CN110483587B - Large steric hindrance ketimine nickel catalyst and ligand compound, preparation method and application thereof - Google Patents
Large steric hindrance ketimine nickel catalyst and ligand compound, preparation method and application thereof Download PDFInfo
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- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
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- C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
- C07C251/16—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
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Abstract
The invention relates to a large steric hindrance ketimine nickel complex as shown in formula (I), a supported catalyst, a ligand compound, a preparation method and application thereof, wherein R1Ar and BAF‑As defined herein. The nickel ketoimine complex with large steric hindrance can be used as a catalyst in the polymerization reaction of low-carbon olefin such as ethylene, and has high catalytic activity (the activity can reach 8 multiplied by 10)6g·mol‑1·h‑1) And high thermal stability, high molecular weight (number average molecular weight up to 1.59X 10)6g/mol) of polyethylene.
Description
Technical Field
The invention relates to the field of catalysis and the field of synthesis of high-molecular polyolefin materials, in particular to a high-steric-hindrance ketimine nickel catalyst, a ligand compound thereof, a preparation method and application thereof.
Background
Late transition metal catalyzed olefin polymerization has attracted considerable interest for more than half a century. The heterogeneous olefin polymerization catalyst has received much attention and preference from an industrial point of view because it allows to control the morphology of the product, avoiding fouling of the reactor, and having the capacity for continuous production. Metallic nickel has entered this area as a "poison". Ziegler and his colleagues demonstrated the well-known "nickel effect" with aluminum alkyls converting ethylene completely to 1-butene in the presence of nickel salts. This finding has been the starting point for the development of ziegler catalysts. At present, many metallic nickel are reported to produce high molecular weight polyethylene. An important work by Brookhart in 1995 was to show that nickel diimine can produce high molecular weight polyethylene with activity comparable to that of early transition metal catalysts. Grubbs and his colleagues developed a nickel salicylaldimine catalyst in 2000 that showed another significant advance in this field. Catalysts of the SHOP type have been commercialized for the synthesis of linear alpha-olefins. With suitable structural modification, this type of catalyst can produce high molecular weight polyethylene. For example, some nickel catalysts with a phosphino-phenol ligand structure have good properties for ethylene polymerization and copolymerization of ethylene and acrylates.
Despite recent research interest in phosphine-related ligands, imine derivative ligands remain attractive systems due to their unique properties such as ease of synthesis. Moreover, phosphine ligands have the disadvantages of being easily oxidized, potentially pyrophoric and toxic. Interestingly, literature investigations have shown that phosphine-containing nickel catalysts generally produce linear polyethylene during ethylene polymerization. In contrast, most nickel catalysts based on N ^ N and N ^ O systems produce different branched polyethylenes. In the industry, to improve the processability and other properties of polyethylene, branching is often introduced by copolymerizing ethylene with an alpha-olefin.
The ability of these nickel catalysts of nitrogen system to produce branched polyethylene using ethylene as the sole feedstock is very attractive from an industrial point of view and indeed extensive research is being done by dupont. WO02/059165a2 discloses the preparation of ligand L6 by reacting 2, 6-diisopropylaniline with 3, 4-hexanedione and the preparation of catalyst 6 by reacting this ligand L6 with allylnickel chloride and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, the reaction scheme being as follows:
however, such a catalyst 6 has a very low activity in the polymerization of ethylene (the activity of catalyzing the polymerization of ethylene at room temperature is only 6.4X 10)4g·mol-1·h-1) And the molecular weight of the resulting polyethylene product is not sufficiently high (number average molecular weight less than 80000).
In addition, the supporting of the early transition metal catalyst has been widely studied, and some systems have been successfully commercialized, however, relatively few studies have been made on the supporting of the late transition metal catalyst. In occasional studies, the support of a homogeneous catalyst on a solid support causes severe steric crowding and some side reactions, which greatly reduce the catalytic activity. Furthermore, since the existing carbonylimine catalyst is a single-component catalyst and has a spatially disclosed characteristic, it is desired to be directly supported on a carrier. Unfortunately, these catalysts, although due to the cationic nature of the catalyst, exhibit very low adsorption to supports such as silica. Also in prior loading studies, the silica supports used required pretreatment with some aluminum co-catalyst such as methylaluminoxane to enhance the adsorptivity of the metal catalyst to the silica support. In addition, a large amount of cocatalyst is required to achieve high activity of the catalyst.
In view of this, there is a need in the art for new catalysts with higher catalytic activity for obtaining ethylene homopolymers of higher molecular weight. Furthermore, for industrial applications, it is desirable that such catalysts be supported directly on a silica support, and that no cocatalyst be required for catalyzing the polymerization of ethylene.
Disclosure of Invention
The invention aims to provide a novel nickel catalyst or a supported nickel catalyst, which is used for C2-C6The homopolymerization reaction of the low-carbon olefin has higher thermal stability and catalytic activity, and the obtained polymer has higher molecular weight. The invention also aims to provide a ligand compound of the nickel catalyst, a preparation method and application thereof.
The application provides a bulky, sterically hindered nickel ketimine complex of formula (I):
wherein
R1Is selected from C1-C6Alkyl, phenyl or substituted phenyl, said substituted phenyl being substituted by one or more groups selected from OH, halogen, nitro, C1-C6Alkyl and C1-C6Substituent in alkoxy;
ar represents a group of formula (101):
in the formula (101), R2、R3And R8Independently of one another, from hydrogen, C1-C6Alkyl, halogen, nitro, methoxy or phenyl; and R is4、R5、R6And R7Independently of one another, from phenyl, substituted phenyl, naphthyl or substituted naphthyl, said substituted phenyl or substituted naphthyl being substituted by one or more groups selected from OH, halogen, nitro, C1-C6Alkyl and C1-C6Substituent in alkoxy; symbol
Represents the point of attachment of the group of formula (101) to the N atom in formula (I);
BAF-represents a tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate anion, and
(symbol)
represents an allyl group bonded to a Ni atom.
In a preferred embodiment, R4、R5、R6And R7Independently of one another, from phenyl or naphthyl; preferably, R2、R3And R8Independently of one another, from hydrogen or C1-C6An alkyl group.
In another aspect, the present invention provides a supported, highly hindered nickel catalyst comprising: the nickel complex of the large steric hindrance ketimine is loaded on a carrier by an impregnation method. Preferably, the carrier is one or more selected from the group consisting of silica, anhydrous magnesium chloride and alumina.
In another aspect, the present invention provides a ketimine ligand compound of formula (II):
wherein R is1And Ar is as defined above.
In another aspect, the present invention provides a process for preparing the above sterically hindered ketimine nickel complex, the process comprising: reacting the ketimine ligand compound of the above formula (II) with an allyl nickel salt and tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate in an organic solvent, wherein the organic solvent is one or more selected from the group consisting of tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane, tetrachloromethane, 1, 4-dioxane, and 1, 2-dichloroethane.
In another aspect, the present invention provides a method of preparing the ketimine ligand compound of formula (II) described above, the method comprising:
in the presence of an organic acid catalyst, at the temperature of 60-150 ℃, leading Ar-NH to be in a formula2With an arylamine compound of formula
The diketone compound of (A) is reacted in an organic solvent for 12-72 h, wherein R1And Ar is as defined above.
In a preferred embodiment, the organic acid catalyst is selected from formic acid, acetic acid, p-toluenesulfonic acid, or camphorsulfonic acid; the organic solvent is one or more selected from tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane, tetrachloromethane, 1, 4-dioxane and 1, 2-dichloroethane.
In another aspect, the present invention provides a method of preparing a polyolefin compound, the method comprising: the sterically hindered nickel ketimine complex described above was used as catalyst pair C2-C6And carrying out catalytic polymerization on the low-carbon olefin.
In another aspect, the present invention provides a method of preparing a polyolefin compound, the method comprising: using the above-mentioned supported highly hindered nickel catalyst pair C2-C6And carrying out catalytic polymerization on the low-carbon olefin.
In a preferred embodiment, the polymerization is carried out at a temperature of 20 to 100 ℃.
The application provides a novel ketimine nickel complex and a supported nickel catalyst supported on a carrier, wherein an Ar substituent group connected with an N atom of imine in a ligand of the novel ketimine nickel complex is specially designed to have a significantly larger steric hindrance structure, so that large steric hindrance is provided on one side of a metal nickel atom. The large steric hindrance structure can effectively protect a Ni metal center in the polymerization reaction of catalyzing low-carbon olefin, thereby improving the thermal stability and chemical activity of the nickel complex as a catalyst.
In addition, since the carbonyl group of the ketimine is designed to be linked with a p-hydroxyphenyl group, the resulting nickel complex is easily adsorbed and supported on a carrier such as silica, resulting in a supported catalyst having high activity and thermal stability, while also eliminating the need for a co-catalyst that is generally necessary.
In addition, the supported nickel catalyst is used for catalyzing ethylene polymerization, and the obtained polyethylene has relatively higher number average molecular weight, so that the supported nickel catalyst can be used for preparing ultrahigh molecular weight polyethylene. Moreover, the polyethylene prepared by the supported nickel catalyst is granular, so the prepared polyethylene polymer does not have the problem of kettle sticking caused by cluster aggregation of common polyethylene products, and the supported nickel catalyst is more suitable for large-scale industrial production.
Detailed Description
In view of the problems of the prior art that the activity of the nickel ketimine catalyst in the ethylene polymerization reaction is very low and the molecular weight of the obtained polyethylene product is not high, the inventors of the present invention have conducted intensive and extensive studies, and unexpectedly discovered that, through a new structural design, an aryl substituent structure having a larger steric hindrance is designed on the aromatic substituent connected to the N atom of imine in the ketimine ligand compound, thereby providing a substantially larger steric hindrance structure that is approximately half-surrounded around the active metal nickel atom, such a large steric hindrance structure can effectively protect the Ni metal center in the polymerization reaction of catalytic ethylene, and at the same time, a p-hydroxyphenyl group is designed to be connected to the carbonyl group of ketimine, thereby being capable of improving the thermal stability and chemical activity of the nickel complex as a catalyst, and simultaneously, using such a large steric hindrance ketimine nickel complex as a catalyst, the ethylene homopolymer obtained may have a higher molecular weight.
In addition, the invention also unexpectedly discovers in the research that the nickel complex of the large-steric-hindrance ketimine with the hydroxyl functional group can be easily supported on a carrier such as silicon dioxide by utilizing the nickel complex of the large-steric-hindrance ketimine designed by the invention, thereby forming a supported heterogeneous nickel catalyst with high activity. In addition, the supported catalyst provided by the invention can avoid the use of a cocatalyst.
Based on this finding, the present invention has been devised and provided, first, a ketimine ligand compound of the following formula (II):
wherein
R1Is selected from C1-C6Alkyl, phenyl or substituted phenyl, said substituted phenyl being substituted by one or more groups selected from OH, halogen, nitro, C1-C6Alkyl and C1-C6Substituent in alkoxy;
ar represents a group of formula (101):
in the formula (101), R2、R3And R8Independently of one another, from hydrogen, C1-C6Alkyl, halogen, nitro, methoxy or phenyl; preferably, R2、R3And R8Independently of one another, from hydrogen or C1-C6An alkyl group; r4、R5、R6And R7Independently of one another, from phenyl, substituted phenyl, naphthyl or substituted naphthyl, said substituted phenyl or substituted naphthyl being substituted by one or more groups selected from OH, halogen, nitro, C1-C6Alkyl and C1-C6Substituent in alkoxy; preferably, R4、R5、R6And R7Independently of one another, from phenyl or naphthyl; and symbol
Represents the point of attachment of the group of formula (101) to the N atom in formula (I).
As used herein, C1-C6The alkyl group represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and examples thereof are a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and isomeric forms thereof, and preferably a methyl group, an ethyl group, or a tert-butyl group.
As used herein, C1-C6Alkoxy represents the above-mentioned C bonded through an oxygen atom (O)1-C6Examples of the alkyl group are methoxy, ethoxy, propoxy, tert-butoxy and the like.
As used herein, halogen includes fluorine, chlorine, bromine and iodine, preferably chlorine or bromine.
In the present invention, the substituent R of the ketimine ligand compound of the formula (II) is substituted by1And Ar, in particular substituents Ar, in which at least four bulky steric hindrance groups R independently selected from phenyl, substituted phenyl, naphthyl or substituted naphthyl are introduced into the specific structural formula (101) represented by the formula4、R5、R6And R7Thereby allowing the ligand compound to form an approximately semi-closed cage structure. This enables formation of a large steric hindrance on the active metal Ni atom side when the ligand compound is complexed with the active metal Ni atom to form a complex, thereby enabling effective protection of the Ni metal center when such a complex is applied as a catalyst in catalyzing the polymerization reaction of ethylene, thereby enabling improvement in thermal stability and chemical activity of the resulting nickel complex as a catalyst. Furthermore, since the carbonyl group of ketimine is designed to be bonded with a p-hydroxyphenyl group, the resulting nickel complex is easily adsorbed and supported on a carrier such as silica, and a supported catalyst having high activity and thermal stability is conveniently formedCatalysts, while also eliminating the need for the co-catalysts that are normally necessary.
The method for preparing the ketimine ligand compound of formula (II) provided by the present invention is not particularly limited, and can be prepared, for example, by the following method: in the presence of an organic acid catalyst, at a temperature of 60-150 ℃, preferably 80-100 ℃, reacting Ar-NH2With an arylamine compound of formula
Reacting the diketone compound or the ketoaldehyde compound in an organic solvent for 12-72 h, wherein R1And Ar is as defined above. Preferably, the reaction is carried out under reflux at elevated temperature. Preferably, the organic acid catalyst used may be selected from formic acid, acetic acid, p-toluenesulfonic acid or camphorsulfonic acid. Preferably, the organic solvent used may be selected from one or more of tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane, tetrachloromethane, 1, 4-dioxane and 1, 2-dichloroethane, for example toluene. Preferably, in the reaction, water produced by the reaction may be removed using, for example, anhydrous magnesium sulfate. Preferably, the molar ratio of the amine to the aldehyde is 1: (0.1-10); in a specific embodiment, formula Ar-NH2With an arylamine compound of formula
The molar ratio of the diketone compound or the ketone-aldehyde compound (b) is 1: 0.1 to 10, and more preferably 1: 1 to 5.
As used herein, among the above arylamine compounds, the Ar substituent representing the structure of formula (101) can be easily obtained from the most basic raw material such as a substituted or unsubstituted benzene or naphthalene compound using a conventional technique well known in the art to obtain the corresponding structure and bonded to the N atom of the amine to obtain the corresponding arylamine compound, for example. Further, the above diketone compound can be obtained by a conventional reaction well known in the art using a corresponding diketone and a para-substituted phenol compound commercially available in the art as raw materials.
In the present invention, it is preferableThe ketimine ligand compound of the above formula (II) may be, for example, the following formula (II)1) The compound of (1):
wherein Ph represents phenyl (i.e. group C)6H5-)。
Based on the ketimine ligand compound of the above formula (II), the present invention provides a bulky steric hindrance ketimine nickel complex of the formula (I):
wherein, the substituent R1And Ar has the same meaning as defined above, BAF-Represents a tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate anion and is given the symbol
Represents an allyl group (CH) bonded to the Ni atom2＝CH-CH2-)。
Such sterically hindered ketimine nickel complexes can be prepared, for example, by the following method: the ketimine ligand compound of the above formula (II) is reacted with an allylnickel salt such as allylnickel chloride and tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate such as tetrakis (3, 5-bis (trifluoromethyl) phenyl) sodium borate in an organic solvent, wherein the organic solvent may be one or more selected from tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane, tetrachloromethane, 1, 4-dioxane and 1, 2-dichloroethane, for example, dichloromethane. Preferably, in the reaction, the ligand compound of formula (II) and the allyl nickel salt and tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate may be reacted in a molar ratio of, for example, but not limited to, 1: 1. Such a reaction can be carried out at room temperature, for example, and the reaction time can be 10 to 20 hours, for example.
In the present invention, preferably, the bulky hindered ketimine nickel complex of the above formula (I) may have, for example, the followingFormula (I)1) The structure of (1);
wherein BAF-And
as defined above, and Ph represents phenyl (i.e. group C)6H5-)。
Based on the bulky sterically hindered ketimine nickel complex of formula (I) above, the present invention also provides a supported bulky sterically hindered nickel catalyst, which can be obtained by, for example, supporting or adsorbing the bulky sterically hindered ketimine nickel complex onto a support by an impregnation method common in the art. For example, the supported nickel catalyst can be obtained by stirring the bulky hindered ketimine nickel complex with a support in an organic solvent such as toluene to mix uniformly, followed by filtration and drying. Preferably, the carrier used may be one or more selected from the group consisting of silica, anhydrous magnesium chloride and alumina. Since the bulky hindered ketimine nickel complexes of the present invention have free hydroxyl groups, they can be readily adsorbed onto supports such as silica.
In one embodiment, the supported nickel catalyst (Ni-OH @ SiO) obtained according to the invention2) Can be expressed as follows:
the nickel complex of the ketone imine with great steric hindrance can be used as a catalyst or the supported nickel catalyst with great steric hindrance can be used for preparing C2-C6Homopolymers of lower olefins such as ethylene. Preferably, the polymerization reaction is carried out at a temperature of 20 to 100 ℃.
Examples
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to illustrate further features and advantages of the invention, rather than to limit the scope of the invention.
The synthesis of the complex and the polymerization process in the following examples were carried out in the absence of water and oxygen, all sensitive substances were stored in a glove box, all solvents were strictly dried to remove water, and the ethylene gas was purified by a water and oxygen removal column. All raw materials are purchased and used without specific mention.
Silica gel with 200-mesh and 300-mesh is used for silica gel column separation; the nuclear magnetism detection is performed by a Bruker 400MHz nuclear magnetism instrument; the element analysis is determined by the physicochemical center of Chinese science and technology university; molecular weight and molecular weight distribution were determined by high temperature GPC; mass spectra were determined using Thermo LTQ Orbitrap XL (ESI +) or P-SIMS-Gly of Bruker Daltonics Inc (EI +).
Example 1: 2- ((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) -1- (4-hydroxyphenyl) propan-1-one (II)1) Preparation of
A solution of 2, 6-bis (diphenylmethyl) -4-methylaniline (1758 mg, 4 mmol), 1- (4-hydroxyphenyl) propane-1, 2-dione (328 mg, 2 mmol) and p-toluenesulfonic acid (20 mg) in toluene (20 ml) was stirred at 80 ℃ for 12 hours under nitrogen in a 250 ml round bottom flask equipped with reflux condenser, magnetic stirrer and oil bath and the reaction was monitored by Thin Layer Chromatography (TLC). The reaction was terminated when a major product spot was indicated on the thin layer chromatography plate. The reaction was cooled to room temperature, a yellow solid precipitated and was isolated by filtration to give a yellow solid (585 mg, 50% yield). The product obtained was subjected to detection analysis, and as a result, it was confirmed to be the title compound.
1H NMR(400MHz，CDCl3) Δ 7.52(br, 2H), 7.35-6.75(m, 20H), 6.66(br, 2H), 6.45(br, 2H), 5.29(s, 2H, CHPh2), 2.13(s, 3H, aryl-CH)3)，1.15(s，3H，N＝CMe)。
13C NMR(100MHz，[D6]DMSO)δ189.82(s，COCH3)，170.44(s)，162.52(s)，144.26(s)，143.07(s)，142.63(s)，133.24(s)，131.76(s)，131.03(s)，129.52(s)，129.21(s)，128.75(s)，128.53(s)，128.35(s)，126.49(s)，126.38(s)，125.45(s)，115.11(s)，51.17(s，CHPh2)，21.02(s)，17.40(s)。
HRMS (m/z): theoretical value C42H36O2N：[M+H]+586.2741, respectively; measured value: 5702742.
example 2: preparation of 2- ((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) -1- (4-hydroxyphenyl) propan-1-one nickel complex (catalyst Ni-OH)
In a glove box, a solution of a mixture of 2- ((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) -1- (4-hydroxyphenyl) propan-1-one (293 mg, 0.5 mmol), allylnickel chloride (67.5 mg, 0.5 mmol) and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (443 mg, 0.5 mmol) in a 20 ml glass vial was stirred at room temperature for 12 hours. The resulting mixture was filtered through celite and evaporated to give a black red solid (619 mg, 80% yield). The product obtained was subjected to detection analysis, and as a result, it was confirmed to be the title compound.
1H NMR(400MHz，CDCl3) δ 7.78-7.50(m, 10H), 7.37(s, 4H), 7.24(t, J ═ 7.3Hz, 4H), 7.18(d, J ═ 6.7Hz, 2H), 7.08(s, 6H), 6.94(s, 4H), 6.87(s, 3H), 6.76(s, 2H), 6.67(d, J ═ 8.6Hz, 2H), 5.68(s, 1H), 5.40-4.95(m, 3H), 2.12(s, 3H, aryl-CH), and pharmaceutically acceptable salts thereof3)，1.02(s，3H，N＝CMe)。
13C NMR(100MHz，CDCl3) δ 195.40(s), 176.51(s), 165.68(s), 142.02(s), 140.56(s), 140.41(s), 138.44(s), 135.55(s), 133.76(s), 129.87(s), 129.50(s), 129.44(s), 129.34(s), 127.84(s), 127.64(s), 125.02(s), 119.46(s, allyl group) 117.45(s), 53.17(s), 21.50(s, aryl-CH)3)，20.50(s，N＝CMe)。
1H-13C HSQC Association (CDCl)3): 119.46(s, allyl)/5.40-4.95 (m, 3H), 21.50(s, aryl-CH)3) 2.12(s, 3H, aryl-CH)3)，20.50(s，N＝CMe)/1.02(s，3H，N＝CMe)。
Elemental analysis: theoretical value C77H52BF24NNiO2: c, 59.72; h, 3.38; measured value: c, 59.86; h, 3.25.
Example 3: supported nickel catalyst (Ni-OH @ SiO)2) Preparation of
Silica (available from Grace-Devison, model 955) as a carrier is calcined at 600 ℃ for 6 hours in a muffle furnace and stored in a glove box for use.
In a glove box in a 20 ml glass bottle under nitrogen protection, 100 mg of the above prepared carrier silica and 1. mu. mol of the catalyst Ni-OH prepared in example 2 were dissolved in 1 ml of toluene and stirred at room temperature for 6 hours. The solid product was then obtained by filtration and washed twice with toluene (15 ml) and finally dried under vacuum to give the desired supported nickel catalyst.
Application examples 1 to 11: complex catalyst (Ni-OH) and supported catalyst (Ni-OH @ SiO)2) Use of catalysts for ethylene polymerization
In a glove box, 28 ml of toluene or 30 ml of n-heptane were added under nitrogen to a 350 ml autoclave (with magnetic stirring, oil bath heating and thermometer). The reactor was connected to a high pressure line and the piping was evacuated, and the reactor was heated to the temperature shown in Table 1 below (20 ℃, 50 ℃, 80 ℃ or 100 ℃) using an oil bath and kept for 15 minutes. Then adding complex catalyst (Ni-OH) or supported catalyst (Ni-OH @) dissolved in 2 ml of dichloromethaneSiO2) (1 micromole), close the valve. After adjusting the ethylene pressure to atmospheric pressure shown in table 1 below, the reaction was carried out for 3 minutes; the reaction was stopped. The reaction vessel was opened, ethanol (50 ml) was added thereto to precipitate a solid, which was filtered under reduced pressure and dried in a vacuum oven (50 ℃ C.) to obtain a white solid. The results are shown in Table 1.
Table 1: nickel catalyst catalyzed ethylene homopolymerizationaAs a result of (A)
aEthylene homopolymerization conditions: catalyst 1 micromole; toluene (28 ml), dichloromethane (2 ml), ethylene (8 atm) for 3 min;
bactivity 10 ═ 107g·mol-1·h-1(ii) a As is known in the art, it is obtained by dividing the mass of polyethylene by the mass of catalyst and then by the reaction time;
cthe molecular weight was measured by GPC using polystyrene as a solvent for trichlorobenzene at 150 ℃; (ii) a
dThe degree of branching per 1000 carbons was determined by nuclear magnetic resonance hydrogen spectroscopy;
ethe melting point is measured by a differential scanning calorimeter;
fthe time is 30 minutes;
g30 ml of n-heptane and 30 minutes.
From the above, it can be seen that by using the nickel ketoimine complex with large steric hindrance as a catalyst, the nickel ketoimine complex has high thermal stability and activity for homopolymerization polymerization of ethylene, and can obtain high molecular weight polyethylene with a certain branching degree. For example, in the case of a single complex as catalyst, the activity thereof may beUp to 1.6X 107g·mol-1·h-1(ii) a The polyethylene product has a number average molecular weight of up to 1.04X 106g/mol; and the melting point can reach 124.6 ℃. In the case of supported catalysts, the activity can reach 8.0X 106g·mol-1·h-1(ii) a The polyethylene product has a number average molecular weight of up to 1.59X 106g/mol; the melting point can reach 131.9 ℃.
In addition, it is noted that although the supported nickel catalyst has relatively low activity compared to the unsupported nickel catalyst, the supported nickel catalyst of the present invention is more suitable for large-scale industrial production because the polyethylene polymer prepared by using the supported nickel catalyst does not have the problem of sticking to the kettle of the polymer product; moreover, the molecular weight of the polyethylene obtained by catalyzing ethylene polymerization by using the supported nickel catalyst is relatively higher.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A sterically hindered nickel ketimine complex of formula (I):
wherein
R1Is selected from C1-C6An alkyl group;
ar represents a group of formula (101):
in the formula (101), R2、R3And R8Independently of one another, from hydrogen or C1-C6An alkyl group; and R is4、R5、R6And R7Independently of one another, from phenyl or naphthyl; symbol
Represents the point of attachment of the group of formula (101) to the N atom in formula (I);
BAF-represents a tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate anion, and
(symbol)
represents an allyl group bonded to a Ni atom.
2. A supported, highly hindered nickel catalyst comprising: a sterically hindered ketimine nickel complex according to claim 1 supported on a support by impregnation.
3. The supported highly hindered nickel catalyst according to claim 2 wherein said support is one or more selected from the group consisting of silica, anhydrous magnesium chloride and alumina.
4. A ketimine ligand compound of formula (II):
wherein R is1And Ar is as defined in claim 1.
5. A process for preparing a sterically hindered ketimine nickel complex of claim 1 which comprises: reacting the ketimine ligand compound of formula (II) as defined in claim 4 with an allyl nickel salt and tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate in an organic solvent, wherein the organic solvent is one or more selected from the group consisting of tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane, tetrachloromethane, 1, 4-dioxane and 1, 2-dichloroethane.
6. A process for preparing a ketimine ligand compound of formula (II) according to claim 4, the process comprising:
in the presence of an organic acid catalyst, at the temperature of 60-150 ℃, leading Ar-NH to be in a formula2With an arylamine compound of formula
The diketone compound of (A) is reacted in an organic solvent for 12-72 h, wherein R1And Ar is as defined in claim 1.
7. The process of claim 6, wherein the organic acid catalyst is selected from formic acid, acetic acid, p-toluenesulfonic acid, or camphorsulfonic acid; the organic solvent is one or more selected from tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane, tetrachloromethane, 1, 4-dioxane and 1, 2-dichloroethane.
8. A method of preparing a polyolefin compound, the method comprising:
use of the sterically hindered nickel ketimine complexes according to claim 1 as catalyst pairs C2-C6And carrying out catalytic polymerization on the low-carbon olefin.
9. A method of preparing a polyolefin compound, the method comprising:
use of the supported, highly sterically hindered nickel catalyst pair C according to claim 2 or 32-C6And carrying out catalytic polymerization on the low-carbon olefin.
10. The process according to claim 8 or 9, wherein the polymerization is carried out at a temperature of 20 to 100 ℃.
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