CN110330529B - Pyridine imine palladium complex for preparing synthetic lubricating oil from alpha-olefin, and preparation method and application thereof - Google Patents

Pyridine imine palladium complex for preparing synthetic lubricating oil from alpha-olefin, and preparation method and application thereof Download PDF

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CN110330529B
CN110330529B CN201910618529.2A CN201910618529A CN110330529B CN 110330529 B CN110330529 B CN 110330529B CN 201910618529 A CN201910618529 A CN 201910618529A CN 110330529 B CN110330529 B CN 110330529B
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高琦
蒋华良
孙进龙
李为民
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Jiangsu Zhongsheng High Tech Environment Co ltd
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    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
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    • C08F110/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants

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Abstract

The invention discloses a pyridine imine palladium complex for preparing synthetic lubricating oil from alpha-olefin, and a preparation method and application thereof. The complex catalyst obtained by the invention is applied to preparation of oligomerization alpha-olefin, can replace a Metallocene (MAO) catalytic system, avoids MAO and other catalysts in the oligomerization process of alpha-olefin, reduces the process cost, does not need to add MAO, has mild reaction conditions, does not need to be carried out under harsh anhydrous and anaerobic conditions, reduces the process difficulty, and can obtain PAO lubricating oil base oil after the prepared oligomerization alpha-olefin is subjected to hydrogenation saturation treatment.

Description

Pyridine imine palladium complex for preparing synthetic lubricating oil from alpha-olefin, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lubricating oil, and particularly relates to a pyridine imine palladium complex for catalyzing alpha-olefin oligomerization to prepare PAO lubricating oil base oil and a preparation method thereof.
Background
The lubricating oil industry, as an important component of the petrochemical industry, plays an indispensable role in various industries. The performance of a lubricant base oil, which is an important component of a lubricant, greatly affects the performance of the lubricant. Although refined mineral oils have been used as lubricant base oils in the early days, mineral base oils are not suitable under extreme conditions such as aviation, aerospace, and polar regions, and in order to satisfy these conditions, various synthetic base oils have been designed, and the types thereof include mainly PAO oils (poly α olefins), ester oils, ether oils, silicone oils, silicate oils, and fluorine-containing oils.
The major alpha-olefin oligomerization catalysts at present can be largely classified into lewis acid catalysts, metallocene catalysts, and ionic liquid type catalysts. Lewis acid catalysts are mainly divided into AlCl3And BF3，AlCl3The PAO oil prepared by catalyzing olefin oligomerization has the advantages of low cost, simple operation, strong adaptability to raw materials and the like (Zhanglianhong, Von Shi, Qin Shi, and the like, the research on novel catalysts for preparing lube base oil by polymerizing alpha-olefin [ J ]]Proceedings of the petroleum institute, 2001,21(2): 13-16.). Compared with mineral oil, the PAO oil has low pour point, good viscosity-temperature property and high viscosity index.
At present, all domestic lubricating oil production companies use AlCl3The catalyst is used for catalyzing the cracking of paraffin to prepare synthetic lubricating oil. Although AlCl3The catalyst has many advantages in olefin oligomerization catalysis, but has strong corrosivity, is easy to sublimate at high temperature to release chlorine, and is difficult to separate from the product, so that AlCl is greatly limited3The application of a catalyst; BF (BF) generator3Is commonly used for producing synthetic oil with low viscosity, and the reaction is easy to control (Lishuhua. BF)3Study on Synthesis of lubricating oil by catalyzing 1-decene polyalphaolefin [ J]Application chemical engineering, 2011,40(3): 492-. But BF3Easily react with water vapor to form HF gas, easily corrode equipment, and BF3Toxic and is gradually being replaced by less harmful catalysts. The metallocene catalyst system is used for catalyzing alpha-olefin polymerization to prepare the lubricant base oil, the catalyst has higher activity, and the productGood performance, but MAO as a catalyst is costly and not easy to store, most importantly because of its presence, the process needs to be carried out under anhydrous and oxygen-free conditions, which are very harsh (zhao yue keen, bunghong, zhang. metallocene/triisobutylaluminum/B (C)6F5)3Research on oligomerization of 1-octene catalyzed by catalytic system [ J]Application chemical, 2012,41(12):2106- > 2108).
The ionic liquid is a novel environment-friendly catalyst, is different from the traditional poly-alpha-olefin catalyst, has the advantages of high reaction speed, environmental friendliness, no pollution, easy separation of the catalyst and products and the like, and can be recycled and recycled (Zhang Yao, Chunghua, Liuyinong, and the like, research on preparation of poly-alpha-olefin by catalyzing oligomerization of 1-decene with the ionic liquid [ J ] research on petroleum refining and chemical industry, 2011,42(11): 62-65.). But the price of the ionic liquid is higher at present, and the large-scale industrial production of alpha-olefin oligomerization catalyzed by an ionic liquid catalytic system is severely restricted.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the pyridine imine palladium complex and the preparation method thereof are provided, the complex catalyst can replace an MAO catalyst to prepare oligomeric alpha-olefin, and PAO lubricating oil base oil prepared by hydrogenating the oligomeric alpha-olefin has the advantages of low pour point, high viscosity index, good thermal oxidation stability and the like.
The technical scheme is as follows: in order to achieve the above object, the present invention provides a pyridine imine palladium complex for preparing synthetic lubricating oil from alpha-olefin, wherein the complex has a structural formula as shown in formula (I):
Figure GDA0003425323280000021
wherein n is 1, 2.
A preparation method of a pyridine imine palladium complex for preparing synthetic lubricating oil from alpha-olefin comprises the following steps:
s1: synthesis of Compound (II)
The method comprises the following steps of (1) filling 6-bromo-2-pyridinecarboxaldehyde, p-toluenesulfonic acid, toluene and ethylene glycol which are well proportioned into a water separator, carrying out stirring reaction by a stirrer, cooling to room temperature after the reaction is finished, then adding a saturated sodium carbonate aqueous solution, then extracting by toluene, drying an organic phase by magnesium sulfate, and concentrating to obtain a brown oily substance, namely a compound (II);
s2: synthesis of Compound (III)
Taking a certain amount of sodium hydride, adding an alkoxy chain compound into the sodium hydride under the protection of nitrogen, stirring at room temperature, adding the compound (II) obtained in the step S1 into the sodium hydride after stirring for reaction, stirring the mixture by using a stirrer for reaction, adding water into the mixture after the reaction is finished and cooled for quenching reaction, extracting the reaction solution by using dichloromethane and water after the reaction solution becomes brown and clear, concentrating the obtained organic phase, drying the organic phase by using magnesium sulfate, filtering the organic phase, concentrating the organic phase, and then drying the organic phase on a vacuum line to obtain a compound (III);
s3: synthesis of Compound (IV)
Taking a certain amount of the compound (III) prepared in the step S2, adding a certain amount of hydrochloric acid and tetrahydrofuran, stirring and reacting through a stirrer, adding a reaction solution into a conical flask after the reaction is finished, adding a sodium bicarbonate solution at a low temperature until the reaction solution does not generate bubbles any more, extracting for multiple times by using chloroform, concentrating an organic phase, drying by using magnesium sulfate, filtering, spin-drying on a rotary evaporator, and finally pumping on a vacuum line to obtain a compound (IV);
s4: synthesis of Compound (V)
Taking a certain amount of a compound (IV), adding 2, 6-diisopropylaniline, formic acid and ethanol, carrying out stirring reaction by a stirrer, adding dichloromethane and water for extraction for multiple times after reaction liquid is dried in a spinning mode, combining organic phases, drying in a spinning mode to obtain a crude product, and finally carrying out polar separation on the crude product by a column chromatography method to obtain a bright yellow oily substance which is a compound (V);
s5: synthesis of Complex (I)
And (3) reacting the compound (V) synthesized in the step S4 with Pd (COD) Me2 in a solvent under the protection of nitrogen at room temperature, and obtaining a synthetic complex (I), namely the pyridine imine palladium complex after the reaction is finished.
Further, the pyridine imine palladium complex prepared in the step S5 is used for catalyzing alpha-olefin oligomerization.
Further, the temperature of the stirrer is set to 140 ℃ in the step S1, the reflux time is 40h, and the reaction formula of the prepared compound (ii) is as follows:
Figure GDA0003425323280000031
。
further, the alkoxy chain compound in step S2 is one of ethylene glycol monomethyl ether and diethylene glycol monomethyl ether.
Further, in the step S2, the stirring time at room temperature is 30min, the temperature of the stirrer is set to be 140 ℃, the stirring time of the stirrer is 24h, and the reaction formula of the compound (iii) is as follows:
Figure GDA0003425323280000032
wherein n is 1, 2.
Further, the mass fraction of the hydrochloric acid in the step S3 is 9-11%, the temperature of the stirrer is set to 100 ℃, the stirring reflux is carried out for 18h, and the reaction formula of the compound (iv) is as follows:
Figure GDA0003425323280000033
wherein n is 1 or 2.
Further, the temperature of the stirrer is set to 100 ℃ in the step S4, and the compound (v) is stirred and refluxed for 3h, and the reaction formula of the compound (v) is as follows:
Figure GDA0003425323280000034
wherein n is 1, 2.
Further, the column chromatography in step S4 is performed by using petroleum ether: ethyl acetate is 100: mode 1.
Further, in the step S5, COD in pd (COD) Me2 is 1, 5-cyclooctadiene, and the compound (v) and pd (COD) Me2 are mixed according to a molar ratio of 1: 1, reacting for 12-24 hours, wherein the obtained complex (I) has a reaction formula as follows:
Figure GDA0003425323280000041
wherein n is 1, 2.
The pyridine imine palladium complex of the invention is used for preparing the catalyst for oligomerization of alpha-olefin, and due to the unique structural characteristics of the pyridine imine palladium complex of the invention, the catalyst can replace MAO catalyst in the preparation process of oligomerization of alpha-olefin, and PAO lubricating oil base oil can be obtained after hydrofining and reduced pressure distillation of oligomerization alpha-olefin prepared under the catalysis of the pyridine imine palladium complex of the invention.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the pyridine imine palladium complex catalyst is applied to preparing oligomerization alpha-olefin, replaces an MAO catalyst, not only reduces the process cost, but also has mild reaction conditions because MAO is not required to be added, does not need to be carried out under the harsh anhydrous and anaerobic conditions, and reduces the process difficulty.
2. The low-poly alpha-olefin prepared by the pyridine imine palladium complex catalyst can obtain PAO lubricating oil base oil which has the advantages of low pour point, high viscosity index, good thermal oxidation stability and the like.
Detailed Description
The invention will be further elucidated with reference to the following specific examples.
Example 1:
this example, named catalyst formula (I) -O2, was prepared by the process of the present invention to prepare a palladium pyridine imine complex, which was specifically prepared as follows:
s1: synthesis of Compound (II)
Adding a certain amount of 6-bromo-2-pyridinecarboxaldehyde, 0.3 equivalent of p-toluenesulfonic acid, 100ml of toluene and 3 equivalent of ethylene glycol into a reactor, stirring and reacting by a stirrer, setting the stirrer at 140 ℃, refluxing for 40h, cooling to room temperature after the reaction is finished, then adding a saturated sodium carbonate aqueous solution, extracting by toluene, drying an organic phase by magnesium sulfate, and concentrating to obtain a tan oily substance, namely a compound (II), wherein the reaction formula of the compound (II) is as follows:
Figure GDA0003425323280000042
s2: synthesis of Compound (III)
Taking 1.8 equivalents of sodium hydride in a glove box, then adding 1.8 equivalents of ethylene glycol monomethyl ether under the protection of nitrogen, stirring for 30min at room temperature, adding the compound (II) obtained in the step S1 into the glove box for reaction after stirring, stirring the mixture by a stirrer for reaction, setting the stirring reactor at 140 ℃, stirring the mixture for 24h at the temperature, adding a small amount of water into the mixture after the reaction is finished and cooling the mixture for quenching reaction, extracting the reaction solution by using a large amount of dichloromethane and water after the reaction solution becomes brown and clear, concentrating the obtained organic phase, drying the organic phase by using magnesium sulfate, filtering the organic phase, concentrating the organic phase, and drying the organic phase on a vacuum line to obtain a compound (III), wherein the reaction formula of the compound (III) is as follows:
Figure GDA0003425323280000051
s3: synthesis of Compound (IV)
Taking a certain amount of corresponding compound (III), adding a certain amount of hydrochloric acid and tetrahydrofuran with the mass fraction of 10%, wherein the amount of the added hydrochloric acid and tetrahydrofuran are 1.8mL/mmol reactant and 3.6mL/mmol reactant respectively, stirring at 100 ℃ in a stirring reactor, refluxing for 18 hours, after the reaction is finished, adding the reaction liquid into a conical flask, adding 1mol/L sodium bicarbonate solution at 0 ℃ until the reaction liquid does not generate bubbles, extracting for multiple times by using chloroform, concentrating an organic phase, drying by using magnesium sulfate, filtering, spin-drying on a rotary evaporator, and finally pumping on a vacuum line to obtain the compound (IV), wherein the reaction formula of the compound (IV) is as follows:
Figure GDA0003425323280000052
s4: synthesis of Compound (V)
Taking a certain amount of the compound (IV), adding 1.05 equivalent of 2, 6-diisopropylaniline, 0.05 equivalent of formic acid and 200 ml of ethanol, stirring and reacting through a stirrer, setting the stirring reactor at 100 ℃, stirring and refluxing for 3 hours, spin-drying reaction liquid, adding dichloromethane and water for extraction for multiple times, combining and spin-drying organic phases to obtain a crude product, and finally carrying out polar separation on the crude product through column chromatography (petroleum ether: ethyl acetate is 100: 1) to obtain a bright yellow oily substance which is the compound (V), namely the ligand formula (V) -O2, wherein the reaction formula of the ligand formula (V) -O2 is as follows:
Figure GDA0003425323280000053
s5: synthesis of Complex (I)
Under the protection of nitrogen at room temperature, the ligand formula (V) -O2 synthesized in the step S4 is mixed according to a molar ratio of 1: 1 Pd (COD) Me2Added to a Schlenk flask with a COD of 1, 5-cyclooctadiene in N2Addition of CH Using a syringe under atmosphere2Cl2(20mL), the mixture was stirred at room temperature for 12 h. The resulting suspension was filtered, the solvent removed in vacuo, the resulting powder washed twice with diethyl ether and then dried under vacuum at room temperature to give complex (I), i.e., catalyst formula (I) -O2, the reaction of catalyst formula (I) -O2 is as follows:
Figure GDA0003425323280000061
example 2:
this example, named catalyst formula (I) -O3, was prepared by the process of the present invention to prepare a palladium pyridine imine complex, which was specifically prepared as follows:
s1: synthesis of Compound (II)
Adding a certain amount of 6-bromo-2-pyridinecarboxaldehyde, 0.3 equivalent of p-toluenesulfonic acid, 100ml of toluene and 3 equivalent of ethylene glycol into a reactor, stirring and reacting through a stirrer, setting the stirring reactor at 140 ℃, refluxing for 40h, cooling to room temperature after the reaction is finished, then adding a saturated sodium carbonate aqueous solution, extracting with toluene, drying an organic phase with magnesium sulfate, and concentrating to obtain a tan oily substance, namely a compound (II), wherein the reaction formula of the compound (II) is as follows:
Figure GDA0003425323280000062
s2: synthesis of Compound (III)
Taking 1.8 equivalents of sodium hydride in a glove box, then adding 1.8 equivalents of diethylene glycol monomethyl ether under the protection of nitrogen, stirring for 30min at room temperature, adding the compound (II) obtained in the step S1 into the glove box for reaction after stirring, stirring the mixture by a stirrer for reaction, setting the stirring temperature of the stirring reactor to be 140 ℃, stirring the mixture for 24h at the temperature, adding a small amount of water into the mixture after the reaction is finished and cooling the mixture for quenching reaction, extracting the reaction liquid after the reaction liquid becomes brown and clear by using a large amount of dichloromethane and water, concentrating the obtained organic phase, drying the organic phase by using magnesium sulfate, filtering the organic phase, concentrating the organic phase, and drying the organic phase on a vacuum line to obtain a compound (III), wherein the reaction formula of the compound (III) is as follows:
Figure GDA0003425323280000063
s3: synthesis of Compound (IV)
Taking a certain amount of corresponding compound (III), adding a certain amount of hydrochloric acid and tetrahydrofuran with the mass fraction of 10%, wherein the amount of the added hydrochloric acid and tetrahydrofuran are 1.8mL/mmol reactant and 3.6mL/mmol reactant respectively, stirring at 100 ℃ in a stirring reactor, refluxing for 18 hours, after the reaction is finished, adding the reaction liquid into a conical flask, adding 1mol/L sodium bicarbonate solution at 0 ℃ until the reaction liquid does not generate bubbles, extracting for multiple times by using chloroform, concentrating an organic phase, drying by using magnesium sulfate, filtering, spin-drying on a rotary evaporator, and finally pumping on a vacuum line to obtain the compound (IV), wherein the reaction formula of the compound (IV) is as follows:
Figure GDA0003425323280000071
s4: synthesis of Compound (V)
Taking a certain amount of the compound (IV), adding 1.05 equivalent of 2, 6-diisopropylaniline, 0.05 equivalent of formic acid and 200 ml of ethanol, stirring and reacting through a stirrer, setting the stirring reactor at 100 ℃, stirring and refluxing for 3 hours, spin-drying reaction liquid, adding dichloromethane and water for extraction for multiple times, combining and spin-drying organic phases to obtain a crude product, and finally carrying out polar separation on the crude product through column chromatography (petroleum ether: ethyl acetate is 100: 1) to obtain a bright yellow oily substance which is the compound (V), namely the ligand formula (V) -O3, wherein the reaction formula of the ligand formula (V) -O3 is as follows:
Figure GDA0003425323280000072
s5: synthesis of Complex (I)
Under the protection of nitrogen at room temperature, the ligand formula (V) -O3 synthesized in the step S4 is mixed according to a molar ratio of 1: 1 Pd (COD) Me2Added to a Schlenk flask with a COD of 1, 5-cyclooctadiene in N2Addition of CH Using a syringe under atmosphere2Cl2(20mL), the mixture was stirred at room temperature for 24 hours, the resulting suspension was filtered, the solvent was removed in vacuo, the resulting powder was washed twice with diethyl ether and then dried under vacuum at room temperature to give complex (I), i.e., catalyst formula (I) -O3, the reaction formula of catalyst formula (I) -O3 is as follows:
Figure GDA0003425323280000073
example 3:
in this example, the catalyst of formula (I) -O2 obtained in example 1 was used to catalyze the oligomerization of alpha-octene, the specific procedure was as follows: a250 mL reactor equipped with a magnetic stirrer was dried at 150 ℃ for 1 hour and cooled to room temperature, 100mL of toluene solvent was added, the reaction temperature was heated to 30 ℃ and allowed to equilibrate for 10 minutes, then the corresponding α -hexene (20mmol) was added, the mixture was stirred for 10 minutes, and finally the catalyst formula (I) -O2 solution (1.5 μmol of catalyst formula (I) -O2 in 2mL of CH)2Cl2) Is introduced into the reactor. After reacting for 0.5h at 5atm and 30 ℃, adding 50mL of acidified methanol (methanol/HCl ═ 50/1) to terminate the polymerization, cooling the reaction product to room temperature, then decompressing, carrying out rotary evaporation and concentration on the obtained oligomer, dissolving the oligomer in hexane, washing the oligomer with distilled water, carrying out rotary evaporation and solvent removal on the organic phase, concentrating to obtain poly-alpha-hexylene, and then carrying out hydrorefining and reduced pressure distillation treatment to obtain the product O2-C6. The catalytic activity of the catalyst of the formula (I) -O2 in this example was 2.31X 106g PE(mol Pd)-1·h-1。
Example 4:
in this example, the catalyst of formula (I) -O2 obtained in example 1 was used to catalyze the oligomerization of alpha-octene, the specific procedure was as follows: a250 mL reactor equipped with a magnetic stirrer was dried at 150 ℃ for 1 hour and cooled to room temperature, 100mL of toluene solvent was added, the reaction temperature was heated to 50 ℃ and allowed to equilibrate for 10 minutes, then the corresponding α -octene (20mmol) was added, the mixture was stirred for 10 minutes, and finally the catalyst formula (I) -O2 solution (5 μmol of catalyst formula (I) -O2 in 2mL of CH)2Cl2) Is introduced into the reactor. After reacting for 1h at 5atm and 50 ℃, terminating the polymerization by adding 50mL of acidified methanol (methanol/HCl ═ 50/1), cooling the reaction product to room temperature, then decompressing, carrying out rotary evaporation and concentration on the obtained oligomer, dissolving the oligomer in hexane, washing the oligomer in distilled water, carrying out rotary evaporation and solvent removal on the organic phase, concentrating to obtain poly alpha-octylene, and carrying out hydrorefining and reduced pressure distillation treatment to obtain the product O2-C8. The catalytic activity of the catalyst of the formula (I) -O2 in this example was 3.5X 106g PE(mol Pd)-1·h-1。
Example 5:
this exampleThe catalyst obtained in example 2, namely the formula (I) -O3, is used for catalyzing the oligomerization of alpha-decene, and the specific process is as follows: a250 mL reactor equipped with a magnetic stirrer was dried in advance at 150 ℃ for 1 hour and cooled to room temperature, 100mL of toluene solvent was added, the reaction temperature was heated to 80 ℃ and allowed to equilibrate for 10 minutes, then the corresponding alpha-decene (20mmol) was added, the mixture was stirred for 10 minutes, and finally the catalyst formula (I) -O3 solution (10. mu. mol of catalyst formula (I) -O3 was dissolved in 2mL of CH)2Cl2) Is introduced into the reactor. After reacting for 2h at 3atm and 80 ℃, terminating the polymerization by adding 50mL of acidified methanol (methanol/HCl ═ 50/1), cooling the reaction product to room temperature, then decompressing, carrying out rotary evaporation and concentration on the obtained oligomer, dissolving the oligomer in hexane, washing the oligomer in distilled water, carrying out rotary evaporation and solvent removal on the organic phase, concentrating to obtain poly alpha-decahydrocarbon, and then carrying out hydrorefining and reduced pressure distillation treatment to obtain the product O3-C10. The catalyst of the formula (I) -O3 in this example had a catalytic activity of 2.5X 106g PE(mol Pd)-1·h-1。
Example 6:
in this example, the catalyst of formula (I) -O3 obtained in example 2 was used to catalyze the oligomerization of alpha-dodecene by the following procedure: a250 mL reactor equipped with a magnetic stirrer was previously dried at 150 ℃ for 1 hour and cooled to room temperature, 100mL of toluene solvent was added, the reaction temperature was heated to 30 ℃ and allowed to equilibrate for 10 minutes, then the corresponding α -dodecene (20mmol) was added, the mixture was stirred for 10 minutes, and finally the catalyst formula (I) -O3 solution (2 μmol of catalyst formula (I) -O3 was dissolved in 2mL of CH)2Cl2) Is introduced into the reactor. After reacting for 0.5h at 1atm and 30 ℃, adding 50mL of acidified methanol (methanol/HCl ═ 50/1) to terminate the polymerization, cooling the reaction product to room temperature, then decompressing, carrying out rotary evaporation and concentration on the obtained oligomer, dissolving the oligomer in hexane, washing the oligomer with distilled water, carrying out rotary evaporation and solvent removal on the organic phase, concentrating to obtain poly-alpha-dodecane, and carrying out hydrorefining and reduced pressure distillation treatment to obtain the product O3-C12. The catalyst of the formula (I) -O3 in this example had a catalytic activity of 2.8X 106g PE(mol Pd)-1·h-1。
Example 7:
in this example, a fixed bed reaction was usedHydrofining is respectively carried out on the products O2-C6, O2-C8, O3-C10 and O3-C12 obtained in the embodiments 3-6 by the device, the reaction pressure is 1.5MPa, the reaction temperature is 180 ℃, and the reaction space velocity is 1-4h-1The hydrogenation catalyst is a conventional olefin hydrogenation saturation catalyst, the obtained product is subjected to reduced pressure distillation to remove light components, and four PAO lubricating oil base oils are obtained, wherein the specific physical and chemical indexes are shown in the following table 1:
TABLE 1-PAO Lubricant base oils physicochemical Properties
Figure GDA0003425323280000091
As can be seen from Table 1, the four PAO lubricant base stocks produced in this example have higher viscosity index and superior performance properties as compared to the MAO catalyzed lubricant base stock.

Claims (4)

1. A pyridine imine palladium complex for alpha-olefin synthetic lubricating oil, which is characterized in that: the structural formula of the pyridine imine palladium complex is shown as the following formula (I):
Figure FDA0003425323270000011
wherein n is 1 or 2.
2. The method for preparing a palladium pyridine imine complex for use in an alpha-olefin synthesis lubricating oil according to claim 1, wherein: the method comprises the following steps:
s1: synthesis of Compound (II)
The method comprises the following steps of (1) filling 6-bromo-2-pyridinecarboxaldehyde, p-toluenesulfonic acid, toluene and ethylene glycol which are well proportioned into a reactor, stirring and reacting through a stirrer, cooling to room temperature after the reaction is finished, then adding a saturated sodium carbonate aqueous solution, extracting with toluene, drying an organic phase with magnesium sulfate, and concentrating to obtain a brown oily substance, namely a compound (II);
s2: synthesis of Compound (III)
Taking sodium hydride, adding an alkoxy chain compound into the sodium hydride under the protection of nitrogen, stirring at room temperature, adding the compound (II) obtained in the step S1 into the sodium hydride after stirring for reaction, stirring the mixture by using a stirrer for reaction, adding water into the mixture after the reaction is finished and cooled for quenching reaction, extracting the reaction solution by using dichloromethane and water after the reaction solution becomes brown and clear, concentrating the obtained organic phase, drying the organic phase by using magnesium sulfate, filtering the organic phase, concentrating the organic phase, and then pumping the organic phase on a vacuum line to obtain a compound (III);
s3: synthesis of Compound (IV)
Taking the compound (III) prepared in the step S2, adding hydrochloric acid and tetrahydrofuran, stirring and reacting through a stirrer, adding a reaction solution into a conical flask after the reaction is finished, adding a sodium bicarbonate solution at a low temperature until the reaction solution does not generate bubbles any more, extracting for multiple times by using chloroform, concentrating an organic phase, drying by using magnesium sulfate, filtering, spin-drying on a rotary evaporator, and finally pumping on a vacuum line to obtain a compound (IV);
s4: synthesis of Compound (V)
Taking a compound (IV), adding 2, 6-diisopropylaniline, formic acid and ethanol, stirring and reacting through a stirrer, adding dichloromethane and water for extraction for multiple times after reaction liquid is dried in a spinning mode, combining organic phases, drying in a spinning mode to obtain a crude product, and finally separating the crude product through column chromatography polarity to obtain a bright yellow oily substance which is a compound (V);
s5: synthesis of Complex (I)
Reacting the compound (V) synthesized in the step S4 with Pd (COD) Me2 in a solvent under the protection of nitrogen at room temperature, and obtaining a synthetic complex (I), namely a pyridine imine palladium complex after the reaction is finished;
the temperature of the stirrer in the step S1 is set to 140 ℃, the reflux time is 40 hours, and the reaction formula of the prepared compound (ii) is as follows:
Figure FDA0003425323270000021
in the step S2, the alkoxy chain compound is ethylene glycol monomethyl ether or diethylene glycol monomethyl ether;
in step S2, the stirring time at room temperature is 30min, the temperature of the stirrer is set to 140 ℃, the stirring time of the stirrer is 24h, and the reaction formula of the compound (iii) is as follows:
Figure FDA0003425323270000022
wherein n is 1, 2;
the mass fraction of the hydrochloric acid in the step S3 is 9-11%, the temperature of the stirrer is set to be 100 ℃, stirring and refluxing are carried out for 18h, and the reaction formula of the compound (IV) is as follows:
Figure FDA0003425323270000023
wherein n is 1, 2;
the temperature of the stirring reactor in the step S4 is set to 100 ℃, and the stirring reflux is performed for 3h, and the reaction formula of the compound (v) is as follows:
Figure FDA0003425323270000024
wherein n is 1, 2.
3. The method for preparing a palladium pyridine imine complex for use in an alpha-olefin synthesis lubricating oil according to claim 2, wherein: the column chromatography in step S4 is performed with petroleum ether: ethyl acetate is 100: mode 1.
4. The method for preparing a palladium pyridine imine complex for use in an alpha-olefin synthesis lubricating oil according to claim 2, wherein: pd (COD) Me in the step S52Wherein COD is 1, 5-cyclooctadiene, said compound (v) and pd (COD) Me2 are in a molar ratio of 1: 1 reaction for 12-24 hours to obtain the reaction product of the complex (I)The formula is as follows:
Figure FDA0003425323270000031
wherein n is 1 or 2.
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