CN115555053A - Ligand compound and application thereof - Google Patents

Ligand compound and application thereof Download PDF

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CN115555053A
CN115555053A CN202211158188.3A CN202211158188A CN115555053A CN 115555053 A CN115555053 A CN 115555053A CN 202211158188 A CN202211158188 A CN 202211158188A CN 115555053 A CN115555053 A CN 115555053A
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chromium
ligand compound
compound
ligand
electron donor
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刘惠
薛丽丽
罗清红
徐人威
武大庆
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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    • C07—ORGANIC CHEMISTRY
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    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a ligand compound, which consists of a chromium compound, a phosphonyl compound, an alkyl aluminum auxiliary agent and an electron donor, wherein the molar ratio of the components is as follows: 1, 0.1 to 100, 1 to 1000, wherein the chromide is chromium isooctanoate, chromium acetylacetonate or chromium tetrahydrofuran chloride, and the alkyl aluminum auxiliary agent is triethyl aluminum, methyl Aluminoxane (MAO), trimethyl aluminum or isobutyl aluminum; the electron donor is tetrachloroethane or hexachloroethane; the ethylene trimerization catalyst system using the phosphino-pyrrole compound as the ligand has the advantages of high catalyst activity, high selectivity of 1-hexene, less polyethylene byproducts in the product, capability of reducing the cost in industrialization and the like when used for catalyzing the ethylene trimerization reaction.

Description

Ligand compound and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a ligand compound and application thereof.
Background
The 1-hexene is a comonomer produced by a high-pressure, low-pressure and full-density device in chemical production, the 1-hexene is an important comonomer for producing linear low-density polyethylene and high-density polyethylene, and polyethylene resin prepared by using the 1-hexene as the comonomer has the advantages of high tensile strength, strong impact resistance and tear resistance and the like, is suitable for producing a plurality of products such as packaging films, agricultural covering films, PVC pipes, cable sleeves and the like, and has wide development prospect.
Another high value-added use of 1-hexene is as a comonomer for full density polyethylene, and the large scale construction of domestic full density polyethylene plants provides a larger market for the application of 1-hexene. The full density polyethylene has a new production capacity of 220 ten thousand tons/year. The demand for 1-hexene as a comonomer will necessarily increase, and the market for 1-hexene is quite large.
At present, five 1-hexene process technologies are mainly available abroad, and the five 1-hexene process technologies comprise: the method comprises a one-step 1-hexene oligomerization synthesis process of the company Schonfilon, a two-step 1-hexene oligomerization synthesis process of the company Ethyl, a 1-hexene oligomerization synthesis process of the company Shell by the SHOP method, a coal dry distillation extraction process of the company south Africa, and a 1-hexene synthesis process of the company Philips by the ethylene oligomerization. The domestic 1-hexene is mainly prepared by a 1-hexene device of Daqing petrochemical company of China petroleum by using a chromium catalyst and a process technology for synthesizing the 1-hexene by ethylene trimerization. The device is the first domestic kettle-type reactor process for synthesizing 1-hexene by ethylene trimerization, which realizes industrial production. A 1-hexene device of a medium petrochemical Yanshan petrochemical company adopts a chromium catalyst to build a 5 ten thousand ton/year 1-hexene device; the same production process is used by the Dushan petrochemical company and the Daqing petrochemical company to build a 2 million tons/year 1-hexene production device.
The activity of an ethylene selective oligomerization catalyst system and the selectivity of a target product are the key points for evaluating the advancement of the technology, most of the existing ethylene trimerization catalyst systems are chromium complexes containing ligands, and under the condition that a chromium source is relatively fixed, the adjustment of the structures of the ligands becomes a necessary means for changing the structure of a main catalyst and adjusting the performance of the catalyst.
There are a number of patents on the selective trimerization of ethylene.
CN103787935B discloses a synthesis method of a non-toxic or low-toxicity sulfur-nitrogen heteroatom ligand, which adopts R1SR2X and ammonia to react under an alkaline condition to obtain (R1 SR 2) 2NH, chromium trichloride (di (2-thiophenyl-ethyl) -amine) prepared by the ligand is used as a catalyst to catalyze ethylene trimerization, and the selectivity of 1-hexene is as high as 99.8%.
CN108686706B protected a dehydropyridine annulene type ligand, with a 1-hexene selectivity of 97.65%.
CN105566044B found in the study of diphosphine ligand that ethylene containing a certain amount of moisture in paraffin solvent has higher trimerization activity, C6 selectivity is 70.1% and 1-hexene purity is as high as 98.4% under the action of the metal main catalyst and aluminum-containing cocatalyst mentioned in the patent.
The catalyst system protected by CN101450326B adopts PNP ligand (diphenyl) phosphorus nitrogen (cyclohexyl) phosphorus (diphenyl), and the selectivity of 1-hexene is 92.48%. The catalyst system is different from the quaternary system in that the catalyst system described in CN102107146B is a five-membered system, and comprises a lattice, a PN ligand and a promoter, and also comprises an electron donor and a carrier, the catalyst enables the lattice to form three empty orbitals under the action of the ligand and the promoter, coordination of ethylene molecules is facilitated, a beta-H elimination reaction is carried out to generate 1-hexene, and the selectivity is 97.2%.
CN107282129B and CN107282114B both relate to a catalyst composition for ethylene trimerization, which comprises a diphosphine ligand or SNS ligand, a transition metal compound, an aluminum-containing cocatalyst and peroxide.
In general, the ethylene trimerization technology, which is currently industrialized or under development, mostly employs pyrrole or pyrrole derivatives as ligands for chromium metal.
Disclosure of Invention
In order to solve the problems, the invention provides a ligand compound, an ethylene trimerization composition is formed by chromium metal salt, pentaphenyl phosphino, alkyl aluminum and organic chloride, the selectivity of 1-hexene in a reaction product is high, compared with the disclosed catalyst (pyrrole is a ligand), the content of byproduct polyethylene is very low, and the activity is higher; in industrialization, the ethylene trimerization reaction can be carried out through in-situ polymerization, and prepolymerization is not needed.
In order to realize the purpose, the technical scheme of the invention is as follows:
a ligand compound comprising the following components:
(1) Chromium compound: chromium isooctanoate, chromium acetylacetonate or chromium tetrahydrofuran chloride;
(2) Ligand: pentaphenylphosphinole, of the formula:
Figure 20184DEST_PATH_IMAGE001
；
(3) An alkyl aluminum additive: triethylaluminum, methylaluminoxane, trimethylaluminum or isobutylaluminum;
(4) Electron donor: tetrachloroethane or hexachloroethane.
Further, the molar ratio of the chromide to the pentacenyl phosphino to the alkyl aluminum auxiliary agent to the electron donor is as follows: 1, 0.1 to 100, 1 to 1000; preferably 1.1 to 10; more preferably 1: 1~8:1 to 100.
Further, the preparation method of the pentaphenylphosphine comprises the following steps: tolane (4.0 g,22 mmol) was dissolved in dry tetrahydrofuran (25 mL) and then lithium turnings (140 mg,20 mmol) were added under argon protection. The reaction was stirred at room temperature overnight to give a dark green solution. Dichlorophenylphosphine (2.5 mL,15 mmol) was added to the system, and the mixture was refluxed for 6 hours. After removal of the organic solvent by rotary evaporation, the remaining residue was extracted with dichloromethane (100 mL) and the organic phase was concentrated in vacuo to 10 mL, overnight at 40 ℃ to finally obtain phosphino in 86% yield (3.5 g) as a yellow-green powder.
The application of the ligand compound comprises the following steps: dissolving the components in the ligand compound in an inert solvent respectively, injecting the components in a homogeneous catalyst form or injecting the components in an ethylene trimerization reaction system in advance in a uniformly mixed manner, then increasing the ethylene pressure, fully contacting the components with the catalyst, and carrying out ethylene trimerization reaction to obtain the 1-hexene.
Further, the conditions for the ethylene trimerization reaction are as follows: the temperature is 30 to 250 ℃, the pressure is 0.5 to 20MPa, and the time is 0.1 to 2h; the inert solvent comprises benzene, toluene, cyclohexane, methylcyclohexane, n-heptane or n-hexane.
Further, the application of the ligand compound in catalyzing ethylene trimerization reaction specifically comprises the following steps:
(1) Ligand compound preparation: dissolving the components in the ligand compound in an inert solvent subjected to water removal treatment respectively to prepare four solutions of a chromide, a pentaphenylphosphine pyrrole, an alkyl aluminum assistant and an electron donor for later use;
(2) Before reaction, firstly placing a reaction kettle body and a lining in an oven for drying overnight at 120 ℃, installing the reaction kettle body and the lining on the reaction kettle, sealing, heating to 105 ℃ under a vacuum condition, keeping the temperature constant at 1h, removing residual water, oxygen and oxygen-containing impurities, setting the temperature to be a reaction temperature, naturally cooling the reaction kettle body, filling nitrogen, vacuumizing, repeating for three times, ensuring that air is completely replaced, then pumping the nitrogen away by using a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is filled with ethylene;
(3) Injecting the alkyl aluminum additive solution prepared in the step (1) by using an injector under the stirring condition, after the temperature is stabilized to the reaction temperature, sequentially injecting a chromide solution, a pentacenyl phosphino solution and an electron donor solution by using the injector, closing an exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to a preset pressure value, recording mass flow meter data, closing ethylene gas after the reaction is finished, stopping the reaction, closing an air inlet valve, unloading a reaction kettle body, and soaking the reaction kettle body in an ice water bath to cool the reaction kettle to below 10 ℃.
After opening the vent valve to allow pressure to escape, a quantity of 5 ml of 10% HCl/ethanol solution was injected under stirring to quench the aluminum alkyl adjuvant, and the weight was weighed and recorded. A small amount of the liquid phase product was taken and analyzed by GC-MS. The remaining sample was filtered, the filter paper weighed in advance to record the mass, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, the resulting polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and the mass of the polymer calculated. The component types can be calibrated according to MS, and the selectivity and the catalyst activity of each product can be calculated according to GC results and the combination of the mass of the liquid phase product and the mass of the polymer.
Compared with the prior art, the invention has the advantages that: pentaphenyl phosphino is synthesized for the first time and used as a ligand in an ethylene trimerization catalyst system, namely, the ethylene trimerization composition is formed by chromium metal salt, pentaphenyl phosphino, alkyl aluminum and organic halide together, the selectivity of 1-hexene in a reaction product is high, and compared with the disclosed catalyst (a pyrrole compound is used as the ligand), the content of byproduct polyethylene is very low, and the activity is higher; the ethylene trimerization reaction can be carried out through in-situ polymerization in industrialization, and prepolymerization is not needed. The heteroatom phosphorus in the phosphonlonil ring in the pentaphenyl phosphonlonil has stronger electron donating performance and is connected with 5 benzene rings, the whole system has moderate electron donating capacity, the electron donating capacity can be coordinated by two conjugated rings and can be acted with metal chromium, triethyl aluminum and chlorine-containing electron donors, the electron donating performance can be adjusted more flexibly, high-efficiency catalytic ethylene molecules and metals form a seven-membered ring, a 1-hexene molecule is released after beta dehydrogenation, and compared with 2,5-dimethylpyrrole, the pentaphenyl phosphonlonil compound has larger steric hindrance, the generation of polymers can be effectively reduced, and the long-period operation of the reaction is facilitated.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a pentacylphosphine prepared in example 1;
FIG. 2 shows the NMR phosphine spectrum of the pentaphenylphosphinole prepared in example 1.
Detailed Description
The invention is further illustrated, but is not limited, by the following specific examples.
Example 1
The pentaphenylphosphinole compound is prepared by a dialkynyl reductive dimerization method, when tolane and metallic lithium are reacted in the proportion of (1:1), the following reaction flow occurs:
Figure 129829DEST_PATH_IMAGE002
；
tolane (4.0 g,22 mmol) was dissolved in dry tetrahydrofuran (25 mL) and then lithium turnings (140 mg,20 mmol) were added under argon protection. The reaction was stirred at room temperature overnight to give a dark green solution. Dichlorophenylphosphine (2.5 mL,15 mmol) was added to the system, and the mixture was refluxed for 6 hours. After removal of the organic solvent by rotary evaporation, the remaining residue was extracted with dichloromethane (100 mL) and the organic phase was concentrated in vacuo to 10 mL, overnight at 40 ℃ to give phosphinothole as a yellow-green powder in 86% yield (3.5 g). 1H NMR (600 MHz, CDCl3): delta 7.44-7.42 (m, 2H), 7.24-7.21 (m, 2H), 7.08-7.01 (m, 16H), 6.99-6.97 (m, 4H). 31P NMR (162 MHz, CDCl3): δ 12.53 (PC 4). The purple nuclear magnetic resonance characterization hydrogen spectrum of the pentaphenylphosphinole (shown in figure 1 and figure 2) is carried out, and the characteristic nuclear magnetic hydrogen spectrum and the phosphine spectrum peak can prove the successful preparation of the compound.
Example 2
The ethylene oligomerization reaction is carried out in a high-pressure stainless steel reaction kettle. Before reaction, the high-pressure reaction kettle is heated to 100 ℃ under the vacuum-pumping condition, the temperature is kept at 1h, then the temperature is set to 80 ℃, the temperature is naturally reduced, nitrogen is replaced for a plurality of times, and then ethylene is replaced for a plurality of times, so that the kettle body is ensured to be filled with ethylene. Subsequently, the solvent cyclohexane and the catalyst, in which the molar ratio of chromium acetylacetonate: pentaphenylphosphinole: triethyl aluminum: hexachloroethane = 1. Controlling the reaction pressure to be 4.5MPa, stopping the reaction after reacting for 1h, closing the air inlet valve, detaching the reaction kettle body, and soaking the reaction kettle body in ice-water bath to cool the reaction kettle to below 10 ℃. After opening the vent valve to allow pressure to escape, 5 mL of 10% HCl/ethanol solution was injected under stirring to quench the aluminum alkyl, which was then weighed and recorded. A small amount of the liquid phase product was taken and analyzed by GC-MS. The remaining sample was filtered, the filter paper weighed in advance to record the mass, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, the resulting polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and the mass of the polymer calculated. The component types can be calibrated according to MS, and the selectivity and the catalyst activity of each product can be calculated according to GC results by combining the mass of the liquid phase product and the mass of the polymer. The data results are shown in Table 1.
Example 3
The same as example 1 except that the reaction temperature was 130 deg.C, the data are shown in Table 1.
Example 4
The same as example 1 except that the reaction pressure was 6MPa, the data results are shown in Table 1.
Example 5
The same as example 1 except that the ratio of chromium acetylacetonate to the phosphinothricin compound was changed to 1:5, and the data are shown in table 1.
Example 6
The same as example 1 except that the ratio of chromium acetylacetonate to triethylaluminum was changed to 1.
Comparative example 1
The same as example 1, except that pentaphenylphosphine was changed to pyrrole, the data results are shown in Table 1.
TABLE 1 summary of the reaction conditions and the reaction Performance for the examples of the invention and the comparative examples
Figure 749029DEST_PATH_IMAGE003
The above examples are merely for clearly illustrating the present invention and the embodiments of the present invention are not limited thereto. Any modification, replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (8)

1. A ligand compound characterized by: comprises the following components:
(1) Chromium compound: chromium isooctanoate, chromium acetylacetonate or chromium tetrahydrofuran chloride;
(2) Ligand: pentaphenylphosphinolol of the formula:
Figure 859126DEST_PATH_IMAGE001
；
(3) An alkyl aluminum additive: triethylaluminum, methylaluminoxane, trimethylaluminum or isobutylaluminum;
(4) Electron donor: tetrachloroethane or hexachloroethane.
2. The ligand compound of claim 1, wherein: the preparation method of the pentaphenyl phosphino comprises the following steps: dissolving tolane in tetrahydrofuran, adding lithium scrap under the protection of argon, stirring the reaction at room temperature overnight to obtain a dark green solution, adding dichlorophenyl phosphine, refluxing the mixture for 6h, removing an organic solvent through rotary evaporation, extracting dichloromethane, concentrating an organic phase in vacuum, and standing overnight at 40 ℃ to obtain yellow green powdery phosphine pyrrole, namely pentaphenyl phosphine pyrrole.
3. The ligand compound of claim 1, wherein: the molar ratio of the chromide to the pentaphenylphosphine to the alkyl aluminum auxiliary to the electron donor is as follows: 1, 0.1 to 100, 1 to 1000.
4. The ligand compound of claim 3, wherein: the molar ratio of the chromide to the pentacenyl phosphino to the alkyl aluminum additive to the electron donor is 1.1 to 10.
5. The ligand compound of claim 4, wherein: the molar ratio of the chromide to the pentacenyl phosphino to the alkyl aluminum additive to the electron donor is 1: 1~8:1 to 100.
6. Use of a ligand compound according to any one of claims 1 to 5, wherein: dissolving the components in the ligand compound in an inert solvent respectively, injecting the components in a homogeneous catalyst form or injecting the components in an ethylene trimerization reaction system in advance in a uniformly mixed manner, then increasing the ethylene pressure, fully contacting the components with the catalyst, and carrying out ethylene trimerization reaction to obtain the 1-hexene.
7. Use according to claim 6, characterized in that: the conditions for the ethylene trimerization reaction are as follows: the temperature is 30 to 250 ℃, the pressure is 0.5 to 20MPa, and the time is 0.1 to 2h.
8. Use according to claim 7, characterized in that: the inert solvent comprises benzene, toluene, cyclohexane, methylcyclohexane, n-heptane or n-hexane.
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GB1110549A (en) * 1964-12-14 1968-04-18 Shell Int Research A process for the preparation of aldehydes and/or alcohols
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