Composite catalyst and preparation method of branched polyethylene

Abstract

The present invention provides a composite catalyst which comprises a specific metallocene catalyst, a specific imine-based catalyst, and a specific non-metallocene catalyst, and which achieves an excellent synergistic effect by combining the three specific catalysts. The invention also provides a preparation method for preparing branched polyethylene by using the composite catalyst, and ethylene is polymerized in the presence of the composite catalyst and a cocatalyst to obtain the branched polyethylene.

Description

Technical Field

[0001] The present invention relates to a composite catalyst, a preparation method of branched polyethylene using the composite catalyst, and application of the composite catalyst in the preparation of branched polyethylene. More specifically, the present invention relates to a composite catalyst comprising a specific α-diimine nickel catalyst, a specific metallocene catalyst, and a specific non-metallocene catalyst, a preparation method of branched polyethylene using the composite catalyst, and application of the composite catalyst in the preparation of branched polyethylene. Prior art

[0002] Polyolefin is the polymer material with the largest output and the widest application among synthetic resins. Polyolefin materials play an irreplaceable role in improving people's production and living standards and promoting the development of new technologies. Polyethylene materials are the largest variety of polyolefin materials. They are widely used due to their good mechanical properties, chemical stability, superior processing performance, reusability and low cost.

[0003] In addition to its advantages of high quality and low price, polyethylene also benefits from the continuous development of olefin polymerization catalysts. The unique physical and chemical properties of branched polyethylene make it valuable for application in many fields, such as replacing rubber, and can be used in inner tubes, soles, medical rubber plugs, lubricant modifiers, etc.; in the application of resin modification, it can be used as a toughening agent, modifier, etc.; due to its unique branched or hyperbranched structure, it can also realize its application value in the replacement of POE.

[0004] At present, the conventional method for preparing branched polyethylene is to use a late transition metal catalyst. In 1995, Professor Brookhart of North Carolina State University in the United States first reported that the (α-diimine) nickel catalyst 1 shown below with a "chain walking mechanism" can prepare high molecular weight, branched polyethylene. Subsequent researchers have synthesized catalysts with other structures (Catal. Sci. Technol. 2013, 3, 1172; Macromolecules 42, 2009, 7789; Angew. Chem. Int. Ed. 2004, 43, 1821; J. Am. Chem. Soc. 2013, 135, 16316; Organometallics 23, 2004, 3276-3283), such as the (α-diimine) nickel catalysts 2 to 7 shown below, and the thermal stability of this type of catalyst has been improved to a certain extent.

[0005]

[0006] On the other hand, the use of metallocene catalysts to prepare branched polyethylene has been ongoing. In 2005, Bianchini et al. used CoCl2 (N2BT) and a single titanocene composite catalyst to catalyze ethylene polymerization and obtained branched polyethylene with a high degree of branching (Macromol Rapid Commun, 2005, 26: 1218-1223), and the polymer morphology can change from crystalline to rubbery. However, the current problem with this type of catalysis is that the α-olefins generated by oligomerization have no specificity and it is not easy to accurately control the properties of polyethylene.

[0007] However, there are relatively few reports on the use of non-metallocene catalysts to manufacture branched polyethylene. In CN110016090A, a method for continuously preparing polyolefins, particularly continuously preparing polyolefin elastomers or their mixtures is provided, wherein a non-metallocene catalyst is used as a catalyst, but its purpose is to prepare a polyolefin elastomer or its mixture of multimodal distribution. In addition, in CN1887925A, the use of a class of non-metallocene polyolefin catalysts in catalyzing the copolymerization of ethylene and cyclic olefins is disclosed. The catalyst is a transition metal complex of the third family to the eleventh family of a class of novel tridentate ligands. Under the action of a low-dosage co-catalyst, the catalyst can be highly active in the copolymerization of catalyzing ethylene and cyclic olefins such as cyclopentene and norbornene, with a narrow molecular weight distribution. However, the insertion rate of cyclic olefins in the copolymer can only reach 50mol% at most, and its tensile stress and elongation at break are all insufficient. Therefore, the resulting copolymer still has a lot of room for improvement in aspects such as physical and mechanical properties such as strength, hardness, and impact strength.

[0008] Chinese patent CN102336846B uses chemical bonding to load α-diimine palladium complex on magnesium chloride / ethanol complex carrier modified by acryloyl chloride for the preparation of hyperbranched polyethylene, which reduces the influence of functional groups on the surface of the carrier on the active center, effectively avoids the active center from falling off during the polymerization process, and improves the catalytic activity. However, the synthesis process of this supported catalyst is cumbersome, the preparation cost is high, and it is not conducive to industrial application. Summary of the invention

[0009] In view of the above technical problems in the art, the inventors of the present invention have conducted in-depth research and found that by combining a specific α-diimine nickel catalyst, a specific metallocene catalyst, and a specific non-metallocene catalyst, the obtained composite catalyst has excellent effects in the preparation of branched polyethylene. In addition, the branching degree of the obtained branched polyethylene can be adjusted, the molecular weight distribution is wide, and the processing properties such as tensile strength and flexural modulus are improved.

[0010] Therefore, the present invention provides a composite catalyst comprising the α-diimine nickel catalyst of the present invention, the metallocene catalyst of the present invention, and the non-metallocene catalyst of the present invention.

[0011] Furthermore, the present invention provides a method for preparing branched polyethylene, wherein ethylene is polymerized in the presence of the composite catalyst of the present invention to obtain the branched polyethylene.

[0012] The present invention also provides use of the composite catalyst of the present invention in a method for preparing branched polyethylene.

[0013] Technical Effects

[0014] Compared with the prior art, in the present invention, by combining three specific catalysts, an excellent synergistic effect is achieved. That is, when it is used as a catalytic system for ethylene polymerization, the degree of branching of branched polyethylene can be regulated, and the obtained polyethylene has a wide molecular weight distribution and excellent processing properties such as tensile strength and bending modulus. In addition, the composite catalyst of the present invention can also effectively improve the polymerization activity of the catalytic system, thereby achieving efficient preparation of branched polyethylene without complex catalyst structure, harsh reaction conditions, or significant changes in polymerization conditions.

[0015] The preparation method of the present invention has the advantages of being simple and easy to operate, having a large adjustable space, being flexible and changeable, and having low production cost, and is very conducive to realizing industrial production.

[0016] In addition, in the preparation method of the branched polyethylene of the present invention, ethylene is used as the only polymerization monomer to obtain branched polyethylene containing branches, without the need to use expensive high-carbon α-olefins as comonomers. Therefore, not only can the branching degree of the branched polyethylene be regulated to obtain branched polyethylene with a wide molecular weight distribution and excellent processing performance, but the preparation method of the present invention also has the advantages of low production cost and simple polymerization process.

[0017] The preparation method of the present invention has a large control range for the branching degree of branched polyethylene, and can obtain polyethylene with adjustable and controllable properties in a wide range from amorphous polyethylene to polyethylene with a certain degree of crystallinity, thereby conveniently controlling the branching degree of polyethylene as needed, further enriching the application range of polyethylene. DETAILED DESCRIPTION

[0018] The specific embodiments of the present invention are described in detail below. However, it should be noted that the protection scope of the present invention is not limited by these specific embodiments but is determined by the appended claims.

[0019] In the context of this specification, except for the contents explicitly described, any matters or items not mentioned are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are regarded as part of the original disclosure or original record of the present invention, and should not be regarded as new contents not disclosed or anticipated herein, unless a person skilled in the art considers that the combination is obviously unreasonable.

[0020] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this specification are based on weight, unless the weight basis does not conform to the common understanding of those skilled in the art.

[0021] The specific embodiments of the present invention are described in detail below. However, it should be noted that the protection scope of the present invention is not limited by these specific embodiments, but is determined by the appended claims.

[0022] In the context of the present invention, unless otherwise specified, the physical properties of a substance (such as boiling point) are measured at normal temperature (25° C.) and normal pressure (101325 Pa).

[0023] [Definition section]

[0024] In the present invention, "alkyl" means a straight or branched alkyl group, which may include "C1-C6 alkyl", "C1-C4 alkyl", "C3-C6 alkyl". For example, it may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers.

[0025] In the present invention, "haloalkyl" means a group obtained by replacing at least one hydrogen atom in the above-mentioned "alkyl" with a halogen group, which may include "C1-C6 haloalkyl" and "C1-C4 haloalkyl". The halogen group is selected from fluorine, chlorine, bromine and iodine. The upper limit of the number of halogen groups in the haloalkyl is the total number of hydrogen atoms that can be replaced in the substituted "alkyl", which may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 1-8, 1-6, 1-4 or 1-2. When multiple halogen groups are present, each halogen group may be the same or different. The halogen group in the "C1-C6 haloalkyl" is preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.

[0026] In the present invention, "C6-C 10 The term "aryl" refers to an aromatic hydrocarbon group having 6 to 10 carbon atoms, and specifically, it may be phenyl or naphthyl.

[0027] In the present invention, "C3-C10 "Cycloalkyl" means a cyclic alkyl group having 3 to 10 carbon atoms, for example, it may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl. "C3-C 10 "Cycloalkyl" includes "C5-C 10 Cycloalkyl", "C3-C6 cycloalkyl".

[0028] In the present invention, "C4-C8 ring" means a cyclic group having 4-8 ring carbon atoms, which may be an unsaturated ring or a saturated ring, and may or may not be aromatic. When it is an unsaturated ring, it may have 1, 2 or 3 double bonds, for example, it may be a cyclopentene ring or a cyclopentadiene ring. When it is an aromatic ring, it may be a benzene ring.

[0029] In the present invention, the substituent in "optionally substituted" or "optionally substituted" is selected from halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, phenyl, and halogenated phenyl. More specifically, it can be selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, cyclobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, halomethyl (e.g., trifluoromethyl), haloethyl (e.g., trifluoroethyl, pentafluoroethyl), halopropyl, haloisopropyl, halobutyl, haloisobutyl, halogenated sec-butyl, halotert-butyl, halopentyl, halohexyl, phenyl, and halophenyl (e.g., chlorophenyl, dichlorophenyl, pentafluorophenyl). The upper limit of the number of the substituents is the upper limit of the positions that can be substituted on the substituted group, and the number of the substituents can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. For example, it can be 1-8, 1-6, 1-5, 1-4, 1-3, 1-2. When there are multiple substituents, each substituent can be the same or different.

[0030] In the present invention, the "halogen atom" or "halogen" means fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

[0031] In the present invention, "halogenated" means at least one of the selected halogens is substituted, and the upper limit of the halogenated group is the upper limit of the position that can be substituted on the substituted group, which can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. For example, it can be 1-8, 1-6, 1-5, 1-4, 1-3, 1-2. When there are multiple halogen groups, each substituent can be the same or different.

[0032] In the present invention, the upper limit of the number of substituents in "optionally substituted by..." is the upper limit of the positions that can be substituted on the substituted group, and the number of substituents can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. For example, it can be 1-8, 1-6, 1-5, 1-4, 1-3, 1-2. When there are multiple substituents, each substituent can be the same or different.

[0033] [Compound Catalyst]

[0034] The composite catalyst of the present invention comprises a metallocene catalyst represented by the following formula (I) (sometimes referred to as a metallocene catalyst in the present invention), an α-diimine catalyst represented by the following formula (II) (sometimes referred to as an imine catalyst in the present invention), and a non-metallocene catalyst represented by the following formula (III) (sometimes referred to as a non-metallocene catalyst in the present invention).

[0035]

[0036] In formula (I), M1 is a metal element selected from Group IVB of the Periodic Table;

[0037] R1 is selected from hydrogen, optionally substituted C1-C6 alkyl and halogen atoms;

[0038] R2 is selected from hydrogen, optionally substituted C1-C6 alkyl and halogen atoms;

[0039] R3 is selected from hydrogen, optionally substituted C1-C6 alkyl, optionally substituted C3-C 10 Cycloalkyl or optionally substituted C6-C 10 Aryl;

[0040] R 10 is selected from hydrogen, optionally substituted C1-C6 alkyl, optionally substituted C3-C 10 Cycloalkyl or optionally substituted C6-C 10 Aryl;

[0041] R4, R5, R6, R7, R8, R 11 , R 12 , R 13 , R 14 , R 15 may be the same or different, and are independently selected from hydrogen, optionally substituted C1-C6 alkyl, optionally substituted C3-C 10 Cycloalkyl, optionally substituted C6-C 10 Aryl, halogen atoms, wherein two or more adjacent groups may be bonded to each other to form an optionally substituted C4-C8 ring;

[0042] R9 forms a bridge bond between ligands and is selected from at least one of the following formulae:

[0043]

[0044] R 16 , R 17 may be the same or different, and are independently selected from hydrogen, an optionally substituted C1-C6 alkyl group, and a halogen atom;

[0045]

[0046] In formula (II), M2 is an element selected from Group VIII of the Periodic Table;

[0047] Each R 21 and each R 22 may be the same or different, and are independently selected from hydrogen, an optionally substituted C1-C6 alkyl group and a halogen atom, or two adjacent R 21 , two adjacent R 22 , adjacent R 21 and R 22 At least one group of is taken together with the carbon atom to which it is bonded to form an optionally substituted C4-C8 ring;

[0048] Each R 23 , each R 25 , each R 27 may be the same or different, and are independently selected from hydrogen, optionally substituted C1-C6 alkyl;

[0049] Each R 24 , each R 26 may be the same or different, and are independently selected from hydrogen, optionally substituted C1-C6 alkyl;

[0050] Each X2 may be the same or different and is independently selected from a halogen atom;

[0051]

[0052] In formula (III), M3 is a metal element selected from Group 3 to Group 11 of the Periodic Table;

[0053] Each R 31 , each R 32 , each R 33 , each R 34 , each R 37 , each R 39 may be the same or different, and are independently selected from hydrogen, an optionally substituted C1-C6 alkyl group and a halogen atom;

[0054] R 35 is selected from optionally substituted C1-C6 alkyl, optionally substituted C6-C 10Aryl group, halogen atom;

[0055] R 36 and R 38 may be the same or different, and are independently selected from hydrogen, optionally substituted C1-C6 alkyl;

[0056] R 40 is selected from hydrogen, optionally substituted C1-C6 alkyl;

[0057] Y is selected from O or S;

[0058] A is selected from O, S or P;

[0059] Each X3 may be the same or different and is independently selected from a halogen atom; the symbol --- represents a coordination bond;

[0060] m is 1, 2, 3 or 4, depending on the valence state of the metal element M3;

[0061] n is an integer of 1-2, depending on the valence state of A.

[0062] Among them, the substituent in "optionally substituted" is selected from at least one of halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 haloalkyl and phenyl.

[0063] The metallocene catalyst of the present invention is a compound represented by formula (I).

[0064]

[0065] In one embodiment of the present invention, in formula (I), M1 is a metal element selected from Group IVB, such as titanium, zirconium or hafnium; preferably zirconium metal element.

[0066] In one embodiment of the present invention, in formula (I), R1 is selected from optionally substituted C1-C4 alkyl and halogen atoms; preferably selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl.

[0067] In one embodiment of the present invention, in formula (I), R2 is selected from optionally substituted C1-C4 alkyl and halogen atoms; preferably selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl.

[0068] In one embodiment of the present invention, in formula (I), R1 and R2 are the same.

[0069] In one embodiment of the present invention, in formula (I), R1 and R2 are different.

[0070] In one embodiment of the present invention, in formula (I), R3 is selected from optionally substituted C1-C6 alkyl, optionally substituted C3-C 10 Cycloalkyl or optionally substituted C6-C 10 Aryl is preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, phenyl, naphthyl, these specific groups are optionally substituted.

[0071] In one embodiment of the present invention, in formula (I), R 10 is selected from optionally substituted C1-C6 alkyl, optionally substituted C3-C 10 Cycloalkyl or optionally substituted C6-C 10 Aryl is preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, phenyl, naphthyl, these specific groups are optionally substituted.

[0072] In one embodiment of the present invention, in formula (I), R3 and R 10 same.

[0073] In one embodiment of the present invention, in formula (I), R3 and R 10 different.

[0074] In one embodiment of the present invention, in formula (I), R4, R6, R7, R8, R 11 , R 13 , R 14 , R 15 They may be the same or different, and are each independently selected from hydrogen, optionally substituted C1-C4 alkyl, preferably each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, and more preferably each independently selected from hydrogen.

[0075] In one embodiment of the present invention, in formula (I), R5, R 12 may be the same or different, and are independently selected from hydrogen, optionally substituted C1-C6 alkyl, optionally substituted C3-C 10 Cycloalkyl, optionally substituted C6-C 10Aryl is more preferably selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, phenyl, naphthyl, and these specific groups are optionally substituted; further preferably hydrogen, optionally substituted methyl, optionally substituted ethyl, optionally substituted propyl, optionally substituted isopropyl, optionally substituted cyclobutyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, optionally substituted cycloheptyl, optionally substituted phenyl, and optionally substituted naphthyl.

[0076] In one embodiment of the present invention, in formula (I), R5 and R 12 same.

[0077] In one embodiment of the present invention, in formula (I), R5 and R 12 different.

[0078] In one embodiment of the present invention, in formula (I), R9 forms a bridge bond between ligands, which is selected from at least one of the following formulae:

[0079]

[0080] In one embodiment of the present invention, in formula (I), R 16 , R 17 They may be the same or different, and are each independently selected from optionally substituted C1-C4 alkyl, a halogen atom, and more preferably each independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, fluorine, chlorine, bromine, and iodine.

[0081] In one embodiment of the present invention, in formula (I), R 16 With R 17 same.

[0082] In one embodiment of the present invention, in formula (I), R 16 With R 17 different.

[0083] In one embodiment of the present invention, in formula (I), the substituent in "optionally substituted" or "optionally substituted" is a substituent selected from the group consisting of halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, phenyl, and halogenated phenyl. More specifically, it can be selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, cyclobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, halomethyl (e.g., trifluoromethyl), haloethyl (e.g., trifluoroethyl, pentafluoroethyl), halopropyl, haloisopropyl, halobutyl, haloisobutyl, halogenated sec-butyl, halotert-butyl, halopentyl, halogenated hexyl, phenyl, and halogenated phenyl (e.g., chlorophenyl, dichlorophenyl, pentafluorophenyl).

[0084] In one embodiment of the present invention, in formula (I), the number of substituents in "optionally substituted" or "optionally (or) substituted" is limited to the number of positions that can be substituted on the substituted group, and can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. For example, it can be 1-8, 1-6, 1-5, 1-4, 1-3, 1-2. When there are multiple substituents, each substituent can be the same or different.

[0085] In one embodiment of the present invention, the metallocene catalyst represented by formula (I) is a compound represented by the following formula (I-1).

[0086]

[0087] In one embodiment of the present invention, the metallocene catalyst represented by formula (I) is a compound represented by the following formula (I-2):

[0088]

[0089] In one embodiment of the present invention, the metallocene catalyst of the present invention can include the following compounds:

[0090] Dimethylsilylene-(2-isopropyl-4-(p-isopropyl-phenyl)indenyl)(2-methyl-4-(p-isopropyl-phenyl)indenyl)zirconium dichloride,

[0091] Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2-methyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0092] Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2,7-dimethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0093] Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2,5,6,7-tetramethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0094] Dimethylsilylene-(2-isopropyl-6-methyl-4-(p-tert-butyl-phenyl)indenyl)(2,6-dimethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0095] Dimethylsilylene-(2-isopropyl-4-(p-sec-butyl-phenyl)indenyl)(2-methyl-4-(p-sec-butyl-phenyl)indenyl)zirconium dichloride,

[0096] Dimethylsilylene-(2-isopropyl-4-(p-cyclohexyl-phenyl)indenyl)(2-methyl-4-(p-cyclohexyl-phenyl)indenyl)zirconium dichloride,

[0097] Dimethylsilylene-(2-isopropyl-4-(p-tris(trifluoromethyl)methyl-phenyl)indenyl)(2-methyl-4-(p-tris(trifluoromethyl)methyl-phenyl)indenyl)zirconium dichloride,

[0098] Dimethylsilylene-(2-isopropyl-4-phenyl-indenyl)(2-methyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0099] Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2-methyl-4-phenyl-indenyl)zirconium dichloride,

[0100] Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2,7-dimethyl-4-phenyl-indenyl)zirconium dichloride,

[0101] Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2,5,6,7-tetramethyl-4-phenyl-indenyl)zirconium dichloride,

[0102] Dimethylsilylene-(2-isopropyl-6-methyl-4-(p-tert-butyl-phenyl)indenyl)(2,6-dimethyl-4-phenyl-indenyl)zirconium dichloride,

[0103] Dimethylsilylene-(2-isopropyl-4-phenyl-indenyl)(2,7-dimethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0104] Dimethylsilylene-(2-isopropyl-4-phenyl-indenyl)(2,5,6,7-tetramethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0105] Dimethylsilylene-(2-isopropyl-6-methyl-4-phenyl-indenyl)(2,6-dimethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0106] Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2-methyl-4-(4-naphthyl)indenyl)indenyl)zirconium dichloride,

[0107] Dimethylsilylene-(2-isopropyl-4-(4-naphthyl)indenyl)indenyl)(2-methyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0108] Dimethylsilylene-bis(2-isopropyl-[4,5]-benzo-indenyl)zirconium dichloride,

[0109] Dimethylsilylene-bis(2-isopropyl-indenyl)zirconium dichloride,

[0110] Dimethylsilylene-bis(2-isopropyl-4-(1-naphthyl)indenyl)zirconium dichloride,

[0111] Dimethylsilylene-bis(2-isopropyl-4-(2-naphthyl)indenyl)zirconium dichloride,

[0112] Dimethylsilylene-bis(2-isopropyl-4-phenyl-indenyl)zirconium dichloride,

[0113] Dimethylsilylene-bis(2-isopropyl-4-tert-butyl-indenyl)zirconium dichloride,

[0114] Dimethylsilylene-bis(2-isopropyl-4-isopropyl-indenyl)zirconium dichloride,

[0115] Dimethylsilylene-bis(2-isopropyl-4-ethyl-indenyl)zirconium dichloride,

[0116] Dimethylsilylene-bis(2,4-diisopropyl-indenyl)zirconium dichloride,

[0117] Dimethylsilylene-bis(2-isopropyl-4-methyl-indenyl)zirconium dichloride

[0118] Dimethylsilylene-bis(2,4,6-triisopropyl-indenyl)zirconium dichloride,

[0119] Dimethylsilylene-bis(2,4,5-triisopropyl-indenyl)zirconium dichloride,

[0120] Dimethylsilylene-bis(2-isopropyl-5-isobutyl-indenyl)zirconium dichloride,

[0121] Dimethylsilylene-bis(2-isopropyl-5-tert-butyl-indenyl)zirconium dichloride,

[0122] Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0123] Dimethylsilylene-bis(2-isopropyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride,

[0124] Dimethylsilylene-bis(2-isopropyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride,

[0125] Dimethylsilylene-bis(2-isopropyl-4-(4'-trifluoromethyl-phenyl)indenyl)zirconium dichloride,

[0126] Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dimethyl,

[0127] Dimethylsilylene-bis(2-isopropyl-4-(4'-methyl-phenyl)indenyl)zirconium dimethyl,

[0128] Dimethylsilylene-bis(2-isopropyl-4-(4'-ethyl-phenyl)indenyl)zirconium dimethyl,

[0129] Dimethylsilylene-bis(2-isopropyl-4-(4'-trifluoromethyl-phenyl)indenyl)zirconium dimethyl,

[0130] Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)hafnium dichloride,

[0131] Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)titanium dichloride,

[0132] Dimethylsilylene-bis(2-isopropyl-4-(4'-n-propyl-phenyl)indenyl)zirconium dichloride,

[0133] Dimethylsilylene-bis(2-isopropyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride,

[0134] Dimethylsilylene-bis(2-isopropyl-4-(4'-hexyl-phenyl)indenyl)zirconium dichloride,

[0135] Dimethylsilylene-bis(2-isopropyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride,

[0136] Dimethylsilylene-bis(2-isopropyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride,

[0137] Dimethylsilylene-bis(2-isopropyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride,

[0138] Dimethylsilylene-bis(2-isopropyl-4-(4'-n-propyl-phenyl)indenyl)zirconium dichloride,

[0139] Dimethylsilylene-bis(2-isopropyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride,

[0140] Dimethylsilylene-bis(2-isopropyl-4-(4'-hexyl-phenyl)indenyl)zirconium dichloride,

[0141] Dimethylsilylene-bis(2-isopropyl-4-(4'-pentyl-phenyl)indenyl)zirconium dichloride,

[0142] Dimethylsilylene-bis(2-isopropyl-4-(4'-cyclohexyl-phenyl)indenyl)zirconium dichloride,

[0143] Dimethylsilylene-bis(2-isopropyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride,

[0144] Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0145] Dimethylsilylene-bis(2-n-propyl-4-phenyl-indenyl)zirconium dichloride,

[0146] Dimethylsilylene-bis(2-n-propyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride,

[0147] Dimethylsilylene-bis(2-n-propyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride,

[0148] Dimethylsilylene-bis(2-n-propyl-4-(4'-isopropyl-phenyl)indenyl)zirconium dichloride,

[0149] Dimethylsilylene-bis(2-n-propyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride,

[0150] Dimethylsilylene-bis(2-n-propyl-4-(4'-hexyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-propyl-4-(4'-cyclohexyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-propyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-propyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-butyl-4-phenyl-indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-butyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-butyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride , dimethylsilylene-bis(2-n-butyl-4-(4'-n-propyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-butyl-4-(4'-isopropyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-butyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-butyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-butyl-4-(4'-hexyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-butyl-4-(4'-cyclohexyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-butyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-butyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride dimethylsilylene-bis(2-hexyl-4-phenyl-indenyl)zirconium dichloride, dimethylsilylene-bis(2-hexyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-hexyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-hexyl-4-(4'-n-propyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-hexyl-4-(4'-isopropyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-hexyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-hexyl-4-(4'-n-hexyl-phenyl)indenyl)zirconium dichloride )indenyl)zirconium dichloride, dimethylsilylene-bis(2-hexyl-4-(4'-cyclohexyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-hexyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-hexyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-phenyl-4-phenyl-indenyl)zirconium dichloride, dimethylsilylene-bis(2-phenyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-phenyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-phenyl-4-(4'-n-propyl-phenyl)indenyl)zirconium dichloride,Dimethylsilylene-bis(2-phenyl-4-(4'-isopropyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-phenyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-phenyl-4-(4'-n-hexyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-phenyl-4-(4'-cyclohexyl-phenyl)indenyl)zirconium dichloride, dimethylsilylene-bis(2-phenyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride,

[0151] Dimethylsilylene-bis(2-phenyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0152] Dimethylsilylene-bis(2-ethyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride,

[0153] Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dimethyl.

[0154] Among them, in one embodiment of the present invention, the metallocene catalyst of the present invention can list the following compounds: dimethylsilylene-bis(2-isopropyl-indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-propyl-4-phenyl-indenyl)zirconium dichloride, and dimethylsilylene-bis(2-hexyl-4-phenyl-indenyl)zirconium dichloride.

[0155] In the composite catalyst of the present invention, the metallocene catalyst may be one kind or a mixture of two or more kinds of metallocene catalysts.

[0156] The imine catalyst of the present invention is a compound represented by (II).

[0157]

[0158] In one embodiment of the present invention, in formula (II), M2 is an element selected from Group VIII of the periodic table, such as iron, cobalt, nickel, palladium and the like, preferably nickel.

[0159] In one embodiment of the present invention, in formula (II), each R 21 and each R 22 They may be the same or different, and are each independently selected from hydrogen, a halogen atom, and an optionally substituted C1-C4 alkyl group, and are preferably each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl.

[0160] In one embodiment of the present invention, in formula (II), two adjacent R 21 , two adjacent R 22, adjacent R 21 and R 22 At least one group of them are bonded to each other and, together with the carbon atoms to which they are connected, form a benzene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl, a cyclopentene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl, or a cyclopentadiene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl.

[0161] In one embodiment of the present invention, in formula (II), two adjacent R 21 They are bonded to each other to form, together with the carbon atoms to which they are connected, a benzene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl, a cyclopentene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl, or a cyclopentadiene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl.

[0162] In one embodiment of the present invention, in formula (II), two adjacent R 22 They are bonded to each other to form, together with the carbon atoms to which they are connected, a benzene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl, a cyclopentene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl, or a cyclopentadiene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl.

[0163] In one embodiment of the present invention, in formula (II), adjacent R 21 and R 22 They are bonded to each other to form, together with the carbon atoms to which they are connected, a benzene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl, a cyclopentene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl, or a cyclopentadiene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl.

[0164] In one embodiment of the present invention, the compound shown in formula (II) is a compound shown in the following formula (II-1),

[0165]

[0166] In formula (II-1), R 21 and R 22 They may be the same or different, and are each independently selected from hydrogen, a halogen atom, and an optionally substituted C1-C6 alkyl group, and are preferably each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl.

[0167] In one embodiment of the present invention, the compound represented by formula (II) is a compound represented by the following formula (II-2), formula (II-3) or formula (II-4).

[0168]

[0169]

[0170] In formula (II-2), formula (II-3) and formula (II-4), each R 28 They may be the same or different, and are each independently selected from hydrogen, halogen, and C1-C6 alkyl; preferably, they are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers.

[0171] In one embodiment of the present invention, in formula (II), each R 24 , each R 26 Each is independently selected from hydrogen, C1-C4 alkyl, preferably each is independently selected from hydrogen, methyl, ethyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, more preferably each is independently selected from hydrogen.

[0172] In one embodiment of the present invention, in formula (II), each R 23 , each R 25 , each R 27 Each is independently selected from hydrogen, C1-C6 alkyl, preferably each is independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and isomers thereof, hexyl and isomers thereof.

[0173] In one embodiment of the present invention, the compound shown in formula (II) of the present invention can include the following compounds:

[0174]

[0175]

[0176] In one embodiment of the present invention, the compound shown in formula (II) of the present invention is more preferably the following compound:

[0177]

[0178] In one embodiment of the present invention, in formula (II), each X2 may be the same or different, and is independently selected from fluorine, chlorine, bromine, and iodine.

[0179] In one embodiment of the present invention, in formula (II), the substituent in "optionally substituted" or "optionally substituted" is a substituent selected from the group consisting of halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, phenyl, and halogenated phenyl. More specifically, it can be selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, cyclobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, halomethyl (e.g., trifluoromethyl), haloethyl (e.g., trifluoroethyl, pentafluoroethyl), halopropyl, haloisopropyl, halobutyl, haloisobutyl, halogenated sec-butyl, halotert-butyl, halopentyl, halogenated hexyl, phenyl, and halogenated phenyl (e.g., chlorophenyl, dichlorophenyl, pentafluorophenyl).

[0180] In one embodiment of the present invention, in formula (II), the number of substituents in "optionally substituted" or "optionally (are) substituted" is limited to the number of positions that can be substituted on the substituted group, and can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. For example, it can be 1-8, 1-6, 1-5, 1-4, 1-3, 1-2. When there are multiple substituents, each substituent can be the same or different.

[0181] In the composite catalyst of the present invention, the imine-based catalyst may be used alone or as a mixture of two or more.

[0182] The non-metallocene catalyst of the present invention is a compound represented by formula (III).

[0183]

[0184] In one embodiment of the present invention, in formula (III), M3 is a metal element selected from Group 3 to Group 11 of the periodic table, for example, it can be selected from Group IVB, such as titanium, zirconium or hafnium; Group VB, such as vanadium; Group VIII, such as iron, cobalt, nickel, palladium and the like. More specifically, Ti(IV), Zr(IV), Hf(IV), Fe(III), Fe(II), Ni(II), Pd(II) or Co(II) can be cited.

[0185] In one embodiment of the present invention, in formula (III), each R 31 , each R 32 , each R 33 , each R 34 , each R 37 , each R 39They may be the same or different, and are each independently selected from hydrogen, optionally substituted C1-C4 alkyl and halogen atoms, preferably each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, and more preferably each is hydrogen.

[0186] In one embodiment of the present invention, in formula (III), R 35 is selected from optionally substituted C1-C4 alkyl, optionally substituted C6-C 10 Aryl, halogen atom; preferably selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, phenyl, naphthyl, these specific groups are optionally substituted.

[0187] In one embodiment of the present invention, in formula (III), R 36 and R 38 may be the same or different, and are independently selected from hydrogen, optionally substituted C 3-6 Alkyl; preferably each independently selected from propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and isomers thereof, hexyl and isomers thereof.

[0188] In one embodiment of the present invention, in formula (III), R 36 and R 38 same

[0189] In one embodiment of the present invention, in formula (III), R 36 and R 38 different.

[0190] In one embodiment of the present invention, in formula (III), Y is O or S, preferably O.

[0191] In one embodiment of the present invention, in formula (III), A is O, S or P, preferably S or P.

[0192] In one embodiment of the present invention, in formula (III), R 40 It is selected from hydrogen, optionally substituted C1-C4 alkyl, preferably selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, more preferably hydrogen.

[0193] In one embodiment of the present invention, in formula (III), each X3 may be the same or different, and is independently selected from fluorine, chlorine, bromine, and iodine.

[0194] In the present invention, coordination bonds are sometimes represented by — (solid line), but those skilled in the art can undoubtedly confirm that they are coordination bonds, for example, the bond between M3 and N, and the bond between M3 and A are coordination bonds.

[0195] In one embodiment of the present invention, in formula (III), m is 1, 2, 3 or 4, depending on the valence state of the metal element M3. For example, when M3 is a tetravalent metal element, m is 3; when M3 is a trivalent metal element, m is 2; when M3 is a divalent metal element, m is 1.

[0196] In one embodiment of the present invention, in formula (III), n is an integer of 1-2, depending on the valence state of A. For example, when A is O or S, n is 1, and when A is P, n is 2.

[0197] In one embodiment of the present invention, in formula (III), the substituent in "optionally substituted" or "optionally substituted" is a substituent selected from the group consisting of halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, phenyl, and halogenated phenyl. More specifically, it can be selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, cyclobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, halomethyl (e.g., trifluoromethyl), haloethyl (e.g., trifluoroethyl, pentafluoroethyl), halopropyl, haloisopropyl, halobutyl, haloisobutyl, halogenated sec-butyl, halotert-butyl, halopentyl, halogenated hexyl, phenyl, and halogenated phenyl (e.g., chlorophenyl, dichlorophenyl, pentafluorophenyl).

[0198] In one embodiment of the present invention, in formula (III), the number of substituents in "optionally substituted" or "optionally (are) substituted" is limited to the number of positions that can be substituted on the substituted group, and can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. For example, it can be 1-8, 1-6, 1-5, 1-4, 1-3, 1-2. When there are multiple substituents, each substituent can be the same or different.

[0199] In one embodiment of the present invention, the compound represented by formula (III) is a compound represented by formula (III-1).

[0200]

[0201] In one embodiment of the present invention, the non-metallocene catalyst represented by formula (III) may include the following compounds:

[0202]

[0203]

[0204] In one embodiment of the present invention, the non-metallocene catalyst represented by formula (III) is preferably the following compound:

[0205]

[0206] In the composite catalyst of the present invention, the non-metallocene catalyst may be used alone or as a mixture of two or more.

[0207] In one embodiment of the present invention, in the composite catalyst of the present invention, the ratio of the metallocene catalyst, the imine catalyst, and the non-metallocene catalyst is 0.4-2.0:1:0.4-2.0 in terms of molar ratio, preferably 0.8-1.5:1:0.8-1.5, for example, 1:1:1, based on the active metal content of each catalyst. However, it is not limited thereto.

[0208] It should be noted that the contents (eg, molar amounts) of the metallocene catalyst, the imine-based catalyst, and the non-metallocene catalyst are calculated based on the contents of the respective active metal elements.

[0209] In the composite catalyst of the present invention, when it contains multiple metallocene catalysts, its content is calculated by the total content of active metals; when it contains multiple imine catalysts, its content is calculated by the total content of active metals; when it contains multiple non-metallocene catalysts, its content is calculated by the total content of active metals.

[0210] Likewise, in the composite catalyst of the present invention, the total content of the composite catalyst is represented by the total content of the active metal content of the metallocene catalyst, the active metal content of the imine catalyst, and the active metal content of the non-metallocene catalyst.

[0211] In one embodiment of the present invention, the composite catalyst comprises a metallocene catalyst, an imine catalyst and a non-metallocene catalyst, and further, optionally comprises other components, including but not limited to a co-catalyst and the like.

[0212] In one embodiment of the present invention, the composite catalyst only includes a metallocene catalyst, an imine-based catalyst and a non-metallocene catalyst.

[0213] In one embodiment of the present invention, the composite catalyst is present in the form of a solution. In this case, the solvent of the catalyst solution is not limited in any way, as long as it can dissolve and / or disperse the components of the composite catalyst. Examples of the solvent include C 4-10 Alkanes (such as butane, pentane, hexane, heptane, octane, nonane or decane, etc.), C6-C 10 Aromatic hydrocarbon solvents (such as toluene and xylene and their isomers), halogenated C6-C 10 Aromatic hydrocarbon solvents (such as chlorobenzene, dichlorobenzene and its isomers, chlorotoluene, etc.). Among them, C4-C 10 Alkanes, C6-C 10Aromatic hydrocarbon solvents, halogenated C6-C 10 The aromatic hydrocarbon solvent is more preferably one or more selected from hexane, toluene, p-xylene, m-xylene, o-xylene, and mesitylene, and further preferably one or more selected from hexane, toluene, and p-xylene.

[0214] [Method for preparing branched polyethylene]

[0215] The present invention provides a method for preparing branched polyethylene, which comprises the following steps:

[0216] The composite catalyst of the present invention is used as a main catalyst, and at least one selected from aluminoxane, modified aluminoxane, alkyl aluminum, alkyl aluminum hydrolyzate, halogenated alkyl aluminum, aryl boron, alkyl boron and borate is used as a co-catalyst to polymerize ethylene in a polymerization solvent to obtain branched polyethylene.

[0217] In the method for preparing branched polyethylene of the present invention, the composite catalyst of the present invention is used as the main catalyst, and the conventional co-catalyst in the art is used to polymerize ethylene to obtain branched polyethylene. It should be noted that branched polyethylene in the present invention is sometimes also referred to as ethylene polymer or polyethylene.

[0218] In the present invention, when the "composite catalyst of the present invention" is used as the main catalyst, it is sufficient that the metallocene catalyst of the present invention, the imine-based catalyst of the present invention and the non-metallocene catalyst of the present invention are simultaneously present in the polymerization reaction system of ethylene. At this time, the composite catalyst of the present invention can be prepared into a catalyst solution in advance and then added to the polymerization solvent, or the composite catalyst of the present invention can be directly added to the polymerization solvent.

[0219] In one embodiment of the present invention, the composite catalyst of the present invention is added to a solvent in advance, and then the prepared catalyst solution is added to a polymerization solvent. At this time, there is no particular limitation on the solvent used at this time, as long as it can dissolve and / or disperse the composite catalyst. As the solvent, for example, C4-C 10 Alkanes (such as butane, pentane, hexane, heptane, octane, nonane or decane, etc.), C6-C 10 Aromatic hydrocarbon solvents (such as toluene and xylene and their isomers), halogenated C6-C 10 Aromatic hydrocarbon solvents (such as chlorobenzene, dichlorobenzene and its isomers, chlorotoluene, etc.). Among them, C4-C 10 Alkanes, C6-C 10 Aromatic hydrocarbon solvents, halogenated C6-C 10The aromatic hydrocarbon solvent is more preferably one or more selected from hexane, toluene, p-xylene, m-xylene, o-xylene, and mesitylene, and further preferably one or more selected from hexane, toluene, and p-xylene.

[0220] In the present invention, the composite catalyst is a composite catalyst comprising the metallocene catalyst of the present invention, the imine catalyst of the present invention and the non-metallocene catalyst of the present invention. Therefore, in the present invention, the order of adding the three catalysts is not particularly limited. The three catalysts can be added in sequence or added together. As long as the metallocene catalyst of the present invention, the imine catalyst of the present invention and the non-metallocene catalyst of the present invention are present in the reaction system solution of the final ethylene polymerization, it is deemed to contain the composite catalyst of the present invention.

[0221] In one embodiment of the present invention, the composite catalyst of the present invention is added to a solvent in advance, and when preparing a catalyst solution, the above-mentioned cocatalyst can be optionally added to the solution, mixed together, and then the catalyst solution is added to the polymerization solvent. At this time, there is no particular limitation on the order of adding the cocatalyst, and the cocatalyst can be added simultaneously with the above-mentioned three catalysts, or sequentially, or interspersed.

[0222] In one embodiment of the present invention, at least one of the metallocene catalyst of the present invention, the imine-based catalyst of the present invention, and the non-metallocene catalyst of the present invention may be directly added to the polymerization solvent.

[0223] In one embodiment of the present invention, the above-mentioned co-catalyst may be directly added into the polymerization solvent.

[0224] As described above, when ethylene polymerization is performed, the metallocene catalyst of the present invention, the imine-based catalyst of the present invention, and the non-metallocene catalyst of the present invention are simultaneously present in the reaction system, which is regarded as the presence of the composite catalyst of the present invention in the reaction system. That is, ethylene polymerization is performed in the presence of the composite catalyst of the present invention.

[0225] In one embodiment of the present invention, the method for preparing branched polyethylene of the present invention is preferably carried out in a solution polymerization mode. At this time, in the polymerization reaction system of ethylene, the composite catalyst is in the form of a homogeneous catalyst.

[0226] There is no particular limitation on the polymerization solvent for preparing branched polyethylene of the present invention, as long as it is a conventional polymerization solvent of the present invention. For example, it includes but is not limited to C 4-10 Alkanes or cycloalkanes (such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclohexane, cycloheptane, etc.), aromatic hydrocarbon solvents (such as toluene and xylene and their isomers), etc. Among them, hexane, cyclohexane, toluene or a mixture thereof is preferably used as the polymerization solvent.

[0227] There is no particular limitation on the temperature for producing branched polyethylene in the present invention, as long as it is a conventional temperature in the present invention. In one embodiment of the present invention, the polymerization reaction temperature is 0-90°C, preferably 30-80°C, and more preferably 50-70°C.

[0228] There is no particular limitation on the pressure for producing branched polyethylene in the present invention, as long as it is a conventional pressure in the present invention. In one embodiment of the present invention, the polymerization pressure is 0.1-4.0 MPa, preferably 0.3-3.0 MPa, and more preferably 0.5-2.5 MPa.

[0229] In the present invention, the time for ethylene polymerization is not particularly limited, and varies according to the amount of the catalyst system used, the amount of ethylene, and the polymerization temperature, and can be adjusted arbitrarily by those skilled in the art as needed. For example, it can be 10 minutes to 2 hours, 20 minutes to 90 minutes, 30 minutes to 1 hour, etc.

[0230] In one embodiment of the present invention, the method for preparing the branched polyethylene of the present invention can be carried out in a continuous polymerization manner or in a batch polymerization manner.

[0231] In the present invention, in the preparation method of branched polyethylene, at least one selected from aluminoxane, modified aluminoxane, alkyl aluminum, alkyl aluminum hydrolyzate, halogenated alkyl aluminum, aryl boron, alkyl boron and borate is used as a co-catalyst.

[0232] There is no limitation on the aluminoxane, modified aluminoxane, alkylaluminum, alkylaluminum hydrolyzate, halogenated alkylaluminum, arylboron, alkylboron and borate, and any compound known in the art that can be used as a co-catalyst can be used. More specifically, each co-catalyst can be the following compounds.

[0233] The aluminoxane as a co-catalyst may be, for example, a linear aluminoxane represented by the following general formula (IV): (R)(R)Al-(Al(R)-O) n -O-Al(R)(R), and a cyclic aluminoxane represented by the following general formula (V): -(Al(R)-O-) n+2 -.

[0234]

[0235] In the aforementioned general formulae (IV) and (V), the groups R may be the same or different (preferably the same), and are independently selected from C1-C8 alkyl, preferably methyl, ethyl, propyl, butyl and isobutyl, most preferably methyl and isobutyl; n is any integer in the range of 1-50, preferably any integer in the range of 10-30.

[0236] As the aluminoxane, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane are preferred, and methylaluminoxane and isobutylaluminoxane are more preferred.

[0237] These aluminoxanes may be used alone or in combination of two or more in any ratio.

[0238] As the alkyl aluminum, for example, there can be mentioned the compound represented by the following general formula (VI):

[0239] Al(R)3(VI)

[0240] In the general formula (VI), the groups R may be the same or different (preferably the same), and are independently selected from C1-C8 alkyl groups, preferably methyl, ethyl, propyl, butyl and isobutyl, and most preferably methyl and isobutyl.

[0241] Specifically, examples of the alkyl aluminum include trimethyl aluminum (Al(CH3)3), triethyl aluminum (Al(CH3CH2)3), tri-n-propyl aluminum (Al(C3H7)3), tri-isopropyl aluminum (Al(i-C3H7)3), tri-isobutyl aluminum (Al(i-C4H9)3), tri-n-butyl aluminum (Al(C4H9)3), tri-isopentyl aluminum (Al(i-C5H 11 )3), tri-n-pentyl aluminum (Al(C5H 11 )3) Tri-n-hexyl aluminum (Al(C6H 13 )3) Triisohexyl aluminum (Al(i-C6H 13 )3), diethylmethylaluminum (Al(CH3)(CH3CH2)2) and dimethylethylaluminum ((Al(CH3CH2)(CH3)2), etc., among which trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferred, and triethylaluminum and triisobutylaluminum are most preferred.

[0242] These aluminum alkyls may be used alone or in combination of two or more in any ratio.

[0243] As the halogenated alkylaluminum, for example, there can be mentioned the compound represented by the following general formula (VII):

[0244] Al(R) n X 3-n (VII)

[0245] In the general formula (VII), the groups R may be the same or different (preferably the same), and are independently selected from C1-C8 alkyl, preferably methyl, ethyl, propyl, butyl and isobutyl, most preferably methyl and isobutyl; X represents fluorine, chlorine, bromine or iodine; and n represents 1 or 2.

[0246] Specifically, as the halogenated alkyl aluminum, for example, there can be mentioned dimethylaluminum monochloride (Al(CH3)2Cl), dimethylaluminum dichloride (Al(CH3)Cl2)), diethylaluminum monochloride (Al(CH3CH2)2Cl), diethylaluminum dichloride (Al(CH3CH2)Cl2), dipropylaluminum monochloride (Al(C3H7)2Cl), dipropylaluminum dichloride (Al(C3H7)Cl2), di-n-butylaluminum monochloride (Al(C4H9)2Cl), di-n-butylaluminum dichloride (Al(C4H9)Cl2), diisobutylaluminum monochloride (Al(i-C4H9)2Cl), diisobutylaluminum dichloride (Al(i-C4H9)Cl2), di-n-pentylaluminum monochloride (Al(C5H 11 )2Cl), dichloropentylaluminum (Al(C5H 11 )Cl2), diisopentylaluminum monochloride (Al(i-C5H 11 )2Cl), dichloroisopentylaluminum (Al(i-C5H 11 )Cl2), di-n-hexylaluminum chloride (Al(C6H 13 )2Cl), dichlorohexyl aluminum (Al(C6H 13 )Cl2), diisohexylaluminum monochloride (Al(i-C6H 13 )2Cl), dichloroisohexylaluminum (Al(i-C6H 13 )Cl2), chloromethyl ethylaluminum (Al(CH3)(CH3CH2)Cl), chloromethyl propylaluminum (Al(CH3)(C3H7)Cl), chloromethyl n-butylaluminum (Al(CH3)(C4H9)Cl), chloromethyl isobutylaluminum (Al(CH3)(i-C4H9)Cl), chloroethyl propylaluminum (Al(CH2CH3)(C3H7)Cl), chloroethyl n-butylaluminum (AlCH2CH3)(C4H9)Cl), chloromethyl isobutylaluminum (Al(CH2CH3)(i-C4H9)Cl), etc., among which diethylaluminum chloride, ethylaluminum dichloride, di-n-butylaluminum chloride, n-butylaluminum dichloride, diisobutylaluminum chloride, isobutylaluminum dichloride, di-n-hexylaluminum chloride, and n-hexylaluminum dichloride are preferred, and diethylaluminum chloride, ethylaluminum dichloride and di-n-hexylaluminum chloride are further preferred, and diethylaluminum chloride is most preferred.

[0247] These alkylaluminum halides may be used alone or in combination of two or more in any ratio.

[0248] In the present invention, the alkyl boron and aryl boron may be compounds represented by the following general formula (VIII):

[0249] B(R')3(VIII)

[0250] In the general formula (VIII), each of the three R' groups may be the same or different from each other, and each R' is independently selected from C1-C6 alkyl and C6-C 10 Aryl, each group is optionally substituted by one or more halogen atoms, halogenated C1-C6 alkyl or phenoxy. Preferably, R' is preferably selected from methyl, ethyl, propyl, butyl, isobutyl, phenyl, tolyl, trifluoromethylphenyl and pentafluorophenyl.

[0251] Specific examples of alkylborons include trimethylboron, triethylboron, triisobutylboron, tripropylboron, or tributylboron. Specific examples of arylborons include triphenylboron, tris(pentafluorophenyl)boron, and tris[3,5-bis(trifluoromethyl)phenyl]boron.

[0252] These alkylboranes and arylboranes may be used alone or in combination of two or more in any ratio.

[0253] In the present invention, the borate may be a compound represented by the following general formula (IX):

[0254] [L] + [BE4] m - (IX)

[0255] In the general formula (IX), L is a cationic group, each E may be the same or different, and each is independently selected from a halogen atom, C 6-10 Aryl, the aryl is optionally substituted by one or more halogen atoms, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or phenoxy. m represents the value of the valence of the group in the L portion. Preferably, the E is selected from fluorine, phenyl, trifluoromethylphenyl and pentafluorophenyl.

[0256] In the general formula (IX), [L] + The moiety may be a common cation in borates, for example, Li + 、Na + , K + , Ca 2+ Mg 2+ 、[Fe(C5H5)2] + (ferrocene group), etc. In addition, the L part can also be an organic amine, in which case the L part can be represented by N(R')3, and each R' is independently selected from H, C1-C6 alkyl and C6-C 10aryl, but not H at the same time; or two R' and N can be bonded to each other to form a 5-7 membered nitrogen-containing heterocyclic ring optionally substituted by C1-C6 alkyl, preferably each R' is independently selected from H, C1-C4 alkyl and phenyl, but not H at the same time; or two R' and N can be bonded to each other to form a 5-7 membered nitrogen-containing heteroaromatic ring or heterocyclic hydrocarbon optionally substituted by C1-C4 alkyl. For example, as the L part, methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, imidazole, 1-butyl-3-methylimidazole, pyridine, piperidine, etc. can be listed. [L] + The moiety may also be a group carrying a carbenium ion, such as a trityl carbenium ion.

[0257] Specific examples of borates include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o-p-dimethylphenyl)borate, triethylammonium tetra(o-p-dimethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(pentafluorophenyl)borate, N,N-diethylanilinium tetraphenylborate, N,N-dimethylanilinium tetra(pentafluorophenyl)borate, N,N-diethylanilinium tetra(pentafluorophenyl)borate, triethylammonium tetra(pentafluorophenyl)borate, triphenylcarbon tetra(pentafluorophenyl)borate, 1-butyl-3-methylimidazolium tetrafluoroborate, and ferrocene tetrafluoroborate.

[0258] These borates may be used alone or in combination of two or more in any ratio.

[0259] In addition, according to the present invention, the co-catalyst may be used alone or in combination of multiple co-catalysts in any proportion as required. Moreover, there is no particular limitation on the proportion of each component in the mixture and it can be selected as required.

[0260] According to the present invention, the co-catalyst is generally used in the form of a solution. When preparing the solution of the co-catalyst, there is no particular limitation on the solvent used at this time, as long as it can dissolve / disperse the co-catalyst. Generally, C 4-10Alkanes or cycloalkanes (such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclohexane, cycloheptane, etc.), aromatic hydrocarbon solvents (such as toluene and xylene and isomers thereof), etc. For example, alkane solvents such as pentane and hexane, or aromatic hydrocarbon solvents such as toluene, ethylbenzene, and xylene can be cited. According to the present invention, in order to facilitate subsequent separation, it is preferred to use the same solvent as the polymerization solvent; or the same solvent as at least one solvent in the mixed solvent for polymerization.

[0261] It should be noted that, unless otherwise specified, in the present invention, when the co-catalyst is aluminoxane, modified aluminoxane, alkyl aluminum, alkyl aluminum hydrolyzate, or halogenated alkyl aluminum, the molar amount of the co-catalyst is calculated based on the molar amount of the Al element; when the co-catalyst is alkyl boron, aryl boron, or borate, the molar amount of the co-catalyst is calculated based on the molar amount of the B element.

[0262] In one embodiment of the present invention, the co-catalyst is preferably selected from aluminoxane, alkylaluminum, halogenated alkylaluminum or a mixture thereof, and more preferably selected from alkylaluminum, halogenated alkylaluminum or a mixture thereof.

[0263] In one embodiment of the present invention, the molar ratio of the promoter calculated in terms of aluminum and / or boron to the composite catalyst calculated in terms of total active metal content is 50-500:1, preferably 60-300:1.

[0264] In the present invention, there is no particular limitation on the amount of the composite catalyst, as long as it is the conventional amount of the main catalyst in the preparation of branched polyethylene. In one embodiment of the present invention, the added amount of the composite catalyst (based on the total amount of active metals of the three catalysts) relative to the total amount of polymerization solvent in the polymerization process (usually the sum of the amount of solvent used to prepare the catalyst solution and the amount of polymerization solvent), based on the total molar content of active metals in the composite catalyst, is (0.1-100)×10 -6 mol / L, preferably (0.5-60)×10 -6 mol / L.

[0265] In the preparation of the branched polyethylene of the present invention, a chain transfer agent may be used or not. As the chain transfer agent, other metal alkyl compounds other than the co-catalyst of the present invention may be listed, for example, one or more of n-butyl lithium, diethyl zinc, dipropyl zinc, dibutyl zinc, diisobutyl zinc, diethyl magnesium, dibutyl magnesium or n-butyl ethyl magnesium may be listed. In one embodiment of the present invention, when a chain transfer agent is used, the molar ratio of the amount of the chain transfer agent based on the metal content of the chain transfer agent to the composite catalyst based on the total amount of active metals is 5-300:1, preferably 10-200:1.

[0266] In the present invention, ethylene polymerization is carried out in the absence of other comonomers. That is, in the present invention, branched polyethylene is prepared by homopolymerizing ethylene in the presence of a specific catalyst system.

[0267] In the present invention, the composite catalyst of the present invention is added to a single reactor to carry out ethylene polymerization, that is, the polymerization of ethylene is carried out under the condition that the composite catalyst of the present invention (that is, the metallocene catalyst of the present invention, the imine-based catalyst of the present invention, and the non-metallocene catalyst of the present invention are simultaneously present) is present in a single reactor.

[0268] The present invention excludes the situation where one or two of the three catalyst components in the composite catalyst of the present invention are added to multiple reactors respectively, and the reactors are connected in series to carry out ethylene polymerization.

[0269] In one embodiment of the present invention, the method for preparing the branched polyethylene of the present invention is carried out in a batch mode.

[0270] In one embodiment of the present invention, the method for preparing the branched polyethylene of the present invention is carried out in a continuous manner.

[0271] In one embodiment of the present invention, the polymerization of ethylene is carried out in the absence of hydrogen.

[0272] In the present invention, after the polymerization reaction is completed, the reaction can be terminated by a method known in the art. For example, the polymerization reaction can be terminated by adding hydrochloric acid to acidify ethanol in the polymerization solution, or the polymerization reaction solution can be poured into the hydrochloric acid acidified ethanol solution to terminate the polymerization reaction.

[0273] In the present invention, after the polymerization reaction is completed, the branched polyethylene can be obtained by separation and purification in a conventional manner in the art.

[0274] [Branched polyethylene]

[0275] By using the preparation method of the present invention, ethylene homopolymerization can be catalyzed to prepare the branched polyethylene of the present invention.

[0276] The branched polyethylene of the present invention may have branches of various lengths.

[0277] In one embodiment of the present invention, the molecular weight distribution of the branched polyethylene is between 5.0 and 9.0.

[0278] In one embodiment of the present invention, the branching degree of the branched polyethylene is between 40-100 / 1000C (ie, 40-100 branches per 1000 carbon main chains), preferably 40-80 / 1000C (ie, 40-80 branches per 1000 carbon main chains).

[0279] [use]

[0280] The present invention provides use of the composite catalyst of the present invention in preparing branched polyethylene.

[0281] Example

[0282] The embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention.

[0283] Unless otherwise specified, the raw materials used in the following examples and comparative examples are all commercially available products.

[0284] The calculation method of the polymerization activity of the catalyst is as follows:

[0285] W=Q / (M×H)

[0286] Wherein, W is the polymerization activity; Q is the yield of the obtained polymer (in g); M is the total molar amount of the catalyst (in mol); and H is the polymerization time (in h).

[0287] The testing method of the molecular weight of polyethylene obtained in the following examples and comparative examples is as follows: The polymer molecular weight is measured by a PL-220 gel permeation chromatograph of Polymer Laboratories. 1,2,4-trichlorobenzene is used as the mobile phase, polystyrene is used as the standard sample, a differential detector is used, the flow rate is 1.0 mL / min, the measuring temperature is 150°C, and the sample concentration is 2.0 mg / mL. PDI (polymer dispersity index) is calculated based on the obtained weight average molecular weight Mw and number average molecular weight Mn.

[0288] The degree of branching of the polyethylene obtained in the following examples and comparative examples is calculated based on the carbon nuclear magnetic resonance spectrum. The specific method is: the microstructure of the polyethylene sample is measured using a Bruker Avance 600M nuclear magnetic resonance spectrometer. The sample is dissolved in deuterated o-dichlorobenzene to prepare a solution. The test temperature is 120°C, and the nuclear magnetic resonance hydrogen spectrum is obtained by scanning 2000 times and 6000 times respectively. 1 H-NMR) and carbon nuclear magnetic resonance spectroscopy ( 13 C-NMR).

[0289] The tensile strength test method of the polymers obtained in the following examples and comparative examples is as follows: the test is carried out according to the standard GB / T1040-1992. Testing instrument: universal material testing machine-Zwick / Roell-Z020, bar type: type I, preparation method: using a micro high-performance composite material molding system of model HAAKE MiniJet II and a tensile barISO527-5A tensile mold (L75mm, W12.5mm, H2mm) to prepare the bar using the polyethylene obtained in each example and comparative example, the injection molding temperature is 280-300°C, the mold temperature is 80-100°C, the holding pressure is 1150bar, and the holding time is 15s.

[0290] The main catalysts in the embodiments and comparative examples are as follows:

[0291] A1: dimethylsilylene-bis(2-isopropyl-indenyl)zirconium dichloride;

[0292] A2: dimethylsilylene-bis(2-n-propyl-4-phenyl-indenyl)zirconium dichloride;

[0293] B1:

[0294]

[0295] B2:

[0296]

[0297] C 1:

[0298]

[0299] C2:

[0300]

[0301] Example 1

[0302] In a glove box, catalyst A1 (0.015mmol), catalyst B1 (0.015mmol), catalyst C1 (0.015mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE1. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0303] Example 2

[0304] In a glove box, catalyst A1 (0.015mmol), catalyst B2 (0.015mmol), catalyst C1 (0.015mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE2. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0305] Example 3

[0306] In a glove box, catalyst A1 (0.015mmol), catalyst B1 (0.015mmol), catalyst C2 (0.015mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE3. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0307] Example 4

[0308] In a glove box, catalyst A1 (0.015mmol), catalyst B2 (0.015mmol), catalyst C2 (0.015mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE4. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0309] Example 5

[0310] In a glove box, catalyst A2 (0.015mmol), catalyst B1 (0.015mmol), catalyst C1 (0.015mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE5. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0311] Example 6

[0312] In a glove box, catalyst A2 (0.015mmol), catalyst B2 (0.015mmol), catalyst C1 (0.015mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE6. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0313] Example 7

[0314] In a glove box, catalyst A2 (0.015mmol), catalyst B1 (0.015mmol), catalyst C2 (0.015mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE7. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0315] Example 8

[0316] In a glove box, catalyst A2 (0.015mmol), catalyst B2 (0.015mmol), catalyst C2 (0.015mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE8. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0317] Example 9

[0318] In a glove box, catalyst A1 (0.015mmol), catalyst B1 (0.015mmol), catalyst C1 (0.015mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 40°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE9. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0319] Example 10

[0320] In a glove box, catalyst A2 (0.015mmol), catalyst B2 (0.015mmol), catalyst C2 (0.015mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 40°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE10. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0321] Embodiment 11

[0322] In a glove box, catalyst A1 (0.012mmol), catalyst B1 (0.02mmol), catalyst C1 (0.012mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE11. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0323] Example 12

[0324] In a glove box, catalyst A1 (0.02mmol), catalyst B1 (0.012mmol), catalyst C1 (0.02mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PE12. The polymerization activity and polymer test results of this embodiment are shown in Table 1.

[0325] Comparative Example 1

[0326] In a glove box, catalyst A1 (0.045 mmol), toluene (15 ml) and methylaluminoxane (3 mmol) were added to a 50 ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800 mL) and the above-prepared catalyst solution were added in sequence, 1.5 MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5 hours under stirring at 200 rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PEC1. The polymerization activity and polymer test results of this comparative example are shown in Table 1.

[0327] Comparative Example 2

[0328] In a glove box, catalyst B1 (0.045 mmol), toluene (15 ml) and methylaluminoxane (3 mmol) were added to a 50 ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800 mL) and the above-configured catalyst solution were added in sequence, 1.5 MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5 hours under stirring at 200 rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PEC2. The polymerization activity and polymer test results of this comparative example are shown in Table 1.

[0329] Comparative Example 3

[0330] In a glove box, catalyst C1 (0.045mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PEC3. The polymerization activity and polymer test results of this comparative example are shown in Table 1.

[0331] Comparative Example 4

[0332] In a glove box, catalyst A2 (0.045 mmol), toluene (15 ml) and methylaluminoxane (3 mmol) were added to a 50 ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800 mL) and the above-prepared catalyst solution were added in sequence, 1.5 MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5 hours under stirring at 200 rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PEC4. The polymerization activity and polymer test results of this comparative example are shown in Table 1.

[0333] Comparative Example 5

[0334] In a glove box, catalyst B2 (0.045mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PEC5. The polymerization activity and polymer test results of this comparative example are shown in Table 1.

[0335] Comparative Example 6

[0336] In a glove box, catalyst C2 (0.045mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PEC6. The polymerization activity and polymer test results of this comparative example are shown in Table 1.

[0337] Comparative Example 7

[0338] In a glove box, catalyst A1 (0.015mmol), catalyst B1 (0.03mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PEC7. The polymerization activity and polymer test results of this comparative example are shown in Table 1.

[0339] Comparative Example 8

[0340] In a glove box, catalyst B1 (0.015mmol), catalyst C1 (0.03mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PEC8. The polymerization activity and polymer test results of this comparative example are shown in Table 1.

[0341] Comparative Example 9

[0342] In a glove box, catalyst A1 (0.015mmol), catalyst C1 (0.03mmol), toluene (15ml) and methylaluminoxane (3mmol) were added to a 50ml conical flask in sequence, mixed and used as a catalyst solution. After purging a 2L high-pressure polymerization reactor with high-purity nitrogen at 80°C for 2 hours, hexane (800mL) and the above-configured catalyst solution were added in sequence, 1.5MPa ethylene was introduced at 60°C, and the polymerization reaction was carried out for 0.5hr under stirring at 200rpm. After the reaction was completed, the polymerization solution was poured into an acidified ethanol solution to precipitate a solid polymer. After filtering and washing, the polymer was vacuum dried at 60°C to constant weight to obtain polymer PEC9. The polymerization activity and polymer test results of this comparative example are shown in Table 1.

[0343] Table 1 Polymerization test results of various embodiments and comparative examples

[0344]

[0345] Above, it is obvious from the embodiments and comparative examples that in the present invention, by using a composite catalyst comprising a metallocene catalyst of the present invention, an imine-based catalyst of the present invention and a non-metallocene catalyst of the present invention, an excellent synergistic effect can be achieved, and in the preparation of branched polyethylene, excellent polymerization activity is shown, and a wide molecular weight distribution, and the tensile strength as a representative of processability is also a high value. In contrast, when the composite catalyst of the present invention is not used, whether a catalyst is used alone or two catalysts are combined, the polymerization activity and tensile strength are all deteriorated, and in addition, the molecular weight distribution is narrowed.

[0346] Industrial Applicability

[0347] In the present invention, the composite catalyst obtained by combining the metallocene catalyst of the present invention, the imine catalyst of the present invention and the non-metallocene catalyst of the present invention exhibits excellent polymerization activity in the preparation of branched polyethylene, and the obtained branched polyethylene has a wide molecular weight distribution and excellent tensile strength as one of the processing properties.

Claims

1. A composite catalyst comprising a metallocene catalyst represented by the following formula (I), an α-diimine catalyst represented by the following formula (II), and a non-metallocene catalyst represented by the following formula (III), In formula (I), M1 is a metal element selected from Group IVB of the Periodic Table; R1 is selected from hydrogen, optionally substituted C1-C6 alkyl and halogen atoms; R2 is selected from hydrogen, optionally substituted C1-C6 alkyl and halogen atoms; R3 is selected from hydrogen, optionally substituted C1-C6 alkyl, optionally substituted C3-C 10 Cycloalkyl or optionally substituted C6-C 10 Aryl; R 10 is selected from hydrogen, optionally substituted C1-C6 alkyl, optionally substituted C3-C 10 Cycloalkyl or optionally substituted C6-C 10 Aryl; R4, R5, R6, R7, R8, R 11 , R 12 , R 13 , R 14 , R 15 may be the same or different, and are independently selected from hydrogen, optionally substituted C1-C6 alkyl, optionally substituted C3-C 10 Cycloalkyl, optionally substituted C6-C 10 Aryl, halogen atoms, wherein two or more adjacent groups may be bonded to each other to form an optionally substituted C4-C8 ring; R9 forms a bridge bond between ligands and is selected from at least one of the following formulae: R 16 , R 17 may be the same or different, and are independently selected from hydrogen, an optionally substituted C1-C6 alkyl group, and a halogen atom; In formula (II), M2 is an element selected from Group VIII of the Periodic Table; Each R 21 and each R 22 may be the same or different, and are independently selected from hydrogen, an optionally substituted C1-C6 alkyl group and a halogen atom, or two adjacent R 21 , two adjacent R 22 , adjacent R 21 and R 22 At least one group of is taken together with the carbon atom to which it is bonded to form an optionally substituted C4-C8 ring; Each R 23 , each R 25 , each R 27 may be the same or different, and are independently selected from hydrogen, optionally substituted C1-C6 alkyl; Each R 24 , each R 26 may be the same or different, and are independently selected from hydrogen, optionally substituted C1-C6 alkyl; Each X2 may be the same or different and is independently selected from a halogen atom; In formula (III), M3 is a metal element selected from Group 3 to Group 11 of the Periodic Table; Each R 31 , each R 32 , each R 33 , each R 34 , each R 37 , each R 39 may be the same or different, and are independently selected from hydrogen, an optionally substituted C1-C6 alkyl group and a halogen atom; R 35 is selected from optionally substituted C1-C6 alkyl, optionally substituted C6-C 10 Aryl group, halogen atom; R 36 and R 38 may be the same or different, and are independently selected from hydrogen, optionally substituted C1-C6 alkyl; R 40 is selected from hydrogen, optionally substituted C1-C6 alkyl; Y is selected from O or S; A is selected from O, S or P; Each X3 may be the same or different and is independently selected from a halogen atom; the symbol --- represents a coordination bond; m is 1, 2, 3 or 4, depending on the valence state of the metal element M3; n is an integer of 1-2, depending on the valence state of A. in, The substituent in "optionally substituted" is selected from at least one of halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 haloalkyl and phenyl.

2. The composite catalyst according to claim 1, wherein In formula (I), M1 is titanium, zirconium or hafnium; preferably zirconium metal element; In formula (I), R1 and R2 may be the same or different, and are independently selected from optionally substituted C1-C4 alkyl and halogen atoms; preferably selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl; In formula (I), R3 and R 10 may be the same or different and are selected from optionally substituted C1-C6 alkyl, optionally substituted C3-C 10 Cycloalkyl or optionally substituted C6-C 10 Aryl, preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, phenyl, naphthyl, these groups are optionally substituted; In formula (I), R4, R6, R7, R8, R 11 , R 13 , R 14 , R 15 may be the same or different, and are each independently selected from hydrogen, optionally substituted C1-C4 alkyl, preferably each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, more preferably each independently selected from hydrogen; In formula (I), R5, R 12 may be the same or different, and are independently selected from hydrogen, optionally substituted C1-C6 alkyl, optionally substituted C3-C 10 Cycloalkyl, optionally substituted C6-C 10 Aryl, more preferably selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, phenyl, naphthyl, these groups are optionally substituted; further preferably hydrogen, optionally substituted methyl, optionally substituted ethyl, optionally substituted propyl, optionally substituted isopropyl, optionally substituted cyclobutyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, optionally substituted cycloheptyl, optionally substituted phenyl, optionally substituted naphthyl, In formula (I), R9 forms a bridge bond between ligands, which is selected from at least one of the following formulae: Among them, R 16 , R 17 They may be the same or different, and are each independently selected from optionally substituted C1-C4 alkyl, a halogen atom, and more preferably each independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, fluorine, chlorine, bromine, and iodine.

3. The composite catalyst according to claim 1 or 2, wherein The metallocene catalyst represented by formula (I) is at least one selected from the following compounds: Dimethylsilylene-(2-isopropyl-4-(p-isopropyl-phenyl)indenyl)(2-methyl-4-(p-isopropyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2-methyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2,7-dimethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2,5,6,7-tetramethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-6-methyl-4-(p-tert-butyl-phenyl)indenyl)(2,6-dimethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-(p-sec-butyl-phenyl)indenyl)(2-methyl-4-(p-sec-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-(p-cyclohexyl-phenyl)indenyl)(2-methyl-4-(p-cyclohexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-(p-tris(trifluoromethyl)methyl-phenyl)indenyl)(2-methyl-4-(p-tris(trifluoromethyl)methyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-phenyl-indenyl)(2-methyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2-methyl-4-phenyl-indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2,7-dimethyl-4-phenyl-indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2,5,6,7-tetramethyl-4-phenyl-indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-6-methyl-4-(p-tert-butyl-phenyl)indenyl)(2,6-dimethyl-4-phenyl-indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-phenyl-indenyl)(2,7-dimethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-phenyl-indenyl)(2,5,6,7-tetramethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-6-methyl-4-phenyl-indenyl)(2,6-dimethyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2-methyl-4-(4-naphthyl)indenyl)indenyl)zirconium dichloride, Dimethylsilylene-(2-isopropyl-4-(4-naphthyl)indenyl)indenyl)(2-methyl-4-(p-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-[4,5]-benzo-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(1-naphthyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(2-naphthyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-phenyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-tert-butyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-isopropyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-ethyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2,4-diisopropyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-methyl-indenyl)zirconium dichloride Dimethylsilylene-bis(2,4,6-triisopropyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2,4,5-triisopropyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-5-isobutyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-5-tert-butyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-trifluoromethyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dimethyl, Dimethylsilylene-bis(2-isopropyl-4-(4'-methyl-phenyl)indenyl)zirconium dimethyl, Dimethylsilylene-bis(2-isopropyl-4-(4'-ethyl-phenyl)indenyl)zirconium dimethyl, Dimethylsilylene-bis(2-isopropyl-4-(4'-trifluoromethyl-phenyl)indenyl)zirconium dimethyl, Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)hafnium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)titanium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-n-propyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-hexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-n-propyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-hexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-pentyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-cyclohexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-propyl-4-phenyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-propyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-propyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-propyl-4-(4'-isopropyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-propyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-propyl-4-(4'-hexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-propyl-4-(4'-cyclohexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-propyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-propyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-butyl-4-phenyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-butyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-butyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-butyl-4-(4'-n-propyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-butyl-4-(4'-isopropyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-butyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-butyl-4-(4'-hexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-butyl-4-(4'-cyclohexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-butyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-n-butyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-hexyl-4-phenyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-hexyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-hexyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-hexyl-4-(4'-n-propyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-hexyl-4-(4'-isopropyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-hexyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-hexyl-4-(4'-n-hexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-hexyl-4-(4'-cyclohexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-hexyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-hexyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-phenyl-4-phenyl-indenyl)zirconium dichloride, Dimethylsilylene-bis(2-phenyl-4-(4'-methyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-phenyl-4-(4'-ethyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-phenyl-4-(4'-n-propyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-phenyl-4-(4'-isopropyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-phenyl-4-(4'-n-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-phenyl-4-(4'-n-hexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-phenyl-4-(4'-cyclohexyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-phenyl-4-(4'-sec-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-phenyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-ethyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dichloride, Dimethylsilylene-bis(2-isopropyl-4-(4'-tert-butyl-phenyl)indenyl)zirconium dimethyl, Preferably, it is at least one selected from dimethylsilylene-bis(2-isopropyl-indenyl)zirconium dichloride, dimethylsilylene-bis(2-n-propyl-4-phenyl-indenyl)zirconium dichloride, and dimethylsilylene-bis(2-hexyl-4-phenyl-indenyl)zirconium dichloride.

4. The composite catalyst according to any one of claims 1 to 3, wherein In formula (II), M2 is iron, cobalt, nickel or palladium, preferably nickel. In formula (II), each R 21 and each R 22 may be the same or different, and are independently selected from hydrogen, a halogen atom, an optionally substituted C1-C4 alkyl group, preferably independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or two adjacent R 21 , two adjacent R 22 , adjacent R 21 and R 22 At least one group of the group is bonded to each other, and together with the carbon atoms to which they are connected, forms a benzene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl, a cyclopentene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl, or a cyclopentadiene ring optionally substituted by at least one selected from halogen and C1-C6 alkyl, In formula (II), each R 24 , each R 26 Each is independently selected from hydrogen, C1-C4 alkyl, preferably each is independently selected from hydrogen, methyl, ethyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, more preferably each is independently selected from hydrogen, In formula (II), each R 23 , each R 25 , each R 27 Each is independently selected from hydrogen, C1-C6 alkyl, preferably each is independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and isomers thereof, hexyl and isomers thereof.

5. The composite catalyst according to any one of claims 1 to 4, wherein The α-diimine catalyst represented by (II) is a compound represented by formula (II-1), formula (II-2), formula (II-3) or formula (II-4), In formula (II-1), R 21 and R 22 may be the same or different, and are each independently selected from hydrogen, a halogen atom, an optionally substituted C1-C6 alkyl group, and are preferably each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl; In formula (II-2), formula (II-3) and formula (II-4), each R 28 They may be the same or different, and are each independently selected from hydrogen, halogen, and C1-C6 alkyl; preferably, they are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers.

6. The composite catalyst according to any one of claims 1 to 5, wherein The α-diimine catalyst represented by formula (II) is at least one selected from the following: Preferably, it is at least one selected from the following:

7. The composite catalyst according to any one of claims 1 to 6, wherein In formula (III), M3 is selected from Ti(IV), Zr(IV), Hf(IV), Fe(III), Fe(II), Ni(II), Pd(II) or Co(II), In formula (III), each R 31 , each R 32 , each R 33 , each R 34 , each R 37 , each R 39 may be the same or different, and are each independently selected from hydrogen, optionally substituted C1-C4 alkyl and halogen atoms, preferably each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, and more preferably each is hydrogen, In formula (III), R 35 is selected from optionally substituted C1-C4 alkyl, optionally substituted C6-C 10 Aryl, halogen atom; preferably selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, phenyl, naphthyl, these groups are optionally substituted, In formula (III), R 36 and R 38 may be the same or different, and are independently selected from hydrogen, optionally substituted C 3-6 Alkyl; preferably each independently selected from propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and isomers thereof, hexyl and isomers thereof, In formula (III), Y is O or S, preferably O, A is O, S or P, preferably S or P, In formula (III), R 40 is selected from hydrogen, optionally substituted C1-C4 alkyl, preferably selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, more preferably hydrogen, In formula (III), when M3 is a tetravalent metal element, m is 3; when M3 is a trivalent metal element, m is 2; when M3 is a divalent metal element, m is 1, In formula (III), n is an integer of 1-2, when A is O or S, n is 1, and when A is P, n is 2.

8. The composite catalyst according to any one of claims 1 to 7, wherein The non-metallocene catalyst represented by formula (III) is a compound represented by formula (III-1), 9. The composite catalyst according to any one of claims 1 to 8, wherein The non-metallocene catalyst represented by formula (III) is at least one selected from the following compounds, Preferably, it is at least one selected from the following compounds, 10. The composite catalyst according to any one of claims 1 to 9, wherein The optionally substituted substituent is a substituent selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and isomers thereof, hexyl and isomers thereof, cyclobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, halogenated methyl (e.g., trifluoromethyl), halogenated ethyl (e.g., trifluoroethyl, pentafluoroethyl), halogenated propyl, halogenated isopropyl, halogenated butyl, halogenated isobutyl, halogenated sec-butyl, halogenated tert-butyl, halogenated pentyl, halogenated hexyl, phenyl, halogenated phenyl (e.g., chlorophenyl, dichlorophenyl, pentafluorophenyl).

11. The composite catalyst according to any one of claims 1 to 10, wherein The ratio of the metallocene catalyst represented by formula (I), the α-diimine catalyst represented by formula (II) and the non-metallocene catalyst represented by formula (III) is 0.4-2.0:1:0.4-2.0, preferably 0.8-1.5:1:0.8-1.5, for example 1:1:1, based on the active metal content of each.

12. A method for preparing branched polyethylene, wherein: The following steps are involved: Using the composite catalyst described in any one of claims 1 to 11 as the main catalyst and at least one selected from aluminoxane, modified aluminoxane, alkyl aluminum, alkyl aluminum hydrolyzate, halogenated alkyl aluminum, aryl boron, alkyl boron and borate as a co-catalyst, ethylene is polymerized in a polymerization solvent to obtain branched polyethylene.

13. The preparation method according to claim 12, wherein: The polymerization pressure is 0.1-4.0 MPa, preferably 0.3-3.0 MPa, more preferably 0.5-2.5 MPa, The polymerization temperature is 0-90°C, preferably 30-80°C, more preferably 50-70°C.

14. The preparation method according to claim 12 or 13, wherein: The molar ratio of the promoter calculated in terms of aluminum and / or boron to the composite catalyst calculated in terms of total active metal content is 50-500:1, preferably 60-300:

1.

15. Branched polyethylene obtained by the method for preparing branched polyethylene according to any one of claims 12 to 14.

16. Use of the composite catalyst according to any one of claims 1 to 11 in a method for preparing branched polyethylene.

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