2-capillary viscometer and correlated with the corresponding iV determined in decahydronaphthalene according to ISO 1628-3 (2010).

[0459] Calibration was performed using several commercially available EP / PP copolymers with iV values ​​ranging from 2 to 4 dL / g.

[0460] Weigh out the PP composition sample to be analyzed at a concentration of 10 mg / ml to 20 mg / ml. Automatically fill the vial with 1,2,4-TCB containing 250 mg / L of 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant. Dissolve the sample at 160°C until completely dissolved, typically for 60 minutes, while continuously stirring at 800 rpm.

[0461] A specific volume of sample solution is injected into a chromatographic column packed with an inert support. The sample crystallizes within the column, separating the soluble and crystalline fractions. This process is repeated twice. During the first injection, the entire sample is measured at high temperature to determine the iV [dl / g] and C2 [wt%] of the PP composition. During the second injection, the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) of the crystallization cycle are determined (wt% SF, wt% C2, iV).

[0462] GPC Analysis

[0463] The high-temperature GPC was equipped with a suitable concentration detector (such as an IR5 or IR4 manufactured by PolymerChar (Valencia, Spain)), an online four-capillary bridge viscometer (PL-BV 400-HT), and a dual light scattering detector with 5° and 90° angles (PL-LS15 / 90 light scattering detector). The stationary phase consisted of Agilent 3x Olexis and 1x Olexis guard columns, the mobile phase was 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg / L 2,6-di-tert-butyl-4-methylphenol), the temperature was 160 °C, and the constant flow rate was 1 mL / min. 200 μL of sample solution was injected for each analysis. All samples were prepared by dissolving 8.0–10.0 mg of polymer in 10 mL (160 °C) of stabilized TCB (same as the mobile phase) and gently shaking continuously at 160 °C for 2.5 hours. The injection concentration of the polymer solution at 160°C (c) 160℃ ) Determine using the following method.

[0464]

[0465] Where: w 25 (polymer weight) and V 25 (Volume of TCB at 25℃).

[0466] GPC Standards: Average molecular weight, molecular weight distribution, and polydispersity index (Mn, Mw, Mw / Mn)

[0467] GPC

[0468] For conventional GPC (GPC) convThe column assembly was calibrated using a universal calibration method (according to ISO 16014-2:2019) and 19 narrow MWD polystyrene (PS) standards ranging from 0.5 kg / mol to 11,500 kg / mol. PS standards were dissolved at 160 °C for 15 minutes or at room temperature, with a concentration of 0.2 mg / ml for molecular weights greater than or equal to 899 kg / mol and 1 mg / ml for molecular weights less than 899 kg / mol. The conversion from the peak molecular weight of polystyrene to the molecular weight of polyethylene can be achieved using Mark Houwink's equation and the following Mark Houwink constant:

[0469] K PS =19x10 -5 ml / g, α PS =0.655

[0470] K PP =39x10 -5 ml / g, α PE =0.725

[0471] K PE =19x10 -5 ml / g, α PE =0.725

[0472] Third-order polynomial fitting was used to fit the calibration data.

[0473] All samples were prepared at concentrations ranging from 0.5 to 1 mg / ml and dissolved by gentle shaking continuously at 160°C for 3 hours.

[0474] The average molecular weight (Mz, Mw, and Mn), molecular weight distribution (MWD), and its width, described by the polydispersity index, PD = Mw / Mn (where Mn is the number-average molecular weight and Mw is the weight-average molecular weight), are determined using the following formula:

[0475]

[0476]

[0477]

[0478]

[0479] For the average molecular weights Mz, Mw, and Mn, the molecular weight (MW) of polyolefins is determined by GPC. conv The values ​​of Mz(LS), Mw(LS), and Mn(LS) represent the average molecular weight determined by GPC. LS The conclusion was reached.

[0480] GPC-VISC-LS processing

[0481] For GPC light scattering method (GPC) LS The inter-detector delay volume was determined using a narrow PS standard with a molar mass of 130,000 g / mol (MWD = 1.01). The corresponding detector constants for the light scattering detector and the online viscometer were determined using the broad standard NIST1475A (Mw = 52,000 g / mol and iV = 1.01 dl / g). The corresponding dn / dc of the PE standard used in TCB was 0.094 cm⁻¹. 3 / g. Calculations were performed using Cirrus Multi-Offline SEC software version 3.2 (Agilent).

[0482] The molar mass of each eluted slice was calculated using a 15° light scattering angle. Data collection, processing, and calculations were performed using Cirrus Multi SEC software version 3.2. dn / dc was used to determine the molecular weight, and its value was 0.094.

[0483] The molecular weight of each slice was calculated in the low-angle manner described by C. Jackson and H. Gbarth. To correlate the elution volume with the molecular weight to calculate the MWD and the corresponding average molecular weight, a linear fit was performed using the molecular weight data for each slice and the corresponding retention volume.

[0484] The average molecular weight (Mz(LS), Mw(LS), and Mn(LS)), molecular weight distribution (MWD), and its width, described by polydispersity, PD(LS) = Mw(LS) / Mn(LS) (where Mn(LS) is the number-average molecular weight, and Mw(LS) is the weight-average molecular weight, obtained from GPC-LS), are calculated by gel permeation chromatography (GPC) using the following formula:

[0485]

[0486]

[0487]

[0488] For a constant elution volume interval ΔV i A i and M i(LS) The peak slice area and polyolefin molecular weight (MW) were determined by GPC-LS.

[0489] Branch calculation g'(85-100%cum)

[0490] The relative amount of branching is determined using the g' index of branched polymer samples. The long-chain branching (LCB) index is defined as g' = [η]. br / [η] lin It is well known that if the g' value increases, the branching content decreases. [η] is the intrinsic viscosity (iV) of a polymer sample of a certain molecular weight in TCB at 160°C, measured by an online viscometer and concentration detector, where [η]... lin This is the intrinsic viscosity (iV) of linear polymers with the same chemical composition. The intrinsic viscosity was measured using the Solomon-Gatesman equation, as described in the Cirrus Multi-Offline SEC Software version 3.2 manual. [η] for a specific molecular weight was obtained using Equation 1 and the corresponding Mark Houwink constant. lin :

[0491] [η]lin=K EPC *M α (Equation 1)

[0492] The constants K and α are specific to the polymer-solvent system, and M is the molecular weight obtained through LS analysis.

[0493] To account for the amount of propylene in the EP copolymer, [K] EPC It needs to be modified as follows:

[0494] K EPC = (1 - 1 / 3 mol. - % (propylene)) 1+α *K PE (Equation 2)

[0495] Where K PE =0.00039, α=0.725, and propylene content through 13 C-NMR determination.

[0496] [η] lin [η] is the intrinsic viscosity (iV) of the linear sample. br This refers to the viscosity of branched samples with the same molecular weight and chemical composition. The intrinsic viscosity [η] of the branched sample is calculated by... br Divide by the intrinsic viscosity (iV)[η] of a linear polymer with the same molecular weight. lin The viscosity branching factor g′ can be calculated.

[0497] In this case, g' (85-100) The calculation method is to calculate g′ in the cumulative score range of 85-100%. M * a M Add the products together, then divide by the concentration signal a. i The corresponding signal area.

[0498]

[0499] Calculation of linear reference lines and g' (85-100) See the calculation Figure 7 .

[0500] The LCB / 1000TC number of the high molecular weight fraction (85-100wt% of the cumulative weight fraction) is calculated using the formula 1000*M0*B / M z *N c Calculate, where B is the number of LCBs per chain, M0 is the molecular weight of the repeating unit, i.e., the propene group, -CH2-CH(CH3)-(42), for PP, M z It is the z-average molecular weight, and N c It is the number of C atoms in the repeating unit of the monomer (3 for polypropylene). The LCB / 1000TC and LCB values ​​per chain reported in this application always represent the LCB / 1000TC number of the high molecular weight fraction or the LCB number per chain (85-100 wt% of the cumulative weight fraction).

[0501] B is calculated using the Zimm-Stockmayer method, as shown in the following formula:

[0502]

[0503] In this context, LCB is assumed to be trifunctional (or Y-type) and multidispersed, and g is the branching index, defined as g = Rg(br) / Rg(lin), where Rg is the radius of gyration (Y.Yu, E.Schwerdtfeger, M.McDaniel, PolymerChemistry, 2012, 50, 1166-1179).

[0504] The branching index g can be derived from the viscosity branching index g', and the relationship is as follows:

[0505] g=g′ ∈

[0506] In this case, ε = 1.33

[0507] catalyst

[0508] synthesis

[0509] The ligands and metallocenes required to form the catalyst of this invention can be synthesized by any method, and skilled organic chemists can devise various synthetic schemes to produce the desired ligand materials. WO2007 / 116034 discloses the necessary chemical processes. Synthetic schemes can also be found in WO2002 / 02576, WO2011 / 135004, WO2012 / 084961, WO2012 / 001052, WO2011 / 076780, WO2015 / 158790, WO2018 / 122134, and WO2019 / 179959, with the scheme in WO2019 / 179959 being the most relevant to this invention.

[0510] Preparation of MAO-silica carrier

[0511] The steel reactor, equipped with a mechanical stirrer and filter, was flushed with nitrogen, and the reactor temperature was set to 20°C. Next, silica-grade DM-L-303 (purchased from AGC Si-Tech Co.) was added from the feed tank and pre-calcined at 600°C (5.0 kg), then carefully pressurized and depressurized with nitrogen using a manual valve. Toluene (22 kg) was then added. The mixture was stirred for 15 minutes. Next, a toluene solution (9.0 kg) of 30 wt% MAO (purchased from Lanxess) was added through the feed line at the top of the reactor over 70 minutes. The reaction mixture was then heated to 90°C and stirred at 90°C for another two hours. The slurry was allowed to settle, and the mother liquor was filtered off. The catalyst was washed twice with toluene (22 kg) at 90°C, followed by precipitation and filtration. The reactor was cooled to 60°C, and the solid was washed with heptane (22.2 kg). Finally, the solid was dried under a nitrogen stream at 60°C for 2 hours, then stirred under vacuum (-0.5 barg) for 5 hours. The collected SiO2 / MAO support was a free-flowing white powder containing 12.2% Al by weight.

[0512] Catalyst preparation (catalyst 1)

[0513] At 20°C, a 30 wt% MAO toluene solution (0.7 kg) was added via burette into a steel-made, nitrogen-sealed reactor. Then, toluene (5.4 kg) was added with stirring. Metallocene racemic trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indendro-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindendro-1-yl]zirconium dichloride (93 g) was added from a metal cylinder, followed by washing with 1 kg of toluene. The mixture was stirred at 20°C for 60 minutes. Then, tetra(pentafluorophenyl)borate tert-butyl ester (91 g) was added from a metal cylinder, followed by washing with 1 kg of toluene. The mixture was stirred at room temperature for 1 hour. Within 1 hour, the resulting solution was added to a stirred filter cake of MAO-silica support prepared as described above. The filter cake was left to stand for 12 hours, then dried under a nitrogen stream at 60°C for 2 hours, and stirred under vacuum (-0.5 barg) for 5 hours. ICP analysis showed that the resulting dried catalyst was a pink, free-flowing powder containing 13.6% Al and 0.105% Zr.

[0514] Preparation of catalysts (catalyst 2, catalyst 3)

[0515] Catalysts 2 and 3 were prepared as described for catalyst 1, by adjusting the amounts of metallocene and tert-butyl tetra(pentafluorophenyl)borate to obtain the compositions reported in Table 1.

[0516] The composition of the catalyst used in this embodiment is summarized below.

[0517] Table 1. Catalyst composition (from ICP).

[0518] catalyst Al Zr B Al / Zr MC in catalyst wt% wt% wt% Moore wt% Catalyst 1 13.6 0.105 0.0123 440 1.05 Catalyst 2 14.7 0.073 0.0087 680 0.73 Catalyst 3 15.4 0.066 0.0080 790 0.66

[0519] polymerization:

[0520] Step 1: Prepolymerization and bulk polymerization

[0521] 3950 g of propylene was packed into an autoclave containing 0.4 bar-g of propylene. Triethylaluminum (0.80 ml of a 0.62 mol / L heptane solution) 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 catalyst was injected as follows: The required amount of solid catalyst was loaded into a 5 ml stainless steel vial in the glove box, and then another 5 ml vial containing 4 ml of n-heptane pressurized with nitrogen at 7 bar was added on top. This dual-feed system was installed on one port of the autoclave lid. The required amount of hydrogen was added directly via a mass flow controller. Subsequently, the valve between the two vials was opened, and the solid catalyst was brought into contact with the heptane under nitrogen pressure for 2 seconds, and then 240 g of propylene was flushed into the reactor. The prepolymerization process lasted for 10 minutes. At the end of the prepolymerization step, the temperature was raised to 75 °C and maintained at a constant temperature throughout the polymerization process. The polymerization time was measured when the internal temperature of the reactor was 2 °C lower than the set polymerization temperature.

[0522] Step 2: Vapor-phase C3C2 copolymerization

[0523] After the bulk step is completed, the stirrer speed is reduced to 50 rpm, and the pressure is reduced to 0.3 bar-g by discharging the monomer. Then, triethylaluminum (0.80 ml, 0.62 mol / L heptane solution) is injected into the reactor along with an additional 250 g of propylene via a cylinder. The pressure is then reduced again to 0.4 bar-g by discharging the monomer. The stirrer speed is set to 180 rpm, and the reactor temperature is set to the target temperature. The target reactor pressure is then achieved by introducing a C3 / C2 gas mixture (see polymerization table), the composition of which is defined as follows:

[0524]

[0525] Wherein, C2 / C3 is the weight ratio of the two monomers, and R is the independently determined reactivity ratio or based on similar experimental hypotheses.

[0526] The temperature is kept constant by a thermostat, a C3 / C2 gas mixture corresponding to the target polymer composition is input by a mass flow controller, and the pressure is kept constant by a thermostat until the set time for this step ends.

[0527] The reactor was then cooled (to approximately 30°C), allowing volatile components to flash out. After purging the reactor three times with N2 and performing one vacuum / N2 cycle, the product was removed and dried overnight in a fume hood. Activation was performed by adding 0.5 wt% Irganox B225 (acetone solution) to 100 g of polymer, followed by overnight drying in a fume hood and then drying in a vacuum drying oven at 60°C for 2 hours.

[0528] polymer

[0529] Under the above conditions, using catalyst 1, catalyst 2 and catalyst 3, with the rubber component set at 25 wt%, the gas phase reactor temperature set at 70 °C, and the gas phase polymerization pressure range of 20 to 35 bar-g, three heterogeneous copolymers were prepared.

[0530] Similar experiments were conducted under the action of catalysts 1 and 3, with the rubber composition set to ~25wt% and the gas phase reactor temperature set to 90℃.

[0531] Other experiments were also conducted, setting the rubber component of catalyst 2 to 70 wt% and 80 wt%.

[0532] The results are listed in Tables 2 to 5.

[0533] Table 2: Polymerization conditions 1 / 2 (bulk propylene homopolymerization step at 75°C, 40 min)

[0534]

[0535] Table 3: Polymerization Conditions 2 / 2 (Gas Phase)

[0536]

[0537] Table 4: Polymer Characterization 1 / 2

[0538]

[0539] Table 5: Polymer Characterization 2 / 2

[0540]

[0541] Relationship between rubber molecular weight and GPR pressure

[0542] Figure 1 The intrinsic viscosity of the three catalysts as pressure increases is shown at 70 °C and approximately 25 wt% C2.

[0543] Figure 2 The intrinsic viscosity of catalysts 1 and 3 as pressure increases is shown under two conditions: temperature and approximately 25 wt% C2.

[0544] Figure 3 The intrinsic viscosity of catalysts 1 and 2 as pressure increases is shown at 90°C and three C2 content levels.

[0545] Relationship between C2 / C3 reactivity ratio and polymer composition with GPR pressure

[0546] Figure 4The relative ethylene / propylene reactivity ratios of the three catalysts are shown as increasing pressure at 70 °C and approximately 25 wt% C2.

[0547] Figure 5 The relative ethylene / propylene reactivity ratios of catalysts 1 and 3 are shown as increasing pressure under two temperatures and approximately 25 wt% C2.

[0548] Figure 6 The results show the relative ethylene / propylene reactivity ratio of catalysts 1 and 2 as pressure increases under three C2 contents and at 90°C.

[0549] As shown in Table 6, the rubber phase (soluble portion) of the heterogeneous copolymer of the present invention contains LCB.

[0550] Table 6. LCB

[0551]

Claims

1. A method for preparing heterogeneous polypropylene resin via a multi-stage polymerization process in the presence of a metallocene catalyst, the method comprising: (I) In the first polymerization step, propylene and optionally at least one C2-10 α-olefin comonomer are polymerized to obtain a polypropylene matrix phase (A); and subsequently (II) In the second polymerization step, in the presence of the metallocene catalyst and the polymer obtained in step (I), propylene, ethylene and optionally at least one C3-10 α-olefin comonomer are polymerized to obtain an ethylene-propylene copolymer phase (B) dispersed in the matrix phase (A). The ethylene-propylene copolymer phase (B) is an amorphous ethylene-propylene copolymer with an intrinsic viscosity (iV) of at least 3.5 dl / g measured in decahydronaphthalene at 135°C, and an ethylene content of at least 15 wt% of the total weight of the ethylene-propylene copolymer. Each copolymer chain contains at least 4 long branches (LCBs), which are measured by partial branching g' (85-100 cum) according to the measurement method. The metallocene catalyst comprises a metallocene complex represented by Formula I. Equation I Where Mt is Zr or Hf; Each X is a σ (sigma) ligand; E is a -CR chemically linked to two cyclopentadienyl ligands. 1 2-、-CR 1 2-CR 1 2-、-CR 1 2-SiR 1 2-, -SiR 1 2- or -SiR 1 2-SiR 1 2-group; the R 1 The groups may be the same or different, and may be hydrogen or optionally contain up to two C atoms of silicon, oxygen, sulfur, or nitrogen. 1-20 Hydrocarbon group, and optionally two Rs 1 The group is part of a C4-C8 ring. R 2 and R 2' They are the same or different from each other; R 2 It is a -CH2R group, where R is H or a straight-chain or branched C. 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl; R 2' C 1-20 hydrocarbon group; Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C 1-6 Alkyl, C 7-20 Aryl alkyl, C 7-20 Alkyl, C 6-20 Aryl and OY groups, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 or R 4 The group is part of a ring, including those with R 3 or R 4 The phenyl carbon linked to the group; Each R 5 R 5' R 6 and R 6' A C atom that is independently hydrogen or optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms. 1-20 Hydrocarbon group, or OY group, where Y is C 1-10 Hydrocarbon group, and is a -CH=, -CY=, -CH2-, -CHY- or -CY2- group, which is part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand; R 7 and R 7' They may be the same as or different from each other, and are H or OY groups or optionally contain up to two C atoms of silicon, oxygen, sulfur or nitrogen. 1-20 Hydrocarbon group, condition is when R 7 When =H, then R 5 R 6 all H, and when R 7' When =H, then R 5' R 6' all H, and another condition is that only if R 7 Unlike hydrogen, R 5 and R 6 Only when R is hydrogen, 7' Unlike hydrogen, R 5' and R 6' Only hydrogen; and Step (II) is carried out in at least one gas-phase reactor at an operating pressure of at least 35 bar.

2. A method for preparing heterogeneous polypropylene resin via a multi-stage polymerization process in the presence of a metallocene catalyst, the method comprising: (I) In the first polymerization step, propylene and optionally at least one C2-10 α-olefin comonomer are polymerized to obtain a polypropylene matrix phase (A); and subsequently (II) In the second polymerization step, in the presence of the metallocene catalyst and the polymer obtained in step (I), propylene, ethylene and optionally at least one C3-10 α-olefin comonomer are polymerized to obtain an ethylene-propylene copolymer phase (B) dispersed in the matrix phase (A). The ethylene-propylene copolymer phase (B) is an amorphous ethylene-propylene copolymer with an intrinsic viscosity (iV) of at least 3.5 dl / g measured in decahydronaphthalene at 135°C, and an ethylene content of at least 15 wt% of the total weight of the ethylene-propylene copolymer. Each copolymer chain contains at least 4 long branches (LCBs), which are measured by partial branching g' (85-100 cum) according to the measurement method. The structure of the metallocene complex is shown in Formula II: Formula II Where Mt is Zr or Hf; X may be the same as or different from each other, X is a halogen, hydrogen, or optionally a C containing at most two silicon, oxygen, sulfur, or nitrogen atoms. 1-20 A hydrocarbon group, or an OY or NY2 group, wherein Y is a C group optionally containing at most two silicon atoms. 1-10 hydrocarbon group; Two Rs on silicon 1 The groups may be the same or different from each other, and may be hydrogen or optionally contain up to two C atoms of silicon, oxygen, sulfur or nitrogen. 1-20 hydrocarbon group; R 2 and R 2' They are the same or different from each other; R 2 It is a -CH2R group, where R is H or a straight-chain or branched C. 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl group, which optionally contains up to two silicon, oxygen, sulfur or nitrogen atoms; R 2' C, optionally containing up to two silicon, oxygen, sulfur, or nitrogen atoms 1-20 hydrocarbon group; Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C 1-6 Alkyl, C 7-20 Araneyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 or R 4 The group is part of a ring of 4 to 7 atoms, including those related to the R group. 3 or R 4 The phenyl carbon linked to the group; Each R 5 R 5' R 6 and R 6' A C atom that is independently hydrogen or optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms. 1-20 Hydrocarbon group, or OY or NY2 group, where Y is C 1-10 A hydrocarbon group, and is a -CH=, -CY=, -CH2-, -CHY-, or -CY2- group, which is part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand; and R 7 and R 7' They may be the same as or different from each other, and are H or OY groups or optionally contain up to two C atoms of silicon, oxygen, sulfur or nitrogen. 1-20 Hydrocarbon group, condition is when R 7 When =H, then R 5 R 6 all H, and when R 7' When =H, then R 5' R 6' all H, and another condition is that only if R 7 Unlike hydrogen, R 5 and R 6 Only when R is hydrogen, and only when R is hydrogen. 7' Unlike hydrogen, R 5' and R 6’ Only hydrogen; Or Formula III Formula III Where Mt is Zr or Hf; X may be the same as or different from each other, and X is a halogen, hydrogen, or carbon. 1-6 Hydrocarbon group, or OY or NY2 group, wherein Y is a C group optionally containing one silicon atom. 1-6 hydrocarbon group; Two Rs on silicon 1 The groups may be the same or different from each other, and may be hydrogen or optionally contain up to two C atoms of silicon, oxygen, sulfur or nitrogen. 1-8 hydrocarbon group; R 2 and R 2' They may be the same or different, and are -CH2R groups, where R is H or a straight-chain or branched C. 1-6 Alkyl, C 3-8 cycloalkyl, C 6-10 Aryl; Each R 3 and R 4 Independently identical or different, and being hydrogen, straight-chain or branched C1-C6 alkyl, C 7-20 Aryl alkyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 or R 4 The group is part of a ring of 4 to 7 atoms, including those related to the R group. 3 or R 4 The phenyl carbon linked to the group; Each R 5 R 5' R 6 and R 6' A C atom that is independently hydrogen or optionally contains up to two silicon, oxygen, sulfur, or nitrogen atoms. 1-20 Hydrocarbon group, or OY group, where Y is C 1-10 Hydrocarbon group, and is a -CH=, -CY=, -CH2-, -CHY- or -CY2- group, which is part of a cyclic structure of 4 to 7 atoms, including carbon atoms at the 5 and 6 positions and / or the 5' and 6' positions of the corresponding indenyl ligand; R 7 The C group is an H or OY group or optionally contains up to two silicon, oxygen, sulfur or nitrogen atoms. 1-20 Hydrocarbon group, condition is when R 7 When =H, then R 5 R 6 all H, and another condition is that only if R 7 Unlike hydrogen, R 5 and R 6 Only hydrogen.

3. The method as described in claim 1 or 2, wherein, R 2 and R 2' The same and either straight or branched C 1-6 alkyl.

4. A method for preparing heterogeneous polypropylene resin via a multi-stage polymerization process in the presence of a metallocene catalyst, the method comprising: (I) In the first polymerization step, propylene and optionally at least one C2-10 α-olefin comonomer are polymerized to obtain a polypropylene matrix phase (A); and subsequently (II) In the second polymerization step, in the presence of the metallocene catalyst and the polymer obtained in step (I), propylene, ethylene and optionally at least one C3-10 α-olefin comonomer are polymerized to obtain an ethylene-propylene copolymer phase (B) dispersed in the matrix phase (A). The ethylene-propylene copolymer phase (B) is an amorphous ethylene-propylene copolymer with an intrinsic viscosity (iV) of at least 3.5 dl / g measured in decahydronaphthalene at 135°C, and an ethylene content of at least 15 wt% of the total weight of the ethylene-propylene copolymer. Each copolymer chain contains at least 4 long branches (LCBs), which are measured by partial branching g' (85-100 cum) according to the measurement method. The structure of the metallocene complex is shown in Formula XIII: Formula XIII Where M is Zr or Hf; X may be the same as or different from each other; X is a halogen; C 1-6 A hydrocarbon group, or an OY or NY2 group, wherein Y is a C group optionally containing at most two silicon atoms. 1-10 hydrocarbon group; Each R 3 and R 4 Independently identical or different, and of hydrogen, straight-chain or branched C 1-6 Alkyl, C 7-20 Araneyl, C 7-20 Alkyl, C 6-20 Aryl, OY or NY2 group, where Y is C 1-10 Hydrocarbon group, and optionally two adjacent R 3 or R 4 The group is part of a ring of 4 to 7 atoms, including those related to the R group. 3 or R 4 A phenyl carbon linked to a group.

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