Cerium-containing organics, methods of making and uses thereof

Abstract

The application relates to the field of lubricating grease, discloses a cerium-containing organic matter and a preparation method and application thereof, a structural formula of the organic matter is shown in the following, the organic matter is used as a thickening agent of lubricating grease, the obtained lubricating grease has a higher dropping point, P B value and P D value, and simultaneously has a lower cone penetration, steel mesh oil separation, water shower loss amount and abrasion mark diameter. ‑ R ‑ [Ce] 3+ -R'.

Description

Technical Field

[0001] This invention relates to the field of lubricating greases, and more specifically to a cerium-containing organic compound, its preparation method, and its uses. Background Technology

[0002] Cerium, a rare earth metal, belongs to Group IIIB and is located in Period 6. Cerium-containing compounds have excellent lubricating and anti-corrosion properties and are often used as lubricant additives and coatings for materials. For example, CN105505546A adds nano-CeO2 or nano-La2O3 as additives to lubricating grease, giving it good tribological properties and thermal stability. US20150059236A1 and WO2008030810A2 disclose a lubricant containing cerium dioxide nanoparticles with an average hydrodynamic diameter of about 1 nm to about 15 nm, which can be used as a lubricant in internal combustion engines. It can effectively protect the engine, reduce engine friction, improve lubrication, and improve fuel efficiency. Although nanoparticles solve the problem of their dispersion in lubricating grease, they are prone to agglomeration and precipitation, thus affecting the performance of the lubricant. CN110373249B reacts cerium oxide with boric acid and phosphoric acid to generate a boron-phosphorus-rare earth friction modifier, which improves the problem of nanoparticle agglomeration.

[0003] In summary, the thickening ability, extreme pressure anti-wear performance, colloidal stability, and water resistance of existing greases containing cerium compounds still need improvement. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems existing in the prior art and to provide a cerium-containing organic compound, its preparation method, and its uses.

[0005] To achieve the above objectives, a first aspect of the present invention provides a cerium-containing organic compound, characterized in that the organic compound has the structure shown in Formula I:

[0006]

[0007] In formula I, R - R1-A-R2-COO - And A is -CO-NH-, R1 is H, alkyl, alkenyl, alkynyl, aryl, halogen-substituted alkyl or halogen-substituted aryl, and R2 is alkylene, alkenylene, alkynylene, arylene, halogen-substituted alkylene or halogen-substituted aryl.

[0008] R' - It is a monovalent aromatic acid radical ion.

[0009] A second aspect of the present invention provides a method for preparing cerium-containing organic compounds, the method comprising: [R' - ]x M1 x+ The first substrate shown, [R1-A-R2-COO] - ] y M2 y+ The second substrate shown reacts with an inorganic base and a water-soluble cerium salt to yield a solid product.

[0010] A third aspect of the present invention provides a pre-made soap containing the organic matter obtained by the method described above.

[0011] A fourth aspect of the present invention provides a method for preparing a lubricating grease, the method comprising: obtaining a solid product according to the method described above; mixing the obtained solid product with a base oil and heating the mixture.

[0012] Using the cerium-containing organic compound of the present invention as a thickener for the grease, the resulting grease has a high dropping point and P... B Value and P D This grease offers a high value while also featuring low cone penetration, low steel mesh oil separation, low water leaching loss, and low wear track diameter. It can be used for bearing lubrication in high-temperature, high-speed, heavy-load operation, oilfield drilling, and other applications. Attached Figure Description

[0013] Figure 1 The image shows the infrared spectrum of the grease obtained in Example 1. Detailed Implementation

[0014] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0015] This invention provides a cerium-containing organic compound, characterized in that the organic compound has the structure shown in Formula I:

[0016]

[0017] In formula I, R - R1-A-R2-COO - And A is -CO-NH-, R1 is H, alkyl, alkenyl, alkynyl, aryl, halogen-substituted alkyl or halogen-substituted aryl, and R2 is alkylene, alkenylene, alkynylene, arylene, halogen-substituted alkylene or halogen-substituted aryl.

[0018] R' - It is a monovalent aromatic acid radical ion.

[0019] In Formula I, the halogen mentioned can be F, Cl, Br or I, preferably F.

[0020] In Formula I, A is -CO-NH-, and preferably, R in Formula I is... - R1-NH-CO-R2-COO - Or R1-CO-NH-R2-COO - .

[0021] In Formula I, R1 can have 4-22 carbon atoms. Preferably, R1 is a straight-chain alkyl group of 4-22 (such as C5, C6, C7, C8, C9, C10, C12, C14, C16, C17, C18, C19 or C20).

[0022] In Formula I, R2 can have 4-30 carbon atoms. Preferably, R2 is an arylene group of C4-C30 (such as C5, C6, C7, C8, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 or C29), more preferably a phenylene group or a phenylene group substituted with an alkyl group of C1-C6 (preferably a straight-chain alkyl group of C1-C4) (wherein, the substitution position can be at least one, preferably 1, 2, 3 or 4).

[0023] In formula I, R' - The number of carbon atoms can be C7-C30, preferably, R' - It is a monovalent aromatic acid ion of C7-C30 (such as C7, C8, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 or C29), more preferably a benzoate ion or a benzoate ion substituted with an alkyl group of C1-C6 (preferably a straight-chain alkyl group of C1-C4) (wherein, the substitution position can be at least one, preferably 1, 2, 3, 4 or 5).

[0024] According to a particularly preferred embodiment of the present invention, R in Formula I - R1-NH-CO-R2-COO - R1 is a C14-C20 straight-chain alkyl group, R2 is a p-phenylene or alkyl-substituted phenylene, and R' - It is either benzoate ion or 4-methylbenzoate ion.

[0025] The present invention also provides a method for preparing cerium-containing organic compounds (or a method for preparing thickeners (for lubricating greases)), characterized in that the method comprises: [R' - ] x M1 x+ The first substrate shown, [R1-A-R2-COO]- ] y M2 y+ The second substrate shown reacts with an inorganic base and a water-soluble cerium salt to give a solid product, wherein A, R1, R2, and R' are... - As defined above, M1 and M2 are each independently a Group IA or Group IIA metal, preferably H, Na, or K. x and y represent valence states and are equal to 1 or 2.

[0026] In this invention, the first substrate is preferably a water-soluble organic compound, that is, a first substrate with a solubility in water of greater than or equal to 0.01g (preferably greater than or equal to 1g or 10g) at the contact temperature of this invention, preferably at least one of sodium benzoate, sodium 4-methylbenzoate and benzoic acid.

[0027] In this invention, the second substrate is preferably the sodium salt of N-octadecyl terephthalic acid monoamide (which can be prepared by referring to the method in US2820012A), and its structure is shown below:

[0028]

[0029] In this invention, the inorganic base may be selected from hydroxides of alkali metals and / or hydroxides of alkaline earth metals, preferably sodium hydroxide and / or potassium hydroxide.

[0030] In this invention, the water-soluble cerium salt is a cerium salt whose solubility in water at the contact temperature of this invention is greater than or equal to 0.01g (preferably greater than or equal to 1g or 10g), and the water-soluble cerium salt is preferably cerium chloride and / or cerium nitrate.

[0031] In this invention, the molar ratio of the first substrate to the second substrate can be 1:0.2-5 (e.g., 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.95, 1, 1.05, 1.1, 1.2, 1.3, 1.4, or any value between the above), preferably 1:0.5-1. More preferably, the amount of inorganic base used results in a pH of 7-12 for the contact system.

[0032] In this invention, the number of moles of anions provided by the first substrate, the second substrate, and the inorganic base is theoretically equal to the number of Ce provided by the water-soluble cerium salt. 3+ The molar number is three times that of the first substrate, the second substrate, and the water-soluble cerium salt, but preferably, the amounts of the first substrate, the second substrate, and the water-soluble cerium salt are such that the total molar number of anions provided by the first substrate and the second substrate is equal to the molar number of Ce provided by the water-soluble cerium salt. 3+ The ratio between the molar numbers is 200:100-110, in other words, the molar excess of water-soluble cerium salt is 1-5 moles.

[0033] In this invention, there are no particular requirements for the contact conditions, but preferably, the contact conditions include: a temperature of 10-90℃ (e.g., 15, 20, 25, 30, 40, 50, 60, 70, 80, 85℃ or any value between these values). Preferably, the contact conditions also include: a time of 0.2-8 hours. To promote the metathesis reaction, the contact is carried out in a high-shear mixing emulsifier, or it can be carried out under ultrasonic conditions. The rotation speed of the high-shear mixing emulsifier can be controlled at 1000-12000 r / min. More preferably, the contact method is as follows: (1) mixing the first substrate, the water-soluble cerium salt, and the solvent, and stirring for 0.2-4 h (e.g., 0.4, 0.5, 0.6, 0.8, 1, 1.5, 2, 3, 3.5 h or any value between the above values); (2) mixing the product of step (1) with the second substrate, and stirring for 0.2-4 h (e.g., 0.4, 0.5, 1, 1.5, 1.8, 2, 2.2, 3, 3.5 h or any value between the above values); (3) adjusting the pH of the product of step (2) to 7-12 using an inorganic base. To make the reaction more complete, the first substrate, the second substrate, and the water-soluble cerium salt are all used in the form of solutions (or dispersions), and the solvent can be common solvents such as water or alcohol.

[0034] In this invention, the precipitate (solid product) obtained after the reaction can be used directly as a thickener for lubricating grease, or the precipitate can be washed and dried before being used as a thickener for lubricating grease.

[0035] The present invention also provides a pre-made soap containing the organic matter obtained by the method described above (or a thickener obtained by the method described above).

[0036] In addition, the present invention provides a grease comprising: a base oil, a thickener, and optional additives, characterized in that the thickener is an organic compound or pre-made soap as described above.

[0037] In this invention, based on the total weight of the grease, the content of thickener in the grease is 3-50% by weight, preferably 5-35% by weight, and more preferably 7-25% by weight.

[0038] In this invention, based on the total weight of the grease, the content of base oil in the grease can be 50-97% by weight, preferably 65-95% by weight, and more preferably 75-93% by weight. The kinematic viscosity of the base oil at 100°C is 2-150 mmHg. 2 / s, preferably 5-100mm 2 / s, preferably 8-50mm 2 / s. The test method for "kinematic viscosity" is GB / T 30515-2014. The base oil can be at least one of mineral oil, ester oil, synthetic hydrocarbons (such as polyalphaolefin synthetic oils), or vegetable oil.

[0039] In this invention, the lubricating grease may or may not contain additives. The additives may be at least one of antioxidants, anti-wear agents, rust inhibitors, extreme pressure agents, etc., or other common additives. Based on the total weight of the lubricating grease, the content of the additives may be 0.2-15% by weight.

[0040] The grease of the present invention can be prepared in a conventional manner. Preferably, the method includes: obtaining a solid product as described above; mixing the obtained solid product with a base oil and heating it. More specifically, the preparation method of the grease of the present invention may include: mixing the solid product and the base oil and heating them, and then mixing them with optional additives. Specifically, it may include: first mixing the base oil and the solid product at room temperature, heating to 90-120°C, holding for 5-30 minutes, continuing to heat to 160-210°C, stopping heating and cooling, and introducing optional additives at 80-120°C, grinding and homogenizing to obtain the grease.

[0041] The present invention will be described in detail below through examples. The drying temperature is 120°C and the time is 60 minutes.

[0042] Example 1

[0043] At room temperature, 14.41 g of sodium benzoate and Ce(NO3)3·6H2O were dissolved in 500 g of water. The sodium benzoate solution was slowly added to the Ce(NO3)3 solution while stirring. The sodium salt of N-octadecyl terephthalic acid monoamide was mixed with 2000 g of water and sheared for 0.5 h using a high-shear emulsifier to ensure thorough dispersion. Shearing continued while the mixture of sodium benzoate and Ce(NO3)3 was slowly added. After addition, shearing was maintained at 8000 r / min for 2 h. After the reaction, the pH was adjusted to 7 with sodium hydroxide. The mixture was filtered to obtain a light gray precipitate. The precipitate was washed with a large amount of water and dried to obtain the composite cerium amide thickener. The molar ratio of sodium benzoate, Ce(NO3)3·6H2O, and sodium salt of N-octadecyl terephthalic acid monoamide was 1:1:1.

[0044] 252.6g of 500N oil (kinematic viscosity 11mm at 100℃) 2The above-mentioned newly prepared composite amide cerium-based thickener (47.4 g) was added to an atmospheric pressure grease pot, stirred, heated to 105℃ and held at that temperature for 10 min, then heated to 210℃ and the heating was stopped. The mixture was stirred and cooled, and then ground at room temperature to obtain the composite amide cerium-based grease. The grease composition was: base oil 84.2 wt%, thickener 15.8 wt%. The physicochemical properties of the obtained grease are detailed in Table 1 below.

[0045] Example 2

[0046] At room temperature, 12.21 g of benzoic acid was dissolved in 200 g of ethanol, and Ce(NO3)3·6H2O was dissolved in 500 g of water. The benzoic acid solution was slowly added to the Ce(NO3)3 solution while stirring. The sodium salt of N-octadecyl terephthalic acid monoamide was mixed with 2000 g of water and sheared for 0.5 h using a high-shear emulsifier to ensure thorough dispersion. Shearing continued, and the mixture of benzoic acid and Ce(NO3)3 was slowly added. After addition, shearing was maintained at 12000 r / min for 2 h. After the reaction, the pH was adjusted to 10 with sodium hydroxide. The mixture was filtered to obtain a light gray precipitate. The precipitate was washed with a large amount of water and dried to obtain the composite amide cerium-based thickener. The molar ratio of benzoic acid, Ce(NO3)3·6H2O, and the sodium salt of N-octadecyl terephthalic acid monoamide was 1:1:1.

[0047] 246g of polyα-olefin (PAO10, kinematic viscosity at 100℃ is 10mm) was used. 2 54g of the newly prepared composite amide cerium-based thickener was added to an atmospheric pressure grease pot, stirred, heated to 105℃ and held at that temperature for 10 minutes, then heated to 210℃ and the heating was stopped. The mixture was stirred and cooled, and then ground at room temperature to obtain the composite amide cerium-based grease. The grease composition was: base oil 82% by weight, thickener 18% by weight. The physicochemical properties of the obtained grease are detailed in Table 1 below.

[0048] Example 3

[0049] The lubricating grease was prepared according to the method of Example 1, except that sodium 4-methylbenzoate was used instead of sodium benzoate, while maintaining the same molar ratio of the three components. The base oil used was diisooctyl sebacate (DOS, kinematic viscosity at 100°C 3.1 mm). 2 / s). Grease composition: 92% by weight base oil, 8% by weight thickener. The properties of the resulting grease are detailed in Table 1 below.

[0050] Comparative Example 1

[0051] 91g of 500N oil (kinematic viscosity 11mm at 100℃) 2(9g) of sodium salt of N-octadecyl terephthalic acid monoamide and 9g of base oil were added to an atmospheric pressure grease pot, stirred, heated to 105℃ and held at that temperature for 10min, then heated to 210℃ and the heating was stopped. The mixture was stirred and cooled, and then ground at room temperature to obtain sodium amide-based grease. Grease composition: base oil 91% by weight, thickener 9% by weight. The physicochemical properties of the obtained grease are detailed in Table 1 below.

[0052] Comparative Example 2

[0053] Dissolve 30.40 g of Ce(NO3)3·6H2O in 500 g of water. Mix 61.54 g of sodium salt of N-octadecyl terephthalic acid monoamide with 2500 g of water, and shear the mixture for 0.5 h using a high-shear mixing emulsifier to ensure thorough dispersion. Continue shearing and slowly add the above Ce(NO3)3 aqueous solution. After the addition is complete, maintain a rotation speed of 12000 r / min and shear for 1.5 h. Adjust the pH to 7 with NaOH, filter to obtain a white precipitate, wash the precipitate with a large amount of water and dry it to obtain the cerium diamide thickener. The molar ratio of Ce(NO3)3·6H2O to sodium salt of N-octadecyl terephthalic acid monoamide is 1:2.

[0054] 84g of 500N oil (kinematic viscosity 11mm at 100℃) 2 16g of the newly prepared cerium diamide thickener was added to an atmospheric pressure grease pot, stirred, heated to 105℃ and held at that temperature for 10 minutes, then heated to 210℃ and the heating was stopped. The mixture was stirred and cooled, and then ground at room temperature to obtain cerium diamide grease. Grease composition: base oil 84% by weight, thickener 16% by weight. The physicochemical properties of the obtained grease are detailed in Table 1 below.

[0055] Comparative Example 3

[0056] The grease was prepared according to the method in Example 1, except that the sodium salt of N-octadecyl terephthalic acid monoamide was replaced with sodium benzoate while keeping other proportions unchanged, resulting in a cerium salt of benzoic acid. The prepared grease was fluid and did not form grease.

[0057] Comparative Example 4

[0058] (1) The diamide cerium-based thickener prepared according to Comparative Example 2 and the cerium salt of benzoic acid prepared according to Comparative Example 3 were mixed in a molar ratio of 1:1 to obtain a mixed thickener.

[0059] (2) The grease was prepared according to the method of Example 1, except that the thickener was replaced with the mixed thickener obtained in step (1). The physicochemical properties of the grease are detailed in Table 1 below.

[0060] Table 1 Physicochemical Properties of Lubricating Greases

[0061]

[0062]

[0063] The above results show that the composite cerium-based grease prepared according to this invention has better extreme pressure anti-wear performance, colloidal stability, and water resistance. Compared with Comparative Example 1, the grease P prepared according to this invention... D When the values ​​are close, the P of the grease prepared according to the method of the present invention is... B The grease P prepared according to this invention has a larger value, a smaller wear track diameter D, and better colloidal stability and water resistance. Compared to Comparative Example 2, the grease P... D When the drop point and wear mark diameter are similar, the grease prepared according to the method of the present invention has a higher dropping point. Compared with Comparative Example 4, the grease of the present invention has a higher dropping point, smaller cone penetration, less oil separation through the stencil, and less water leaching, resulting in superior overall performance.

[0064] From the infrared spectrum of the lubricating grease of the present invention (e.g. Figure 1 As can be seen, the composite amide cerium-based thickener prepared by this invention contains carbonyl and amide bonds. Based on the preparation process, it can be understood that the composite amide cerium-based thickener mainly contains the compound shown in Formula I.

[0065] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A cerium-containing organic compound used as a grease thickener, characterized in that, The structure of this organic compound is shown in Formula I: Equation I In formula I, R - R1-A-R2-COO - And A is -CO-NH-, R1 is a C12-C20 straight-chain alkyl group, and R2 is a phenylene or a C1-C6 alkyl-substituted phenylene. R' - It is a benzoate ion or a C1-C6 alkyl-substituted benzoate ion.

2. The organic compound according to claim 1, wherein, R in Equation I - R1-NH-CO-R2-COO - Or R1-CO-NH-R2-COO - .

3. The organic compound according to claim 1 or 2, wherein, R in Equation I - R1-NH-CO-R2-COO - R1 is a C14-C20 straight-chain alkyl group, R2 is a p-phenylene or a C1-C4 straight-chain alkyl-substituted phenylene, and R' - It is either benzoate ion or 4-methylbenzoate ion.

4. A method for preparing the cerium-containing organic compound of claim 1, characterized in that, The method includes: [R' - ] x M1 x+ The first substrate shown, [R1-A-R2-COO] - ] y M2 y+ The second substrate shown reacts with an inorganic base and a water-soluble cerium salt to give a solid product, wherein A is -CO-NH-; R1 is a C12-C20 straight-chain alkyl group; R2 is a phenylene or a C1-C6 alkyl-substituted phenylene; R' - It is a benzoate ion or a C1-C6 alkyl-substituted benzoate ion; M1 and M2 are each independently H, a Group IA metal or a Group IIA metal.

5. The method according to claim 4, wherein, R1-A-R2-COO in the second substrate - R1-NH-CO-R2-COO - Or R1-CO-NH-R2-COO - ; And / or, M1 and M2 are each independently H, Na, or K; And / or, the inorganic base is selected from alkali metal hydroxides and / or alkaline earth metal hydroxides.

6. The method according to claim 4 or 5, wherein, R1-A-R2-COO in the second substrate - R1-NH-CO-R2-COO - R1 is a C14-C20 straight-chain alkyl group, R2 is a p-phenylene or a C1-C4 straight-chain alkyl-substituted phenylene, and R' - The cerium salt is a benzoate ion or a 4-methylbenzoate ion, and the water-soluble cerium salt is at least one of cerium nitrate, cerium chloride, and their hydrates.

7. The method according to claim 4 or 5, wherein, The molar ratio of the first substrate to the second substrate is 1:0.2-5; And / or, the amount of the inorganic base used makes the pH of the contact system 7-12; And / or, the amounts of the first substrate, the second substrate, and the water-soluble cerium salt are such that: the total number of moles of anions provided by the first substrate and the second substrate is equal to the number of moles of Ce provided by the water-soluble cerium salt. 3+ The ratio between the number of moles is 200:100-110.

8. The method according to claim 7, wherein, The molar ratio of the first substrate to the second substrate is 1:0.5-1.

9. The method according to claim 4 or 5, wherein, The contact conditions include a temperature of 10-90℃ and a time of 0.2-8h.

10. The method according to claim 4 or 5, wherein, The contact method is as follows: (1) Mix the first substrate, water-soluble cerium salt and solvent, and stir for 0.2-4 hours; (2) Mix the product from step (1) with the second substrate and stir for 0.2-4 hours; (3) Adjust the pH of the product from step (2) to 7-12 using an inorganic base.

11. A pre-made soap containing the organic matter obtained by the method of any one of claims 4-10.

12. A method for preparing lubricating grease, characterized in that, The method includes: obtaining a solid product according to any one of claims 4-10; mixing the obtained solid product with base oil and heating it to a higher temperature.

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