Ligand compounds, iron / nickel complexes, catalysts, and methods of making and using the same

Abstract

The application discloses a ligand compound, an iron / nickel complex, a catalyst and a preparation method and application thereof, wherein the ligand compound is shown as formula I, formula II or formula III, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 The iron / nickel complex is shown as formula IV, formula V or formula VI, and the supported iron / nickel catalyst comprises a carrier and the iron / nickel complex supported on the carrier. The supported iron / nickel catalyst is applied to catalyze the polymerization of olefins. By introducing a sodium sulfonate substituent into the amine ligand compound, the amine nickel / iron complex containing the sodium sulfonate substituent is obtained. After the amine nickel / iron complex containing the sodium sulfonate substituent is supported to form the catalyst, the catalyst has higher stability and activity, and the polymerization efficiency is improved.

Description

Technical Field

[0001] This invention belongs to the field of polymers, specifically relating to a ligand compound, an iron / nickel complex, its preparation method, and its application. Background Technology

[0002] Synthesizing polyolefins via coordination insertion mechanisms is an important topic in polymer science. Heterogeneous catalysts are commonly used, offering advantages such as the ability to control polymer morphology and prevent reactor fouling. However, post-transition metal catalysts can directly copolymerize olefins with polar monomers to obtain functionalized polyolefins. These post-transition metal catalysts include homogeneous palladium and nickel catalysts. Therefore, to leverage the advantages of both, loading homogeneous catalysts onto solid supports to create heterogeneous catalysts is an important strategy bridging these two fields.

[0003] There are three main methods for anchoring metal complexes onto supports in post-transition metal heterogeneous catalysts. Method 1: Directly loading the metal complex (or a metal complex activated by a co-catalyst) onto a solid support to prepare a supported catalyst, such as a phosphonate-palladium system supported on clay or silica, exhibiting moderate activity (142 kg / mol). -1 h -1 Method 1: This method yields catalysts with higher acrylate comonomer insertion (4.3%) and lower copolymer molecular weight (Mn = 4700 g / mol), but the resulting catalysts are not suitable for polymerization of sensitive active substances. Method 2: Introducing metal complexes into a support pretreated with a cocatalyst to form ion pairs and prepare supported catalysts. This method is widely used in modified α-diimine nickel catalytic systems, such as silica, magnesium chloride, and zirconium sulfate. Method 3: Designing metal complexes with specific reaction sites and reacting them with an aluminum cocatalyst to form covalent bonds between the metal complex and the support, thus preparing supported catalysts. These metal complexes typically possess reactive functional groups such as hydroxyl, amino, cyano, or carbonyl groups. Most of these methods require pretreatment of the support with large amounts of alkylaluminum or other reagents. These pretreatment reagents can lead to chain transfer and other side reactions during polymerization, complicating the polymerization process.

[0004] A novel loading strategy, based on hydrogen bonding or ion anchoring, allows for direct non-covalent interactions between the support and catalyst, enabling homogeneous catalyst loading onto a solid support without pretreatment. Catalysts obtained using this method can achieve highly active ethylene homopolymerization and copolymerization of ethylene with polar monomers. For example, by using the ion anchoring strategy to introduce sodium oxygen ions into the ligand structure, the catalyst achieves higher loading efficiency and copolymerizes ethylene with a series of polar monomers (methyl acrylate, allyl chloride, acrylonitrile, etc.), yielding a catalyst with a molecular weight of 83.4 × 10⁻⁶. 4Copolymer of g / mol.

[0005] To expand research on ion anchoring strategies for designing novel heterogeneous catalysts, it is still necessary to find other anchoring functional groups that can form stronger non-covalent interactions with solid supports in order to better suppress catalyst leaching during olefin polymerization, improve loading efficiency, and prepare high-performance heterogeneous polyolefin catalysts. Summary of the Invention

[0006] In view of this, the main objective of the present invention is to provide a ligand compound, an iron / nickel complex, a catalyst, a method for preparing the same, and its application. Based on a novel loading strategy, the ligand compound can form anchored functional groups with a solid support that have stronger non-covalent interactions, thereby loading a catalyst with better performance and improving the efficiency of olefin polymerization.

[0007] To achieve the above objectives, the present invention provides a ligand compound having the structural formula shown in Formula I, Formula II, or Formula III:

[0008]

[0009] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each methyl group is independently selected from H, C1-C20 alkyl, and C6-C20 aryl substituted.

[0010] According to an embodiment of the present invention, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each group is independently selected from one of the following: hydrogen, methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, isopropyl, group A, group B, group C, group D, and group E.

[0011]

[0012] According to an embodiment of the present invention, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 They are isopropyl, respectively.

[0013] The present invention also provides a method for preparing the ligand compound as described above, comprising:

[0014] Compound F and compound G are reacted to generate a ligand compound as shown in Formula I;

[0015]

[0016] Compounds H, J, and K are reacted to generate ligand compounds as shown in Formula II;

[0017]

[0018] Compounds L, O, and P are reacted to generate ligand compounds as shown in Formula III.

[0019]

[0020] The present invention also provides an iron / nickel complex formed from the above-described ligand compounds, the structural formula of which is shown in Formula IV, Formula V or Formula VI:

[0021]

[0022] According to an embodiment of the present invention, M is nickel or iron, and X is chlorine or bromine.

[0023] The present invention also provides a method for preparing the iron / nickel complex as described above, comprising:

[0024] Under nitrogen atmosphere, the ligand compound and MX compound were added to an organic solvent and stirred for 11-13 hours. After filtration, the mixture was recrystallized to obtain the iron / nickel complex.

[0025] According to embodiments of the present invention, the MX compound includes: DMENiBr2 or FeCl2.

[0026] The present invention also provides a supported iron / nickel catalyst, comprising a support and an iron / nickel complex as described above supported on the support.

[0027] According to embodiments of the present invention, the carrier includes one or more of silicon dioxide, magnesium chloride, and aluminum oxide.

[0028] The present invention also provides a method for preparing the supported iron / nickel catalyst as described above, comprising:

[0029] The iron / nickel complex, support, and organic solvent were stirred under nitrogen atmosphere for 11-13 hours.

[0030] After filtration and drying, the supported iron / nickel catalyst can be obtained.

[0031] The present invention also provides the application of the supported iron / nickel catalyst as described above in the catalytic polymerization reaction of olefins, wherein the olefin is selected from at least one of C2 to C20 olefins.

[0032] According to the ligand compounds, nickel-iron complexes, their preparation methods, and applications provided by the present invention, by introducing sodium sulfonate substituents into amine ligand compounds, amine nickel / iron complexes containing sodium sulfonate substituents are obtained. After the amine nickel / iron complexes containing sodium sulfonate substituents are supported to form catalysts, the oxygen atoms on the sodium sulfonate groups can form strong hydrogen bonds with the hydrogen atoms on the support, allowing the nickel / iron complex to contact the support more closely, achieving a better loading effect. This results in the catalyst exhibiting higher tolerance to polar monomers during the polymerization reaction, thus exhibiting higher stability and activity, improving polymerization efficiency, increasing the molecular weight of the polymerized product, and enabling good control over the product morphology. Attached Figure Description

[0033] Figure 1 The 1H NMR spectrum of the ligand compound obtained in Example 1 according to an embodiment of the present invention is shown;

[0034] Figure 2 The carbon NMR spectrum of the ligand compound obtained in Example 1 according to an embodiment of the present invention is shown;

[0035] Figure 3 The mass spectrum of the ligand compound obtained in Example 1 according to an embodiment of the present invention is shown;

[0036] Figure 4 The 1H NMR spectrum of the ligand compound obtained in Example 2 according to an embodiment of the present invention is shown;

[0037] Figure 5 The mass spectrum of the ligand compound obtained in Example 2 according to an embodiment of the present invention is shown;

[0038] Figure 6 The 1H NMR spectrum of the ligand compound obtained in Example 3 according to an embodiment of the present invention is shown;

[0039] Figure 7 The carbon NMR spectrum of the ligand compound obtained in Example 3 according to an embodiment of the present invention is shown;

[0040] Figure 8 The mass spectrum of the ligand compound obtained in Example 3 according to an embodiment of the present invention is shown;

[0041] Figure 9 The mass spectrum of the complex Ni1 obtained in Example 4 according to an embodiment of the present invention is shown;

[0042] Figure 10 The mass spectrum of the complex Ni2 obtained according to Example 5 of the present invention is shown;

[0043] Figure 11 The mass spectrum of the complex Fe1 obtained according to Example 6 of the present invention is shown. Detailed Implementation

[0044] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments.

[0045] This invention provides a ligand compound with the structural formula shown in Formula I, Formula II, or Formula III:

[0046]

[0047] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each methyl group is independently selected from H, C1-C20 alkyl, and C6-C20 aryl substituted.

[0048] According to the ligand compound provided by the present invention, a sodium sulfonate substituent is introduced into an amine ligand compound. The amine nickel / iron complex obtained based on this specific structure contains a sodium sulfonate substituent. After being supported to form a catalyst, the oxygen atom on the sodium sulfonate group can form a strong hydrogen bond with the hydrogen atom on the support, allowing the nickel / iron complex to contact the support more closely, achieving a better loading effect. This results in the catalyst exhibiting higher polar monomer tolerance during the polymerization reaction, thus exhibiting higher stability and activity, improving polymerization efficiency, increasing the molecular weight of the polymerized product, and enabling good control over the product morphology.

[0049] According to an embodiment of the present invention, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each group is independently selected from one of the following: hydrogen, methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, isopropyl, group A, group B, group C, group D, and group E.

[0050]

[0051] According to an embodiment of the present invention, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 They are isopropyl, respectively.

[0052] The present invention also provides a method for preparing the ligand compound as described above, comprising:

[0053] Compound F and compound G are reacted to generate a ligand compound as shown in Formula I;

[0054]

[0055] Compounds H, J, and K are reacted to generate ligand compounds as shown in Formula II;

[0056]

[0057] Compounds L, O, and P are reacted to generate ligand compounds as shown in Formula III.

[0058]

[0059] According to an embodiment of the present invention, as shown in the following reaction formula, aniline substituted with R1 and R2 reacts with concentrated sulfuric acid and sodium bicarbonate to generate compound F.

[0060]

[0061] The reaction steps that generate compound F may include, for example:

[0062] The aniline substituted with R1 and R2 was stirred with concentrated sulfuric acid at room temperature for 20 min; the mixture was then heated in an oil bath to 160℃ and reacted for 30 min, during which a white solid was observed to form in the flask; the temperature was further increased to 190℃ and reacted for 4 h, during which a gray solid was observed to form in the flask; the temperature was lowered to 80℃ and NaOH was added and refluxed for 1.5 h; the reaction solution was filtered while hot, and the pH of the solid was adjusted to 1.5 with hydrochloric acid; 12 ml of water and NaHCO3 were added to adjust the pH to 8, and the mixture was refluxed for 2 h; NaCl was filtered while hot, and the filtrate was allowed to evaporate naturally, crystals were precipitated, and the filtrate was filtered to obtain compound F.

[0063] According to embodiments of the present invention, as shown in the following reaction formula, replacing the aniline substituted with R1 and R2 with aniline substituted with R3 and R4 yields compound H; replacing the aniline substituted with R1 and R2 with aniline substituted with R7 and R8 yields compound L; replacing the aniline substituted with R1 and R2 with R9 and R4 yields compound L. 10 The substituted aniline yields compound O.

[0064]

[0065] According to an embodiment of the present invention, compound F and compound G are reacted to generate a ligand compound as shown in Formula I, the reaction steps including:

[0066] Compound F, compound G, formic acid, and methanol were mixed and refluxed at 80°C for 12 hours. The solution was concentrated and anhydrous diethyl ether was added, and a yellow-green solid precipitated from the solution. The yellow-green solid was separated by filtration, washed with diethyl ether, and dried under high vacuum to obtain the ligand compound shown in Formula I.

[0067] According to an embodiment of the present invention, compounds H, J, and K are reacted to generate a ligand compound as shown in Formula II, the reaction steps including:

[0068] Compounds H, J, and K, formic acid, and methanol were mixed and refluxed at 80°C for 12 hours. The solution was concentrated and anhydrous diethyl ether was added, resulting in the precipitation of an orange-yellow solid. The orange-yellow solid was separated by filtration, washed with diethyl ether, and dried under high vacuum to obtain the ligand compound shown in Formula II.

[0069] According to an embodiment of the present invention, compound L, compound O and compound P are reacted to generate a ligand compound as shown in Formula III, the reaction steps including:

[0070] Compound L, compound O, compound P, formic acid, and methanol were mixed and refluxed at 80°C for 12 hours. The solution was concentrated and anhydrous diethyl ether was added, and a grayish-yellow solid precipitated from the solution. The grayish-yellow solid was separated by filtration, washed with diethyl ether, and dried under high vacuum to obtain the ligand compound shown in Formula III.

[0071] According to an embodiment of the present invention, the washing with ether is performed three times or more.

[0072] The present invention also provides an iron / nickel complex formed from the above-described ligand compounds, the structural formula of which is shown in Formula IV, Formula V or Formula VI:

[0073]

[0074] Where M is nickel or iron, and X is chlorine or bromine.

[0075] According to an embodiment of the present invention, when M is Ni, X is preferably Br; when M is Fe, X is preferably Cl.

[0076] The present invention also provides a method for preparing the iron / nickel complex as described above, comprising:

[0077] Under nitrogen atmosphere, the ligand compound and MX compound were added to an organic solvent and stirred for 11-13 hours. After filtration, the mixture was recrystallized to obtain the iron / nickel complex.

[0078] According to embodiments of the present invention, the MX compound includes: DMENiBr2 or FeCl2.

[0079] According to embodiments of the present invention, the reaction of ligand compound I with MX compound generates iron / nickel complex IV, the reaction of ligand compound II with MX compound generates iron / nickel complex V, and the reaction of ligand compound III with MX compound generates iron / nickel complex VI.

[0080] According to an embodiment of the present invention, when the MX compound is DMENiBr2, the reaction steps of ligand compound I with DMENiBr2 include:

[0081] Under nitrogen atmosphere, ligand compound I and DMENiBr2 were added to dichloromethane and stirred for 12 h. After filtering NaBr, the filtrate was dried under vacuum, and hexane was added for recrystallization. The recrystallized solid was filtered and dried under vacuum to obtain a yellow-green solid, which yielded nickel complex VII.

[0082]

[0083] According to an embodiment of the present invention, when the MX compound is DMENiBr2, the reaction steps of ligand compound II with DMENiBr2 include:

[0084] Under nitrogen atmosphere, ligand compound II and DMENiBr2 were added to dichloromethane and stirred for 12 h. NaBr was filtered off and the filtrate was dried. Hexane was added for recrystallization. The recrystallized solid was filtered off and dried to obtain nickel complex VIII.

[0085]

[0086] According to an embodiment of the present invention, when the MX compound is FeCl2, the reaction step of ligand compound III with FeCl2 includes:

[0087] Under nitrogen atmosphere, ligand compound III and FeCl2 were added to tetrahydrofuran and stirred for 12 h. NaCl was filtered off and the filtrate was dried. Hexane was added for recrystallization. The recrystallized solid was filtered off and dried to obtain iron complex IX.

[0088]

[0089] The present invention also provides a supported iron / nickel catalyst, comprising a support and an iron / nickel complex as described above supported on the support.

[0090] According to embodiments of the present invention, the carrier includes one or more of silicon dioxide, magnesium chloride, and aluminum oxide.

[0091] According to an embodiment of the present invention, the carrier is preferably silicon dioxide.

[0092] The present invention also provides a method for preparing the supported iron / nickel catalyst as described above, comprising:

[0093] The iron / nickel complex, support, and organic solvent are stirred under nitrogen for 11-13 hours; after filtration and drying, the supported iron / nickel catalyst is obtained.

[0094] According to embodiments of the present invention, the organic solvent includes dichloromethane.

[0095] The present invention also provides the application of the supported iron / nickel catalyst as described above in the catalytic polymerization reaction of olefins, wherein the olefin is selected from at least one of C2 to C20 olefins.

[0096] According to embodiments of the present invention, the polymerization reaction of olefins includes ethylene homopolymerization, ethylene copolymerization, and long-chain olefin homopolymerization.

[0097] According to an embodiment of the present invention, the ethylene homopolymerization reaction includes: adding a co-catalyst and an organic solvent to a reaction vessel, and then injecting a supported iron / nickel catalyst while ethylene gas is introduced, thereby carrying out a coordination polymerization reaction in ethylene gas at a pressure of 1-50 atmospheres. After the reaction is completed, the reaction is quenched with methanol to complete the homopolymerization of ethylene.

[0098] According to an embodiment of the present invention, the ethylene copolymerization reaction includes: adding a cocatalyst, a comonomer, and an organic solvent to a reaction vessel, and then injecting a supported iron / nickel catalyst while ethylene gas is introduced, thereby carrying out a coordination polymerization reaction in ethylene gas at a pressure of 1-50 atmospheres. After the reaction is completed, the reaction is quenched with methanol to complete the copolymerization of ethylene.

[0099] According to an embodiment of the present invention, the homopolymerization reaction of long-chain olefins includes: adding a co-catalyst, a long-chain olefin monomer, and an organic solvent to a reaction vessel, and then injecting a supported iron / nickel catalyst under nitrogen atmosphere to carry out a coordination polymerization reaction at room temperature and pressure. After the reaction is completed, the reaction is quenched with methanol to complete the homopolymerization of the long-chain olefins.

[0100] According to embodiments of the present invention, the co-catalyst includes: trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, tri-n-butylaluminum, and one or more of alkali metals such as lithium, sodium, and potassium or their alkali metal salts.

[0101] According to embodiments of the present invention, the organic solvent includes one or more of toluene, benzene, and n-heptane.

[0102] According to embodiments of the present invention, the comonomers in the ethylene copolymerization reaction include: methacrylic acid, methyl methacrylate, ethyl methacrylate, 10-undecenol, 10-undecenic acid, 6-chloro-1-hexene, 1-hexene, and 1-octene.

[0103] According to embodiments of the present invention, the long-chain olefin monomers in the homopolymerization reaction of long-chain olefins include: 10-undecenol, 10-undecenic acid, 6-chloro-1-hexene, 1-hexene, and 1-octene.

[0104] The technical solution of the present invention will be further illustrated below with specific examples and accompanying drawings. It should be noted that the specific examples below are merely illustrative, and the data provided include ligand synthesis, metal compound synthesis, ethylene polymerization or copolymerization methods. The synthesis of the complex and the polymerization process are carried out under anhydrous and oxygen-free conditions. Sensitive substances are stored in a glove box, solvents are 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 commercially available.

[0105] Example 1: Preparation of sodium 3,5-diisopropyl-4-((pyridin-2-methylene)amino)benzenesulfonate, the method is as follows:

[0106] 2,6-Diisopropyl-4-(sodium sulfonate)aniline (0.558 g, 2 mmol), 2-pyridinylamine (0.214 g, 2 mmol), and a small amount of formic acid were mixed and stirred in methanol (20 mL) and refluxed at 80 °C for 12 hours. The mixture was analyzed by thin-layer chromatography until a major spot appeared on the TLC plate, indicating high product purity. The solvent was then evaporated under reduced pressure, and the remaining mixture was diluted in diethyl ether (30 mL) and stirred for 1 hour. The pale yellow solid (0.515 g, 73%) was then separated by filtration to obtain sodium 3,5-diisopropyl-4-((pyridin-2-methylene)amino)benzenesulfonate. The synthetic route of this ligand compound is shown in Formula 1.

[0107]

[0108] The pale yellow solid obtained from the reaction was analyzed by proton nuclear magnetic resonance spectroscopy, carbon-13 nuclear magnetic resonance spectroscopy, and high-resolution mass spectrometry. The results are as follows: 1 H NMR (400MHz, DMSO-d6) δ8.74(m,1H),8.28–8.21(m,2H),8.01(m,1H),7.60(m,1H),7.43(s,2H),2.87(p,J=6.9Hz,2H),1.12(d,J=6.9Hz,12H). 13 C NMR(101MHz,DMSO-d6)δ163.93,153.85,150.28,148.80,144.60,137.85,136.28,126.57,121.49,120.86,28.03,23.63.HRMS(m / z):calcd.for C 18 H 21 N2NaO3S:368.1171, found:[M+Na]:391.1037. This indicates that the final product is sodium 3,5-diisopropyl-4-((pyridin-2-methylene)amino)benzenesulfonate. Figure 1The 1H NMR spectrum of the ligand compound obtained in Example 1 according to an embodiment of the present invention is shown. Figure 2 The carbon NMR spectrum of the ligand compound obtained in Example 1 according to an embodiment of the present invention is shown. Figure 3 The mass spectrum of the ligand compound obtained in Example 1 according to an embodiment of the present invention is shown.

[0109] Example 2: Preparation of sodium 4-(1E,2E)-2-(2,6-diisopropylphenyl)imino)acenaphthene-1(2H)-imino)amino)-3,5-diisopropylbenzenesulfonate, the method is as follows:

[0110] 2,6-Diisopropyl-4-(sodium sulfonate)aniline (0.558 g, 2 mmol), 2-[[2,6-bis(1-methylethyl)phenyl]imino]-1(2H)-acenaphthene (1.124 g, 2 mmol), and a small amount of formic acid were mixed and stirred in methanol (20 mL) and refluxed at 80 °C for 12 hours. The mixture was analyzed by thin-layer chromatography until a major spot was found on the TLC plate, indicating high product purity. The solvent was then evaporated under reduced pressure, and the mixture was diluted in diethyl ether (30 mL) and stirred for 1 hour. The orange solid (0.915 g, 76%) was separated by filtration to obtain sodium 4-(1E,2E)-2-(2,6-diisopropylphenyl)imino)acenaphthene-1(2H)-imino)amino)-3,5-diisopropylbenzenesulfonate. The synthetic route of this ligand compound is shown in Formula 2.

[0111]

[0112] The orange solid obtained from the reaction was analyzed by proton nuclear magnetic resonance spectroscopy, carbon-13 nuclear magnetic resonance spectroscopy, and high-resolution mass spectrometry. The results are as follows: 1 H NMR (400MHz, Methanol-d4) δ8.10–8.05(m,2H),7.86(s,2H),7.48(dd,J=11.4,7.5Hz,2H),7.39–7.22(m,3H),6.81(d,J=5.2Hz,1 H),6.68(d,J=4.5Hz,1H),3.05–2.95(m,4H),1.25(dd,J=13.4,6.8Hz,12H),1.02(dd,J=17.6,6.9Hz,12H).HRMS(m / z):calcd.for C 36 H 39 N2NaO3S:602.2579, found:[M+H]:603.2659. This indicates that the final product is sodium 4-(1E,2E)-2-(2,6-diisopropylphenyl)imino)acenaphthene-1(2H)-imino)amino)-3,5-diisopropylbenzenesulfonate. Figure 4 The 1H NMR spectrum of the ligand compound obtained in Example 2 according to an embodiment of the present invention is shown. Figure 5 The mass spectrum of the ligand compound obtained according to Example 2 of the present invention is shown.

[0113] Example 3: Preparation of 4,4'-((1E, 1'E)-pyridine-2,6-diacylbis(ethane-1-yl-1-ylidene))bis(azaacylylidene))bis(sodium 3,5-diisopropylbenzenesulfonate), the method is as follows:

[0114] 2,6-Diisopropyl-4-(sodium sulfonate)aniline (0.558 g, 2 mmol), 1,1'-(pyridin-2,6-diacyl)bis(ethane-1-one) (0.163 g, 1 mmol), and a small amount of formic acid were mixed and stirred in methanol (20 mL) and refluxed at 80 °C for 12 hours until a major spot was observed on a TLC plate, indicating high product purity. The solvent was then evaporated under reduced pressure. The remaining mixture was diluted in diethyl ether (30 mL) and stirred for 1 hour. The brown solid (0.423 g, 65%) was separated by filtration to obtain 4,4'-((1E, 1'E)-pyridin-2,6-diacylbis(ethane-1-yl-1-ylidene))bis(azaacylylidene))bis(3,5-diisopropylbenzenesulfonate). The synthetic route of this ligand compound is shown in Formula 3.

[0115]

[0116] The brown solid obtained from the reaction was analyzed by proton nuclear magnetic resonance spectroscopy, carbon-13 nuclear magnetic resonance spectroscopy, and high-resolution mass spectrometry. The results are as follows: 1 H NMR(400MHz,DMSO-d6)δ8.46(d,J=7.8Hz,1H),8.14(t,J=7.8Hz,1H),7.44(s,3H ),3.16(d,J=4.8Hz,2H),2.70(p,J=6.7Hz,3H),2.22(s,3H),1.13–1.08(m,13H). 13 C NMR(101MHz,Methanol-d4)δ167.78,154.83,147.93,140.15,137.31,135.85,122.24,120.88,28.38,22.04,21.52,21.43,16.32.HRMS(m / z):calcd.for C 33 H 41N3Na2O6S2:653.2232,found:[M+Na]:708.2099. indicates that the final product is 4,4'-((1E,1'E)-pyridin-2,6-diacylbis(ethane-1-yl-1-ylidene))bis(azaacylylidene))bis(sodium 3,5-diisopropylbenzenesulfonate). Figure 6 The 1H NMR spectrum of the ligand compound obtained in Example 3 according to an embodiment of the present invention is shown. Figure 7 The carbon NMR spectrum of the ligand compound obtained in Example 3 according to an embodiment of the present invention is shown. Figure 8 The mass spectrum of the ligand compound obtained in Example 3 according to an embodiment of the present invention is shown.

[0117] Example 4: Preparation of sodium nickel 3,5-diisopropyl-4-(pyridin-2-methylene)amino)benzenesulfonate complex, the method is as follows:

[0118] Under a nitrogen atmosphere, 0.368 g (1 mmol) of sodium 3,5-diisopropyl-4-((pyridin-2-methylene)amino)benzenesulfonate, 0.262 g (1 mmol) of DMENiBr2 (DME being 1,2-dimethoxyethane), and 10 mL of dichloromethane were introduced into 50 mL of Schlenk. After stirring at room temperature for 12 hours, the product was pretreated with n-hexane, separated by filtration, and dried under vacuum to obtain a pale yellow solid (0.287 g, 78%), which is the nickel complex of sodium 3,5-diisopropyl-4-(pyridin-2-methylene)amino)benzenesulfonate. This complex is denoted as Ni1, and its synthetic route is shown in Formula 4.

[0119]

[0120] The pale yellow solid obtained from the reaction was analyzed by time-of-flight mass spectrometry. The results were: MALDI-TOF-MS (m / z): calcd for C 18 H 21 Br2N2NaNiO3S:583.8891,found:[M-Br] + 503.4431.Anal.Calcd.forC 18 H 21 Br2N2NaNiO3S: C, 36.84; H, 3.61; N, 4.77. Found: C, 36.81; H, 3.65; N, 4.72. This indicates that the final product is a sodium nickel 3,5-diisopropyl-4-(pyridin-2-methylene)amino)benzenesulfonate complex. Figure 9 The mass spectrum of the complex Ni1 obtained in Example 4 according to an embodiment of the present invention is shown.

[0121] Example 5: Preparation of sodium nickel 4-(1E,2E)-2-(2,6-diisopropylphenyl)imino)acenaphthene-1(2H)-imino)amino)-3,5-diisopropylbenzenesulfonate complex, the method is as follows:

[0122] Under a nitrogen atmosphere, 0.602 g (1.0 mmol) of sodium 4-(1E,2E)-2-(2,6-diisopropylphenyl)imino)acenaphthene-1(2H)-ylidene)amino)-3,5-diisopropylbenzenesulfonate, 0.262 g (1 mmol) of DMENiBr2 (DME being 1,2-dimethoxyethane), and 10 mL of dichloromethane were introduced into 50 mL of Schlenk. After stirring at room temperature for 8 hours, the product was precipitated with hexane, separated by filtration, and dried under vacuum to obtain a red solid (0.687 g, 84%), which is the nickel complex of sodium 4-(1E,2E)-2-(2,6-diisopropylphenyl)imino)acenaphthene-1(2H)-ylidene)amino)-3,5-diisopropylbenzenesulfonate. This complex is designated as Ni2, and its synthetic route is shown in Formula 5.

[0123]

[0124] The red solid obtained from the reaction was analyzed by time-of-flight mass spectrometry. The results were: MALDI-TOF-MS (m / z): calcd for C 36 H 39 Br2N2NaNiO3S:818.0299,found:[2M-Br-Na] + 1532.7795.Anal.Calcd.for C 36 H 39 Br2N2NaNiO3S: C, 52.65; H, 4.79; N, 3.41. Found: C, 52.68; H, 4.81; N, 3.43. This indicates that the final product is a sodium nickel complex of 4-(1E, 2E)-2-(2,6-diisopropylphenyl)imino)acenaphthene-1(2H)-imino)amino)-3,5-diisopropylbenzenesulfonate. Figure 10 The mass spectrum of the complex Ni2 obtained according to Example 5 of the present invention is shown.

[0125] Example 6: Preparation of the 4,4'-((1E, 1'E)-pyridine-2,6-diacylbis(ethane-1-yl-1-ylidene))bis(azaacylylidene))bis(sodium 3,5-diisopropylbenzenesulfonate)iron complex, the method is as follows:

[0126] Under a nitrogen atmosphere, 50 mL of Schlenk was charged with 0.685 g (1 mmol) of 4,4'-((1E, 1'E)-pyridin-2,6-diacylbis(ethane-1-yl-1-ylidene))bis(azinoyl-ylidene))bis(3,5-diisopropylbenzenesulfonate sodium salt), FeCl2 (0.128 g, 1 mmol), and 10 mL of tetrahydrofuran. After stirring at room temperature for 8 hours, the product was precipitated with hexane, separated by filtration, and dried under vacuum to give a blue solid (0.632 g, 78%), which is the 4,4'-((1E, 1'E)-pyridin-2,6-diacylbis(ethane-1-yl-1-ylidene))bis(azinoyl-ylidene))bis(3,5-diisopropylbenzenesulfonate sodium salt) iron complex, denoted as Fe1. The synthetic route is shown in Formula 6.

[0127]

[0128] The blue solid obtained from the reaction was analyzed by time-of-flight mass spectrometry. The results were: MALDI-TOF-MS (m / z): calcd for C 33 H 41 Cl2FeN3Na2O6S2:811.0959,found:[M-Cl-Na] + 751.66.Anal.Calcd.forC 33 H 41 Cl2FeN3Na2O6S2:C,48.78;H,5.09;N,5.17.Found:C,48.80;H,5.05;N,5.13. This indicates that the final product is a 4,4'-((1E,1'E)-pyridin-2,6-diacylbis(ethane-1-yl-1-ylidene))bis(azaacylylidene))bis(3,5-diisopropylbenzenesulfonate sodium) iron complex. Figure 11 The mass spectrum of the complex Fe1 obtained according to Example 6 of the present invention is shown.

[0129] Example 7: Preparation of silica catalyst supported on sodium nickel 3,5-diisopropyl-4-(pyridin-2-methylene)amino)benzenesulfonate complex, the method is as follows:

[0130] 2 μg of sodium nickel 3,5-diisopropyl-4-(pyridin-2-methylene)amino)benzenesulfonate complex, 100 mg of silica, and 15 mL of dichloromethane were mixed and stirred at room temperature for 12 h in a glove box. The mixture was filtered and the residue was dried to obtain a light yellow solid, which is the silica-supported catalyst of sodium nickel 3,5-diisopropyl-4-(pyridin-2-methylene)amino)benzenesulfonate complex. This catalyst is denoted as Ni1@SiO2, and its synthetic route is shown in Formula 7.

[0131]

[0132] Example 8: Preparation of silica catalyst supported on sodium nickel 4-(1E,2E)-2-(2,6-diisopropylphenyl)imino)acenaphthene-1(2H)-imino)amino)-3,5-diisopropylbenzenesulfonate complex, the method is as follows:

[0133] 5 μg of the sodium nickel sodium nickel sodium nickel sodium nickel sodium nickel sodium nickel sodium nickel sodium silicate complex, 100 mg of silica, and 15 mL of dichloromethane were stirred in a glove box at room temperature for 12 h. After filtration and drying, a light orange solid was obtained, which is the silica catalyst supported on the sodium nickel sodium nickel sodium nickel sodium nickel sodium silicate complex. This catalyst is denoted as Ni2@SiO2, and its synthesis route is shown in Formula 8.

[0134]

[0135] Example 9: Preparation of silica catalyst supported on 4,4'-((1E, 1'E)-pyridine-2,6-diacylbis(ethane-1-yl-1-ylidene))bis(azaacylylidene))bis(sodium 3,5-diisopropylbenzenesulfonate) iron complex, the method is as follows:

[0136] 10 μg of the 4,4'-((1E, 1'E)-pyridine-2,6-diacylbis(ethane-1-yl-1-ylidene))bis(azinoyl-ylidene))bis(sodium 3,5-diisopropylbenzenesulfonate) iron complex, 100 mg of silica, and 15 mL of dichloromethane were stirred in a glove box at room temperature for 12 h. The mixture was filtered and the residue was dried to obtain a light gray solid, which is the 4,4'-((1E, 1'E)-pyridine-2,6-diacylbis(ethane-1-yl-1-ylidene))bis(azinoyl-ylidene))bis(sodium 3,5-diisopropylbenzenesulfonate) iron complex supported on silica catalyst. This catalyst is denoted as Fe1@SiO2, and its synthetic route is shown in Formula 9:

[0137] Example 10: Ethylene polymerization catalyzed by sodium sulfonate-substituted amine nickel / iron catalysts before and after loading, as follows:

[0138] When the catalyst is Ni1 / Ni1@SiO2 / Ni2 / Ni2@SiO2, 500 eq AlEt2Cl, 18 mL n-hexane, and a magnetic stir bar are loaded into a 350 mL thick-walled glass pressure vessel in a glove box. The pressure vessel is connected to a high-pressure line, and the solution is degassed. The vessel is heated to the desired temperature using an oil bath and allowed to equilibrate for 15 minutes. 2 mL of 5 μmol Ni1 / 5 μmol Ni1@SiO2 or 0.5 μmol Ni2 / 0.5 μmol Ni2@SiO2 catalyst in CH2Cl2 is injected into the polymerization system using a syringe. The reactor is pressurized under rapid stirring and maintained at 8.0 atm of ethylene. After 30 min, the pressure vessel is vented, and the polymer is precipitated in acidified methanol (methanol / HCl = 50 / 1) and dried under vacuum at 50 °C for 24 hours.

[0139] When the catalyst is Fe1 / Fe1@SiO2, Al(iBu)3, 18 mL of n-hexane, and a magnetic stir bar are loaded into a 350 mL thick-walled glass pressure vessel in a glove box. The pressure vessel is connected to a high-pressure pipeline, and the solution is degassed. The vessel is heated to the desired temperature using an oil bath and allowed to equilibrate for 15 minutes. 2 μmol of Fe1 / 2 μmol of Fe1@SiO2 catalyst in 2 mL of CH2Cl2 is injected into the polymerization system using a syringe. The reactor is pressurized under rapid stirring and maintained at 8.0 atm of ethylene. After 30 min, the pressure vessel is vented, and the polymer is precipitated in acidified methanol (methanol / HCl = 50 / 1) and dried under vacuum at 50 °C for 24 hours.

[0140] The products of the above ethylene polymerization reaction were analyzed. At 150°C, the molecular weight of the products was determined by gel permeation chromatography (GPC) using polystyrene standards in trichlorobenzene. The activity of the products was determined by differential scanning calorimetry (DSC, with secondary heating), and the degree of branching was determined. The degree of branching was defined as the number of branches per 1000 carbon atoms, calculated as (CH3 / 3) / [(CH+CH2+CH3) / 2]*1000. The test results are shown in Table 1, where the unit of activity is 10-1. 6 g.mol -1 .h -1 The unit of molecular weight is 10. 4 g.mol -1 .

[0141] Table 1 Ethylene Polymerization

[0142]

[0143] Example 11: Copolymerization of ethylene and undecenoic acid catalyzed by sodium sulfonate-substituted amine nickel / iron catalysts before and after loading, as follows:

[0144] In a glove box, a total of 18 mL of 1500 eq AlEt2Cl, 20 mL of n-hexane, and 1 M undecenoic acid were added to a 350 mL thick-walled glass pressure vessel, along with a magnetic stir bar. The pressure vessel was connected to a high-pressure line, and the solution was degassed. The vessel was heated to the desired temperature using an oil bath and allowed to equilibrate for 15 minutes. 15 μmol of Ni1 / Ni1@SiO2 / Ni2 / Ni2@SiO2 in 2 mL of CH2Cl2 was injected into the polymerization system using a syringe. The reactor was pressurized under rapid stirring and maintained at 2.0 atm for ethylene. After 30 min, the solvent was evaporated, and the polymer was vacuum dried at 50 °C for 24 hours.

[0145] The products of the copolymerization reaction of ethylene and undecenoic acid were analyzed. The insertion ratio was calculated using proton nuclear magnetic resonance spectroscopy based on the ratio of the product to the original 1-undecenoic acid feed. The molecular weight of the product was determined by gel permeation chromatography (GPC) in trichlorobenzene using polystyrene standards at 150°C. The activity of the product was determined by differential scanning calorimetry (DSC, with secondary heating). The test results are shown in Table 2, where the unit of activity is 10-1. 6 g.mol -1 .h -1 The unit of molecular weight is 10. 4 g.mol -1 .

[0146] Table 2 Copolymerization of ethylene and undecenoic acid

[0147]

[0148] 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 supported iron / nickel catalyst, comprising: A carrier and an iron / nickel complex loaded on the carrier; wherein the carrier is selected from one or more of silicon dioxide and aluminum oxide; The iron / nickel complex has the structural formula shown in Formula V or Formula VI: Where M is nickel or iron, and X is chlorine or bromine; R3, R4, R5, R6, R7, R8, R9, R 10 Select H and C1~C independently. 20 One of the alkyl groups.

2. The supported iron / nickel catalyst according to claim 1, wherein, R3, R4, R5, R6, R7, R8, R9, R 10 Each of the following is independently selected from hydrogen, methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, and isopropyl.

3. The supported iron / nickel catalyst according to claim 1, wherein, R3, R4, R5, R6, R7, R8, R9, R 10 They are isopropyl, respectively.

4. The supported iron / nickel catalyst according to claim 1, wherein the iron / nickel complex is formed from a ligand compound, wherein the ligand compound has the structural formula shown in Formula II or Formula III:

5. The supported iron / nickel catalyst according to claim 4, wherein, The ligand compounds represented by Formula II or Formula III were obtained by the following methods: Compounds H, J, and K are reacted to generate ligand compounds as shown in Formula II: Compounds L, O, and P are reacted to generate ligand compounds as shown in Formula III:

6. The supported iron / nickel catalyst according to claim 1, wherein, The iron / nickel complex was obtained through the following method: Under nitrogen atmosphere, the ligand compound and MX compound are added to an organic solvent and stirred for 11-13 hours. After filtration, recrystallization is performed to obtain the iron / nickel complex. The MX compound is selected from (DME)NiBr2 or FeCl2. The ligand compound has the structural formula shown in Formula II or Formula III.

7. A method for preparing a supported iron / nickel catalyst as described in any one of claims 1 to 6, comprising: The iron / nickel complex, support, and organic solvent were stirred under nitrogen atmosphere for 11-13 hours. The iron / nickel complex is shown in Formula V or Formula VI: ； The carrier is selected from one or more of silicon dioxide and aluminum oxide; The supported iron / nickel catalyst can be obtained after filtration and drying.

8. The application of a supported iron / nickel catalyst as described in any one of claims 1 to 6 in the catalytic polymerization of olefins, wherein, The olefin is selected from C2~C6. 20 At least one of the olefins.

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