CN112473738A - Ethylene oligomerization catalyst system and preparation method and application thereof - Google Patents

Ethylene oligomerization catalyst system and preparation method and application thereof Download PDF

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CN112473738A
CN112473738A CN202011142599.4A CN202011142599A CN112473738A CN 112473738 A CN112473738 A CN 112473738A CN 202011142599 A CN202011142599 A CN 202011142599A CN 112473738 A CN112473738 A CN 112473738A
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ethylene oligomerization
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魏东初
柳庆先
叶健
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Hangzhou Xiaoling Technology Co ltd
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Abstract

The invention discloses a novel ethylene oligomerization catalyst system with high activity and high selectivity, a preparation method and application thereof. The catalyst system comprises a novel PNP ligand, a transition metal compound and a cocatalyst; the PNP ligand uses a binary aromatic group to replace a phenyl group in the conventional PNP ligand, the binary aromatic group has more substitution positions, more abundant aromatic ring electron cloud distribution modes and larger space volume than a benzene ring, and can provide more and stronger influence on a donor part of the ligand, so that the catalyst shows more excellent linear alpha-olefin (LAO) selectivity in the ethylene oligomerization reaction, and can be used for preparing 1-hexene or 1-octene with high selectivity.

Description

Ethylene oligomerization catalyst system and preparation method and application thereof
Technical Field
The invention belongs to the field of industrial catalysts, relates to an ethylene oligomerization catalyst system, a preparation method and application thereof, and particularly relates to an ethylene selective oligomerization catalyst system and a method for preparing 1-hexene and/or 1-octene by using the catalyst system.
Background
Linear alpha-olefins are understood to mean C with a double bond at the end of the molecule4And the straight chain olefins are important petrochemical raw materials with wide application. Among them, the higher alpha-olefins such as 1-hexene and 1-octene can be used not only for preparing high-end polyolefin materials, but also for producing many important products such as high-end detergents, higher alcohols, high-performance PAO lubricating oil, surfactants, oil additives and the like, and the market demand is huge. However, the domestic yields of higher alpha-olefins such as 1-hexene, 1-octene and the like are still small at present, and particularly, the domestic large-scale production of 1-octene is still blank and depends heavily on import, so that the autonomous development of domestic related application fields is greatly limited.
Presently, ethylene oligomerization is the most dominant and promising process for the production of linear alpha-olefins, and more than 90% of the alpha-olefins are produced by this process. Most of the traditional ethylene oligomerization processes are nonselective, the product is a mixture of a series of alpha-olefins, and the product distribution conforms to Schulz-Flory distribution or Poisson distribution. For example, the Gulf one-step Process disclosed in German patent DE1443927, the Ethyl two-step Process disclosed in US3906053, the Higher alpha-Olefin production Process (i.e., the SHOP Process) of Shell as disclosed in US3676523, US3686351 and US3726938, and the ethylene oligomerization Process of light-emitting company disclosed in Japanese patent JP6259225, etc., are all ethylene non-selective oligomerization processes. In these process technologies, the selectivity is very low, generally not exceeding 30%, in the case of 1-hexene or 1-octene. Meanwhile, the final product contains a large amount of C with low market demand due to wide product distribution4Component (A) and (C)20And the solid oligomer not only obviously reduces the process economy, but also seriously influences the stable operation of equipment. The existence of the solid oligomer easily causes the problems of wall sticking of the reaction kettle, pipeline blockage and the like, and greatly increases the energy consumption and the cost of subsequent product separation.
In view of the shortcomings of ethylene non-selective oligomerization in the aspect of directional preparation of specific products, researchers begin to focus on the development of ethylene selective oligomerization technology. Wherein, the technology for preparing 1-hexene by ethylene trimerization is developed by Chevron Phillips company, and a plurality of domestic and foreign companies master related technologies at present; the technology for preparing 1-octene by ethylene tetramerization was developed by Sasol company, and a production device has been built. To date, a large number of patented technologies for selective trimerization or tetramerization of ethylene have been published by domestic and foreign research institutes to achieve high selective production of 1-hexene or 1-octene. Patent documents WO2004/056478a1, US20090118117, US7906681, US7829749, US7511183, US7381857, US7297832, CN1741849A, CN1741850A, CN101032695A, CN101351424A, CN101415494A, CN101291734A and the like disclose ethylene tetramerization catalyst systems using a PNP ligand and a chromium complex as a main catalyst, and the content of 1-octene in the final product for catalyzing ethylene oligomerization reaches more than 60 percent, even more than 70 percent. However, no ethylene trimerization and tetramerization co-production reactions have been reported. How to simultaneously produce 1-hexene and 1-octene, flexibly select and adjust the proportion of 1-hexene to 1-octene, or improve the total selectivity of 1-octene and 1-hexene, inhibit the formation of waxy oligomers, and have important economic benefits for flexibly selecting 1-hexene to 1-octene.
In the ethylene oligomerization catalytic system, the micro chemical environment and the essence of the active center are the key points for regulating and controlling the selectivity of the oligomerization products. The ligand provides the most main coordination environment for the active center, and the change of the steric hindrance effect and the electronic effect of the ligand can obviously influence the micro chemical environment of the active center, so that the innovative design of the ligand is the key for developing a high-selectivity ethylene oligomerization catalytic system, and becomes a hotspot for research and development in the field of ethylene selective oligomerization in recent years.
Disclosure of Invention
The invention aims to solve the problems and the defects of the existing ethylene oligomerization technology, and provides a novel ethylene oligomerization catalyst system with high activity and high selectivity, a preparation method and application thereof.
In one aspect, the present invention provides an ethylene oligomerization catalyst system comprising a PNP ligand, a transition metal compound, and a cocatalyst.
The PNP ligand has the following structural general formula I:
Figure BDA0002738204520000021
wherein: r1Is alkyl, including straight, branched or cyclic alkyl;
R2is one of the groups described in the following (A), (B) and (C):
(A)R2is a binary polycyclic aryl group, and the chemical structural general formula is as follows:
Figure BDA0002738204520000022
wherein: ra3-Ra9The same or different, each independently selected from hydrogen, fluorine, alkyl or alkoxy;
in some embodiments, the alkyl is C1-C6Alkyl or C1-C4Alkyl, said alkoxy is C1-C6Alkoxy or C1-C4An alkoxy group; preferably the alkyl group is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
(B)R2Is a binary polycyclic aryl group, and the chemical structural general formula is as follows:
Figure BDA0002738204520000031
wherein: one or two of x are N, the remainder are C-R ', and R' is Rb6、Rb7Or Rb8；Rb3、Rb4、Rb5、Rb6、Rb7、Rb8The same or different, each independently selected from hydrogen, fluorine, alkyl or alkoxy;
in some embodiments, the alkyl is C1-C6Alkyl or C1-C4Alkyl, said alkoxy is C1-C6Alkoxy or C1-C4An alkoxy group; the alkyl group preferably includes C1-C4Alkyl including methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl;
in some embodiments, the bicyclic aryl is selected from the following structures:
Figure BDA0002738204520000032
Figure BDA0002738204520000041
(C)R2is a binary polycyclic aryl group, and the chemical structural general formula is as follows:
Figure BDA0002738204520000042
wherein: y, Z are each independently O, S, N, C-R 'and R' is Rc6、Rc7；Rc3、Rc4、-Rc5、Rc6、Rc7The same or different, each independently selected from hydrogen, fluorine, alkyl or alkoxy;
in some embodiments, the alkyl is C1-C6Alkyl or C1-C4Alkyl, said alkoxy is C1-C6Alkoxy or C1-C4An alkoxy group; preferably said alkyl group comprises C1-C4Alkyl including methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl;
in some embodiments, the bicyclic aromatic group is selected from the following structures:
Figure BDA0002738204520000043
Figure BDA0002738204520000051
in the novel PNP ligand, when a binary aromatic group is used for replacing a phenyl group, the binary aromatic group has more substitution positions, more abundant aromatic ring electron cloud distribution modes and larger space volume than a benzene ring, and can provide more and stronger influence on a donor part of the ligand, so that the catalyst shows more excellent linear alpha-olefin (LAO) selectivity in an ethylene oligomerization reaction, and can be used for preparing 1-hexene or 1-octene with high selectivity.
The transition metal compound may be selected from one or more of the following chromium compounds: an inorganic salt, an organic salt, a coordination complex or an organometallic complex of trivalent chromium. The transition metal compound can be selected from one or more of the following chromium compounds: chromium acetate, chromium caproate, chromium 2-ethylhexanoate, chromium isooctanoate, chromium n-octanoate, chromium acetylacetonate, chromium diisoprenate, chromium diphenyloxide, CrCl3(THF)3、CrCl2(THF)2Chromium tricarbonyl and chromium hexacarbonyl.
The cocatalyst is an organoaluminum compound, an organoboron compound, or a combination thereof.
In some embodiments, the organoaluminum compound is selected from one or more of the following compounds: alkylaluminums, alkylaluminum halides, alkylaluminum alkoxides, or alkylaluminoxanes.
In some embodiments, the organoaluminum compound may be selected from one or more of the following compounds: c1～C10Alkyl aluminium, halogenated C1～C10Alkyl aluminium, C1～C10Alkoxy aluminium, C1～C10Alkylaluminoxane or modified C1～C10An alkylaluminoxane.
In some embodiments, the organoaluminum compound may be specifically selected from one or more of the following compounds: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, aluminum isopropoxide, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane.
In some embodiments, the organoboron compound can be specifically selected from one or more of the following compounds: boroxine, triethylborane, triphenylborane ammonia complex, NaBH4Tributyl borate, triisopropyl borate, tris (pentafluorophenyl) borane, trityltetrakis (pentafluorophenyl) borate, dimethylphenylammonium tetrakis (pentafluorophenyl) borate, diethylphenylammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, ethyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, trioctylammonium tetrakis (pentafluorophenyl) borate.
In another aspect, the present invention provides a method for preparing the catalyst system for ethylene oligomerization, wherein the chemical synthesis of the PNP ligand comprises reacting aryl bromide as a starting material with butyl lithium or magnesium metal to form aryl lithium or grignard reagent, reacting with phosphorus trichloride to obtain diaryl phosphorus chloride, and finally condensing with alkylamine to obtain the PNP ligand, wherein the reaction route is as shown in the following formula:
Figure BDA0002738204520000061
in a further aspect, the invention provides the use of the ethylene oligomerization catalyst system, wherein the catalyst system is used for catalyzing the trimerization or tetramerization reaction of ethylene with high selectivity to prepare 1-hexene or 1-octene.
In the application, the PNP ligand, the transition metal compound and the cocatalyst are premixed or respectively added into an oligomerization reactor containing a reaction medium, ethylene gas is introduced to the reaction pressure, the reaction temperature is controlled to carry out oligomerization reaction, a gas-phase product and a liquid-phase product are respectively collected after the reaction is finished, a terminator is added into the liquid-phase product to terminate the reaction, and a 1-hexene or 1-octene product is obtained through separation.
In such use, the reaction medium is selected from one or more of the following compounds: aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, cycloaliphatic hydrocarbons, olefins or ether compounds.
In some embodiments of said use, the ethylene oligomerization medium is C6～C18Aromatic hydrocarbons, halogenated C6～C18Aromatic hydrocarbon, C1～C18Aliphatic hydrocarbons, halogenated C1～C18Aliphatic hydrocarbons, C5～C18Cycloaliphatic hydrocarbon, C5～C18Linear alpha-olefins, C5～C18Cyclo-olefins or C4～C18One or more ether compounds.
In some embodiments of the use, the ethylene oligomerization medium is selected from one or more of benzene, toluene, xylene, chlorobenzene, ethylbenzene, chlorotoluene, cumene, pentane, isopentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, chloromethane, chloroethane, 1-hexene, 1-octene, cyclohexene, diethyl ether, and tetrahydrofuran.
In some embodiments of the use, the reaction medium is further selected from one or more of n-hexane, cyclohexane, methylcyclohexane, n-heptane, toluene.
In some embodiments of the use, the ethylene oligomerization reaction temperature is 0 to 200 ℃, preferably 30 to 150 ℃.
In some embodiments of the use, the ethylene oligomerization reaction pressure is 0.1 to 50MPa, preferably 1 to 10 MPa.
In some embodiments of the use, the ethylene oligomerization reaction time is 1 to 180min, preferably 30 to 120 min.
In some embodiments of the use, the molar ratio of the PNP ligand, the transition metal compound and the cocatalyst in the reaction system is 1: 0.5-100: 1-5000, 1: 0.5-50: 1-1000, or 1: 0.5-10: 1-500.
In some embodiments of the use, the ligand, the transition metal compound, and the cocatalyst may be pre-mixed and added to the reactor, or may be added separately and directly to the reactor to form the catalytically active sites in situ.
In some embodiments of the use, the concentration of the transition metal compound in the reaction system is 1 × 10-8To 1X 10-3mol metal/L, or 1X 10-7～1×10-5mol metal/L.
Compared with the prior art, the invention has the following advantages: the catalyst has high activity, long service life, high alpha-olefin linearity (more than 97 percent) and high target olefin selectivity, the total content of 1-hexene and 1-octene in the product is more than 88 weight percent, the content of 1-octene can reach more than 60 weight percent, and the content of solid oligomer is extremely low (less than or equal to 0.5 percent).
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following specific examples, which should not be construed as limiting the scope of the present invention. All changes and modifications that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Example 1
1. Synthesis of perfluoronaphthyl PNP ligand
1.1 preparation of 2-bromoheptafluoronaphthalene
Figure BDA0002738204520000071
Dissolving 25g of octafluoronaphthalene in 150mL of ethanol, stirring and heating to reflux, dropwise adding 10g of hydrazine hydrate within 30min, continuously heating and refluxing for 4 hours after dropwise adding is finished, evaporating ethanol at normal pressure, adding 200mL of water into residues, stirring and cooling to room temperature, filtering and collecting solids.
The solid is added into a mixture of 150mL hydrobromic acid and 20g copper bromide, stirred, heated and refluxed for 6 hours, cooled to room temperature, the reaction mixture is extracted three times by 80mL ethyl acetate, organic layers are combined, washed by water, dried and desolventized, and the obtained solid is recrystallized by methanol to obtain 18g yellow solid.
1.2 preparation of PNP ligand
Figure BDA0002738204520000081
Dissolving 18g of 2-bromoheptafluoronaphthalene in 50mL of diethyl ether, dropwise adding the solution into 50mL of diethyl ether suspension containing 1.5g of magnesium chips at room temperature, keeping stirring, and controlling the reaction to slightly reflux until the magnesium chips completely disappear; and dropwise adding 3.7g of phosphorus trichloride into the mixed solution at 0 ℃, then heating to room temperature, stirring for reaction for 1 hour, filtering to remove magnesium salts under the protection of argon, and carrying out reduced pressure desolventization on the filtrate to obtain 14g of bis (heptafluoronaphthalene-2-yl) phosphorous oxychloride brown solid.
14g of bis (heptafluoronaphthalen-2-yl) phosphorochloridite was added to a mixed solution of 100mL of methylene chloride and 10mL of triethylamine at 0 ℃ and stirred to dissolve, 0.7g of isopropylamine was slowly added to the above mixture at 0 ℃ and the reaction was continued at 0 ℃ for half an hour, followed by further reaction at room temperature for 12 hours, triethylamine hydrochloride was removed by filtration, the filtrate was desolventized under reduced pressure, and the residue was separated by column chromatography to give 6.9g of a white solid of N, N-bis (heptafluoronaphthalen-2-yl) phosphorousidenyl) isopropylamine.
2. Preparation of procatalyst precursor
Combining an amount of a PNP ligand N, N-bis (di (heptafluoronaphthalen-2-yl) phosphonous) isopropylamine with a chromium compound Cr (acac)3The main catalyst precursor solution with the concentration (calculated by chromium atoms) of 2 mu mol/mL is prepared by mixing the components according to the molar ratio of 1: 1 and the solvent is dehydrated toluene.
3. Evaluation of ethylene oligomerization experiment
3.1 ethylene oligomerization experimental method
The ethylene oligomerization reaction was carried out in a 750mL autoclave. Firstly, heating a reaction kettle to more than 100 ℃, vacuumizing and baking for 2 hours, and replacing with high-purity nitrogen for many times. The reactor temperature was then adjusted to the reaction temperature by circulation of jacketed cooling water, 200mL of methylcyclohexane was added as the reaction medium. The addition amount of the main catalyst precursor solution is set to be 10mL, the chromium atom is 20 mu mol, a certain amount of the cocatalyst MMAO is added according to the set amount according to the molar ratio of [ Al ] to [ Cr ] being 500, and the main catalyst precursor solution is added and stirred for reaction. And opening an ethylene pressure regulating valve, rapidly introducing ethylene and keeping a certain reaction pressure, wherein the oligomerization reaction time is 30 min.
And after the reaction is finished, adding 1mL of ethanol to terminate the reaction, carrying out gas-liquid-solid separation on the obtained product, and carrying out qualitative and quantitative analysis on the liquid-phase alpha-olefin product by GC-MS.
3.2 results of ethylene oligomerization experiment
When the reaction temperature was 50 ℃ and the reaction pressure was 3.5MPa, the reaction product was analyzed to have a 1-hexene content of 19.9 wt%, a 1-octene content of 67.4 wt%, a solid oligomer content of 0.1 wt% in the total product, and a total catalytic activity of 2800kg (mol-Cr)-1·h-1。
When the reaction temperature is 70 ℃ and the reaction pressure is 4.5MPa, the analysis on the reaction product shows that the content of 1-hexene is 12.1 wt%, the content of 1-octene is 73.5 wt%, the content of solid oligomer in the total product is 0.3 wt%, and the total catalytic activity is 3500kg (mol-Cr)-1·h-1。
Example 2
1. Synthesis of 5-quinolylppnp ligands
1.1 preparation of 5-bromoquinoline
Figure BDA0002738204520000091
15g of quinoline is dissolved in 300mL of dichloromethane, 35g of NBS is added under the stirring at room temperature, the reaction is stopped until the raw materials are completely reacted at room temperature, the reaction is washed by saturated saline solution, dried and desolventized, and 10.4g of light yellow solid is obtained by column chromatography separation.
1.2 preparation of PNP ligand
Figure BDA0002738204520000101
Dissolving 10.4g of 5-bromoquinoline in 50mL of diethyl ether, dropwise adding the solution into 50mL of diethyl ether suspension containing 1.4g of magnesium chips at room temperature, keeping stirring, and controlling the reaction to slightly reflux until the magnesium chips completely disappear; 3.4g of phosphorus trichloride is added into the mixture at 0 ℃, then the mixture is heated to room temperature and stirred for reaction for 1 hour, magnesium salts are removed by filtration under the protection of argon, and 7.7g of bis (quinoline-5-yl) phosphorous oxychloride light brown solid is obtained by decompression and desolventization of the filtrate.
7.7g of bis (quinolin-5-yl) phosphorochloridite was added to a mixed solution of 100mL of methylene chloride and 10mL of triethylamine at 0 ℃ to dissolve it with stirring, 0.6g of cyclopropylamine was slowly added to the above mixture at 0 ℃ to conduct the reaction at 0 ℃ for half an hour, followed by continuing the reaction at room temperature for 12 hours, triethylamine hydrochloride was removed by filtration, the filtrate was desolved under reduced pressure, and the residue was separated by column chromatography to give 4.1g of an off-white N, N-bis (quinolin-5-yl) phosphorochloridite) cyclopropylamine as a solid.
2. Preparation of procatalyst precursor
Combining an amount of a PNP ligand N, N-bis (di (quinolin-5-yl) phosphono) cyclopropylamine with a chromium compound Cr (acac)3The main catalyst precursor solution with the concentration (calculated by chromium atoms) of 2 mu mol/mL is prepared by mixing the components according to the molar ratio of 1: 1 and the solvent is dehydrated toluene.
3. Evaluation of ethylene oligomerization experiment
3.1 ethylene oligomerization experimental method
The experimental procedure for ethylene oligomerization was the same as in example 1.
3.2 results of ethylene oligomerization experiment
When the reaction temperature was 50 ℃ and the reaction pressure was 3.5MPa, the reaction product was analyzed to have a 1-hexene content of 11.2 wt%, a 1-octene content of 78.3 wt%, a solid oligomer content of 0.2 wt% in the total product, and a total catalytic activity of 2600 kg. (mol-Cr)-1·h-1。
When the reaction temperature was 80 ℃ and the reaction pressure was 4.5MPa, the reaction product was analyzed to have a 1-hexene content of 13.7 wt%, a 1-octene content of 73.7 wt%, a solid oligomer content of 0.2 wt% in the total product, and a total catalytic activity of 4100kg (mol-Cr)-1.h-1。
Example 3
1. Synthesis of 6-daizinyl PNP ligands
1.1, 6-bromo-peptide-oxazine preparation
Figure BDA0002738204520000111
The tetrahydrofuran suspension (350mL) containing 8.2g of lithium aluminum hydride was cooled to-78 ℃ with stirring, 200mL of a tetrahydrofuran solution containing 27g of 4-bromophthalic acid was slowly added dropwise over 2 hours, and after completion of the addition, the temperature was raised to room temperature over 2 hours, and the reaction was heated to reflux for 2 hours. Subsequently, the mixture was cooled to 0 ℃ and 100mL of 15% sodium hydroxide solution was slowly added dropwise, vacuum filtration was carried out, the filter residue was washed with 200mL of water and 200mL of tetrahydrofuran, respectively, the filtrate and the washing solution were combined, extraction was carried out with diethyl ether (100 mL. times.3), the oil layers were combined, washed with brine, dried, and desolventized to obtain 16.4g of 4-bromophthalic alcohol as a white solid.
Stirring and cooling a mixed solution of 15mL of oxalyl chloride and 180mL of dichloromethane to-78 ℃, slowly dropwise adding a mixed solution of 25mL of dimethyl sulfoxide and 50mL of dichloromethane into the mixed solution, stirring for 15 minutes after dropwise addition, then adding 16.4g of 4-bromophthalic alcohol in batches, stirring for 1 hour at-78 ℃, then adding 200mL of triethylamine dropwise, continuing stirring for 10 minutes, removing a cold bath, naturally heating to room temperature, pouring a reaction mixture into 300mL of ice water while stirring, extracting twice with 400mL of dichloromethane, combining oil layers, washing with saline, drying, and desolventizing to obtain a crude product of 4-bromophthalic dicarboxaldehyde, and purifying by column chromatography to obtain 11.9g of white solid.
11.9g of 4-bromophthalaldehyde is dissolved in 120mL of ethanol, the mixture is stirred and cooled to 0 ℃, 3.5g of 80% hydrazine hydrate is dripped in the mixture, the mixture is kept at 0 ℃ and is continuously stirred for 2 hours, the mixture is decompressed and desolventized, 150mL of toluene is added into the residue, the mixture is stirred, heated and refluxed for 2 hours, the decompression and desolventization are carried out, and 8.3g of 6-bromophthalazine white solid is obtained by the column chromatography separation of a crude product.
1.2 preparation of PNP ligand
Figure BDA0002738204520000121
Dissolving 8.3g of 6-bromodaizine in 40mL of diethyl ether, dropwise adding the solution into 40mL of diethyl ether suspension containing 1.2g of magnesium chips at room temperature, keeping stirring, and slightly refluxing the reaction until the magnesium chips completely disappear; cooling to 0 deg.C, adding 2.7g of phosphorus trichloride into the above mixture, heating to room temperature, stirring for 1 hr, filtering under argon protection to remove magnesium salt, and removing solvent from the filtrate under reduced pressure to obtain 7.1g of bis (phthalazin-6-yl) phosphorophosphoidene chloride as light brown solid.
Adding 7.1g of bis (quinol-5-yl) phosphorochloridite into a mixed solution of 100mL of dichloromethane and 8mL of triethylamine at 0 ℃, stirring for dissolving, slowly adding 0.9g of 3-pentylamine into the mixture at 0 ℃, stirring for reacting for half an hour, subsequently raising the temperature to room temperature, continuing to react for 12 hours, filtering to remove triethylamine hydrochloride, performing decompression and desolvation on the filtrate, and separating the residue by column chromatography to obtain 3.2g of white N, N-bis (di (phthalazin-6-yl) phosphorochloridite) 3-pentylamine solid.
2. Preparation of procatalyst precursor
Certain amounts of PNP ligand N, N-bis (di (phthalazine-6-yl) phosphoramidite) 3-pentanamine and chromium compound Cr (acac)3The main catalyst precursor solution with the concentration (calculated by chromium atoms) of 2 mu mol/mL is prepared by mixing the components according to the molar ratio of 1: 1 and the solvent is dehydrated toluene.
3. Evaluation of ethylene oligomerization experiment
3.1 ethylene oligomerization experimental method
The experimental procedure for ethylene oligomerization was the same as in example 1.
3.2 results of ethylene oligomerization experiment
When the reaction temperature was 50 ℃ and the reaction pressure was 3.5MPa, the reaction product was analyzed to have a 1-hexene content of 21.1 wt%, a 1-octene content of 67.2 wt%, a solid oligomer content of 0.2 wt% in the total product, and a total catalytic activity of 3100 kg. (mol-Cr)-1.h-1。
When the reaction temperature was 70 ℃ and the reaction pressure was 4.5MPa, the reaction product was analyzed to have a 1-hexene content of 12.2 wt%, a 1-octene content of 77.1 wt%, a solid oligomer content of 0.3 wt% in the total product, and a total catalytic activity of 4150kg (mol-Cr)-1.h-1。
Example 4
1. Synthesis of 6-benzothiazolylpnp ligand
1.1 preparation of 6-bromobenzothiazole
Figure BDA0002738204520000131
Stirring and mixing 20g of p-bromoaniline, 17.6g of ammonium thiocyanate and 150mL of glacial acetic acid at room temperature, dissolving 18.6g of bromine in 40mL of glacial acetic acid, and dropwise adding the mixture into the mixture for not less than 30 minutes; after the dropwise addition, the mixture was stirred at room temperature for 24 hours, then the reaction mixture was poured into ice, the pH value was adjusted to 10 with concentrated ammonia water, filtration was carried out, the filter residue was washed with water and dried, and recrystallization was carried out with toluene to obtain 17.3g of 6-bromo-2-benzothiazoloamine.
17.3g of 6-bromo-2-benzothiazolylamine and 250mL of 85% phosphoric acid are mixed, stirred and cooled to 0 ℃, 25g of sodium nitrite-containing aqueous solution (40mL) is slowly dripped, the dripping temperature is controlled to be 0 ℃, stirring is continued at 0 ℃ for 30 minutes after the dripping is finished, the obtained slurry is slowly poured into 50% stirred hypophosphorous acid aqueous solution (250mL) and is naturally heated to room temperature, sodium carbonate is added to adjust the pH value to be 6, dichloromethane is used for extracting organic matters, a dichloromethane layer is washed with water and is desolventized, and 11.6g of yellow 6-bromobenzothiazole solid is obtained by column chromatography separation of residues.
1.2 preparation of PNP ligand
Figure BDA0002738204520000132
Dissolving 11.6g of 6-bromobenzothiazole in 40mL of diethyl ether, dropwise adding the solution into 50mL of diethyl ether suspension containing 1.5g of magnesium chips at room temperature, keeping stirring, and controlling the reaction to slightly reflux until the magnesium chips completely disappear; cooling to 0 deg.C, adding 3.7g of phosphorus trichloride into the above mixture, heating to room temperature, stirring for reaction for 1 hr, filtering under argon protection to remove magnesium salt, and removing solvent from the filtrate under reduced pressure to obtain 7.4g of bis (benzothiazol-6-yl) phosphorous oxychloride as light brown solid.
Adding 7.4g of bis (benzothiazol-6-yl) phosphorous oxychloride into a mixed solution of 100mL of dichloromethane and 10mL of triethylamine at 0 ℃, stirring for dissolving, slowly adding 0.6g of isopropylamine into the mixture at 0 ℃, stirring for reacting for half an hour, then raising the temperature to room temperature, continuing the reaction for 12 hours, filtering to remove triethylamine hydrochloride, performing desolventization on the filtrate under reduced pressure, and separating the residue by column chromatography to obtain 5.1g of white N, N-bis (benzothiazol-6-yl) phosphorous acyl) isopropylamine solid.
2. Preparation of procatalyst precursor
Combining an amount of a PNP ligand N, N-bis (benzothiazol-6-yl) phosphono) isopropylamine with a chromium compound Cr (acac)3The main catalyst precursor solution with the concentration (calculated by chromium atoms) of 2 mu mol/mL is prepared by mixing the components according to the molar ratio of 1: 1 and the solvent is dehydrated toluene.
3. Evaluation of ethylene oligomerization experiment
3.1 ethylene oligomerization experimental method
The experimental procedure for ethylene oligomerization was the same as in example 1.
3.2 results of ethylene oligomerization experiment
When the reaction temperature was 60 ℃ and the reaction pressure was 3.5MPa, the reaction product was analyzed to have a 1-hexene content of 13.5 wt%, a 1-octene content of 74.3 wt%, a solid oligomer content of 0.1 wt% in the total product, and a total catalytic activity of 4210kg (mol-Cr)-1·h-1。
When the reaction temperature is 80 ℃ and the reaction pressure is 4.5MPa, the analysis on the reaction product shows that the content of 1-hexene is 12.5wt percent, the content of 1-octene is 76.7wt percent, the content of solid oligomer in the total product is 0.1wt percent, and the total catalytic activity is 3950kg (mol-Cr)-1.h-1。
TABLE 1 summary of the results of the examples
Figure BDA0002738204520000141
It can be seen from the above examples that the ethylene selective oligomerization catalyst system provided by the invention has the advantages of high catalytic activity, high selectivity of target olefin, and the like when used for ethylene oligomerization, the total content of 1-hexene and 1-octene in the product is more than 85 wt%, the content of 1-octene can reach more than 75 wt%, and the content of solid oligomer is extremely low (less than or equal to 0.3%).

Claims (14)

1. An ethylene oligomerization catalyst system is characterized by comprising a PNP ligand, a transition metal compound and a cocatalyst; wherein the PNP ligand has the following structural general formula I:
Figure FDA0002738204510000011
wherein R is1Is alkyl, including straight, branched or cyclic alkyl; r2Is a binary polycyclic aryl group, and the chemical structural general formula is as follows:
Figure FDA0002738204510000012
wherein Y, Z are each independently O, S, N, C-R 'and R' is Rc6、Rc7；Rc3、Rc4、-Rc5、Rc6、Rc7The same or different, each independently selected from hydrogen, fluorine, alkyl or alkoxy.
2. The ethylene oligomerization catalyst system of claim 1, wherein the alkyl group is C1-C6Alkyl, said alkoxy is C1-C6An alkoxy group.
3. The ethylene oligomerization catalyst system of claim 2, wherein the alkyl group is C1-C4Alkyl groups including methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
4. The ethylene oligomerization catalyst system of claim 1, wherein the binary fused-ring aromatic group is selected from the following structures:
Figure FDA0002738204510000013
25) substituted benzofuran-7-yl 26) substituted benzofuran-6-yl 27) substituted benzofuran-5-yl 28) substituted benzofuran-4-yl
Figure FDA0002738204510000021
29) Substituted benzothiophen-7-yl 30) substituted benzothiophen-6-yl 31) substituted benzothiophen-5-yl 32) substituted benzothiophen-4-yl
Figure FDA0002738204510000022
33) Substituted benzenes
Figure FDA0002738204510000024
Oxazol-7-yl 34) substituted benzo
Figure FDA0002738204510000025
Oxazol-6-yl 35) substituted benzo
Figure FDA0002738204510000026
Oxazol-5-yl 36) substituted benzo
Figure FDA0002738204510000027
Azol-4-yl
Figure FDA0002738204510000023
37) Substituted benzothiazol-7-yl 38) substituted benzothiazol-6-yl 39) substituted benzothiazol-5-yl 40) substituted benzothiazol-4-yl.
5. The ethylene oligomerization catalyst system of claim 1, wherein the transition metal compound is selected from one or more of the following chromium compounds: an inorganic salt, an organic salt, a coordination complex or an organometallic complex of trivalent chromium.
6. The ethylene oligomerization catalyst system of claim 5, wherein the transition metal compound is selected from one or more of the following chromium compounds: chromium acetate, chromium caproate, chromium 2-ethylhexanoate, chromium isooctanoate, chromium n-octanoate, chromium acetylacetonate, chromium diisoprenate, chromium diphenyloxide, CrCl3(THF)3、CrCl2(THF)2Chromium tricarbonyl and chromium hexacarbonyl.
7. The ethylene oligomerization catalyst system of claim 1, wherein the cocatalyst is an organoaluminum compound, an organoboron compound, or a combination thereof.
8. The ethylene oligomerization catalyst system of claim 7, wherein the organoaluminum compound is selected from one or more of the following compounds: alkylaluminums, alkylaluminum halides, alkylaluminum alkoxides, or alkylaluminoxanes.
9. The ethylene oligomerization catalyst system of claim 8, wherein the organoaluminum compound is selected from one or more of the following: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, aluminum isopropoxide, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane; the organoboron compound is selected from one or more of the following compounds: boroxine, triethylborane, triphenylborane ammonia complex, NaBH4Tributyl borate, triisopropyl borate, tris (pentafluorophenyl) borane, trityltetrakis (pentafluorophenyl) borate, dimethylphenylammonium tetrakis (pentafluorophenyl) borate, diethylphenylammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, ethyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, trioctylammonium tetrakis (pentafluorophenyl) borate.
10. A process for preparing a catalyst system for oligomerization of ethylene according to any of claims 1-9, wherein the chemical synthesis of the PNP ligand comprises reacting a binary fused-ring aryl bromide as a starting material with butyl lithium or magnesium metal to form aryl lithium or grignard reagent, reacting with phosphorus trichloride to obtain diaryl phosphorus chloride, and finally condensing with alkylamine to obtain the PNP ligand, wherein the reaction scheme is as follows:
Figure FDA0002738204510000031
11. use of the ethylene oligomerization catalyst system of claims 1-9, wherein the catalyst system is used for high selectivity catalysis of ethylene trimerization or tetramerization for the production of 1-hexene or 1-octene.
12. The use of claim 11, wherein the PNP ligand, the transition metal compound, and the cocatalyst are premixed or added separately to an oligomerization reactor containing a reaction medium, ethylene gas is introduced to a reaction pressure, the reaction temperature is controlled to perform oligomerization, a gas-phase product and a liquid-phase product are collected separately after the reaction is completed, a terminator is added to the liquid-phase product to terminate the reaction, and a 1-hexene or 1-octene product is obtained by separation.
13. Use according to claim 12, wherein the reaction medium is selected from one or more of the following compounds: aromatic hydrocarbon, halogenated aromatic hydrocarbon, aliphatic hydrocarbon, halogenated aliphatic hydrocarbon, cycloaliphatic hydrocarbon, olefin or ether compound; the reaction temperature is 0-200 ℃; the reaction pressure is 0.1-50 MPa; the reaction time is 1-180 min.
14. The use of claim 12, wherein the molar ratio of the PNP ligand, the transition metal compound and the cocatalyst in the reaction system is 1: 0.5-100: 1-5000; the concentration of the transition metal compound in the reaction system is 1X 10-8To 1X 10-3mol metal/L.
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