Process for the preparation of oil-soluble polyether polyol intermediates for lubricating oil base stocks and use thereof

Abstract

The application belongs to the technical field of chemical synthesis, and particularly relates to a preparation method and application of a lubricating oil base oil oil-soluble polyether polyol intermediate. The preparation method comprises the following steps: using a mixture of a high-carbon alcohol and a small-molecule compound containing active hydrogen as a starting agent, using an alkali metal as a catalyst, and synthesizing a lubricating oil base oil oil-soluble polyether polyol intermediate crude polymer with propylene oxide under a pressure of 0-0.5 MPa and a temperature of 90-50 DEG C. The lubricating oil base oil oil-soluble polyether polyol intermediate product is obtained by refining the polyether polyol intermediate crude polymer. When the product is used for preparing an oil-soluble lubricating oil base oil, the mutual solubility with mineral oil can be improved, the viscosity index and flash point of the lubricating oil base oil can be improved, the pour point of the lubricating oil base oil can be reduced, and the low-temperature fluidity of the lubricating oil base oil can be improved. The traditional production process is improved, the formula system no longer has butylene oxide, the whole polymerization system is more green and environmentally friendly, and the production cost is reduced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of chemical synthesis, and particularly relates to a preparation method and application of a lubricating oil base oil oil-soluble polyether polyol intermediate. BACKGROUND

[0002] Lubricating oil is a liquid lubricant widely used in mechanical equipment. Lubricating oil can not only reduce the friction of the metal surface and reduce wear, but also continuously take away heat from the friction surface to reduce the friction temperature, thereby playing a role of cooling and protecting the mechanical equipment and prolonging the service life. Therefore, the selection and performance of lubricating oil have an important influence on the mechanical processing industry.

[0003] Polyether polyols have high viscosity index and flash point, and can significantly improve the performance of lubricating oil base oil as an additive, thereby greatly improving the applicability of the base oil. Therefore, polyether polyols are widely used as additives in the field of lubricating oil. However, the insolubility of polyether polyols with mineral oil has become a bottleneck that seriously restricts the application of polyether polyols in the field of lubricating oil.

[0004] Most of the oil-soluble polyether polyols for lubricating oil base oil on the market are copolymerized from propylene oxide and butylene oxide, or homopolymerized from single butylene oxide. Butylene oxide raw material is expensive and highly toxic, which seriously restricts the popularization and application of butane oil-soluble polyether polyol in the field of oil-soluble lubricating oil base oil. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a preparation method of a lubricating oil base oil oil-soluble polyether polyol intermediate. When the lubricating oil base oil oil-soluble polyether polyol intermediate is used for the preparation of oil-soluble lubricating oil base oil, on the one hand, the mutual solubility with mineral oil can be effectively improved, the viscosity index and flash point of the lubricating oil base oil can be improved, the pour point can be reduced, and the low-temperature fluidity of the product can be improved; on the other hand, the production process of the traditional oil-soluble lubricating oil base oil is effectively improved, the formula system no longer has butylene oxide, the whole polymerization system is more green and environmentally friendly, and the production cost is also significantly reduced.

[0006] The preparation method of the lubricating oil base oil oil-soluble polyether polyol intermediate provided by the present application comprises the following steps:

[0007] (1) a mixed starter is synthesized with propylene oxide under the action of an alkali metal catalyst to obtain a lubricating oil base oil oil-soluble polyether polyol intermediate crude polymer;

[0008] (2) the lubricating oil base oil oil-soluble polyether polyol intermediate crude polymer prepared in step (1) is subjected to a refining treatment to obtain a lubricating oil base oil oil-soluble polyether polyol intermediate product;

[0009] The mixed initiator is a mixture of a high carbon alcohol and a small molecule compound containing an active hydrogen group.

[0010] The synthesis pressure in step (1) is 0-0.5 MPa, and the temperature is 90-150℃.

[0011] The high carbon alcohol is one or more of C12 alcohol, C14 alcohol, C12-14 alcohol, C16 alcohol, C18 alcohol, C16-18 alcohol, C20 alcohol, C22 alcohol, C20-22 alcohol, and isomeric tridecanol.

[0012] The small molecule compound containing an active hydrogen group is one or more of n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol.

[0013] The high carbon alcohol in the mixed initiator accounts for 85-99% of the total mass of the mixed initiator.

[0014] The amount of the mixed initiator in step (1) accounts for 3.54-6.56% of the mass of the crude polymer of the lubricating oil base oil oil-soluble polyether polyol intermediate.

[0015] The alkali metal catalyst in step (1) is one or more of sodium methoxide, sodium ethoxide, potassium hydroxide, and sodium hydroxide, and preferably, the alkali metal is potassium hydroxide.

[0016] The amount of the alkali metal catalyst accounts for 0.1-1% of the mass of the crude polymer of the lubricating oil base oil oil-soluble polyether polyol intermediate.

[0017] The viscosity of the crude polymer of the lubricating oil base oil oil-soluble polyether polyol intermediate in step (1) at 40℃ is 250-400 mPa·s.

[0018] The refining process in step (2) is that the crude polymer of the lubricating oil base oil oil-soluble polyether polyol intermediate is subjected to neutralization, adsorption, crystallization, filtration, and volatile organic compound treatment device separation treatment.

[0019] The volatile organic compound treatment device is a conventional volatile organic compound treatment device in the art.

[0020] The lubricating oil base oil oil-soluble polyether polyol intermediate in the application is mainly applied to the preparation of oil-soluble lubricating oil base oil.

[0021] Compared with the prior art, the application has the following beneficial effects:

[0022] 1. When the polyether polyol intermediate prepared by the application is used for the preparation of oil-soluble lubricating oil base oil, the mutual solubility with mineral oil can be effectively improved, the viscosity index and flash point of the lubricating oil base oil can be improved, the product pour point can be reduced, and the low-temperature fluidity of the product can be improved.

[0023] 2. The polyether polyol intermediate prepared by the application is used for preparing oil-soluble lubricating oil base oil, effectively improving the production process of traditional oil-soluble lubricating oil base oil, and the formula system no longer has butylene oxide, so that the whole polymerization system is more green and environmental protection, and the production cost is also significantly reduced.

[0024] 3. The preparation method is scientific and reasonable, and simple and easy to implement. DETAILED DESCRIPTION

[0025] The application will be further described below in combination with examples, but the protection scope of the application is not limited to this.

[0026] All raw materials used in the examples are commercially available, except for special instructions.

[0027] Example 1

[0028] 5 liters of stainless steel reaction kettle are added with 260g of C18 alcohol, 2.62g of n-butanol and 4g of potassium hydroxide, nitrogen is replaced, and the oxygen content in the reaction kettle is measured to be lower than 100ppm. The reaction kettle is heated to 90℃, and potassium hydroxide is dissolved. The temperature in the reaction kettle is kept at 125℃, the pressure is kept at 0.2±0.02MPa, 3733.38g of propylene oxide is continuously added for polymerization, then the reaction kettle is kept at 125℃ for internal pressure reaction until the pressure in the kettle no longer decreases, and the crude polymer of the oil-soluble polyether polyol intermediate of the lubricating oil base oil is obtained. The above crude polymer of the polyether polyol is separated and treated by neutralization, adsorption, crystallization, filtration and volatile organic matter treatment device, and the oil-soluble polyether polyol intermediate of the lubricating oil base oil of the application is obtained.

[0029] Example 2

[0030] 5 liters of stainless steel reaction kettle are added with 160g of C12-14 alcohol, 7.55g of glycerol, 30g of potassium hydroxide and 10g of sodium hydroxide, nitrogen is replaced, and the oxygen content in the reaction kettle is measured to be lower than 100ppm. The reaction kettle is heated to 90℃, and potassium hydroxide and sodium hydroxide are dissolved. The temperature in the reaction kettle is kept at 90℃, the pressure is kept at 0.3±0.02MPa, 3792.48g of propylene oxide is continuously added for polymerization, then the reaction kettle is kept at 90℃ for internal pressure reaction until the pressure in the kettle no longer decreases, and the crude polymer of the oil-soluble polyether polyol intermediate of the lubricating oil base oil is obtained. The above crude polymer of the polyether polyol is separated and treated by neutralization, adsorption, crystallization, filtration and volatile organic matter treatment device, and the oil-soluble polyether polyol intermediate of the lubricating oil base oil of the application is obtained.

[0031] Example 3

[0032] 5 L stainless steel reactor was charged with 80 g of C18 alcohol, 81 g of C16-18 alcohol, 24 g of propylene glycol, 4.42 g of diethylene glycol and 14.24 g of sodium hydroxide, and replaced with nitrogen, and the oxygen content in the reactor was measured to be less than 100 ppm. The reactor was heated to 90°C, and sodium hydroxide was dissolved. The temperature in the reactor was maintained at 140°C, and the pressure was maintained at 0.15±0.02 MPa, and 4080 g of propylene oxide was continuously added for polymerization, and then the reactor was maintained at 140°C for internal pressure reaction until the pressure in the reactor no longer decreased, to obtain a crude polymer of the lubricating oil base oil oil-soluble polyether polyol intermediate. The crude polymer of the polyether polyol was separated and treated by neutralization, adsorption, crystallization, filtration and volatile organic matter treatment device, to obtain the lubricating oil base oil oil-soluble polyether polyol intermediate of the present application.

[0033] Example 4

[0034] 5 L stainless steel reactor was charged with 80 g of C18 alcohol, 81 g of C16-18 alcohol, 24 g of propylene glycol, 4.42 g of diethylene glycol and 14.24 g of sodium hydroxide, and replaced with nitrogen, and the oxygen content in the reactor was measured to be less than 100 ppm. The reactor was heated to 90°C, and sodium hydroxide was dissolved. The temperature in the reactor was maintained at 140°C, and the pressure was maintained at 0.15±0.02 MPa, and 4080 g of propylene oxide was continuously added for polymerization, and then the reactor was maintained at 140°C for internal pressure reaction until the pressure in the reactor no longer decreased, to obtain a crude polymer of the lubricating oil base oil oil-soluble polyether polyol intermediate. The crude polymer of the polyether polyol was separated and treated by neutralization, adsorption, crystallization, filtration and volatile organic matter treatment device, to obtain the lubricating oil base oil oil-soluble polyether polyol intermediate of the present application.

[0035] Example 5

[0036] 5 L stainless steel reactor was charged with 80 g of C18 alcohol, 81 g of C16-18 alcohol, 24 g of propylene glycol, 4.42 g of diethylene glycol and 14.24 g of sodium hydroxide, and replaced with nitrogen, and the oxygen content in the reactor was measured to be less than 100 ppm. The reactor was heated to 90°C, and sodium hydroxide was dissolved. The temperature in the reactor was maintained at 140°C, and the pressure was maintained at 0.15±0.02 MPa, and 4080 g of propylene oxide was continuously added for polymerization, and then the reactor was maintained at 140°C for internal pressure reaction until the pressure in the reactor no longer decreased, to obtain a crude polymer of the lubricating oil base oil oil-soluble polyether polyol intermediate. The crude polymer of the polyether polyol was separated and treated by neutralization, adsorption, crystallization, filtration and volatile organic matter treatment device, to obtain the lubricating oil base oil oil-soluble polyether polyol intermediate of the present application.

[0037] Example 6

[0038] 5L stainless steel reactor was added with 210g C20 alcohol, 20g n-butanol and 12g sodium hydroxide respectively, and replaced by nitrogen, and the oxygen content in the reactor was measured to be less than 100ppm. The reactor was heated to 90℃, and the sodium hydroxide was dissolved. The temperature in the reactor was kept at 120℃, and the pressure was kept at 0.35±0.02MPa, and 3758g propylene oxide was continuously added for polymerization, and then the reactor was kept at 120℃ for internal pressure reaction until the pressure in the reactor no longer decreased, and a crude polymer of the lubricating oil base oil oil-soluble polyether polyol intermediate was obtained. The crude polymer of the polyether polyol was separated and treated by neutralization, adsorption, crystallization, filtration and volatile organic compound treatment device, and the lubricating oil base oil oil-soluble polyether polyol intermediate of the application was obtained.

[0039] Comparative Example 1

[0040] 5L stainless steel reactor was added with 269.3g C18 alcohol and 4g potassium hydroxide respectively, and replaced by nitrogen, and the oxygen content in the reactor was measured to be less than 100ppm. The reactor was heated to 90℃, and the potassium hydroxide was dissolved. The temperature in the reactor was kept at 125℃, and the pressure was kept at 0.2±0.2MPa, and 3726.70g propylene oxide was continuously added for polymerization, and then the reactor was kept at 125℃ for internal pressure reaction until the pressure in the reactor no longer decreased, and a crude polymer of the polyether polyol intermediate was obtained, and then the crude polymer was refined to obtain the polyether polyol intermediate.

[0041] Comparative Example 2

[0042] 5L stainless steel reactor was added with 74.4g n-butanol and 4g potassium hydroxide respectively, and replaced by nitrogen, and the oxygen content in the reactor was measured to be less than 100ppm. The reactor was heated to 90℃, and the potassium hydroxide was dissolved. The temperature in the reactor was kept at 125℃, and the pressure was kept at 0.2±0.2MPa, and 3238g propylene oxide was continuously added for polymerization, and then the reactor was kept at 125℃ for internal pressure reaction until the pressure in the reactor no longer decreased, and a crude polymer of the polyether polyol intermediate was obtained, and then the crude polymer was refined to obtain the polyether polyol intermediate.

[0043] The lubricating oil base oil oil-soluble polyether polyol intermediates prepared by Examples 1-6 and the polyether intermediates prepared by Comparative Examples 1-2 were compared in performance, and the test results are shown in Table 1.

[0044] Table 1 Performance test results of polyether intermediates

[0045]

[0046]

[0047] (Viscosity test standard: GB / T 265; Viscosity index test standard: GB / T 1995; Open flash point test standard: GB / T 3536; Pour point test standard: GB / T 3535)

[0048] As can be seen from Table 1, the oil-soluble polyether polyol intermediates prepared by using the mixture of the starting agents in Examples 1-6 can all be miscible with mineral oil, and the viscosity index, open flash point and pour point test results thereof are all better than those of Comparative Examples 1-2; although Comparative Example 1 can be miscible with mineral oil, the viscosity index, open flash point and pour point test results thereof are not as good as those of Examples 1-6; the polyether intermediate prepared in Comparative Example 2 cannot be miscible with mineral oil, and the viscosity index, open flash point and pour point test results thereof are obviously not as good as those of Examples 1-6.

[0049] In summary, the oil-soluble polyether polyol intermediate prepared by using the mixture of the high-carbon alcohol and the small-molecule compound containing active hydrogen groups as the starting agent can not only be miscible with mineral oil, but also has good viscosity-temperature performance, high open flash point and low pour point, and has good application prospect when used as an oil-soluble lubricating oil base oil.

Claims

1. A process for the preparation of a lubricating oil base oil oil-soluble polyether polyol intermediate, characterized in that, It comprises the following steps: (1) Synthesizing the lubricating oil base oil oil-soluble polyether polyol intermediate crude polymer by mixing initiator and propylene oxide under the action of alkali metal catalyst; (2) The polyether polyol intermediate crude polymer prepared in step (1) is refined to obtain the lubricating oil base oil oil-soluble polyether polyol intermediate product; The mixing initiator is a mixture of high carbon alcohol and small molecule compound containing active hydrogen group; The high carbon alcohol is one or more of C12 alcohol, C14 alcohol, C12-14 alcohol, C16 alcohol, C18 alcohol, C16-18 alcohol, C20 alcohol, C22 alcohol, C20-22 alcohol and isomeric tridecanol; The small molecule compound containing active hydrogen group is one or more of n-butanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and glycerol; The high carbon alcohol in the mixing initiator accounts for 85-99% of the total mass of the mixing initiator; The amount of the mixing initiator in step (1) accounts for 3.54-6.56% of the mass of the lubricating oil base oil oil-soluble polyether polyol intermediate crude polymer; The alkali metal catalyst in step (1) is one or more of sodium methoxide, sodium ethoxide, potassium hydroxide and sodium hydroxide.

2. The process for the preparation of a lubricating oil base oil oil-soluble polyether polyol intermediate according to claim 1, characterized in that, The synthesis pressure in step (1) is 0-0.5 MPa, and the temperature is 90-150℃.

3. The process for the preparation of a lubricating oil base oil oil-soluble polyether polyol intermediate according to claim 1, characterized in that, The amount of the alkali metal catalyst accounts for 0.1-1% of the mass of the lubricating oil base oil oil-soluble polyether polyol intermediate crude polymer.

4. The process for the preparation of a lubricating oil base oil oil-soluble polyether polyol intermediate according to claim 1, characterized in that, The refining process in step (2) is sequentially through neutralization, adsorption, crystallization, filtration and volatile organic matter treatment device separation treatment.

5. Use of the oil-soluble polyether polyol intermediate produced by the process according to any one of claims 1 to 4, characterized in that For the preparation of oil-soluble lubricating oil base oil.

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