CN116003773A - Polyether lubricating oil base oil and preparation method thereof - Google Patents
Polyether lubricating oil base oil and preparation method thereof Download PDFInfo
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- CN116003773A CN116003773A CN202211734273.XA CN202211734273A CN116003773A CN 116003773 A CN116003773 A CN 116003773A CN 202211734273 A CN202211734273 A CN 202211734273A CN 116003773 A CN116003773 A CN 116003773A
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Abstract
The invention relates to polyether lubricating oil base oil and a preparation method thereof. Compared with the prior art, the invention synthesizes the polyether lubricating oil base oil with excellent performance at room temperature by adopting a one-step method, avoids using a high-temperature high-pressure reaction kettle, widens the reaction conditions for synthesizing the polyether lubricating oil base oil, and reduces the cost.
Description
Technical Field
The invention relates to the technical field of preparation of lubricating oil base oil, in particular to polyether lubricating oil base oil and a preparation method thereof.
Background
The polyether product is oligomer obtained by ring-opening polymerization of alkylene oxide. The product has excellent performance and wide application. With the development of petrochemical industry, a large number of applications using ethylene oxide and propylene oxide as raw materials become excellent varieties for preparing lubricating oil base oil.
The polyether base oil has ether bond and hydroxyl group, so that it has unique performance, and has excellent water solubility, heat stability, shearing resistance, lubricity, less coking at high temperature and high pressure, volatile decomposition product, no precipitate, no corrosion to equipment, no toxicity, etc. The polyether structure is changed to obtain different hydrophilic-lipophilic balance values and surfactants with different performances, so that the modified polyether is an excellent raw material for producing special lubricating oil.
According to the Lewis acid-base theory, all molecules, ions or radicals that can provide electron pairs are defined as bases. Alkylene oxide, as defined herein, is a strong Lewis base. According to this theory, the ring-opening polymerization of alkylene oxides can only be initiated with cationic catalysts. However, alkylene oxides contain a three-membered ring, have high molecular tension and high potential energy, and require severe external conditions to carry out ring-opening polymerization.
The traditional polyether base oil synthesis method mainly comprises cationic ring-opening polymerization, anionic ring-opening polymerization and coordination polymerization. Anionic polymerization is produced by first generating anionic active species, mainly alkali metal hydroxides and the like, which interact with an initiator containing active hydrogen or are directly initiated by the existing anions. The compound containing active hydrogen can carry out ring-opening polymerization on alkylene oxide under the action of anion catalysis. Cationic polymerization means that the cyclic oxyalkane can undergo cationic ring-opening polymerization under the catalysis of electrophiles such as hydrogen ions. The cationic catalysis ring-opening polymerization block is not easy to form macromolecular polyether, and byproducts are more. The complex catalytic polymerization mainly comprises a double metal cyanide system, a metalloporphyrin catalytic system, a quaternary phosphonium salt and a phosphazene base catalytic system. According to different catalysts, different ring-opening polymerization processes are corresponding.
From the above, the existing synthetic method of polyether base oil has the following defects: (1) The ring-opening polymerization method of the alkylene oxide is more, but because of the special property of the ternary ring, a high-pressure high-temperature reaction kettle is needed in the polymerization process, and the reaction condition is severe; (2) It is difficult to form high molecular weight polyethers with conventional catalytic systems; (3) The obtained polyether base oil product has difficulty in achieving both excellent viscosity-temperature performance and low-temperature fluidity.
Disclosure of Invention
The invention aims to provide polyether lubricating oil base oil and a preparation method thereof, and the polyether lubricating oil base oil with excellent performance is synthesized at room temperature.
The aim of the invention can be achieved by the following technical scheme: the preparation method of the polyether lubricating oil base oil comprises the following steps of carrying out polymerization reaction on alkylene oxide and tetrahydrofuran at room temperature by taking alcohols as an initiator and trifluoromethanesulfonic acid as a catalyst to obtain the polyether lubricating oil base oil.
Preferably, the method specifically comprises the following steps:
(1) Stirring and fully dissolving an initiator and a catalyst at room temperature, repeatedly vacuumizing and filling nitrogen for a plurality of times, and adding tetrahydrofuran into a reaction system;
(2) Slowly and dropwise adding alkylene oxide into the dissolved initiator, catalyst and tetrahydrofuran, stirring at room temperature, and performing polymerization reaction to obtain alkylene oxide-tetrahydrofuran polyether, namely the polyether lubricating oil base oil.
Further preferably, in step (1), tetrahydrofuran is added to the reaction system through a constant pressure funnel, and in step (2), alkylene oxide is slowly added dropwise through a constant pressure funnel.
Preferably, the initiator is selected from methanol, 1, 4-butanediol, isooctanol or diethylene glycol.
Preferably, the catalyst is selected from yttrium triflate, cerium triflate, indium triflate or hafnium triflate.
Preferably, the alkylene oxide is selected from propylene oxide, epichlorohydrin, hexane oxide or methyl propylene oxide.
Preferably, the molar ratio of the alkylene oxide to the tetrahydrofuran is 2:1 to 1:2.
preferably, the molar ratio of the initiator to the catalyst is (15-25): 1.
further preferably, the molar ratio of the initiator to the catalyst is 20:1.
preferably, the molar ratio of the initiator to tetrahydrofuran is 0.1:1.
Preferably, the initiator is used in an amount of 0.01mol and the catalyst is used in an amount of 0.0005mol.
Preferably, the polymerization reaction temperature is 20-25 ℃ and the time is 9-12h.
In the invention, the reaction equation of the preparation method of the polyether lubricating oil base oil is as follows:
a polyether lubricating oil base oil is prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, tetrahydrofuran and alkylene oxide are used as raw materials, trifluoromethanesulfonic acid is used as a catalyst, and the polyether lubricating oil base oil with excellent performance is synthesized at room temperature by a one-step method, so that a high-temperature high-pressure reaction kettle is avoided, the reaction conditions for synthesizing the polyether lubricating oil base oil are widened, and the cost is reduced;
(2) According to the invention, the comprehensive performance of the polyether lubricating oil base oil product is further improved by regulating and controlling the raw materials and the proportion, so that the lubricating oil base oil with excellent performance is synthesized, the lubricating oil base oil with the viscosity index of more than 130 and the pour point of less than-35 ℃ can be obtained, the reaction condition of polyether synthetic polyether lubricating oil base oil is widened, and the cost is reduced;
(3) The polyether lubricating oil base oil is composed of two monomers of alkylene oxide and tetrahydrofuran, the trifluoromethanesulfonic acid is used as a catalyst, the trifluoromethanesulfonic acid has high thermodynamic stability and strong proton donating property, is insensitive to common redox reaction, is used for catalyzing ring-opening reaction which is difficult to occur under common conditions, so that the reaction can be carried out at room temperature, severe conditions of a traditional polyether using a high-temperature high-pressure reaction kettle are avoided, alkylene oxide such as propylene oxide can have strong molecular tension due to ternary ring and methyl, strong oil solubility and high viscosity temperature characteristics can be provided for polyether products, a special five-membered ring structure of tetrahydrofuran has a long liquid range, corresponding water solubility can be provided for the polyether base oil, moderate movement viscosity of the polyether base oil at 40 ℃ is ensured, and further the viscosity temperature performance of the polyether lubricating oil base oil is improved.
Drawings
FIG. 1 is an infrared chart of the propylene oxide-tetrahydrofuran polyether base oil prepared in example 1 of the present invention.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The following examples are given by way of illustration of detailed embodiments and specific procedures based on the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
Each of the raw materials used in the following examples was a commercially available product.
The method for measuring the kinematic viscosity in the invention is carried out according to GB/T265-1988 petroleum product kinematic viscosity measurement method, and the method for measuring the pour point is carried out according to GB510-1983 petroleum product condensation point measurement.
Example 1
A preparation method of polyether lubricating oil base oil at room temperature comprises the following specific steps:
0.90g (0.01 mol) of 1, 4-butanediol and 0.268g (0.0005 mol) of yttrium trifluoromethane sulfonate are sequentially added into a three-neck flask provided with an electric stirrer, a temperature controller, a constant pressure dropping funnel, a reflux condenser and a nitrogen inlet pipe, the reaction temperature is 20-25 ℃, all reactants are dissolved, the three-neck flask is simultaneously introduced with nitrogen for 2-3 min, then the three-neck flask is vacuumized for about 1-2 min, and the three-neck flask is repeated for 3 times to remove air in a reaction system. 7.2g (0.1 mol) of tetrahydrofuran was injected into the constant pressure dropping funnel using a 50ml disposable syringe, and the whole of tetrahydrofuran was injected into the three-necked flask within 1 minute. After pre-reaction for 15 minutes, 5.2g (0.1 mol) of propylene oxide was injected into the constant pressure dropping funnel using a 50ml disposable syringe, and propylene oxide was slowly added dropwise at a rate of 1 drop per minute. The polymerization took place under stirring and refluxing for 10 hours. After the reaction is finished, washing the obtained reactant for 3-4 times by distilled water until the liquid is neutral, distilling the reaction liquid under reduced pressure, and vacuum drying for 5 hours at 60 ℃ to obtain the epoxypropane-tetrahydrofuran polyether base oil. The final product was obtained and measured. The measurement results are as follows: the yield was 82%, the viscosity index was 151 and the pour point was-40 ℃.
The infrared appearance of the product propylene oxide-tetrahydrofuran polyether base oil is shown in figure 1.
Example 2
The difference from example 1 is that 5.2g (0.1 mol) of propylene oxide are added and 9.2g (0.1 mol) of epichlorohydrin are added instead. The measurement results are as follows: the yield was 77%, the viscosity index was 111 and the pour point was-37 ℃.
Example 3
The difference from example 1 is that 5.2g (0.1 mol) of propylene oxide was added and instead 10.0g (0.1 mol) of hexane oxide was added. The measurement results are as follows: the yield was 79%, the viscosity index was 124 and the pour point was-38 ℃.
Example 4
The difference from example 1 is that 5.2g (0.1 mol) of propylene oxide are added and 7.2g (0.1 mol) of methyl propylene oxide are added instead. The measurement results are as follows: the yield was 83%, the viscosity index was 148 and the pour point was-39 ℃.
Example 5
The difference from example 1 is that 0.90g (0.01 mol) of 1, 4-butanediol is added, instead of 0.32g (0.01 mol) of methanol. The measurement results are as follows: the yield was 72%, the viscosity index 140 and the pour point-33 ℃.
Example 6
The difference from example 1 is that 0.90g (0.01 mol) of 1, 4-butanediol is added, instead of 1.30g (0.01 mol) of isooctanol. The measurement results are as follows: the yield was 75%, the viscosity index 137 and the pour point-35 ℃.
Example 7
The difference from example 1 is that 0.90g (0.01 mol) of 1, 4-butanediol are added, instead 1.06g (0.01 mol) of diethylene glycol are added. The measurement results are as follows: the yield was 80%, the viscosity index 149 and the pour point-35 ℃.
Example 8
The difference from example 1 is that 0.268g (0.0005 mol) of yttrium trifluoromethane sulfonate is added instead of 0.293g (0.0005 mol) of cerium trifluoromethane sulfonate. The measurement results are as follows: the yield was 68%, the viscosity index was 150 and the pour point was-38 ℃.
Example 9
The difference from example 1 is that 0.268g (0.0005 mol) of yttrium trifluoromethane sulfonate is added instead of 0.387g (0.0005 mol) of hafnium trifluoromethane sulfonate. The measurement results are as follows: the yield was 77%, the viscosity index 149 and the pour point-39 ℃.
Example 10
The difference from example 1 is that 0.268g (0.0005 mol) of yttrium trifluoromethane sulfonate is added instead of 0.281g (0.0005 mol) of indium trifluoromethane sulfonate. The measurement results are as follows: the yield was 75%, the viscosity index was 150 and the pour point was-40 ℃.
Comparative example 1
The difference from example 1 is that 5.2g (0.1 mol) of propylene oxide are added and instead 10.4g (0.2 mol) of epichlorohydrin are added. The measurement results are as follows: the yield was 80%, the viscosity index was 78 and the pour point was-39 ℃.
Comparative example 2
The difference from example 1 is that 7.2g (0.1 mol) of tetrahydrofuran are added instead of 14.4g (0.2 mol) of tetrahydrofuran. The measurement results are as follows: the yield was 77%, the viscosity index was 148 and the pour point was-41 ℃.
Comparative example 3
The difference from example 2 is that 9.2g (0.1 mol) of epichlorohydrin are added and 18.4g (0.2 mol) of epichlorohydrin are added instead. The measurement results are as follows: the yield was 72%, the viscosity index was 95 and the pour point was-34 ℃.
Comparative example 4
The difference from example 2 is that 7.2g (0.1 mol) of tetrahydrofuran are added instead of 14.4g (0.2 mol) of tetrahydrofuran. The measurement results are as follows: the yield was 75%, the viscosity index 102 and the pour point-35 ℃.
Comparative example 5
The difference from example 3 is that 10.0g (0.1 mol) of hexane oxide was added instead of 20.0g (0.2 mol) of hexane oxide. The measurement results are as follows: the yield was 76%, the viscosity index was 112 and the pour point was-36 ℃.
Comparative example 6
The difference from example 3 is that 7.2g (0.1 mol) of tetrahydrofuran are added instead of 14.4g (0.2 mol) of tetrahydrofuran. The measurement results are as follows: the yield was 79%, the viscosity index was 127 and the pour point was-37 ℃.
Comparative example 7
The difference from example 4 is that 7.2g (0.1 mol) of methyl propylene oxide was added, instead of 14.4g (0.2 mol) of methyl propylene oxide. The measurement results are as follows: the yield was 80%, the viscosity index was 131 and the pour point was-38 ℃.
Comparative example 8
The difference from example 4 is that 7.2g (0.1 mol) of tetrahydrofuran are added instead of 14.4g (0.2 mol) of tetrahydrofuran. The measurement results are as follows: the yield was 81%, the viscosity index was 150 and the pour point was-39 ℃.
As can be seen from the comparison of the above examples and comparative examples, the polyether can be synthesized by catalyzing with trifluoromethane sulfonic acid catalyst at room temperature, and the reaction conditions are mild and feasible; when propylene oxide and tetrahydrofuran are used as raw materials, the raw material ratio is 1:1, yttrium triflate is used as a catalyst, 1, 4-butanediol is used as an initiator to react for 10 hours at 20-25 ℃, the obtained product has a yield of 82%, the viscosity index can reach 151, the pour point is lower than-40 ℃, and the product has good viscosity temperature performance and low-temperature flow performance, and is excellent polyether lubricating oil base oil.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A preparation method of polyether lubricating oil base oil is characterized in that alkylene oxide and tetrahydrofuran are subjected to polymerization reaction under the condition of room temperature by taking alcohols as an initiator and trifluoromethanesulfonic acid as a catalyst to prepare the polyether lubricating oil base oil.
2. The method for preparing polyether lubricating oil base oil according to claim 1, comprising the following steps:
(1) Stirring and fully dissolving an initiator and a catalyst at room temperature, repeatedly vacuumizing and filling nitrogen for a plurality of times, and adding tetrahydrofuran into a reaction system;
(2) Slowly and dropwise adding alkylene oxide into the dissolved initiator, catalyst and tetrahydrofuran, stirring at room temperature, and performing polymerization reaction to obtain alkylene oxide-tetrahydrofuran polyether, namely the polyether lubricating oil base oil.
3. The method for producing polyether lubricating oil base oil according to claim 2, wherein in the step (1), tetrahydrofuran is added to the reaction system through a constant pressure hopper, and in the step (2), alkylene oxide is slowly added dropwise through a constant pressure hopper.
4. The method for preparing polyether lubricating base oil according to claim 1, wherein in the step (1), the initiator is selected from methanol, 1, 4-butanediol, isooctanol and diethylene glycol.
5. The method for preparing polyether lubricating oil base oil according to claim 1, wherein in the step (1), the catalyst is selected from yttrium trifluoromethane sulfonate, cerium trifluoromethane sulfonate, indium trifluoromethane sulfonate or hafnium trifluoromethane sulfonate.
6. The method for producing polyether lubricating oil base oil according to claim 1, wherein in the step (2), the alkylene oxide is selected from propylene oxide, epichlorohydrin, hexane oxide or methyl propylene oxide.
7. The method of preparing a polyether lubricant base oil according to claim 1, wherein in step (2), the molar ratio of alkylene oxide to tetrahydrofuran is 2:1 to 1:2.
8. the method for preparing polyether lubricating oil base oil according to claim 1, wherein in the step (2), the molar ratio of the initiator to the catalyst is (15 to 25): 1.
9. the method for preparing polyether lubricating oil base oil according to claim 1, wherein in the step (2), the polymerization reaction temperature is 20-25 ℃ and the time is 9-12h.
10. A polyether lubricating oil base oil prepared by the preparation method according to any one of claims 1 to 9.
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