Organoboron compounds, processes for their preparation, uses thereof

Abstract

This invention discloses an organoboron compound, its preparation method, and its uses. The organoboron compound of this invention has the structure shown in formula (Ⅰ): wherein the R group is selected from C1-C6 straight-chain or branched alkylene groups, each R0 group is independently selected from H, C1-C4 straight-chain or branched alkylene groups, x is an integer between 0 and 3, y is an integer between 0 and 3, and the R' group is selected from C1-C4 straight-chain or branched alkylene groups. 30 The compounds contain straight-chain or branched hydrocarbon groups. The organoboron compounds of this invention exhibit excellent antioxidant, anti-wear, and anti-corrosion properties.

Description

Technical Field

[0001] This invention relates to an organoboron compound, and more particularly to a sulfur-free and phosphorus-free organoboron compound, its preparation method, and its uses. Background Technology

[0002] Lubricants are substances used in mechanical equipment to reduce friction and protect mechanical parts, and are widely used in various types of machinery. The main functions of lubricants are to reduce friction, decrease wear, improve efficiency, and extend service life. The performance of a lubricant depends primarily on the properties of its base oil and lubricating oil additives. For lubricating oil additives, only by developing towards high-temperature resistance, environmental compliance, high efficiency, and multi-functionality can the requirements of higher-grade lubricants be met. Currently, boron-containing lubricating materials possess excellent extreme pressure anti-wear properties, corrosion and rust prevention, sealing properties, are non-toxic and odorless, sulfur- and phosphorus-free, and environmentally friendly. Because environmental regulations in many countries and regions impose strict restrictions on lubricants and additives containing sulfur and phosphorus, nitrogen-containing, sulfur- and phosphorus-free organic boron lubricating materials have attracted widespread attention in the modern friction and lubrication field.

[0003] CN1566293A discloses a borate ester lubricating oil additive prepared by reacting n-dodecyl alcohol, 2-di-n-dodecyl dithiophosphate ethanol, and boric acid. This additive exhibits good anti-wear and friction-reducing properties. CN102936527A discloses an organoboron friction reducer prepared by reacting boric acid, natural oils, and organic alcohol amines. This additive exhibits good thermal stability, oil solubility, and anti-wear and friction-reducing properties. CN103601748A discloses a borate ester lubricating oil additive prepared by reacting N,N-dihydroxyethyloctadecylamine, DMTO, and boric acid. This additive can protect equipment machinery, increase the anti-friction performance of lubricating oil, and reduce energy consumption. CN116655671A discloses a borate ester compound prepared by reacting (4-(2-(2,4-dinitrophenyl)hydrazide)methyl)phenylboronic acid dodecyl ester and n-dodecyl alcohol. This compound exhibits good anti-wear and friction-reducing effects in base oils such as liquid paraffin.

[0004] Although existing organoboron compounds have good anti-wear and friction-reducing properties, their antioxidant and anti-corrosion properties still need further improvement. Summary of the Invention

[0005] This invention proposes an organoboron compound, its preparation method, and its uses.

[0006] The organoboron compound of the present invention has the structure shown in formula (I):

[0007]

[0008] The R group is selected from C1-C6 straight-chain or branched alkylene groups, each R0 group is independently selected from H, C1-C4 straight-chain or branched alkylene groups, x is an integer between 0 and 3, y is an integer between 0 and 3, and the R' group is selected from C1-C4 straight-chain or branched alkylene groups. 30 Straight-chain or branched hydrocarbon groups.

[0009] According to the present invention, preferably, the R group is selected from methylene, each RO group is independently selected from H, methyl and tert-butyl, each RO group is located at the ortho or para position of OH on the same benzene ring, x is 0 or 1, y is 0 or 1, and the R' group is selected from C 10 ~C 20 Straight-chain or branched alkyl groups, containing 1 to 3 carbon-carbon double bonds. 10 ~C 20 The straight-chain or branched alkenyl group, with the OH group located on the same benzene ring as the R' group at the ortho or para position of the R group, and the OH group located on the same benzene ring as the R' group at the meta position.

[0010] According to the present invention, the organoboron compound may be one or more of the following compounds:

[0011]

[0012]

[0013] According to the present invention, the method for preparing the organoboron compound includes the following steps: reacting compound (X) and compound (Y) with C1-C6 aldehydes and collecting the products;

[0014]

[0015] Each R0 group is independently selected from H, C1-C4 straight-chain or branched alkyl groups, x is an integer between 0 and 3, y is an integer between 0 and 3, and R' groups are selected from C1-C4 straight-chain or branched alkyl groups. 30 Straight-chain or branched hydrocarbon groups.

[0016] According to the present invention, preferably, each RO group is independently selected from H, methyl, and tert-butyl, each RO group is located at the ortho or para position of OH on the same benzene ring, x is 0 or 1, y is 0 or 1, and R' group is selected from C 10 ~C 20 Straight-chain or branched alkyl groups, containing 1 to 3 carbon-carbon double bonds. 10 ~C 20 The aldehydes are straight-chain or branched alkenyl groups; the C1 to C6 aldehydes are selected from formaldehyde or paraformaldehyde.

[0017] According to the present invention, the compound of formula (X) may be selected from one or more of p-hydroxyphenylboronic acid, 3-tert-butylp-hydroxyphenylboronic acid, and 3,5-di-tert-butylp-hydroxyphenylboronic acid; the compound of formula (Y) may be selected from 3-methylphenol, 3-ethylphenol, 3-propylphenol, 3-butylphenol, 3-pentylphenol, 3-hexylphenol, 3-heptylphenol, 3-octylphenol, 3-nonylphenol, 3-decylphenol, 3-undecylphenol, 3-dodecylphenol, 3-tetrazylphenol, 3-tetradecylphenol, 3-pentadecanylphenol, 3-pentadecanylphenol, 3-(pentadecan-8-enyl)phenol, and 3-(pentadecan-8,11-dienyl)phenol. The phenol, 3-(pentadecano-8,11,14-trienyl)phenol, 3-hexadecylphenol, 3-heptadecylphenol, 3-octadecylphenol, 3-nonadecanylphenol, 3-eicosylphenol, 3-monodecylphenol, 3-monodidecylphenol, 3-trinylphenol, 3-tetradecylphenol, 3-pentadecanylphenol, 3-hexadecylphenol, 3-heptadecylphenol, 3-octadecylphenol, 3-nonadecanylphenol, and 3-trianedecylphenol may be one or more of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentaldehyde, and hexanal.

[0018] According to the present invention, the molar ratio between the compound of formula (X), the compound of formula (Y) and the aldehyde of C1 to C6 can be 1:0.05 to 6:0.05 to 10, preferably 1:0.1 to 3:0.1 to 5.

[0019] According to the present invention, the reaction temperature of the compound of formula (X) and the compound of formula (Y) with the aldehyde of C1 to C6 can be 40°C to 160°C, preferably 50°C to 120°C.

[0020] According to the present invention, the longer the reaction time of the compound of formula (X) and the compound of formula (Y) with the aldehyde of C1 to C6 is generally preferred, and the reaction time is preferably 1 to 10 hours, more preferably 3 to 7 hours.

[0021] According to the present invention, an alkaline catalyst may be added to the reaction of compound (X) and compound (Y) with C1-C6 aldehydes. The alkaline catalyst may be one or more of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, and ammonia water. The amount of alkaline catalyst added is preferably 0.01% to 5% of the sum of the masses of compound (X) and compound (Y). After the reaction is complete, the alkaline catalyst can be removed by acid washing and / or water washing. The acid used in the acid washing method may be one or more of sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, or an aqueous solution thereof. The concentration and amount used are preferably for neutralizing the alkaline catalyst and are not particularly limited.

[0022] According to the present invention, a solvent may be added in the reaction of compound (X) and compound (Y) with C1-C6 aldehydes. The solvent is preferably an aqueous solution of an alcohol, such as one or more of aqueous solutions of ethanol, propanol, and butanol. In the aqueous solution of the alcohol, the mass concentration of the alcohol is preferably 50% to 90%, and the amount of solvent added is preferably 100% to 800% of the sum of the masses of compound (X) and compound (Y). After the reaction is complete, the solvent can be removed by distillation and / or washing with water.

[0023] According to the present invention, a surfactant may be added in the reaction of compound (X) and compound (Y) with C1-C6 aldehydes. The surfactant may be one or more selected from alkyl sulfates, alkyl sulfonates, polyethylene glycol, haloalkylpyridines, and ammonium halide quaternary ammonium salts, for example, sodium dodecyl sulfate, zinc octadecyl sulfate, sodium dodecyl sulfonate, polyethylene glycol 10000-11000, hexadecyl pyridine bromide, tetrabutylammonium bromide, and hexadecyltrimethylammonium bromide. The amount of surfactant added may be 1% to 10% of the sum of the masses of compound (X) and compound (Y).

[0024] According to the present invention, optionally, after the reaction of the compound of formula (X) and the compound of formula (Y) with the aldehyde of C1 to C6 is completed, the impurities in the reaction product can be removed by filtration or distillation methods known in the art, without any particular limitation.

[0025] According to the present invention, the aforementioned method for preparing organoboron compounds can produce a single organoboron compound or a mixture of multiple organoboron compounds as reaction products. These reaction products are all intended for use in the present invention, and their different forms do not affect the achievement of the intended effects. Therefore, in the context of this specification, these reaction products are collectively referred to as organoboron compounds without distinction. In view of this, the present invention does not have an absolute necessity for further purification of the reaction products or for further separation of organoboron compounds with a specific structure from the reaction products. Of course, such purification or separation is preferred for further enhancing the intended effects of the present invention, but it is not essential for the present invention. Nevertheless, methods for purification or separation, such as column chromatography or preparative chromatography, can be cited as examples.

[0026] The method for preparing the organoboron compounds of the present invention is simple and the reaction process has a high conversion rate.

[0027] The organoboron compounds of the present invention can be used as antioxidants, anti-wear agents, and corrosion inhibitors for lubricating oils.

[0028] The organoboron compounds of this invention have excellent antioxidant, anti-wear, and anti-corrosion properties. Attached Figure Description

[0029] Figure 1 The infrared spectrum of the product of Example 1 is shown below.

[0030] Figure 2 NMR of the product of Example 1 1 H spectrum. Detailed Implementation

[0031] The present invention will be further illustrated below by way of examples, but these are not intended to limit the invention. Unless otherwise specified, all percentages mentioned in the context of the present invention are percentages by mass.

[0032] The main sources of the raw materials used are as follows:

[0033] Phosphoric acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0034] Sodium hydroxide, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0035] p-Hydroxyphenylboronic acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0036] 3-tert-butyl-p-hydroxyphenylboronic acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0037] 2-tert-butyl-5-pentadecanylphenol, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0038] 3-Pentadecylphenol, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0039] 3-(pentadecane-8-enyl)phenol, Sinopharm Chemical Reagent Co., Ltd., chemically pure; 3-(pentadecane-8,11-dienyl)phenol, Sinopharm Chemical Reagent Co., Ltd., chemically pure; formaldehyde, Sinopharm Chemical Reagent Co., Ltd., chemically pure; ethanol, Sinopharm Chemical Reagent Co., Ltd., chemically pure.

[0040] Zinc octadecyl sulfate, Sinopharm Chemical Reagent Co., Ltd., chemically pure.

[0041] Cetyl alcohol, Sinopharm Chemical Reagent Co., Ltd., chemically pure ethanolamine, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0042] Boric acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0043] Octyl alcohol, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0044] N-(2-Hydroxyethyl)ethylenediamine, Sinopharm Chemical Reagent Co., Ltd., chemically pure.

[0045] Concentrated sulfuric acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure.

[0046] Antioxidant T501, Xingpu Company, Petrochemical Research Institute, Industrial Product

[0047] Antioxidant T512, Xingpu Company, Petrochemical Research Institute, Industrial Products

[0048] Sulfene T321, Xingpu Company, Petrochemical Research Institute, Industrial Product

[0049] Polyol ester (commercial designation 5101), Sinopec Lubricating Oil Chongqing Branch, Industrial Product Example 1

[0050] 3.45 g (0.025 mol) of p-hydroxyphenylboronic acid, 7.6 g (0.025 mol) of 3-pentadecanylphenol, 0.17 g of sodium hydroxide, 0.3 g of octadecyl zinc sulfate, and 50.00 g of 75% ethanol aqueous solution were placed in a flask equipped with a condenser and a thermometer. The mixture was stirred and heated to 80 °C. 12 g of 37% formaldehyde aqueous solution was weighed and added dropwise to the flask through a constant pressure dropping funnel. After the addition was complete, the temperature was 79 °C. The mixture was then reacted at 80 °C for 4.5 h. After the reaction was completed, the temperature was lowered to obtain a reddish-brown turbid liquid. The liquid was washed with 5% phosphoric acid aqueous solution and then with distilled water until neutral. The organic phase was then distilled under reduced pressure at 100 Pa and 150 °C for 1 h to remove water and unreacted raw materials, yielding organoboron compound W-01. The conversion rate of the reaction was measured to be 95.3%.

[0051] The example reaction formula for Example 1 is shown below.

[0052]

[0053] The organoboron compound W-01 prepared in Example 1 was subjected to infrared spectroscopy and nuclear magnetic resonance spectroscopy. 1 H-spectral analysis, the tested infrared spectrum is shown in [reference needed]. Figure 1 The analysis results are shown in Table 1. The NMR spectroscopy results were obtained. 1 See H spectrum Figure 2 The analysis results are shown in Table 2.

[0054] Table 1 Infrared analysis results of organoboron compound W-01

[0055]

[0056] Depend on Figure 1As shown in Table 1, the organoboron compound W-01 contains multiple characteristic peaks such as OH stretching vibration peaks, B-O stretching vibration peaks, and B-C stretching vibration peaks, which indicates that the synthesized product is the target compound.

[0057] Table 2 NMR spectra of organoboron compound W-01 1 H-spectral analysis results

[0058]

[0059] Depend on Figure 2 As shown in Table 2, organoboron compound W-01 contains characteristic peaks such as the proton peak connecting the benzene ring, the proton peak on the benzene ring, the proton peak on CH3, the proton peak on B-OH, and the proton peak on the phenolic hydroxyl group, which indicates that the synthesized product is the target compound.

[0060] Example 2

[0061] 4.85 g (0.025 mol) of 3-tert-butyl-p-hydroxyphenylboronic acid, 7.6 g (0.025 mol) of 3-pentadecanylphenol, 0.19 g of sodium hydroxide, 0.35 g of octadecyl zinc sulfate, and 50.00 g of 75% ethanol aqueous solution were placed in a flask equipped with a condenser and a thermometer. The mixture was stirred and heated to 80 °C. 12 g of 37% formaldehyde aqueous solution was weighed and added dropwise to the flask through a constant pressure dropping funnel. After the addition was complete, the temperature was 79 °C. The mixture was then reacted at 80 °C for 4.5 h. After the reaction was completed, the temperature was lowered to obtain a reddish-brown turbid liquid. The liquid was washed with 5% phosphoric acid aqueous solution and then with distilled water until neutral. The organic phase was then distilled under reduced pressure at 100 Pa and 150 °C for 1 h to remove water and unreacted raw materials, yielding organoboron compound W-02. The conversion rate of the reaction was measured to be 94.8%.

[0062] The example reaction formula for Example 2 is shown below.

[0063]

[0064] Example 3

[0065] 3.45 g (0.025 mol) of p-hydroxyphenylboronic acid, 9.0 g (0.025 mol) of 2-tert-butyl-5-pentadecanylphenol, 0.19 g of sodium hydroxide, 0.3 g of octadecyl zinc sulfate, and 50.00 g of 75% ethanol aqueous solution were placed in a flask equipped with a condenser and a thermometer. The mixture was stirred and heated to 80 °C. 12 g of 37% formaldehyde aqueous solution was weighed and added dropwise to the flask through a constant pressure dropping funnel. After the addition was complete, the temperature was 79 °C. The mixture was then reacted at 80 °C for 4.5 h. After the reaction was completed, the temperature was lowered to obtain a reddish-brown turbid liquid. The liquid was washed with 5% phosphoric acid aqueous solution and then with distilled water until neutral. The organic phase was then distilled under reduced pressure at 100 Pa and 150 °C for 1 h to remove water and unreacted raw materials, yielding organoboron compound W-03. The conversion rate of the reaction was measured to be 92.3%.

[0066] The example reaction formula for Example 3 is shown below.

[0067]

[0068] Comparative Example 1

[0069] 36.3 g cetyl alcohol, 18.3 g ethanolamine, 6.2 g boric acid, and 90 g toluene were added to a reaction vessel, stirred, and heated to 145 °C for 6 hours. Finally, the solvent and unreacted ethanolamine were removed by filtration and evaporation to obtain the comparative organoboron compound V-01.

[0070] Comparative Example 2

[0071] 12g of boric acid, 52g of octanol, 21g of N-(2-hydroxyethyl)ethylenediamine, and 0.5g of concentrated sulfuric acid were placed in a flask equipped with a water separator and reflux device and a thermometer. The mixture was stirred and heated to 190℃ for 5 hours, during which the water produced was removed. After the reaction was completed, the mixture was cooled to obtain a pale yellow transparent liquid. The liquid was washed with distilled water until neutral. The organic phase was then distilled under reduced pressure at 100 Pa and 150℃ for 1 hour to remove water and unreacted reactants, yielding the comparative organoboron compound V-02.

[0072] Example 4

[0073] Organic boron compounds W-01, W-02, and W-03, and comparative additives V-01, V-02, T501, and T512 were added to polyol ester 5101 at a dosage of 0.5% to prepare test oil samples of lubricating oil compositions (where the additives accounted for 0.5% of the total mass of the lubricating oil composition). The anti-wear properties of the test oil samples with additives and the blank sample were determined using a four-ball milling machine. The test method followed the National Energy Administration standard NB / SH / T0189-2017, with the following test conditions: temperature 75℃, load 392N, and test time 1 hour. The oxidation resistance of the test oil samples with additives and the blank sample was determined using a TA5000 DSC instrument from TA Instruments (USA), with the following test conditions: 210℃, oxygen pressure 0.5MPa, and heating rate 50℃ / min. The formulation composition and test results of the anti-wear and oxidation resistance of the test oil samples are shown in Table 3.

[0074] Table 3. Test results of wear resistance and oxidation resistance

[0075]

[0076] Example 5

[0077] Add 3% of thioene T321 (which accounts for 3% of the total mass of the two) to polyol ester 5101, mix thoroughly, and use as a base solution. Add W-01, W-02, W-03, and comparative additives V-01, V-02, T501, and T512 to the base solution at a dosage of 0.05% (the additives account for 0.05% of the total oil mass). Conduct corrosion stability tests on the prepared samples and blank samples according to GB / T5096 Petroleum Products Copper Strip Corrosion Test Method. The test conditions are: 100℃, 3h. The formulation composition and test results of the test oil samples are shown in Table 4.

[0078] Table 4 Corrosion stability test results

[0079]

Claims

1. An organoboron compound, the structure of which is shown in formula (Ⅰ): wherein the R groups are selected from C1-C6 straight or branched chain alkylene groups, each R0group is independently selected from H, C1-C4 straight or branched chain alkyl groups, x is an integer between 0 and 3, y is an integer between 0 and 3, the R' groups are selected from C1-C 30 straight or branched chain hydrocarbon groups.

2. The organoboron compound according to claim 1, characterized in that, R groups are selected from methylene, each R° group is independently selected from H, methyl and tert-butyl, each R° group is located at the ortho or para position relative to OH on the same phenyl ring, x is 0 or 1, y is 0 or 1, R' groups are selected from C 10 ~C 20 straight or branched chain alkyl, C 10 ~C 20 straight or branched chain alkenyl containing 1 to 3 carbon-carbon double bonds, OH located on the same phenyl ring as the R' group is located at the ortho or para position relative to the R group, R' group is located at the meta position relative to OH on the same phenyl ring.

3. The organoboron compound according to claim 1, characterized in that, The organoboron compound is one or more of the following compounds:

4. A method for preparing organoboron compounds, comprising the following steps: React compounds of formula (X) and (Y) with C1-C6 aldehydes and collect the products; Each R0 group is independently selected from H, C1-C4 straight-chain or branched alkyl groups, x is an integer between 0 and 3, y is an integer between 0 and 3, and R' groups are selected from C1-C4 straight-chain or branched alkyl groups. 30 Straight-chain or branched hydrocarbon groups.

5. The preparation method according to claim 4, characterized in that, Each R0 group is independently selected from H, methyl, and tert-butyl, and each R0 group is located at the ortho or para position of OH on the same benzene ring. x is 0 or 1, y is 0 or 1, and R' group is selected from C. 10 ~C 20 Straight-chain or branched alkyl groups, containing 1 to 3 carbon-carbon double bonds. 10 ~C 20 The aldehydes are straight-chain or branched alkenyl groups; the C1 to C6 aldehydes are selected from formaldehyde or paraformaldehyde.

6. The preparation method according to claim 4, characterized in that, The compound of formula (X) is selected from one or more of p-hydroxyphenylboronic acid, 3-tert-butylp-hydroxyphenylboronic acid, and 3,5-di-tert-butylp-hydroxyphenylboronic acid; the compound of formula (Y) is selected from 3-methylphenol, 3-ethylphenol, 3-propylphenol, 3-butylphenol, 3-pentylphenol, 3-hexylphenol, 3-heptylphenol, 3-octylphenol, 3-nonylphenol, 3-decylphenol, 3-undecylphenol, 3-dodecylphenol, 3-tetrazylphenol, 3-tetradecylphenol, 3-pentadecanylphenol, 3-pentadecanylphenol, 3-(pentadecan-8-enyl)phenol, 3-(pentadecan-8,11-dienyl)phenol, 3 -(pentadecanyl-8,11,14-trienyl)phenol, 3-hexadecylphenol, 3-heptadecylphenol, 3-octadecylphenol, 3-nonadecanylphenol, 3-eicosylphenol, 3-monodecylphenol, 3-monodecylphenol, 3-monodidecylphenol, 3-monotridecylphenol, 3-monotetradecylphenol, 3-monopentylphenol, 3-monohexadecylphenol, 3-monooctadecylphenol, 3-monononadecanylphenol, and 3-trianedecylphenol; wherein the C1 to C6 aldehyde is selected from one or more of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentaldehyde, and hexanal.

7. The preparation method according to claim 4, characterized in that, The molar ratio between compound (X), compound (Y) and C1-C6 aldehydes is 1:0.05-6:0.05-10 (preferably 1:0.1-3:0.1-5); the reaction temperature between compound (X), compound (Y) and C1-C6 aldehydes is 40℃-160℃ (preferably 50℃-120℃); the reaction time between compound (X), compound (Y) and C1-C6 aldehydes is 1-10h (preferably 3-7h).

8. The preparation method according to claim 4, characterized in that, In the reaction of compound (X) and compound (Y) with aldehydes of C1 to C6, an alkaline catalyst is added, wherein the alkaline catalyst is selected from one or more of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and ammonia water.

9. The preparation method according to claim 4, characterized in that, A surfactant is added to the reaction of compound (X) or compound (Y) with aldehydes of C1 to C6, wherein the surfactant is selected from one or more of alkyl sulfates, alkyl sulfonates, polyethylene glycol, haloalkylpyridines and ammonium halide quaternary ammonium salts.

10. The organoboron compound according to any one of claims 1 to 3 or the organoboron compound prepared according to any one of claims 4 to 9 is used as an antioxidant, anti-wear agent, or corrosion inhibitor for lubricating oils.

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