CN109749812B - Method for preparing poly-alpha-olefin synthetic lubricating oil base oil - Google Patents
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Abstract
The invention relates to a method for preparing poly-alpha-olefin synthetic lubricating oil base oil, which changes the adding mode of reactants, a main catalyst and an auxiliary catalyst in the reaction process, namely dropwise adding 1-hexene into a mixed solution of the main catalyst and the auxiliary catalyst by using a constant-pressure dropping funnel, thereby changing the selectivity of different oligomerization products. The 1-hexene oligomerization reaction carried out according to the method of the invention has higher catalytic activity and selectivity of oligomerization products of more than seven polymerization, overcomes the problem of more oligomer content in the 1-hexene oligomerization reaction, and realizes the purposes of regulating and controlling the distribution of the oligomerization products and improving the content of effective components of the lubricating oil base oil. Meanwhile, the 1-hexene reactant is added dropwise, so that the reaction process is mild, and the problem that the reaction temperature is rapidly increased due to a large amount of heat release in the reaction process, so that the reaction cannot be controlled is solved.
Description
Technical Field
The invention belongs to the technical field of preparation of lubricating oil base oil, and relates to a method for preparing poly-alpha-olefin synthetic lubricating oil base oil.
Background
The synthetic lubricant base oil is an important lubricant base oil prepared by an organic synthesis method. Compared with the traditional mineral lubricating oil base oil, the synthetic lubricating oil base oil has a certain chemical structure and excellent physicochemical properties because the polymerized monomer is a pure substance or a homologue. The synthetic lubricating oil base oil has more types, mainly comprises hydrocarbon oil, ester oil and other synthetic oil, wherein the poly-alpha-olefin synthetic oil (PAO) is a type of synthetic lubricating oil base oil which is used more, and the yield of the synthetic lubricating oil base oil accounts for about 45 percent of the market share of the synthetic lubricating oil base oil in the world.
The PAO is a kind of lubricant base oil prepared by oligomerization reaction of alpha-olefin and hydrogenation saturation under the action of catalyst, compared with other lubricant base oil, the PAO has better viscosity-temperature performance and oxidation stability, higher viscosity index and lower pour point, and can be used in harsher environment.
The catalyst for synthesizing PAO mainly comprises aluminum trichloride catalyst, boron trifluoride catalyst, Ziegler-Natta catalyst, metallocene catalyst, ionic liquid catalyst and the like. Metallocene catalysts have been a research hotspot in recent years and have been successfully applied to industrial production due to their single active center and high catalytic activity. The PAO molecules synthesized with metallocene catalysts have a unique comb-like structure, without the presence of upstanding side chains, which determines their higher viscosity index and better thermal stability compared to conventional PAO products.
The performance of the PAO product is determined by the degree of polymerization and molecular weight distribution of the oligomer product, generally speaking, the product viscosity and thermal stability increase with the increase of the carbon number of the PAO molecule, and more side chain structures and relatively shorter straight chain segments are beneficial to good fluidity of the PAO at low temperature. By changing the composition and reaction conditions of the catalyst system, the product distribution of the oligomerization reaction can be regulated, thereby adjusting the performance of the PAO product. For example, patent CN 105885929 discloses a method for reducing the dimer content in the product by adding a chain shuttling agent, which uses metallocene as a main catalyst, organic boride as a cocatalyst, and coal-made α -olefin as a reactant, and greatly reduces the dimer content in the polymerization product by adding a chain shuttling agent dialkyl zinc, thereby improving the yield of the lubricating oil base oil component, and the obtained product has better low-temperature fluidity.
The alpha-olefin serving as a raw material for synthesizing the PAO mainly comprises C6-C14 alpha-olefin, wherein 1-decene is an ideal raw material for synthesizing the PAO product, and the molecules of the PAO product produced by the alpha-olefin have a straight-chain alkane framework and a regular long-side-chain comb structure, so that the PAO product has excellent viscosity-temperature performance and low-temperature fluidity. 1-decene, mainly derived from ethylene oligomerization and paraffin cracking, is one of many products in the production of linear alpha-olefins (C4-C20), and the yield thereof accounts for about 10% -25% of the yield of all linear alpha-olefins, and the production cost of PAO is increased due to limited productivity and high price thereof, thereby limiting the use thereof as a raw material for synthesizing PAO. When 1-decene is used as a raw material for producing PAO, 1-decene dimer generated by oligomerization is not suitable as an effective component for producing PAO, and the dimer needs to be separated and sold as a separate product or polymerized with other olefins to produce PAO. In order to reduce the production cost of PAO, low-carbon α -olefins (e.g., 1-hexene) with low price are used as raw materials for producing PAO, and the production of oligomers should be minimized during production to obtain polymers with longer carbon chains. Patents US 5859159 and CN 101130467 report that the metallocene complex 1, 1-dimethylsilyl-bridged-bis (4,5,6, 7-tetrahydroindenyl) zirconium dichloride and 2- (tetramethylcyclopentadienyl) -4,6-di-tert-butylphenoxy titanium dichloride are used as catalysts, and 1-hexene and 1-octene are used as reactants for oligomerization, respectively, the conversion rate of the reactants can reach more than 60% under optimized reaction conditions, and the average molecular weight of the oligomerization product can reach more than 3000 by adjusting reaction parameters.
The cocatalyst is an important component of the metallocene catalyst system and is an essential component for initiating oligomerization. The cocatalyst which can be used for the oligomerization of alpha-olefin at present mainly comprises alkylaluminoxane, modified alkylaluminoxane and organic boride. The alkyl aluminoxane mainly comprises methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane and the like, which have complex structures and are sensitive to water oxygen, and the use amount of the alkyl aluminoxane serving as a cocatalyst is large, so that the cost is high. Organic borides are used in combination with aluminum alkyls as cocatalysts for oligomerization reactions, and although relatively stable in nature and in small amounts, are less stable to metal atoms and to active sites than alkyl aluminoxanes.
Because the dimer cannot be used as an effective component of the lubricating oil base oil, the problem of more oligomers can be faced when the oligomerization reaction is carried out by taking alpha-olefin of C8-C14 as a raw material; meanwhile, when the carbon atom number of the raw material alpha-olefin is small, the obtained oligomerization product has poor low-temperature fluidity; when the carbon atom number of the raw material alpha-olefin is larger, the obtained oligomerization product has poorer viscosity-temperature performance; at present, C10 is the most ideal raw material, however, when n-decene is used as the raw material for preparing lubricating oil, the cost of reactants is high; when 1-hexene with lower price is used as a raw material, the effective components of the lubricating oil base oil are less due to more oligomers (including dimers) generated, so that the product distribution needs to be changed, and the selectivity of the high molecular weight oligomers needs to be increased, namely the product distribution of the oligomerization reaction needs to be changed.
Disclosure of Invention
In order to overcome the problem that the effective components of the lubricating oil base oil are less due to more oligomers in PAO (polyamide olefin) generated by oligomerization of low-carbon olefins such as 1-hexene, the invention provides a preparation method for synthesizing the lubricating oil base oil by poly-alpha-olefin, which realizes the purposes of regulating and controlling the distribution of oligomerization products and improving the content of the effective components of the lubricating oil base oil by changing the adding mode of reactants and catalysts in the oligomerization process of 1-hexene.
To this end, the present invention provides a method for preparing a polyalphaolefin synthetic lubricant base oil, comprising:
step L, uniformly mixing the main catalyst metallocene complex and the cocatalyst alkyl aluminoxane at room temperature, heating to the reaction temperature and keeping the reaction temperature to obtain a catalyst mixture at the reaction temperature;
step M, dropwise adding the reactant at the reaction temperature into the catalyst mixture at the reaction temperature, reacting, and obtaining a reacted solution after the reaction is finished;
and step N, adding the reacted solution into dilute glacial hydrochloric acid, and stopping the reaction to obtain the polyalphaolefin synthetic lubricating oil base oil.
In the invention, the step L and the step M are both carried out under the conditions of no water and no oxygen. For example, in some embodiments of the present invention, the main catalyst and the cocatalyst are uniformly mixed in step L by mixing the main catalyst and the cocatalyst under anhydrous and oxygen-free conditions and stirring for at least 10 min.
In the present invention, the main catalyst and the cocatalyst are prepared into a main catalyst solution and a cocatalyst solution respectively with an organic solvent before the reaction, and the organic solvent is selected from toluene, cyclohexane, diethyl ether, methylcyclohexane, tetrahydrofuran, ethanol, benzene, xylene, and dichloromethane, preferably selected from toluene and xylene, and more preferably toluene.
In some embodiments of the invention, the concentration of the main catalyst solution is 0.015 to 0.5mol/L, preferably 0.015 mol/L.
In some embodiments of the invention, the concentration of the promoter solution is 1.5 to 5mol/L, preferably 1.5 mol/L.
In some preferred embodiments of the present invention, step J is further included before step L, and the reaction system is subjected to N2Replacement to ensure that the reaction system has no water and oxygen.
In other preferred embodiments of the present invention, step K is further included before step L, the reactants are placed in a constant pressure dropping funnel and warmed to the reaction temperature.
According to the process of the invention, in step M, the rate of the dropwise addition is from 0.2 to 2mL/min, preferably from 0.4 to 1 mL/min.
In some preferred embodiments of the present invention, in step M, the reactant is added dropwise using a constant pressure dropping funnel.
In the present invention, the reactant is selected from the group consisting of 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene, and is preferably 1-hexene.
In the present invention, the metallocene complex is a non-bridged metallocene complex or a bridged metallocene complex.
In some embodiments of the invention, the non-bridged metallocene complex is selected from one or more of bis (cyclopentadienyl) zirconium dichloride (bis (cyclopentadienyl) zirconium dichloride), bis (tetramethylcyclopentadienyl) zirconium dichloride (bis (tetramethylcyclopentadienyl) zirconium dichloride), bis (indenyl) zirconium dichloride (bis (indenyl) zirconium dichloride), bis (n-butylcyclopentadienyl) zirconium dichloride (bis (n-butylcyclopentadienyl) zirconium dichloride), and bis (ethylcyclopentadienyl) zirconium dichloride (bis (ethylcyclopentadienyl) zirconium dichloride), preferably bis (cyclopentadienyl) zirconium dichloride and/or bis (tetramethylcyclopentadienyl) zirconium dichloride.
In other embodiments of the invention, the bridged metallocene complex is selected from dimethylsilicon-bridged bis (tetrahydroindenyl) zirconium dichloride (. eta.) (dimethylilybis [)5-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, 2-tetramethylcyclopentadienyl-4, 6-di-tert-butylphenyloxyzirconium dichloride (2- (tetramethylcyclopentylpentadienyl) -4, 6-di-tert-butylphenyloxyzirconium dichloride), ethyl bridged bis-indenyl zirconium dichloride (ethyl) and diphenyl carbon bridged bis-indenyl zirconium dichloride (indenyl) one or more.
In some preferred embodiments of the present invention, the metallocene complex is selected from bis (cyclopentadienyl) zirconium dichloride and bis (tetramethylcyclopentadienyl) zirconium dichloride, preferably the metallocene complex is bis (tetramethylcyclopentadienyl) zirconium dichloride.
In the invention, the alkyl aluminoxane is C1-C4 alkyl aluminoxane, wherein C1-C4 alkyl is straight chain or branched chain alkyl.
In some preferred embodiments of the present invention, the aluminoxane is selected from Methylaluminoxane (MAO), modified methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane; preferably, the aluminoxane is methylaluminoxane.
In some embodiments of the present invention, the molar ratio of aluminum in the cocatalyst to zirconium in the main catalyst is 50-1000, preferably 100-600, more preferably 400-600, and still more preferably 400.
In other embodiments of the invention, the molar ratio of reactants to procatalyst is (1-4). times.104Preferably (1.5-3). times.104More preferably (2.1-3). times.104More preferably 2.13X 104。
In the present invention, an organic solvent may or may not be used in the reaction process.
In some preferred embodiments, an organic solvent is used during the reaction, and the organic solvent is selected from the group consisting of toluene, cyclohexane, diethyl ether, methylcyclohexane, tetrahydrofuran, ethanol, benzene, xylene, and dichloromethane, preferably selected from the group consisting of toluene and xylene, and further preferably toluene.
In some embodiments of the present invention, in steps L and M, the reaction temperature is 30 to 80 ℃, preferably 40 to 60 ℃, and more preferably 60 ℃.
In other embodiments of the present invention, in step M, the reaction time is 0.25 to 3 hours, preferably 0.5 to 1 hour.
In the present invention, steps J-M are all at N2The reaction is carried out under an atmosphere.
In the invention, the poly-alpha-olefin synthetic lubricating oil base oil is an oligomerization product. For example, in some embodiments, when the reactant is 1-hexene, the polyalphaolefin synthesis lubricant base oil is a mixture of dimers, trimers, tetramers, pentamers, hexamers, and higher than heptamers of 1-hexene monomer.
The inventor researches and discovers that when the reactant is 1-hexene, the distribution of oligomerization products can be regulated and controlled by preparing the poly-alpha-olefin synthetic lubricating oil base oil by the method, namely the content of dimer and trimer in the 1-hexene oligomerization products is reduced and is higher than that of heptamer by changing the adding mode of the reactant and the catalyst, and the content of tetramer-hexamer is not obviously changed.
In the present invention, a reaction kettle can be used for reaction, and in some preferred embodiments, the reaction kettle is a glass reaction kettle or a stainless steel reaction kettle.
In the present invention, both mixing and stirring are achieved under stirring conditions, and in some preferred embodiments, the stirring is by magnetic stirring or mechanical stirring.
In the invention, because the reaction process needs to release heat, the adopted temperature control mode must be capable of timely taking away the heat generated in the reaction process, namely ensuring that the reaction is carried out at a constant temperature. Therefore, the temperature control mode used in the invention can be water bath temperature control or oil bath temperature control, but the electric heating jacket cannot be directly used for heating and controlling the temperature.
In the invention, the addition sequence of the reactants and the catalyst is that the main catalyst and the cocatalyst are added firstly, and the reactants are added after being stirred and mixed evenly.
In the step L, the main catalyst and the cocatalyst are added into the reaction kettle in the sequence of first adding the main catalyst metallocene complex and then adding the cocatalyst alkyl aluminoxane under continuous stirring.
In some embodiments of the present invention, the preparation of a polyalphaolefin synthetic lubricant base stock from 1-hexene comprises the steps of:
(1) subjecting the reaction system to N2Replacement, ensuring that the reaction system is anhydrous and oxygen-free;
(2) putting a certain amount of 1-hexene reactant into a constant-pressure dropping funnel, and heating to the reaction temperature;
(3) uniformly mixing a main catalyst metallocene complex and a cocatalyst alkylaluminoxane in a reaction kettle at room temperature, heating to the reaction temperature and keeping the reaction temperature;
(4) dropwise adding the reactant obtained in the step (2) into the mixture obtained in the step (3);
(5) after the dropwise addition is finished, keeping the reaction temperature for reacting for a certain time, and after the reaction is finished, obtaining a solution after the reaction;
(6) and (3) after the reaction is finished, adding the solution obtained after the reaction in the step (5) into dilute ice hydrochloric acid, and stopping the reaction (quenching).
The term "polyalphaolefin synthetic lubricant base oil" as used herein means a polyalphaolefin synthetic oil which is used as a lubricant base oil.
The term "reaction system" as used herein refers to a system or space containing reactants, products, procatalysts, cocatalysts, solvents and reaction equipment.
The term "no organic solvent is used in the reaction process" as used herein means that no organic solvent is added in addition to a small amount of organic solvent used for preparing the main catalyst solution and the cocatalyst solution in advance before the reaction; the organic solvent used for preparing the main catalyst solution and the cocatalyst solution is added with the catalyst, and the dosage of the organic solvent is smaller and far smaller than the addition of the reactants, so the organic solvent is not considered as the organic solvent for reaction.
Accordingly, the term "organic solvent used in the reaction process" as used herein means that in addition to a small amount of organic solvent used for preparing the main catalyst solution and the cocatalyst solution in advance before the reaction, an additional amount of organic solvent is added in the reaction process, and the additional amount of organic solvent is used as a reaction solvent and is larger than the added amount of the reactants.
The term "water" as used herein means deionized water, distilled water or ultrapure water unless otherwise specified or indicated.
The invention mainly aims at the problem that the effective components of the lubricating oil base oil are less due to more generated oligomers when the oligomerization reaction is carried out on the alpha-olefin with lower carbon number. The method of the invention is used for 1-hexene oligomerization, and after the reaction is finished, the oligomerization activity can reach 10 by chromatographic analysis6g·mol Zr-1·h-1The conversion rate of reactants reaches more than 95 percent, the selectivity of products of more than heptapolymerization in the oligomerization products can reach more than 45 percent, and the yield of effective components of the lubricating oil is improved. Meanwhile, the 1-hexene reactant is added dropwise, so that the reaction process is mild, and the problem that the reaction cannot be controlled due to rapid rise of the reaction temperature caused by a large amount of heat release in the reaction process is avoidedTo a problem of (a). When 1-octene is used as a reactant, it has similar advantages to oligomerization of 1-hexene. When alpha-olefins above C10 are used as reactants, a higher viscosity lubricant base oil will be produced.
The method for preparing the polyalpha-olefin synthetic lubricating oil base oil can be understood as a method for regulating and controlling the distribution of 1-hexene oligomerization reaction products, and the selectivity of different oligomerization products is changed by changing the adding modes of reactants, a main catalyst and an auxiliary catalyst in the reaction process, namely dropwise adding the reactants (low-carbon olefin, such as 1-hexene) into a mixed solution of the main catalyst and the auxiliary catalyst by using a constant-pressure dropping funnel. The 1-hexene oligomerization reaction carried out according to the method has higher catalytic activity and selectivity of oligomerization products of more than seven polymerization, overcomes the problem of higher oligomer content in the 1-hexene oligomerization reaction, and achieves the purposes of regulating and controlling the distribution of the oligomerization products and improving the content of effective components of the lubricating oil base oil. Meanwhile, the 1-hexene reactant is added dropwise, so that the reaction process is mild, and the problem that the reaction temperature is rapidly increased due to a large amount of heat release in the reaction process, so that the reaction cannot be controlled is solved.
Detailed Description
For easy understanding of the present invention, the present invention will be described in detail with reference to examples, which are provided for illustrative purposes only and are not intended to limit the scope of the present invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
The reaction products were quantitatively analyzed by an internal standard curve method. The specific method comprises the following steps:
firstly, drawing an internal standard curve of each component to be detected, then adding a certain amount of internal standard substance into quenched reaction liquid (poly alpha-olefin synthetic lubricating oil base oil) and analyzing by using a capillary gas chromatograph, wherein the chromatograph model is Agilent GC-7890A, the capillary chromatographic column model is HP-5, the chromatographic column parameters are 30m multiplied by 0.32mm multiplied by 0.25 mu m, and the detector is an FID detector.
The contents of the respective components in the reaction liquid (polyalphaolefin synthetic lubricant base oil) were calculated according to the following formula.
In the above formula:
Fi/s-a relative correction factor;
wi-sample mass fraction;
ws-internal standard mass fraction;
Ai-chromatographic peak area of the sample;
Asinternal standard chromatographic peak area.
The conversion, selectivity, yield and activity were calculated according to the following formulas.
Yield ═ conversion × selectivity × 100%
In the above formula:
n1mass of reactant (e.g. 1-hexene) added, g;
n2mass of unreacted reactant (e.g. 1-hexene), g;
na-mass of target product produced, g;
nb-mass of polymer formed, g;
t-reaction time, h;
ncatthe moles, mol, of zirconium added in the reaction.
In the above formula:
the "conversion" is the mass ratio of the reactants reacted to all reactants, expressed as a percentage.
The "selectivity" refers to the selectivity of a catalyst for a specific polymer component (e.g., dimer, trimer, tetramer, pentamer, hexamer, or heptamer or higher polymer) constituting a "polyalphaolefin synthesis lubricant base oil" (i.e., polyalphaolefin synthesis oil).
The "yield" refers to the yield of "polyalphaolefin synthetic lubricant base oil" (i.e., polyalphaolefin synthetic oil) based on the reactants.
The "activity" means the amount of the "polyalphaolefin synthetic lubricant base oil" (i.e., polyalphaolefin synthetic oil) obtained by calculation based on the unit reaction time and the number of moles of the unit zirconium added.
Examples
Example 1:
and (3) building a reaction device, ensuring the reaction system to be closed, and replacing air in the reaction system with nitrogen for three times to ensure that the reaction is carried out in an anhydrous and oxygen-free environment. 20mL of 1-hexene is placed in a constant pressure dropping funnel, 0.5mL of 0.015mol/L bis (tetramethylcyclopentadiene) zirconium dichloride/toluene solution and 2mL of 1.5mol/L MAO/toluene solution (the molar ratio of aluminum in the cocatalyst to zirconium in the main catalyst is 400) are added into a reaction kettle at room temperature, and after uniform magnetic stirring, the temperature is gradually increased to 60 ℃ and maintained. 20mL of 1-hexene (molar ratio of reactant to main catalyst is 2.13X 10) is dropwise added by using a constant pressure dropping funnel4) Adding into a reaction kettle, controlling the dropping speed to be about 0.4mL/min, controlling the temperature of the reaction system to be 60 ℃ by utilizing a water bath, and reacting for 1 h. And after the reaction is finished, adding a small amount of solution after the reaction into dilute ice hydrochloric acid to terminate the reaction, and analyzing the composition of a product (poly-alpha-olefin synthetic lubricating oil base oil) by using Agilent GC-7890A type gas chromatography. The data are shown in Table 1.
Example 2:
the same as in example 1, except that 20mL of 1-hexene was added in a single portion. The data are shown in Table 1.
Example 3:
the same as in example 1, except that the reaction temperature was 50 ℃. The data are shown in Table 1.
Example 4:
the same as example 1, except that the reaction time was 0.5 h. The data are shown in Table 1.
Example 5:
the difference from example 1 is that the stirring was mechanical stirring. The data are shown in Table 1.
Example 6:
the same as in example 1, except that bis (cyclopentadienyl) zirconium dichloride was used as the catalyst. The data are shown in Table 1.
Example 7:
the same as example 1, except that 20mL of toluene was added to the reaction vessel and then the main catalyst and the cocatalyst were added. The data are shown in Table 1.
Example 8:
the same as in example 1, except that the dropping rate was 0.5 ml/min. The data are shown in Table 1.
Comparative example 1 (abbreviated D1):
and (3) building a reaction device, ensuring the reaction system to be closed, and replacing air in the reaction system with nitrogen for three times to ensure that the reaction is carried out in an anhydrous and oxygen-free environment. 0.5mL of 0.015mol/L bis (tetramethylcyclopentadiene) zirconium dichloride/toluene solution and 2mL of 1.5mol/L MAO/toluene solution were placed in a constant pressure dropping funnel, 20mL of 1-hexene was added to the reaction vessel at room temperature, and the temperature was gradually raised to 60 ℃ with continuous magnetic stirring and maintained. Dropwise adding the mixed solution of bis (tetramethylcyclopentadiene) zirconium dichloride/toluene and MAO/toluene into the reaction kettle by using a constant-pressure dropping funnel, controlling the dropwise adding speed to be about 0.4mL/min, controlling the temperature of the reaction system to be 60 ℃ by using a water bath, and reacting for 1 h. And after the reaction is finished, adding a small amount of solution after the reaction into dilute ice hydrochloric acid to terminate the reaction, and analyzing the composition of a product (poly-alpha-olefin synthetic lubricating oil base oil) by using Agilent GC-7890A type gas chromatography. The data are shown in Table 1.
Comparative example 2 (abbreviated D2):
the same as in example 3, except that the mixed solution of bis (tetramethylcyclopentadienyl) zirconium dichloride/toluene and MAO/toluene was added in one portion. The data are shown in Table 1.
Comparative example 3 (abbreviated D3):
and (3) building a reaction device, ensuring the reaction system to be closed, and replacing air in the reaction system with nitrogen for three times to ensure that the reaction is carried out in an anhydrous and oxygen-free environment. Gradually heating the reaction kettle to 60 ℃ under magnetic stirring and keeping the temperature, sequentially adding 0.5mL of 0.015mol/L bis (tetramethylcyclopentadiene) zirconium dichloride/toluene solution, 2mL of 1.5mol/L MAO/toluene solution and 20mL of 1-hexene into the reaction kettle, controlling the temperature of the reaction system to be 60 ℃ by utilizing a water bath, and reacting for 1 h. After the reaction is finished, a small amount of solution after the reaction is added into frozen dilute hydrochloric acid to terminate the reaction, and the composition of a product (poly-alpha-olefin synthetic lubricating oil base oil) is analyzed by using Agilent GC-7890A type gas chromatography. The data are shown in Table 1.
Comparative example 4 (abbreviated D4):
and (3) building a reaction device, ensuring the reaction system to be closed, and replacing air in the reaction system with nitrogen for three times to ensure that the reaction is carried out in an anhydrous and oxygen-free environment. 20mL of 1-hexene was added to the reaction kettle at room temperature, and gradually warmed to 60 ℃ with magnetic stirring and held. 0.5mL of 0.015mol/L bis (tetramethylcyclopentadiene) zirconium dichloride/toluene solution and 2mL of 1.5mol/L MAO/toluene solution are sequentially added into a reaction kettle, the temperature of a reaction system is controlled to be 60 ℃ by utilizing a water bath, and the reaction is carried out for 1 h. After the reaction is finished, a small amount of solution after the reaction is added into frozen dilute hydrochloric acid to terminate the reaction, and the composition of a product (poly-alpha-olefin synthetic lubricating oil base oil) is analyzed by using Agilent GC-7890A type gas chromatography. The data are shown in Table 1.
TABLE 1
The symbol "+" in table 1 indicates that the product includes all polymers above heptamer.
The data in table 1 show that the 1-hexene oligomerization reaction performed by the method for preparing polyalpha-olefin synthetic lubricating oil base oil according to the invention has higher catalytic activity and selectivity of oligomerization products of more than seven groups, overcomes the problem of higher oligomer content in the 1-hexene oligomerization reaction, and achieves the purposes of regulating and controlling the distribution of the oligomerization products and improving the content of effective components in the lubricating oil base oil. Meanwhile, the 1-hexene reactant is added dropwise, so that the reaction process is mild, and the problem that the reaction temperature is rapidly increased due to a large amount of heat release in the reaction process, so that the reaction cannot be controlled is solved.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (21)
1. A process for preparing a polyalphaolefin synthetic lubricant base stock comprising:
step L, uniformly mixing the main catalyst metallocene complex and the cocatalyst alkyl aluminoxane at room temperature, heating to the reaction temperature and keeping the reaction temperature to obtain a catalyst mixture at the reaction temperature;
step M, dropwise adding the reactant at the reaction temperature into the catalyst mixture at the reaction temperature, reacting, and obtaining a solution after the reaction, wherein the dropwise adding speed is 0.4-1 mL/min;
step N, adding the reacted solution into dilute glacial hydrochloric acid, and stopping the reaction to obtain poly-alpha-olefin synthetic lubricating oil base oil;
wherein, the step L and the step M are both carried out under the conditions of no water and no oxygen.
2. The method as claimed in claim 1, wherein in step M, the reactant is dropwise added using a constant pressure dropping funnel.
3. The method of claim 1, wherein the reactant is selected from the group consisting of 1-hexene, 1-octene, 1-decene, 1-dodecene, and 1-tetradecene.
4. A process according to any one of claims 1 to 3, characterized in that the metallocene complex used is a non-bridged metallocene complex or a bridged metallocene complex.
5. The process according to claim 4, wherein the non-bridged metallocene complex is selected from one or more of bis (cyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bisindenyl zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride and bis (ethylcyclopentadienyl) zirconium dichloride.
6. The process according to claim 5, characterized in that the non-bridged metallocene complex is bis (cyclopentadienyl) zirconium dichloride and/or bis (tetramethylcyclopentadienyl) zirconium dichloride.
7. The process according to claim 4, wherein the bridged metallocene complex is selected from one or more of dimethylsilyl-bridged bis (tetrahydroindenyl) zirconium dichloride, 2-tetramethylcyclopentadienyl-4, 6-di-tert-butylphenyloxyzirconium dichloride, ethyl-bridged bis-indenyl zirconium dichloride and diphenylcarbon-bridged bis-indenyl zirconium dichloride.
8. A process according to any one of claims 1 to 3, wherein the alkylaluminoxane is a C1-C4 alkylaluminoxane, wherein C1-C4 alkyl is a linear or branched alkyl.
9. The method of claim 8, wherein the alkylaluminoxane is selected from the group consisting of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
10. The method of claim 8, wherein the alkylalumoxane is methylalumoxane.
11. A process according to any one of claims 1 to 3, wherein the molar ratio of aluminium in the cocatalyst to zirconium in the procatalyst is from 50 to 1000.
12. The method as claimed in claim 11, wherein the molar ratio of aluminum in the cocatalyst to zirconium in the main catalyst is 100-600.
13. The method as claimed in claim 12, wherein the molar ratio of aluminum in the cocatalyst to zirconium in the main catalyst is 400-600; and/or the molar ratio of the reactants to the main catalyst is (1-4). times.104。
14. The process of claim 13 wherein the molar ratio of reactants to procatalyst is (1.5-3) x 104。
15. The process of claim 14 wherein the molar ratio of reactants to procatalyst is (2.1-3) x 104。
16. A process according to any one of claims 1 to 3, characterized in that an organic solvent selected from the group consisting of toluene, cyclohexane, diethyl ether, methylcyclohexane, tetrahydrofuran, ethanol, benzene, xylene and dichloromethane is used or not used during the reaction.
17. The method of claim 16, wherein the organic solvent is selected from the group consisting of toluene and xylene.
18. The process according to any one of claims 1 to 3, wherein in steps L and M, the reaction temperature is from 30 to 80 ℃.
19. The process according to claim 18, wherein in steps L and M, the reaction temperature is 40-60 ℃.
20. The process according to any one of claims 1 to 3, wherein in step M, the reaction time is from 0.25 to 3 hours.
21. The process according to claim 20, wherein in step M, the reaction time is 0.5 to 1 h.
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| WO2008010865A2 (en) * | 2006-07-19 | 2008-01-24 | Exxonmobil Chemical Patents Inc. | Process to produce high viscosity fluids |
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