Butanedione ligand compounds and metal complexes thereof, metal catalyst compositions and use thereof

Abstract

The application relates to a butanedione ligand compound, a metal complex of the butanedione ligand compound, a metal catalyst composition and application thereof, and belongs to the technical field of catalysts. The ligand compound has a structural formula shown in formula I, wherein R1, R2, R3, R4 and R5 are independently selected from hydrogen, halogen, substituted or unsubstituted C1-C 30 alkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heterocyclyl, substituted or unsubstituted C1-C 30 alkoxy, substituted or unsubstituted C6-C 50 fused ring group; when the alkyl, aryl, heterocyclyl or fused ring group is substituted, the substituent is at least one selected from C1-C 60 alkoxy, C1-C 60 alkyl, C1-C 60 fluoroalkyl, nitro and halogen. The butanedione ligand compound of the application selects the skeleton with a Lewis base of butanedione to control the steric hindrance, and the butanedione has a strong electron-withdrawing effect, which is beneficial to the coordination polymerization of subsequent olefin monomers.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a diacetone ligand compound and its metal complex, a metal catalyst composition and its application. Background Technology

[0002] Polyolefins are among the polymers with relatively large annual production and practical applications. They are widely used in all aspects of life and industry, and have become one of the most important polymers in materials history. Since the discovery of the Ziegler-Natta catalyst, the iteration of transition metal catalysts has become the main driving force for the development of the polyolefin industry.

[0003] In related technologies, ligand steric factors play a crucial role in the evolution of structural modification in different types of post-transition metal catalysts, such as diimine catalysts. However, due to the unique chain travel of these diimine catalysts, the polyethylene polymerized still exhibits low thermal stability and is prone to producing highly branched, oily, and low-molecular-weight polymers.

[0004] Therefore, the diimine-based metal catalysts in related technologies have low thermal stability, making it difficult to control the molecular weight and structure of the polymers prepared during the catalytic polymerization process, and thus difficult to promote in production. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention provides a diacetone ligand compound and its metal complex, a metal catalyst composition and its application, in order to at least partially solve at least one of the aforementioned technical problems.

[0006] One object of the present invention is to provide a diacetone ligand compound.

[0007] Another object of the present invention is to provide a butanedione metal complex.

[0008] Another object of the present invention is to provide a metal catalyst composition.

[0009] Another object of the present invention is to provide an application of the above-described metal catalyst composition.

[0010] The above-mentioned objectives of the present invention are achieved through the following technical solutions.

[0011] According to one aspect of the present invention, a butanedione ligand compound of formula I is provided, wherein R1, R2, R3, R4, and R5 are each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C1 atoms. 30 Alkyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30 Heterocyclic groups, substituted or unsubstituted C1-C30 Alkoxy, substituted or unsubstituted C6-C 50 Any one of the fused ring groups; when there is a substituent on the alkyl, aryl, heterocyclic, alkoxy, or fused ring group, the substituent is selected from hydrogen, deuterium, C1-C6. 60 alkoxy groups, C1-C 60 Alkyl groups, C1-C 60 At least one of fluoroalkyl, nitro, and halogen.

[0012]

[0013] According to embodiments of the present invention, R1, R2, R3, and R4 are each independently selected from substituted or unsubstituted C1-C6 alkyl groups, C6-C6 alkyl groups, and C6-C6 alkyl groups. 30 aryl, C5-C 20 heteroaryl, C8-C 20 Fused aryl or C8-C 20 R5 is selected from any one of the fused heteroaryl groups; R5 is selected from substituted or unsubstituted C1-C6 alkyl groups, halogens, C1-C6 alkyl groups, and C6 alkyl groups. 10 Any one of the alkoxy groups; when there is a substituent on the alkyl, aryl, alkoxy, heteroaryl, fused aryl or fused heteroaryl group, the substituent is independently selected from at least one of hydrogen, deuterium, C1-C6 alkoxy, C1-C6 alkyl, C1-C6 fluoroalkyl, fluorine, chlorine, and bromine.

[0014] Preferably, R1, R2, R3, and R4 are each independently selected from substituted or unsubstituted C2-C5 alkyl groups, C8-C4 alkyl groups, and C5-C6 alkyl groups. 25 aryl, C2-C8 alkoxy, C8-C 15 heteroaryl, C8-C 15 Fused aryl, C8-C 15 Fused heteroaryl, C 10 ~C 15 Any one of the fused ring groups.

[0015] More preferably, R1, R2, R3, and R4 are each independently selected from substituted or unsubstituted C3-C4 alkyl groups, C4 ... 10 ~C 20 aryl, C4-C6 alkoxy, C 10 ~C 13 heteroaryl, C 10 ~C 13 Fused aryl, C 10 ~C 13 Fused heteroaryl, C 11 ~C 14 Any one of the fused ring groups.

[0016] According to embodiments of the present invention, the above-mentioned ligand compounds include formulas I1 to I 12 Compounds with the structure shown:

[0017]

[0018]

[0019] According to another aspect of the present invention, a metal complex of formula II is provided, wherein M comprises any one of nickel and palladium; X and Y are each independently selected from any one of halogens, C1-C6 alkanes, C2-C6 alkenes, allyl groups, and substituted or unsubstituted aryl groups; R1, R2, R3, R4, and R5 are each independently selected from any one of hydrogen, halogens, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted fused-ring groups; when the alkyl, aryl, heterocyclic, alkoxy, or fused-ring group has a substituent, the substituent is independently selected from hydrogen, deuterium, C1-C6 alkenes, C2 ... 60 alkoxy groups, C1-C 60 Alkyl groups, C1-C 60 At least one of fluoroalkyl, nitro, and halogen.

[0020]

[0021] According to embodiments of the present invention, the definitions of R1, R2, R3, and R4 are as described above and will not be repeated here.

[0022] According to an embodiment of the present invention, R5 is defined as described above and will not be repeated here.

[0023] According to embodiments of the present invention, the above-mentioned metal complexes include formulas II1 to II. 12 Compounds with the structure shown:

[0024]

[0025]

[0026] According to an embodiment of the present invention, the metal complex is formed by coordination of the ligand compound described above with a divalent metal compound; the divalent metal compound includes at least one of NiCl2, NiBr2, NiI2, (DME)NiBr2, Ni(allyl)Cl, and [Ni(PPh3)2PhCl].

[0027] According to another aspect of the present invention, a metal catalyst composition is provided, comprising a metal complex and a co-catalyst as described above, and optionally comprising a support activated by said co-catalyst. The co-catalyst comprises an organoboron compound or an alkylaluminum compound.

[0028] According to embodiments of the present invention, the organoboron compound includes tris(pentafluoroaryl)borane or methylaluminoxane.

[0029] According to an embodiment of the present invention, the support is prepared by the following method: the original support and the co-catalyst are subjected to heat treatment at 450-550°C for 2-6 hours in an inert gas atmosphere to obtain the support; wherein the mass ratio of the original support to the co-catalyst is 3:2 or higher, and the original support includes at least one of silicon dioxide, magnesium chloride or aluminum oxide.

[0030] According to another aspect of the present invention, the above-described metal catalyst composition is provided for catalytic reaction of C2-C2 catalysts. 11 olefin monomers or C2-C 11 Applications in the polymerization of olefin monomers and polar olefin monomers; the use of co-catalysts or supports activated with co-catalysts, C2-C 11 olefin monomers or C2-C 11 The addition of olefin monomers and polar olefin monomers to an organic solvent results in C2-C... 11 olefin monomers or C2-C 11 The olefin monomers and polar olefin monomers undergo coordination polymerization.

[0031] According to embodiments of the present invention, the olefin monomers include at least one of ethylene, propylene, butene, hexene, and norbornene; the polar olefin monomers include at least one of methyl 10-undecenoate, hexachloro-1-hexene, acrylate, methyl acrylate, vinyl ether, vinyl acetate, and polar norbornene; the polar norbornene includes at least one of 5-norbornen-2-methanol, methyl 5-norbornen-2-carboxylic acid, 5-norbornen-2-ylacetic acid, 5-norbornen-2-carboxylic acid, and 5-norbornen-2-ol; the coordination polymerization conditions are: at a temperature of 0–100°C, at a pressure of 0.1–10 MPa, and a coordination polymerization time of 0.1–1 h.

[0032] Based on the above technical solutions, it can be seen that the diacetone ligand compounds and their metal complexes, metal catalyst compositions and their applications provided by the present invention have at least one or a part of the following beneficial effects:

[0033] This invention utilizes the steric hindrance effect of the [N,O]-type diacetyl framework with a Lewis base. The electronic and steric hindrance effects can be modulated through subsequent activation with a Lewis acid, improving the activity and thermal stability of the prepared metal catalyst composition. The interaction between the Lewis acid and the diacetyl framework facilitates the regulation of the interaction between the ligand compound and the metal center in subsequent catalytic reactions, thereby improving the efficiency and controllability of branching in the catalytic polymerization reaction. Furthermore, the strong electron-withdrawing effect of the diacetyl framework enhances the Lewis acidity of the metal center during subsequent metal coordination, thus benefiting the coordination polymerization of olefin monomers. Attached Figure Description

[0034] The present invention will be further described in detail below with reference to the accompanying drawings.

[0035] Figure 1 The 1H NMR spectrum of the ligand compound L1 prepared in Example 1 of this invention;

[0036] Figure 2 The 1H NMR spectrum of the ligand compound L2 prepared in Example 2 of this invention;

[0037] Figure 3 This is an X-ray diffraction single-crystal structure diagram of the nickel complex Ni1 prepared in Example 3 of the present invention;

[0038] Figure 4 The above is the 1H NMR spectrum of the nickel complex Ni2 prepared in Example 4 of this invention.

[0039] Figure 5 The image shows the carbon NMR spectrum of the nickel complex Ni2 prepared in Example 4 of this invention.

[0040] Figure 6 The two-dimensional nuclear magnetic resonance spectrum of the nickel complex Ni2 prepared in Example 4 of this invention;

[0041] Figure 7 The above is the 1H NMR spectrum of the nickel complex Ni2 catalyst for the copolymerization of ethylene and methyl 10-undecenoate prepared in Example 4 of this invention.

[0042] Figure 8 The hydrogen nuclear magnetic resonance spectrum of the Ni2-BCF / SiO2-catalyzed copolymer of ethylene and methyl 10-undecenoate prepared in Example 5 of this invention;

[0043] Figure 9 The 1H NMR spectrum of the Ni2-BCF / SiO2-catalyzed copolymer of ethylene and 6-chloro-1-hexene prepared in Example 5 of this invention;

[0044] Figure 10 The relative molecular weight diagram of the Ni2-BCF / SiO2-catalyzed ethylene polymer prepared in Example 5 of this invention; and

[0045] Figure 11 These are comparative graphs showing the morphology and activity curves at 80°C of the polymers prepared at 50°C in Examples 7 and 10 of this invention, respectively; wherein... Figure 11 (a) is a diagram of the apparent morphology of the polymer prepared by Ni2-BCF at 50°C in Example 10 of the present invention in solution state; Figure 11 (b) is a diagram of the apparent morphology of the polymer prepared by Ni2-MAO / SiO2 at 50°C in Example 7 of the present invention in solution state; Figure 11 (c) is Figure 11 (a) The apparent morphology of the prepared polymer in the solid state; Figure 11 (d) is Figure 11 (b) The apparent morphology of the prepared polymer in the solid state; Figure 11 (e) is a graph showing the relationship between the activity of Ni2-BCF / SiO2 and Ni2-BCF nickel catalysts and time at 80℃; Figure 11 (f) is a graph showing the relationship between the activity of Ni2-MAO / SiO2 and Ni2-MAO nickel catalysts and time at 80℃. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings.

[0047] Related technologies often utilize metal complexes based on diimine ligands to study their performance in olefin-polar monomer copolymerization. However, due to the unique chain walk of the diimine catalysts prepared above, the polymerized polyethylene still exhibits low thermal stability and is prone to producing highly branched, oily, and low-molecular-weight polymers. In realizing this invention, it was discovered that using a diacetyl backbone as a complex is beneficial for regulating its steric hindrance effect during subsequent Lewis acid activation, thus facilitating the coordination polymerization of subsequent olefin monomers.

[0048] Specifically, according to one aspect of the present invention, a butanedione ligand compound of formula I is provided, wherein R1, R2, R3, R4, and R5 are each independently selected from hydrogen, halogen, substituted or unsubstituted C1 to C5. 30 Alkyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30 Heterocyclic groups, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C6-C 50Any one of the fused ring groups; when there is a substituent on the alkyl, aryl, heterocyclic, alkoxy, or fused ring group, the substituent is independently selected from hydrogen, deuterium, C1-C6, etc. 60 alkoxy groups, C1-C 60 Alkyl groups, C1-C 60 At least one of fluoroalkyl, nitro, and halogen.

[0049]

[0050] According to embodiments of the present invention, the ligand compound shown in Formula I utilizes the steric hindrance effect of the diacetyl skeleton structure with a Lewis base. Through subsequent activation by a Lewis acid, its electronic and steric hindrance effects can be modulated, improving the activity and thermal stability of the subsequently prepared metal catalyst composition. The subsequent interaction between the Lewis acid and the diacetyl skeleton structure facilitates the regulation of the interaction between the ligand compound and the metal center in subsequent catalytic reactions, thereby improving the efficiency of the catalytic polymerization reaction and the controllability of the degree of branching. Furthermore, relying on the strong electron-withdrawing effect of the diacetyl skeleton, it is beneficial to increase the Lewis acidity of the metal center during subsequent metal coordination, thus facilitating the coordination polymerization of subsequent olefin monomers.

[0051] According to embodiments of the present invention, R1, R2, R3, and R4 are each independently selected from substituted or unsubstituted C1-C6 alkyl groups, C6-C6 alkyl groups, and C6-C6 alkyl groups. 30 aryl, C1-C 10 alkoxy groups, C5-C 20 heteroaryl, C8-C 20 Fused aryl or C8-C 20 R5 is selected from any one of the fused heteroaryl groups; R5 is selected from substituted or unsubstituted C1-C6 alkyl groups, halogens, C1-C6 alkyl groups, and C6 alkyl groups. 10 Any one of the alkoxy groups. When there is a substituent on the alkyl, aryl, alkoxy, heteroaryl, fused aryl, or fused heteroaryl group, the substituent is independently selected from at least one of hydrogen, deuterium, C1-C6 alkoxy, C1-C6 alkyl, C1-C6 fluoroalkyl, fluorine, chlorine, and bromine. In the process of conducting the relevant preliminary experiments of this invention, it was found that when R1, R2, R3, R4, and R5 are selected from the above groups, the degree of branching of the subsequently prepared olefin polymer is lower and the molecular weight is higher.

[0052] Preferably, R1, R2, R3, and R4 are each independently selected from substituted or unsubstituted C2-C5 alkyl groups, C8-C4 alkyl groups, and C5-C6 alkyl groups. 25 aryl, C2-C8 alkoxy, C8-C 15 heteroaryl, C8-C 15 Fused aryl, C8-C 15 Fused heteroaryl, C 10~C 15 Any one of the fused ring groups;

[0053] More preferably, R1, R2, R3, and R4 are each independently selected from substituted or unsubstituted C3-C4 alkyl groups, C4 ... 10 ~C 20 aryl, C4-C6 alkoxy, C 10 ~C 13 heteroaryl, C 10 ~C 13 Fused aryl, C 10 ~C 13 Fused heteroaryl, C 11 ~C 14 Any one of the fused ring groups.

[0054] In this specification, C a ~C b The expression indicates that the group has a to b number of carbon atoms. Unless otherwise specified, this number of carbon atoms generally does not include the number of carbon atoms of the substituents. In this invention, the description of chemical elements includes the concept of isotopes with the same chemical properties, such as the description of "hydrogen", as well as the concepts of "deuterium" and "tritium" with the same chemical properties.

[0055] In this specification, C6~C 30 Aryl is a group consisting of aryl, naphthyl, anthracene, benzo[a]anthrayl, phenanthryl, benzo[a]phenanthryl, pyrene, pyryl, peryl, fluoranthyl, tetra[a]aryl, penta[a]aryl, benzo[a]pyrene, biaryl, aramid, tri[a]aryl, trimeric[a]aryl, tetra[a]aryl, fluorene, spirodifluorene, dihydrophenanthryl, dihydropyrene, tetrahydropyrene, cis or trans[a]fluorene, trimerinyl, isotrimericininyl, spirotrimericininyl, and spiroisotrimericininyl. Specifically, the biaryl group is selected from 2-biaryl, 3-biaryl, and 4-biaryl; the triaryl group includes p-triaryl-4-yl, p-triaryl-3-yl, p-triaryl-2-yl, meta-triaryl-4-yl, meta-triaryl-3-yl, and meta-triaryl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracel group is selected from 1-anthrayl, 2-anthrayl, and 9-anthrayl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the pyrene group is selected from 1-pyrene, 2-pyrene, and 4-pyrene; and the tetraaryl group is selected from 1-tetraaryl, 2-tetraaryl, and 9-tetraaryl.

[0056] In this invention, heteroatoms generally refer to atoms or groups of atoms selected from N, O, S, P, Si and Se, preferably selected from N, O and S.

[0057] C3 to C in this invention 30 Heterocyclic groups include C3 to C4. 30cycloalkyl, C6-C 30 Aryl, C3~C 30 heteroaryl, C8-C 30 At least one of the fused aryl groups, C3-C 30 Cycloalkyl groups include monocycloalkyl and polycycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. (C3~C4) 30 Examples of heteroaryl groups include: oxygen-containing heteroaryl groups, nitrogen-containing heteroaryl groups, sulfur-containing heteroaryl groups, etc. Specific examples include: furanyl, thiopheneyl, pyrroleyl, pyridyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, isobenzothiopheneyl, indolyl, isoindolyl, dibenzofuranyl, dibenzothiopheneyl, carbazoleyl and its derivatives, quinolinyl, isoquinolinyl, acridineyl, phenanthridineyl, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl.

[0058] In this specification, C1 to C 30 Alkyl groups, for example, include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, adamantyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, etc. C1~C 30 Alkoxy groups are similar to C1-C30 alkyl groups, except that a -O- is added to each group.

[0059] Examples of halogens in this specification include fluorine, chlorine, bromine, iodine, etc., with fluorine being preferred.

[0060] According to embodiments of the present invention, the diacetone ligand compounds include those of formulas I1 to I2. 12 Compounds with the structure shown:

[0061]

[0062]

[0063]

[0064] According to embodiments of the present invention, a method for preparing a ligand compound of formula I butanedione is also provided. The present invention does not particularly limit the preparation method of the compound having the structure shown in formula I, and conventional preparation methods well known to those skilled in the art can be used. Those skilled in the art can select and adjust the method according to actual production conditions, product requirements and usage requirements.

[0065] Specifically, the preparation method of the dimethylglyoxal ligand compound may include: dissolving 2,3-dimethylglyoxal and the compound shown in Formula A in a first organic solvent, adding formic acid dropwise and stirring thoroughly, heating and refluxing until the reaction is complete, separating the obtained yellow solid, and performing vacuum distillation to obtain the ligand compound shown in Formula I.

[0066]

[0067] The reaction process is as follows:

[0068]

[0069] According to an embodiment of the present invention, the compound shown in Formula A is prepared by Friedel-Crafts alkylation of aniline. Formic acid is used as a catalyst in this reaction. During the catalytic process, formic acid first forms an intermediate with 2,3-butanedione, and then further reacts with an amino group, thereby further promoting the forward reaction.

[0070] According to an embodiment of the present invention, the first organic solvent includes at least one selected from methanol, tetrahydrofuran, N,N-dimethylformamide, p-toluenesulfonamide, toluene, and dichloromethane.

[0071] According to embodiments of the present invention, there are no particular limitations on 2,3-butanedione and the compound shown in Formula A, and they can be selected and adjusted according to actual production conditions, product requirements, and usage requirements. Preferably, the molar ratio of 2,3-butanedione and the compound shown in Formula A is greater than 1, so that 2,3-butanedione is in excess, thereby promoting the forward reaction.

[0072] According to embodiments of the present invention, a metal complex of formula II is also provided, wherein M includes any one of nickel and palladium; X and Y are each independently selected from any one of halogens, C1-C6 alkanes, C2-C6 alkenes, allyl groups, and substituted or unsubstituted aryl groups; R1, R2, R3, R4, and R5 are each independently selected from any one of hydrogen, halogens, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted fused-ring groups; when there are substituents on the alkyl, aryl, heterocyclic, alkoxy, or fused-ring groups, the substituents are each independently selected from hydrogen, deuterium, C1-C6 alkenes, C2 ... 60 alkoxy groups, C1-C 60 Alkyl groups, C1-C 60 Fluoroalkyl, C1-C 60 At least one of alkyl, nitro, and halogen groups.

[0073]

[0074] According to an embodiment of the present invention, the definitions of R1, R2, R3, R4, and R5 in Formula II are as described above and will not be repeated here.

[0075] According to embodiments of the present invention, the insertion position of the metal coordination center in the formed metal complex has a good regulatory effect on the catalytic polymerization of olefin monomers. By constructing a suitable steric space, the selectivity and yield of the reaction are improved, chain transfer is suppressed, thereby reducing the branching degree of the prepared polymer and improving the controllability of the reaction.

[0076] According to embodiments of the present invention, the above-mentioned metal complexes include formulas II1 to II. 12 Compounds with the structure shown:

[0077]

[0078]

[0079] According to an embodiment of the present invention, the metal complex is formed by coordination of the ligand compound as described above with a divalent metal compound; the divalent metal compound includes at least one of NiCl2, NiBr2, NiI2, (DME)NiBr2, Ni(allyl)Cl, and [Ni(PPh3)2PhCl].

[0080] According to embodiments of the present invention, a method for preparing metal complexes of formula II is also provided.

[0081] According to an embodiment of the present invention, taking the preparation of a divalent nickel complex as an example, the specific preparation steps may include: under anhydrous and oxygen-free conditions, adding 1 mmol of the compound shown in Formula I and 1.1 mmol of lithium diisopropylamino (LDA) to a second organic solvent and mixing and stirring, then filtering and washing to remove the solvent, followed by adding 1 mmol of the divalent metal compound Ni(allyl)Cl and mixing and stirring overnight, then filtering, concentrating, washing, and drying to obtain the metal complex shown in Formula II. The reaction process is shown below:

[0082]

[0083] It should be noted that the bond form below Ni in the above reaction formula represents the coordination of the allyl group with the nickel center, not a covalent or ionic bond. The second organic solvent can be, for example, tetrahydrofuran solvent dried with calcium hydride. In the formula, [Ni(allyl)Cl]2 indicates that the divalent metal compound Ni(allyl)Cl is a repeating unit in the reaction.

[0084] According to embodiments of the present invention, the step of preparing the metal complex of formula II is preferably carried out in a protective atmosphere, and the reaction conditions are more preferably carried out under anhydrous and oxygen-free or nearly anhydrous and oxygen-free conditions. The protective atmosphere may be, for example, nitrogen or other inert gases.

[0085] According to an embodiment of the present invention, the molar ratio of the compound shown in Formula I, LDA, and the divalent metal compound is preferably 1:1.1:1.

[0086] According to embodiments of the present invention, a metal catalyst composition is also provided, comprising the metal complex described above and a co-catalyst, and optionally including a support for co-catalyst activation treatment. The co-catalyst comprises an organoboron compound or an alkylaluminum. Here, "optional" means that the above-described support may or may not be added.

[0087] According to embodiments of the present invention, by introducing a soluble co-catalyst with Lewis acidity into the butanedione framework, the electron cloud density of the metal center can be significantly reduced, and the introduction of the support can increase the steric hindrance effect, which is beneficial to improving the catalytic activity and thermal stability of subsequent olefin coordination polymerization, and is beneficial to increasing the molecular weight of the product.

[0088] According to embodiments of the present invention, the organoboron compound includes tris(pentafluoroaryl)borane or methylaluminoxane. Tris(pentafluoroaryl)borane or methylaluminoxane has strong acidity, can effectively donate electron pairs, thereby promoting the formation of positive charges in the reaction, and has high catalytic activity.

[0089] According to an embodiment of the present invention, the support activated by the co-catalyst is prepared by the following method: the original support is subjected to heat treatment at 450–550°C for 2–6 hours in an inert gas atmosphere to dehydrate, and then stirred with the co-catalyst in an organic solvent to finally obtain the support; wherein the mass ratio of the original support to the co-catalyst is 3:2 or higher, and the original support includes at least one of silica, magnesium chloride, or aluminum oxide. The support modified with a co-catalyst possessing Lewis acidity can significantly reduce the electron cloud density of the metal center while increasing the steric hindrance effect, thereby enhancing the interaction force between the metal catalyst composition and the support, increasing the number of active sites on the support surface, and thus enhancing the active sites of the metal catalyst composition.

[0090] According to an embodiment of the present invention, preferably, the original support is silica. Preliminary experiments conducted according to the present invention revealed that when the original support is silica, the subsequent catalytic effect on the olefin polymerization reaction is better.

[0091] According to embodiments of the present invention, the metal catalyst composition preferably includes the aforementioned support activated by the co-catalyst, thereby constituting a supported metal catalyst. A method for preparing a supported metal catalyst is also provided, using silica and tris(pentafluoroaryl)borane as an example. The specific preparation method is as follows: Under an anhydrous and oxygen-free atmosphere, 2.0 g of silica is vacuum heat-treated and then mixed with 3.2 g of tris(pentafluoroaryl)borane in a Schlenk flask. A first organic solvent and a small amount of deionized water are added. The resulting solid is collected, washed, and dried to obtain a support modified by the co-catalyst. Further, the metal complex of formula II and the support modified by the co-catalyst are added to the first organic solvent and stirred for 8–16 h, followed by filtration and drying to obtain the supported metal catalyst.

[0092] According to embodiments of the present invention, a metal catalyst composition as described above is also provided for catalyzing C2-C2 catalysts. 11 olefin monomers or C2-C 11 Applications of olefin monomers and polar olefin monomers in polymerization reactions.

[0093] According to embodiments of the present invention, a co-catalyst or a support activated by a co-catalyst, C2-C 11 olefin monomers or C2-C 11 The addition of olefin monomers and polar olefin monomers to an organic solvent results in C2-C... 11 olefin monomers or C2-C 11 The olefin monomers and polar olefin monomers undergo coordination polymerization.

[0094] According to embodiments of the present invention, the olefin monomer includes at least one selected from ethylene, propylene, butene, hexene, and norbornene; the polar olefin monomer includes at least one selected from methyl 10-undecenoate, hexachloro-1-hexene, acrylate, methyl acrylate, vinyl ether, vinyl acetate, and polar norbornene; the polar norbornene includes at least one selected from 5-norbornen-2-methanol, methyl 5-norbornen-2-carboxylate, 5-norbornen-2-ylacetate, 5-norbornen-2-carboxylic acid, and 5-norbornen-2-ol. During the screening of polar olefin monomers and olefin monomers, it was found that when the polar olefin monomers and olefin monomers were selected from the specific compounds mentioned above, the resulting polymers had higher molecular weights, stronger activity, and lower branching degrees. The conditions for coordination polymerization are as follows: a temperature of 0–100°C, for example, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, but not limited thereto; a pressure of 0.1–10 MPa, for example, 0.1 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, or 10 MPa, but not limited thereto; and a coordination polymerization time of 0.1–1 h, for example, 0.1 h, 0.2 h, 0.3 h, 0.4 h, 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, or 1 h, but not limited thereto.

[0095] This invention provides butanedione ligand compounds and their metal complexes, metal catalyst compositions, and their applications. By introducing [N,O]-type ligand compounds with Lewis base molecules to form metal complexes with nickel or palladium metals, and then combining them with Lewis acids (such as co-catalysts) for regulation, catalytic activity and molecular weight of olefin polymerization products are improved. For example, the catalytic behavior of nickel catalysts in homogeneous ethylene polymerization can be adjusted by adding Lewis acids, such as extending soluble Lewis acids to their supported counterparts (e.g., BCF / SiO2 or MAO / SiO2). Heterogeneous catalytic ethylene polymerization systems were also explored. Compared to homogeneous catalysts, heterogeneous nickel catalyst mixtures exhibit higher activity and thermal stability during ethylene polymerization, and can obtain higher molecular weight polyethylene (M...) with better morphology control. n Content reaches 2.05×10 6 (g / mol). Furthermore, these immobilized nickel catalyst systems can promote the copolymerization of ethylene with polar monomers, generating copolymers with higher molecular weight and higher activity. The ease of Lewis acid-induced olefin (co)polymerization provides more opportunities for the synthesis of high-performance polyolefin materials and may inspire further applications in other metal catalysis fields.

[0096] The present invention will be further illustrated by the following embodiments. In the detailed description below, numerous specific details are set forth for ease of explanation to provide a comprehensive explanation of the embodiments of the present invention. However, it will be apparent that one or more embodiments may be practiced without these specific details. Moreover, the details in the following embodiments can be arbitrarily combined to form other feasible embodiments without conflict.

[0097] It should be noted that the following embodiments illustrate the specific content of the present invention, and the data given include the synthesis of ligands, the synthesis of metal compounds, and methods for ethylene polymerization or copolymerization. The synthesis of complexes and polymerization processes are carried out under anhydrous and oxygen-free conditions. All sensitive substances are stored in a glove box at -30°C, all solvents are rigorously dried to remove water, and ethylene gas is purified by passing it through a dehydration and deoxygenation column. Unless otherwise specified, all raw materials are used directly after purchase. The methods used in the following embodiments, such as column chromatography, are methods well-known in the art and can be described in textbooks or relevant literature, and will not be elaborated further.

[0098] In this embodiment of the invention, 200-300 mesh silica gel was used for the silica gel column, NMR was performed using a Bruker 400MHz NMR instrument, and elemental analysis was conducted by the Physical and Chemical Research Center of the University of Science and Technology of China. The molecular weight and molecular weight distribution of amorphous polymers were determined by GPC, specifically using polystyrene columns (HR2 and HR4), at an oven temperature of 45°C, using Water1515 and Water2414 pumps. The mobile phase was tetrahydrofuran, with a flow rate of 1.0 mL / min, and polydisperse polystyrene was used as the standard. The molecular weight and molecular weight distribution of crystalline polymers were determined by high-temperature GPC, specifically at 150°C, using a PL-GPC220 with an infrared probe (658 nm), and 1,2,4-trichlorobenzene as the mobile phase, with a flow rate of 1.0 mL / min. Mass spectrometry was performed using a Thermo LTQ Orbitrap XL (ESI+) or P-SIMS-Gly of Bruker Daltonics Inc (EI+). Single-crystal X-ray diffraction analysis was performed using an Oxford Diffraction Gemini S Ultra CCD single-crystal diffractometer, CuKα. Room temperature radiation.

[0099] Example 1:

[0100] Synthesis of ligand compound L1:

[0101]

[0102] 2,3-Butanedione and 2,6-diisopropylaniline were mixed in a 250 mL round-bottom flask. Toluene was used as the organic solvent, and the catalyst p-toluenesulfonamide (PTSA) was added to the mixture. The mixture was heated to reflux until the reaction was confirmed to be complete by thin-layer chromatography. The heater was then turned off, and the reaction was allowed to cool naturally to room temperature. The toluene was then concentrated and evaporated. The separated liquid was collected and distilled under reduced pressure to give a yellow liquid containing the ligand compound L1, with a yield of 92%. Figure 1 The above is the 1H NMR spectrum of the ligand compound L1 prepared in Example 1 of this invention, as shown below. Figure 1 The structure of the prepared product can be determined as shown. 1 H NMR (400MHz, CDCl3) δ7.19-7.13(m,2H),7.13-7.07(m,1H),2.59(s,2H),2.57(d,J=10.5Hz,5H),1.82(s,3H),1.14(dd,J=6.9,5.2Hz,12H).

[0103] Example 2:

[0104] Synthesis of ligand compound L2:

[0105]

[0106] 2,3-Butanedione and 2,6-diphenylmethyl-4-methylaniline were mixed in a 250 mL round-bottom flask. Toluene was used as the organic solvent, and the catalyst PTSA was added to the mixture. The mixture was heated to reflux until the reaction was confirmed to be complete by thin-layer chromatography. The heater was then turned off, and the reaction was allowed to cool naturally to room temperature. The toluene was then concentrated and evaporated, and recrystallized from dichloromethane / methanol to give a yellow solid of ligand compound L2 in 90% yield. Figure 2 The 1H NMR spectrum of the ligand compound L2 prepared in Example 2 of this invention is shown below. Figure 2 The structure of the prepared product can be determined as shown. 1 H NMR (400MHz, CDCl3) δ7.31-7.08(m,14H),7.07-6.93(m,8H),6.65(s,2H),5.10(s,2H),2.32(s,3H),2.14(s,3H),0.67(s,3H).

[0107] Example 3:

[0108] Synthesis of nickel complex Ni1:

[0109]

[0110] Anhydrous tetrahydrofuran (THF) was added to a Schlenk flask at -78°C, followed by 1 mmol of the ligand compound L1 prepared in Example 1. Then, 1.1 mmol of lithium diisopropylamino (LDA) was slowly added dropwise. After mixing and stirring for 1 h, the mixture was filtered through diatomaceous earth and distilled under reduced pressure to remove the organic solvent, yielding the lithium salt of ligand compound L1. 1 mmol of Ni(allyl)Cl was mixed with the lithium salt of ligand compound L1, and an appropriate amount of anhydrous dichloromethane solution was added. The mixture was stirred overnight. The resulting solution was then filtered through diatomaceous earth to obtain a yellow-green solution, which was subsequently concentrated and recrystallized from dichloromethane / n-hexane. The solution was then filtered through a glove box, washed three times with n-hexane, and finally dried under a nitrogen atmosphere to obtain a yellow solid Ni1 with a reaction yield of 88%. Figure 3 The image shows the X-ray diffraction single-crystal structure of the nickel complex Ni1 prepared in Example 3 of this invention, with reference to... Figure 3 As shown, the specific spatial structure of the prepared Ni1 can be determined.

[0111] Example 4:

[0112] Synthesis of nickel complex Ni2:

[0113]

[0114] The preparation steps in Example 4 are the same as in Example 3, the only difference being the added raw materials, which will not be repeated here. A yellow solid Ni2 was finally obtained, with a reaction yield of 92%. Figure 4 The image shows the 1H NMR spectrum of the nickel complex Ni2 prepared in Example 4 of this invention.

[0115] Figure 5 This is the carbon NMR spectrum of the nickel complex Ni2 prepared in Example 4 of the present invention.

[0116] Figure 6 This is a two-dimensional nuclear magnetic resonance spectrum of the nickel complex Ni2 prepared in Example 4 of the present invention.

[0117] 1H NMR (400MHz, CDCl3) δ7.32(m,7H),7.25-7.07(m,12H),7.03(s,3H),6.81(s,1H),6.72(s,1H),5.88(s,1H),5.57(s,1H),5.14(m,1H),4.69( s,1H),4.28(s,1H),3.10(d,J=5.0Hz,1H),2.21(s,3H),1.98(d,J=13.1Hz,1H),1.59(d,J=6.7Hz,1H),0.88(d,J=12.8Hz,1H),0.74(s,3H). 13 CNMR(101MHz, CDCl3)δ183.20,167.06,144.93,142.14,142.05,141.99,141.82,135.66,134.96,134.92,130.03,129.89,129.86,1 29.57,129.09,128.99,128.74,128.67,128.63,126.77,126.66,126.60,110.77,95.03,52.37,52.30,52.25,51.19,21.50,15.84. refer to Figure 4 and Figure 5 The diagram shows the structure of the prepared product. (Reference) Figure 6 As shown, the coupling effect of hydrogen atoms on the allyl group can be further verified. Figure 4 The arrangement of hydrogen atoms.

[0118] Example 5:

[0119] Synthesis of the supported nickel catalyst Ni2-BCF / SiO2:

[0120] Under a nitrogen atmosphere, 2.0 g of SiO2 was heat-treated at 500 °C under vacuum for 4 h, and then mixed with 3.2 g of tris(pentafluoroaryl)borane (B(C6F5)3) in a Schlenk flask. 100 mL of toluene and a small amount of deionized water were added, and the resulting solid product was collected and washed with dry toluene (3 × 10 mL). The powder was then transferred to a Schlenk tube and dried under vacuum at 100 °C for 3 h to obtain solid BCF / SiO2, where BCF represents B(C6F5)3, which has Lewis acidity.

[0121] The nickel complex Ni2 was then mixed with Lewis acid-modified BCF / SiO2 and stirred in toluene for 3 h. The solid precipitate was then washed three times with toluene. The maximum loading of this catalyst composition was approximately 5 μmol Ni2 / 100 mg BCF / SiO2.

[0122] Example 6:

[0123] Synthesis of the supported nickel catalyst Ni1-BCF / SiO2:

[0124] The preparation method of Example 6 is largely the same as that of Example 5, and will not be repeated here. The only difference is that the added nickel complex is Ni1, and the final product is Ni1-BCF / SiO2.

[0125] Example 7:

[0126] Synthesis of the supported nickel catalyst Ni2-MAO / SiO2:

[0127] Under a nitrogen atmosphere, 2.0 g of SiO2 was heat-treated at 500 °C under vacuum for 4 h, then mixed with 2 g of methylaluminoxane (MAO) in a Schlenk flask, and then 50 mL of toluene was added and stirred thoroughly. The resulting solid product was collected and washed with dry toluene (3 × 10 mL), and the powder was transferred to a Schlenk tube and dried under vacuum at 100 °C for 3 h to obtain solid MAO / SiO2.

[0128] The nickel complex Ni2 was then mixed with Lewis acid-modified MAO / SiO2 and stirred in toluene for 3 h. The solid precipitate was then washed three times with toluene. The maximum loading of this catalyst composition was approximately 5 μmol Ni2 / 100 mg MAO / SiO2.

[0129] Example 8:

[0130] Synthesis of supported nickel catalyst Ni1-MAO / SiO2:

[0131] The preparation method of Example 8 is largely the same as that of Example 7, and will not be repeated here. The only difference is that the added nickel complex is Ni1, and the final product is Ni1-MAO / SiO2.

[0132] Example 9:

[0133] Synthesis of the nickel catalyst composition Ni1-BCF:

[0134] Under a nitrogen atmosphere, a stir bar, 10 equivalents of BCF, and a nickel complex Ni1 were added to a 350 mL pressure-resistant bottle in a glove box and mixed to finally prepare the nickel catalyst composition Ni1-BCF.

[0135] Example 10:

[0136] Synthesis of the nickel catalyst composition Ni2-BCF:

[0137] The preparation method of Example 10 is largely the same as that of Example 9, and will not be repeated here. The only difference is that the added nickel complex is Ni2, and Ni2-BCF is finally prepared.

[0138] Example 11:

[0139] Synthesis of the nickel catalyst composition Ni1-MAO:

[0140] The preparation method of Example 11 is largely the same as that of Example 9, and will not be repeated here. The only difference is that the added co-catalyst is MAO, and Ni1-MAO is finally prepared.

[0141] Example 12:

[0142] Synthesis of the nickel catalyst composition Ni2-MAO:

[0143] The preparation method of Example 12 is largely the same as that of Example 10, and will not be repeated here. The only difference is that the added nickel complex is Ni2, and Ni2-MAO is finally prepared.

[0144] The nickel complexes and nickel catalyst compositions prepared in Examples 3-4 and 9-12 were tested for their catalytic performance in ethylene polymerization.

[0145] In a typical experiment, for the nickel complex and nickel catalyst composition, under a nitrogen atmosphere in a glove box, a stir bar and 28 mL of toluene were added to a 350 mL pressure vessel. The pressure vessel was connected to a high-pressure pipeline and the solution was degassed. The vessel was heated to 30°C, 50°C, and 80°C respectively using an oil bath and allowed to equilibrate for 15 minutes. 2 μmol of the nickel complex and nickel catalyst composition prepared in Examples 3-4 and 9-12 of CH2Cl2 was injected into the polymerization system using a syringe. The reactor was pressurized under rapid stirring and maintained at 8.0 atm of ethylene. After 30 minutes, the pressure vessel was vented and a 5% methanol-hydrochloric acid solution was added to precipitate the solid. The solid was washed three times with pure methanol and dried.

[0146] The relevant data obtained for the catalytic ethylene polymerization reaction are shown in Table 1 below. Table 1 shows the specific experimental conditions for ethylene polymerization provided by this invention, including data on the polymerization results such as catalyst (Cat.), co-catalyst (Cocat.), temperature (T), yield (yield), catalytic activity (Act.), polymer molecular weight (Mn), and polymer molecular weight distribution (PDI).

[0147] Table 1: Polyethylene Polymerization Data

[0148]

[0149] a Polymerization conditions: Catalyst: 5 μmol, 2 mL dichloromethane, 18 mL toluene, ethylene pressure: 8 atm, reaction time: 0.5 h, activity unit: (10) 5 K. Moore -1 ·Hour -1 ). b Yields and activities were averaged from at least two runs. c was determined by gel permeation chromatography (GPC) in trichlorobenzene at 150°C, using polystyrene as a standard. d From C2D2Cl4 at 120 degrees Celsius 1 H NMR determination. e Measured by differential scanning calorimetry (DSC, with secondary heating).

[0150] The supported nickel catalysts prepared in Examples 5 and 7 were tested for their catalytic performance in the homopolymerization of ethylene.

[0151] For the supported nickel catalyst, under a nitrogen atmosphere, in a glove box, a stir bar and 28 mL of toluene were added to a 100 mL round-bottom flask. The reaction temperature was adjusted to the required value, and the supported nickel catalysts prepared in Examples 5 and 7 were injected into the polymerization system. After reacting for 1 hour, a 5% methanol-hydrochloric acid solution was added to precipitate the solid. The solid was washed three times with pure methanol, dried, and weighed. The degree of branching was calculated using the polymer's proton NMR spectrum. The relevant data for the catalytic homopolymerization of ethylene are shown in Table 2 below. Table 2 shows the specific experimental conditions for homopolymerization of ethylene provided by this invention, including data on the polymerization results such as catalyst (Cat.), co-catalyst (Cocat.), temperature (T), yield (yield), catalytic activity (Act.), polymer molecular weight (Mn), and polymer molecular weight distribution (PDI).

[0152] Table 2 Data on heterogeneous homopolymers of polyethylene

[0153]

[0154] Polymerization conditions: For nickel catalyst: 5 μmol catalyst, 28 mL toluene, ethylene pressure of 8 atm, reaction time of 0.5 h, activity unit of (10) 5 K. Moore -1 ·Hour -1 ). b Yield and activity are averages from at least two runs. c The determination was performed using gel permeation chromatography (GPC) with polystyrene as the standard in trichlorobenzene at 150°C. d From C2D2Cl4 at 120 degrees Celsius 1H NMR was measured. e was determined by differential scanning calorimetry (DSC, with secondary heating).

[0155] As shown in Table 2, the catalytic activity of the supported nickel catalyst was improved, and the molecular weight of the prepared polyolefin was significantly increased. Ultra-high molecular weight polyethylene was synthesized, with a relative molecular weight as high as 2.05 × 10⁻⁶. 6 g / mol, enabling control over polymer morphology.

[0156] Figure 7 The image shows the 1H NMR spectrum of the nickel complex Ni2 catalyzing the copolymerization of ethylene and methyl 10-undecenoate obtained in Example 4 of this invention. Figure 8 The above is the 1H NMR spectrum of the Ni2-BCF / SiO2-catalyzed copolymer of ethylene and methyl 10-undecanate prepared in Example 5 of this invention. Figure 9 The image shows the 1H NMR spectrum of the Ni2-BCF / SiO2-catalyzed copolymer of ethylene and 6-chloro-1-hexene prepared in Example 5 of this invention. Figures 7-9 As shown, the nickel catalyst composition was verified to catalyze the insertion polymerization of olefin monomers.

[0157] The supported nickel catalysts and nickel catalyst compositions prepared in Examples 5 to 12 were tested for their catalytic performance in the polymerization of ethylene and polar olefin monomers.

[0158] Under a nitrogen atmosphere, in a glove box, 18 mL of toluene and a certain amount of polar monomer were added to a 350 mL autoclave (equipped with a magnetic stirrer, oil bath heating device, and thermometer). The autoclave was connected to a high-pressure pipeline and the pipeline was evacuated. The autoclave was heated to 50°C using an oil bath and held at that temperature for 15 minutes. Quantitative amounts of the nickel catalyst compositions from Examples 5 to 12 and the supported nickel catalyst were injected into the polymerization system using a syringe. The valves were closed, and the ethylene pressure was adjusted to 8 atm. The reaction was allowed to proceed for 1 hour. The reaction was stopped, the reactor was opened, and ethanol / hydrochloric acid (50 / 1) was added to precipitate the solid. The mixture was filtered under reduced pressure and dried in a vacuum drying oven to obtain a white solid.

[0159] The relevant data obtained from the catalytic polymerization reaction of ethylene and polar olefin monomers are shown in Table 3 below. Table 3 shows the specific experimental conditions for homopolymerization of ethylene provided by this invention, including data on the polymerization results such as catalyst (Cat.), co-catalyst (Cocat.), temperature (T), yield (yield), catalytic activity (Act.), polymer molecular weight (Mn), and polymer molecular weight distribution (PDI).

[0160] Table 3: Catalytic polymerization data of ethylene and olefin polar monomers

[0161]

[0162] Polymerization conditions: For nickel catalyst: 10 μmol catalyst, 18 mL toluene, 0.5 M polar monomer, ethylene pressure of 8 atm, reaction time of 1 h, activity unit of (10) 4 K. Moore -1 ·Hour -1 ). b Yield and activity are averages from at least two runs. c The determination was performed using gel permeation chromatography (GPC) with polystyrene as the standard in trichlorobenzene at 150°C. d From C2D2Cl4 at 120 degrees Celsius 1 H NMR determination. e Measured by differential scanning calorimetry (DSC, with secondary heating).

[0163] As shown in Table 3, by comparing the data in the table, it can be seen that the catalytic activity of the supported nickel catalyst is improved, the molecular weight of the prepared polyolefin is significantly increased, and the degree of branching is significantly reduced, indicating that the supported system is more effective than the one using the nickel catalyst composition.

[0164] Figure 10 This is a graph showing the relative molecular weight of the Ni2-BCF / SiO2-catalyzed ethylene polymer prepared in Example 5 of this invention. Figure 10 As shown, it can be demonstrated that the loading activated by Lewis acidic organoboron compounds can improve the control of polyolefin morphology and significantly improve the mechanical properties of the polymer products. Figure 11 These are comparative graphs showing the morphology and activity curves at 80°C of the polymers prepared at 50°C in Examples 7 and 10 of this invention, respectively; wherein... Figure 11 (a) is a diagram of the apparent morphology of the polymer prepared by Ni2-BCF at 50°C in Example 10 of the present invention in solution state;

[0165] Figure 11 (b) is a diagram of the apparent morphology of the polymer prepared by Ni2-MAO / SiO2 at 50°C in Example 7 of the present invention in solution state; Figure 11 (c) is Figure 11 (a) The apparent morphology of the prepared polymer in the solid state; Figure 11 (d) is Figure 11 (b) The apparent morphology of the prepared polymer in the solid state; Figure 11 (e) is a graph showing the relationship between the activity of Ni2-BCF / SiO2 and Ni2-BCF nickel catalysts and time at 80℃; Figure 11(f) shows the relationship between the activity of Ni2-MAO / SiO2 and Ni2-MAO nickel catalysts and time at 80℃. Figure 11 (a)~ Figure 11 (d) Comparison shows that the nickel catalyst, after being supported, can better control the polymer morphology compared to the nickel catalyst composition. Through... Figure 11 (e)~ Figure 11 (f) The comparison shows that the supported nickel catalyst has a significantly improved thermal stability compared to the catalyst with only Lewis acid added.

[0166] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A metal catalyst composition, comprising a metal complex and a carrier activated by a cocatalyst; wherein The cocatalyst is tris (pentafluoroaryl) borane; The metal complex has a structural formula shown in formula (II) : Formula (II) wherein M is selected from any one of nickel, palladium; X, Y are independently selected from any one of halogen, C1-C6 alkane or X, Y form ; R1, R2, R3, R4are each independently selected from any one of substituted or unsubstituted C1-C6alkyl, C6-C10aryl, C1-C6alkoxy; 30 10 alkoxy;​ R5is selected from any one of substituted or unsubstituted C1-C6alkyl, halogen, C1-C6alkoxy, 10 alkoxy; When there are substituents on the alkyl group, the aryl group, and the alkoxy group, the substituents are independently selected from at least one of hydrogen, deuterium, C1-C6 alkoxy, C1-C6 alkyl, C1-C6 fluoroalkyl, fluorine, chlorine, and bromine. 2.The metal catalyst composition according to claim 1, wherein the carrier is prepared by the following method: The original carrier and the cocatalyst are placed in an inert gas atmosphere and subjected to heat treatment at 450-550 ℃ for 2-6 h to obtain the carrier; The mass ratio of the original carrier to the cocatalyst is 3:2 or more, and the original carrier is selected from at least one of silicon dioxide, magnesium chloride, and aluminum oxide. The metal complex is formed by coordination of a ligand compound and a divalent metal compound; 3. The metal catalyst composition of claim 1, wherein, The divalent metal compound is selected from at least one of NiCl2, NiBr2, NiI2, (DME) NiBr2, Ni (allyl) Cl, and [Ni (PPh3) 2PhCl]. The ligand compound has a structural formula shown in formula (I) :

4. The metal catalyst composition of claim 3, wherein, R1, R2, R3, R4, and R5 are the same as in claim 1. Formula (I) 9.The use according to claim 8, wherein the olefin monomer is selected from at least one of ethylene, propylene, butene, hexene, and norbornene; 5. The metal catalyst composition of claim 1, wherein, R1, R2, R3, R4are each independently selected from any one of substituted or unsubstituted C2-C5alkyl, C8-C12aryl, C2-C8alkoxy. 25 R1, R2, R3, R4are each independently selected from any one of substituted or unsubstituted C2-C5alkyl, C8-C12aryl, C2-C8alkoxy.

6. The metal catalyst composition of claim 1, wherein, R1, R2, R3, R4are each independently selected from any one of substituted or unsubstituted C3-C4alkyl, C 10 20 aryl, C4-C6alkoxy.​ 7. The metal catalyst composition of claim 4, wherein, The ligand compound has a structure represented by any one of Formulas (I1) to (I 12 ) below: Formula (I1) Formula (I2) Formula (I3) Formula (I4) Formula (I5) Formula (I6) Formula (I7) Formula (I8) Formula (I9) Formula (I 10 ) Formula (I 11 ) Formula (I 12 ).

8. Use of a metal catalyst composition as claimed in any one of claims 1 to 7 in catalysing the polymerisation of C2 to C4 olefin monomers or C2 to C4 olefin monomers and polar olefin monomers. 11 11 monomers.​ The metal catalyst composition, C2~C 11 olefin monomer or C2~C11olefin monomer and a polar olefin monomer are added to an organic solvent, so that the C2~C 11 olefin monomer or the C2~C 11 olefin monomer and the polar olefin monomer undergo coordination polymerization. The polar olefin monomer is selected from at least one of 10-undecylenic acid methyl ester, hexachloro-1-hexene, acrylate, vinyl ether, vinyl acetate, and polar norbornene; The polar norbornene is selected from at least one of 5-norbornene-2-methanol, 5-norbornene-2-carboxylic acid methyl ester, 5-norbornene-2-yl acetate, 5-norbornene-2-carboxylic acid, and 5-norbornene-2-ol; The coordination polymerization conditions are a temperature of 0-100 ℃, a pressure of 0.1-10 MPa, and a coordination polymerization time of 0.1-1 h. ​ ​

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