Nitrogen-containing boron compound and preparation method and application thereof
The nitrogen-containing boron compounds are prepared by reacting boric acid with branched chain fatty alcohols and amine compounds with high nitrogen content, which solves the problem of insufficient anti-wear and friction reduction performance of sulfur-free and phosphorus-free organic boron lubricating materials, and achieves efficient lubricating performance improvement. Antiwear and friction reducing agents suitable for lubricating oils.
Patent Information
- Application Number
- CN202310675602.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-06-08
- Publication Date
- 2024-12-10
Smart Images
Figure CN119101077A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a nitrogen-containing boron compound, in particular to a sulfur-free and phosphorus-free nitrogen-containing boron compound and a preparation method and application thereof. Background Art
[0002] With the rapid development of industrial technology, the related technologies of lubricants and their additives have also developed rapidly. For lubricant additives, only by developing in the direction of high temperature resistance, environmental protection, high efficiency and multi-effect can the requirements of more advanced lubricants be met. Boron-containing lubricating materials have good extreme pressure and anti-wear properties, corrosion and rust resistance, sealing and environmental adaptability, and are non-toxic and odorless; while nitrogen-containing lubricating materials have the characteristics of being ash-free, highly electronegative, small atomic radius, and easy to form hydrogen bonds between molecules adsorbed on the metal surface to improve the strength of the oil film; and both types of lubricating materials have the advantages of multi-function, designable molecular structure and combinable active elements. Therefore, the research on nitrogen-containing organic boron lubricating materials has attracted widespread attention in the field of modern friction and lubrication.
[0003] CN106366106A discloses a nitrogen-containing borate lubricant additive prepared by the reaction of boric acid, fatty alcohol, and ethanolamine, which has good anti-hydrolysis ability and anti-wear and friction reduction properties. CN102936527A discloses an organic boron friction reducer prepared by the reaction of boric acid, natural oils and organic alcohol amines, which has good thermal stability, oil solubility, and anti-wear and friction reduction properties. CN112410096A discloses a nitrogen-containing borate lubricant additive prepared by the reaction of boric acid, thiocyanate, and aromatic diethanolamide, which can protect equipment machinery, increase the anti-friction performance of lubricants, and reduce energy consumption. CN101735255A discloses a boron-containing nitride prepared by the reaction of oleic acid, triethanolamine, tributyl borate, butanol or ethanolamine, which has good anti-wear and friction reduction effects when added to liquid paraffin.
[0004] At present, sulfur- and phosphorus-containing additives are subject to certain restrictions due to environmental protection issues, and sulfur-free and phosphorus-free extreme pressure and anti-wear organic boron additives have received attention. However, the anti-wear and friction-reducing properties of sulfur-free and phosphorus-free organic boron need to be further improved. Summary of the invention
[0005] The invention provides a nitrogen-boron compound and a preparation method and application thereof. The nitrogen-boron compound has excellent anti-wear and friction-reducing properties.
[0006] The present invention includes the following aspects.
[0007] In a first aspect, the present invention provides a nitrogen-containing boron compound, the structure of which is shown in formula (I) and / or formula (II):
[0008]
[0009] In formula (I), the G groups are each independently selected from the group represented by formula (III), the R' groups are each independently selected from C 10 ~C 30 In formula (I), there are one or two G groups selected from the group shown in formula (III);
[0010]
[0011] The R group in formula (III) is selected from a C2-C8 straight chain or branched alkylene group, and the R" groups are each independently selected from a C2-C8 20 A straight or branched alkylene group, wherein n is an integer between 1 and 5;
[0012] In formula (II), the R' group is selected from C 10 ~C 30 The R groups are each independently selected from a C2 to C8 straight or branched alkylene group, and the G' group is selected from a group represented by formula (IV);
[0013]
[0014] The R0 group in formula (IV) is selected from C 10 ~C 30 A straight chain or branched chain alkyl group.
[0015] According to the present invention, preferably, the R' group is selected from C 15 ~C 25 The R group is selected from a C2-C6 straight chain or branched chain alkylene group, and the R" group is selected from a C2-C 18 A straight or branched alkylene group, n is 1, 2, 3 or 4, and the R0 group is selected from C 15 ~C 25 A straight chain or branched chain alkyl group.
[0016] According to the present invention, the nitrogen-boron-containing compound is one or more of the following compounds with specific structures:
[0017]
[0018]
[0019] The nitrogen-boron compound of the invention has excellent anti-wear and friction-reducing properties.
[0020] In a second aspect, the present invention provides a method for preparing a nitrogen-containing boron compound, comprising reacting boric acid, R'OH, a compound represented by formula (X) and / or a compound represented by formula (Y), and collecting the product;
[0021]
[0022] The R' group is selected from C 10 ~C 30 The R groups are each independently selected from a C2 to C8 straight chain or branched chain alkylene group; the R" groups are each independently selected from a C2 to C8 straight chain or branched chain alkylene group. 20 A straight or branched alkylene group, n is an integer between 1 and 5; the R0 group is selected from C 10 ~C 30 A straight chain or branched chain alkyl group.
[0023] According to the present invention, preferably, the R' group is selected from C 15 ~C 25 The R group is selected from a C2-C6 straight chain or branched chain alkylene group, and the R" group is selected from a C2-C 18 A straight or branched alkylene group, n is 1, 2, 3 or 4; R0 group is selected from C 15 ~C 25 A straight chain or branched chain alkyl group.
[0024] According to the present invention, the R'OH can be selected from C 10 ~C 30 The branched chain fatty alcohol is preferably C 15 ~C 25 The Guerbet alcohol may be, for example, one or more of 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol and 2-dodecylhexadecanol.
[0025] According to the present invention, the compound represented by formula (X) can be N-(2-hydroxyethyl)ethylenediamine.
[0026] According to the present invention, the compound represented by formula (Y) can be selected from one or more of N,N-dihydroxyethyldodecylamine, N,N-dihydroxyethyltetradecylamine, N,N-dihydroxyethylhexadecylamine and N,N-dihydroxyethyloctadecylamine.
[0027] According to the present invention, the molar ratio of R'OH, the compound represented by formula (X) and / or the compound represented by formula (Y) as a whole to boric acid is 0.5 to 6: 1, more preferably 1 to 3: 1. Further preferably, the molar ratio of boric acid, R'OH, the compound represented by formula (X) and / or the compound represented by formula (Y) is 1: 0.5 to 3: 0.5 to 4, more preferably 1: 0.5 to 1.5: 0.5 to 3.
[0028] According to the present invention, the temperature for reacting boric acid, R'OH, the compound represented by formula (X) and / or the compound represented by formula (Y) is 80°C to 280°C, preferably 100°C to 200°C.
[0029] According to the present invention, the longer the time for reacting boric acid, R'OH, the compound represented by formula (X) and / or the compound represented by formula (Y) is, the better. Generally speaking, the reaction time can be 1 to 10 hours, preferably 3 to 6 hours.
[0030] According to the present invention, a catalyst may be added to the reaction of boric acid, R'OH, the compound represented by formula (X) and / or the compound represented by formula (Y), and the catalyst is preferably an acidic catalyst, for example, one or more of concentrated sulfuric acid, zinc chloride, aluminum chloride, benzenesulfonic acid and titanate may be selected, and the amount of the catalyst added is preferably 0.01% to 2% of the sum of the mass of boric acid, R'OH, the compound represented by formula (X) and / or the compound represented by formula (Y). After the reaction is completed, the catalyst may be removed by alkali washing and / or water washing.
[0031] According to the present invention, a solvent may or may not be added during the reaction of boric acid, R'OH, the compound represented by formula (X) and / or the compound represented by formula (Y). The solvent may be selected from C 6-20 Aromatic hydrocarbons (such as benzene, toluene, xylene and cumene), C 6-10 The solvent can be removed after the reaction is completed by a method known to those skilled in the art, such as distilling off the solvent under normal pressure or reduced pressure.
[0032] According to the present invention, the reaction of boric acid, R'OH, the compound represented by formula (X) and / or the compound represented by formula (Y) can be carried out under the protection of an inert gas atmosphere. The inert gas may include nitrogen and argon, etc., without particular limitation.
[0033] The preparation method of the nitrogen-boron compound of the present invention has simple steps and high conversion rate in the reaction process.
[0034] In a third aspect, the present invention proposes the use of the nitrogen-boron-containing compound proposed in the first aspect and the use of the nitrogen-boron-containing compound prepared by the method of the second aspect.
[0035] The nitrogen-boron compound can be used as an anti-wear agent and a friction reducer for lubricating oil. BRIEF DESCRIPTION OF THE DRAWINGS
[0036] Figure 1 It is the infrared spectrum of the product of Example 1.
[0037] Figure 2 The NMR of the product of Example 1 is 1 H spectrum. DETAILED DESCRIPTION
[0038] The present invention is further described below by way of examples, but they are not intended to limit the present invention.
[0039] The main raw materials used are as follows:
[0040] Concentrated sulfuric acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade
[0041] Boric acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure
[0042] N-Hydroxyethylethylenediamine, Sinopharm Chemical Reagent Co., Ltd., chemically pure
[0043] N,N-Dihydroxyethyl octadecylamine, Sinopharm Chemical Reagent Co., Ltd., chemically pure
[0044] 2-Octyldodecanol, Sinopharm Chemical Reagent Co., Ltd., chemically pure
[0045] 2-Hexyldecanol, Sinopharm Chemical Reagent Co., Ltd., chemically pure
[0046] Hexadecanol, Sinopharm Chemical Reagent Co., Ltd., chemically pure
[0047] Ethanolamine, Sinopharm Chemical Reagent Co., Ltd., chemically pure
[0048] Polyol ester (commercial grade 5101), Sinopec Lubricant Chongqing Branch, industrial product Example 1
[0049] 12g of boric acid, 120g of 2-octyl dodecanol, 21g of N-hydroxyethylethylenediamine and 0.5g of concentrated sulfuric acid were placed in a flask equipped with a water separation and reflux device and a thermometer, stirred, heated, and reacted at 190°C for 5h. The water produced by the reaction was removed during the reaction. After the reaction was completed, the temperature was lowered to obtain a slightly yellow transparent liquid. The reaction product was washed with distilled water until neutral, and the organic phase was distilled under reduced pressure at 100Pa and 150°C for 1h to remove water and unreacted raw materials to obtain nitrogen-containing boron compound W-01, with a reaction conversion rate of 95.8%.
[0050] An example reaction formula is as follows.
[0051]
[0052] The product prepared in Example 1 was subjected to infrared spectroscopy and nuclear magnetic resonance. 1 H spectrum analysis, infrared spectrum see Figure 1 , the analysis results are shown in Table 1, NMR 1 H spectrum Figure 2 , the analysis results are shown in Table 2.
[0053] Table 1 Infrared analysis results of products
[0054]
[0055] Table 1 shows that the product has characteristic peaks such as C-NH stretching vibration peak, C-N stretching vibration peak, B-O stretching vibration peak, etc., which can indicate that the synthesized product is the target compound.
[0056] Table 2 Product NMR 1 H spectrum analysis results
[0057]
[0058] Table 2 shows that the product has characteristic peaks such as the proton peak on O-CH2, the proton peak on N-CH2, and the proton peak on NH2, which indicates that the synthesized product is the target compound.
[0059] Example 2
[0060] 12g of boric acid, 49g of 2-hexyldecanol and 42g of N-hydroxyethylethylenediamine were placed in a flask equipped with a water separation and reflux device and a thermometer, stirred, heated, and reacted at 170°C for 6h. The water produced by the reaction was removed during the reaction. After the reaction was completed, the temperature was lowered to obtain a slightly yellow transparent liquid. The reaction product was washed with distilled water until neutral, and the organic phase was distilled under reduced pressure at 100Pa and 150°C for 1h to remove water and unreacted raw materials to obtain nitrogen-containing boron compound W-02, with a reaction conversion rate of 96.1%.
[0061] An example reaction formula is as follows.
[0062]
[0063] Example 3
[0064] 12g of boric acid, 49g of 2-hexyldecanol and 72g of N,N-dihydroxyethyl octadecylamine were placed in a flask equipped with a water separation and reflux device and a thermometer, stirred, heated, and reacted at 160°C for 4h. The water produced by the reaction was removed during the reaction. After the reaction was completed, the temperature was lowered to obtain a slightly yellow transparent liquid. The reaction product was washed with distilled water until neutral, and the organic phase was distilled under reduced pressure at 100Pa and 150°C for 1h to remove water and unreacted raw materials to obtain nitrogen-containing boron compound W-03 with a reaction conversion rate of 96.3%.
[0065] An example reaction formula is as follows.
[0066]
[0067] Comparative Example 1
[0068] 36.3 g of hexadecanol, 18.3 g of ethanolamine, 6.2 g of boric acid and 90 g of toluene solvent were added into a reaction container, stirred, heated, and reacted at 145° C. for 6 hours. Finally, the solvent and unreacted ethanolamine were filtered and evaporated to obtain a comparative nitrogen-containing boron compound V-01.
[0069] Comparative Example 2
[0070] 12g of boric acid, 52g of octanol, 21g of N-hydroxyethylethylenediamine and 0.5g of concentrated sulfuric acid were placed in a flask equipped with a water separation and reflux device and a thermometer, stirred, heated, and reacted at 190°C for 5h. The water produced in the reaction was removed during the reaction. After the reaction was completed, the temperature was lowered to obtain a slightly yellow transparent liquid, which was washed with distilled water until neutral. The organic phase was distilled under reduced pressure at 100Pa and 150°C for 1h to remove water and unreacted raw materials to obtain a comparative nitrogen-containing boron compound V-02.
[0071] Example 4
[0072] W-01, W-02, W-03, V-01, and V-02 were added to polyol esters at a dosage of 0.5% (nitrogen-boron compounds and contrast agents accounted for 0.5% of the total mass of the oil products, respectively) to prepare test oils. These test oils were subjected to SRV anti-wear and friction reduction evaluation tests and four-ball test machine anti-wear evaluation tests to evaluate the anti-wear and friction reduction performance of the additives. The SRV anti-wear and friction reduction evaluation test adopted the National Energy Administration standard NB / SH / T0847-2010 method, and the test conditions were: temperature 30°C, load 100N, stroke 1mm, test time 1 hour, and frequency 50Hz. The four-ball test machine anti-wear evaluation test adopted the National Energy Administration standard NB / SH / T0189-2017 method, and the test conditions were: temperature 75°C, load 392N, speed 1200r / min, and test time 1 hour. The test results are shown in Tables 3 and 4, respectively.
[0073] Table 3 SRV anti-wear and friction reduction test results
[0074] Test oil number Types of organic boron additives Wear spot diameter / mm Friction coefficient 1 — 0.56 0.115 2 W-01 0.50 0.102 3 W-02 0.48 0.101 4 W-03 0.51 0.103 5 V-01 0.54 0.106 6 V-02 0.55 0.111
[0075] Table 4 Four-ball testing machine anti-wear evaluation test results
[0076] Test oil number Types of organic boron additives Wear spot diameter / mm 1 — 0.95 2 W-01 0.66 3 W-02 0.57 4 W-03 0.62 5 V-01 0.68 6 V-02 0.72
[0077] It can be seen from Tables 3 and 4 that the nitrogen-containing boron compound of the present invention has better anti-wear and friction-reducing properties.
Claims
1. A nitrogen-boron compound, the structure of which is shown in formula (I) and / or formula (II): In formula (I), the G groups are each independently selected from the group represented by formula (III), the R' groups are each independently selected from C 10 ~C 30 In formula (I), there are one or two G groups selected from the group shown in formula (III); The R group in formula (III) is selected from a C2-C8 straight chain or branched alkylene group, and the R" groups are each independently selected from a C2-C8 20 A straight or branched alkylene group, wherein n is an integer between 1 and 5; In formula (II), the R' group is selected from C 10 ~C 30 The R groups are each independently selected from a C2 to C8 straight or branched alkylene group, and the G' group is selected from a group represented by formula (IV); The R0 group in formula (IV) is selected from C 10 ~C 30 A straight chain or branched chain alkyl group.
2. The nitrogen-boron compound according to claim 1, characterized in that R' group is selected from C 15 ~C 25 The R group is selected from a C2-C6 straight chain or branched chain alkylene group, and the R" group is selected from a C2-C 18 A straight or branched alkylene group, n is 1, 2, 3 or 4, and the R0 group is selected from C 15 ~C 25 A straight chain or branched chain alkyl group.
3. The nitrogen-boron compound according to claim 1, characterized in that The nitrogen-boron compound is one or more of the following compounds with specific structures:
4. A method for preparing a nitrogen-containing boron compound, comprising reacting boric acid, R'OH, a compound represented by formula (X) and / or a compound represented by formula (Y), and collecting the product; R' group is selected from C 10 ~C 30 The R groups are each independently selected from a C2 to C8 straight chain or branched chain alkylene group; the R" groups are each independently selected from a C2 to C8 straight chain or branched chain alkylene group. 20 A straight or branched alkylene group, n is an integer between 1 and 5; the R0 group is selected from C 10 ~C 30 A straight chain or branched chain alkyl group.
5. The method according to claim 4, characterized in that R' group is selected from C 15 ~C 25 The R group is selected from a C2-C6 straight chain or branched chain alkylene group, and the R" group is selected from a C2-C 18 A straight or branched alkylene group, n is 1, 2, 3 or 4; R0 group is selected from C 15 ~C 25 A straight chain or branched chain alkyl group.
6. The method according to claim 4, characterized in thatThe R'OH is selected from C 10 ~C 30 The compound represented by formula (X) is selected from N-(2-hydroxyethyl)ethylenediamine; the compound represented by formula (Y) is selected from one or more of N,N-dihydroxyethyldodecylamine, N,N-dihydroxyethyltetradecylamine, N,N-dihydroxyethylhexadecylamine and N,N-dihydroxyethyloctadecylamine.
7. The method according to claim 4, characterized in that The R'OH is selected from C 15 ~C 25 of Guerbet alcohol.
8. The method according to claim 4, characterized in that The R'OH is selected from one or more of 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol and 2-dodecylhexadecanol.
9. The method according to claim 4, characterized in that The molar ratio of R'OH, the compound represented by formula (X) and / or the compound represented by formula (Y) as a whole to boric acid is 0.5 to 6:1; the temperature for reacting boric acid, R'OH, the compound represented by formula (X) and / or the compound represented by formula (Y) is 80°C to 280°C.
10. The method according to claim 9, characterized in that The molar ratio of boric acid, R'OH, the compound represented by formula (X) and / or the compound represented by formula (Y) is 1:0.5-3:0.5-4.
11. The nitrogen-containing boron compound according to any one of claims 1 to 3 or the nitrogen-containing boron compound prepared by the method according to any one of claims 4 to 10 is used as an antiwear agent or friction reducer for lubricating oil.