Phosphate ester and / or phosphate ester amine salt as well as preparation method and application thereof

Abstract

The invention provides phosphate and / or phosphate amine salt as well as a preparation method and application thereof. The structure of the phosphate ester and / or phosphate ester amine salt is as shown in a formula (I): # imgabs0 #, in the formula (I), each R1 group is independently selected from H, C1-C30 straight chain or branched chain alkyl, C3-C30 cycloalkyl, C7-C30 alkyl phenyl and C7-C30 alkoxy phenyl, an R2 group is selected from C8-C30 straight chain or branched chain alkyl, and n is any number between 0 and 4.4; in the formula (I), m R1 groups are respectively and independently selected from straight chain or branched chain alkyl of C1 to C30, naphthenic base of C3 to C30, alkyl phenyl of C7 to C30 and alkoxy phenyl of C7 to C30, and m is any number between 1 and 4. The phosphate ester and / or phosphate ester amine salt provided by the invention has excellent wear resistance, friction reduction performance and extreme pressure performance, and has better corrosion resistance.

Description

Technical Field

[0001] The present invention relates to a phosphate ester and / or a phosphate ester amine salt, and in particular to a phosphate ester and / or a phosphate ester amine salt which has good anti-wear and friction-reducing properties, extreme pressure properties and better corrosion resistance and is suitable for being used as an extreme pressure and anti-wear agent for lubricating oil. Background Art

[0002] With the rapid development of equipment manufacturing industries such as high-speed rail, robots, large and heavy helicopters, and wind turbines, the requirements for thermal stability, load, and corrosion resistance of lubricants have also been further improved. As one of the core technologies in the field of lubricants, extreme pressure anti-wear agents are crucial to improving the anti-wear, extreme pressure, and corrosion resistance of lubricants. Sulfur-based extreme pressure anti-wear agents often have a higher load-bearing capacity, but since the manufacturing industry has higher requirements for the corrosion resistance of lubricants, extreme pressure anti-wear agents containing corrosive elements such as sulfur and chlorine in the existing technology are difficult to meet the requirements.

[0003] In recent years, phosphorus-based extreme pressure anti-wear agents have become a research hotspot for scholars at home and abroad. Phosphorus-based extreme pressure anti-wear agents mainly include phosphites, acidic phosphates and neutral phosphates. Since the hydrolysis stability of phosphites needs to be improved and neutral phosphates have problems such as insufficient activity, acidic phosphates have gradually become the main research direction. At present, common acidic phosphate amine salt additives on the market include 349 additives from BASF of Germany, T349 additives from Hangzhou Shitan Chemical Co., Ltd., and T349 additives from Shenyang Hualun Lubricant Additives Co., Ltd.

[0004] US 5354484 discloses a phosphate compound obtained by reacting phosphorus pentoxide with compounds such as alkyl alcohols and alkyl phenols, and further reacting the phosphate compound with an organic amine to finally prepare a phosphate amine salt compound for improving the lubricity of lubricating oil.

[0005] US 5552068 discloses a phosphate amine salt compound, wherein several phosphate amine salt compounds are prepared and synthesized by introducing organic amines of different structures into commercial neutral phosphate esters and acidic phosphate esters, and the phosphate amine salt compounds are added to mineral oil to improve oxidation stability and wear resistance.

[0006] Although phosphorus-based extreme pressure anti-wear agents have lower corrosiveness than sulfur-based extreme pressure anti-wear agents, further improving their extreme pressure and anti-wear properties is still a research and development direction for those skilled in the art. Summary of the invention

[0007] The invention provides a phosphate ester and / or a phosphate ester amine salt and a preparation method and application thereof.

[0008] The phosphoric acid ester and / or phosphoric acid ester amine salt of the present invention has a structure as shown in formula (I):

[0009]

[0010] In formula (I), each R1 group is independently selected from H, C1 to C 30 Straight or branched alkyl, C3~C 30 Cycloalkyl, C7~C 30 Alkylphenyl, C7~C 30 Alkoxyphenyl, R2 group is selected from C8~C 30 wherein n is any number between 0 and 4.4; and wherein m R1 groups in formula (I) are independently selected from C1 to C 30 Straight or branched alkyl, C3~C 30 Cycloalkyl, C7~C 30 Alkylphenyl, C7~C 30 The alkoxyphenyl group is an alkoxyphenyl group, wherein m is any number between 1 and 4.

[0011] According to the present invention, n may be any number between 1 and 4, for example, any number between 1 and 2, any number between 2 and 3, or any number between 3 and 4.

[0012] According to the present invention, m can be any number between 1 and 4, for example, it can be 1, 1.5, 2, 2.5, 3, 3.5, 4, or any number between 1 and 2, any number between 2 and 3, or any number between 3 and 4.

[0013] According to the present invention, the C7~C 30 The alkylphenyl group may be selected from the following groups: 4-eicosylphenyl, 4-nonadecylphenyl, 4-octadecylphenyl, 4-heptadecylphenyl, 4-hexadecylphenyl, 4-pentadecylphenyl, 4-tetradecylphenyl, 4-tridecylphenyl, 4-dodecylphenyl, 4-undecylphenyl, 4-decylphenyl, 4-nonylphenyl, 4-octylphenyl, 4-heptylphenyl, 4-hexylphenyl, 4-pentylphenyl, 4-butylphenyl, 4-propylphenyl, 4-ethylphenyl, 4-methylphenyl, 4-sec-octylphenyl; the C7-C 30 The alkoxyphenyl group may be selected from the following groups: 4-eicosyloxyphenyl, 4-nonadecyloxyphenyl, 4-octadecyloxyphenyl, 4-heptadecyloxyphenyl, 4-hexadecyloxyphenyl, 4-pentadecyloxyphenyl, 4-tetradecyloxyphenyl, 4-tridecyloxyphenyl, 4-dodecyloxyphenyl, 4-undecyloxyphenyl, 4-decyloxyphenyl, 4-nonyloxyphenyl, 4-octyloxyphenyl, 4-heptyloxyphenyl, 4-hexyloxyphenyl, 4-pentyloxyphenyl, 4-butoxyphenyl, 4-propoxyphenyl, 4-ethoxyphenyl, 4-methoxyphenyl.

[0014] According to the present invention, the R2 group can be selected from tert-butyl, tert-hexyl, 1,1,3,3-tetramethylbutyl, 2-decyltetradecyl, preferably 1,1,3,3-4-methylbutyl, 2-decyltetradecyl.

[0015] According to the present invention, the phosphate ester and / or phosphate amine salt may be any group of compounds in the following group (a), group (b), group (c), group (d) or a composition obtained by combining them in any proportion:

[0016]

[0017] The method for preparing the phosphate ester and / or phosphate amine salt of the present invention comprises the following step (1) and optional step (2):

[0018] (1) allowing methylene diphosphoric acid to undergo an esterification reaction with R1OH, and collecting the esterification product; wherein the R1 group is selected from C1 to C 30 Straight or branched alkyl, C3~C 30 Cycloalkyl, C7~C 30 Alkylphenyl, C7~C 30 Alkoxyphenyl;

[0019] (2) subjecting the esterification product of step (1) to an amination reaction with H2N-R2, and collecting the product; wherein the R2 group is selected from C8 to C 30 A straight chain or branched chain alkyl group.

[0020] According to the present invention, an exemplary reaction formula for the preparation method of the phosphate ester and / or phosphate amine salt is as follows:

[0021]

[0022] According to the preparation method of the present invention, optionally, in step (1), the molar ratio of methylene diphosphoric acid to R1OH is 1:1.1-4.1; the temperature for the esterification reaction of methylene diphosphoric acid and R1OH is -30°C-50°C; and the time for the esterification reaction of methylene diphosphoric acid and R1OH is 2-24h.

[0023] According to the preparation method of the present invention, optionally, in step (1), a catalyst can be added to the esterification reaction of the methylene diphosphoric acid and R1OH, and the catalyst can be one or more of concentrated sulfuric acid, p-toluenesulfonic acid, pyridine, picoline, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and the molar ratio of each catalyst to methylene diphosphoric acid can be 1:0.15 to 4.1.

[0024] According to the preparation method of the present invention, optionally, in step (2), the molar ratio between the esterification product of step (1) and H2N-R2 is 1:0-4.1, for example, it can be 1:1-4.1, 1:0-1, 1:1-2, 1:2-3, 1:3-4; the temperature of the amination reaction between the esterification product of step (1) and H2N-R2 is 40-120°C; the time for the amination reaction between the esterification product of step (1) and H2N-R2 is generally as long as possible, generally 0.5-20h; the pressure of the amination reaction between the esterification product of step (1) and H2N-R2 can be low pressure, normal pressure or high pressure, and there is no special limitation.

[0025] According to the preparation method of the present invention, preferably, in step (2), the esterification product of step (1) is first reacted with H2N-R2 at 40-90°C for 1-6 hours (preferably at 40-80°C for 2-4 hours), and then reacted at 90-120°C for 1-6 hours (preferably at 90-100°C for 2-4 hours).

[0026] According to the preparation method of the present invention, optionally, a solvent is added to the reaction in step (1), and the solvent may be an aprotic non-polar solvent or a polar solvent, for example, one or more of hexane, cyclohexane, petroleum ether, dichloromethane, 1,4-dioxane, N,N'-dimethylformamide, and tetrahydrofuran. The amount of the solvent added may be appropriate to promote the smooth progress of the reaction, and there is no particular limitation. For example, the ratio between the weight of the solvent and the total weight of the methylene diphosphoric acid and R1OH may be 10 to 20:1. The solvent may be removed by conventional methods in the art after the reaction is completed, such as distillation, rectification, etc.

[0027] According to the preparation method of the present invention, optionally, a solvent is added to the reaction in step (2), and the solvent is preferably a hydrocarbon solvent, more preferably an aromatic solvent, for example, one or more of toluene, xylene, petroleum ether, n-hexane, and cyclohexane. The amount of the solvent added can be appropriate to promote the smooth progress of the reaction, and there is no special limitation. For example, the ratio between the weight of the solvent and the total weight of the esterification product and H2N-R2 of step (1) can be 0.5 to 10:1. The solvent can be removed by conventional methods in the art after the reaction is completed, such as distillation, rectification, etc.

[0028] According to the preparation method of the present invention, optionally, the R1OH can be selected from C1 to C 30 Fatty alcohols, C7~C 30 Aromatic alcohols, C7~C 30The alkoxy aromatic alcohol may be selected from ethanol, n-butanol, hexanol, isooctyl alcohol, nonanol, dodecanol, 1-octanol, 1-decanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, oleyl alcohol, linoleyl alcohol, phytol, triacontanol, lauryl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, 4-eicosylphenol, 4-nonadecylphenol, 4-octadecylphenol, 4-heptadecylphenol, 4-hexadecylphenol, 4-pentadecylphenol, 4-tetradecylphenol, 4-tridecylphenol, 4-dodecylphenol, 4-undecylphenol, 4-decylphenol, 4-nonylphenol, 4-octylphenol, 4-heptylphenol, 4-hex ...ylphenol, 4-pentylphenol, 4-pentylphenol, 4-decylphenol, 4-nonylphenol, 4-octylphenol, 4-heptylphenol, 4-hexylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentylphenol, 4-pentyl The invention can be selected from the group consisting of phenol, 4-butylphenol, 4-propylphenol, 4-ethylphenol, 4-methylphenol, 4-sec-octylphenol, 4-eicosyloxyphenol, 4-nonadecyloxyphenol, 4-octadecyloxyphenol, 4-heptadecyloxyphenol, 4-hexadecyloxyphenol, 4-pentadecyloxyphenol, 4-tetradecyloxyphenol, 4-tridecyloxyphenol, 4-dodecyloxyphenol, 4-undecyloxyphenol, 4-decyloxyphenol, 4-nonyloxyphenol, 4-octyloxyphenol, 4-heptyloxyphenol, 4-hexyloxyphenol, 4-pentyloxyphenol, 4-butoxyphenol, 4-propoxyphenol, 4-ethoxyphenol, and 4-methoxyphenol.

[0029] According to the preparation method of the present invention, optionally, the H2N-R2 can be selected from C8 to C 30 The straight-chain or branched alkylamine can be selected from one or more of n-octylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, n-eicosylamine, n-docosylamine, n-triacontylamine, 1,1,3,3-tetramethylbutylamine, 1,1,3,3,5,5-hexamethylhexylamine, 1,1,3,3,5,5,7,7,9,9-decamethyldecylamine and 2-decyltetradecylamine.

[0030] According to the preparation method of the present invention, preferably, the reaction of step (1) and / or step (2) is carried out under the protection of an inert gas, and the inert gas may be nitrogen or argon.

[0031] According to the preparation method of the present invention, optionally, after the reaction of step (1) and / or step (2) is completed, the reaction product can be purified, and the purification method includes one or more of water washing, extraction, distillation, rectification, molecular distillation, filtration, drying and recrystallization methods, without particular limitation.

[0032] According to the preparation method of the present invention, optionally, after the reaction of step (1) is completed, the reaction product can be subjected to extraction treatment, and the extractant used can be one or more of diethyl ether, ethyl acetate, and dichloromethane.

[0033] According to the preparation method of the present invention, as a reaction product, a phosphate ester and / or a phosphate amine salt of a single structure can be prepared, and a mixture consisting of phosphate esters and / or phosphate amine salts of multiple structures can also be prepared. These reaction products are all expected by the present invention, and the difference in their existence forms does not affect the realization of the effect of the present invention. Therefore, in the context of this specification, these reaction products are all collectively referred to as phosphate esters and / or phosphate amine salts without distinction. In view of this, according to the present invention, there is no absolute necessity to further purify the reaction product, or to further separate a phosphate ester and / or a phosphate amine salt of a specific structure from the reaction product. Of course, this purification or separation is preferred for further improvement of the expected effect of the present invention, but it is not necessary for the present invention. Nevertheless, as the purification or separation method, for example, the reaction product can be purified or separated by a silica gel column chromatography method or a preparative chromatography method.

[0034] The phosphate ester and / or phosphate amine salt of the present invention and the phosphate ester and / or phosphate amine salt prepared according to the preparation method of the present invention can be used as an extreme pressure antiwear agent for lubricating oil.

[0035] The phosphate ester and / or phosphate amine salt of the present invention has excellent anti-wear performance, friction reduction performance, extreme pressure performance, and has better corrosion resistance.

[0036] The present invention also provides a lubricating oil composition, comprising a base oil, the above-mentioned phosphate ester and / or phosphate amine salt or the phosphate ester and / or phosphate amine salt prepared according to the above-mentioned method, wherein the phosphate ester and / or phosphate amine salt may account for 0.05% to 5% of the total mass of the lubricating oil composition.

[0037] The lubricating oil composition of the present invention has excellent anti-wear performance, friction reduction performance, extreme pressure performance, and better corrosion resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is the mass spectrum of product 1 in Example 1 of the present invention.

[0039] Figure 2 It is the mass spectrum of product 2 in comparative example 1 of the present invention.

[0040] Figure 3 It is the mass spectrum of product 3 in Example 2 of the present invention.

[0041] Figure 4 It is the mass spectrum of product 4 in comparative example 2 of the present invention. DETAILED DESCRIPTION

[0042] The present invention is explained and illustrated below through specific implementation modes, but it does not constitute a limitation of the present invention.

[0043] Main raw materials used and their sources:

[0044] Methylene diphosphonic acid (95%, Jiangxi Ruiweier Biotechnology Co., Ltd.), methylphosphonic acid (98%, Chongqing Zhangbang Pharmaceutical Technology Co., Ltd.), 2-ethylhexanol (99%, Aladdin Industrial Corporation), 1,1,3,3-tetramethylbutylamine (95%, Acros Organics), 2-decyltetradecylamine (95%, Suzhou Nakai Technology Co., Ltd.), 4-dimethylaminopyridine (99%, TCI (Shanghai) Chemical Industry Development Co., Ltd.), triethylamine (99%, ThermoScientific), dicyclohexylcarbodiimide (98%, TCI (Shanghai) Chemical Industry Development Co., Ltd.), toluene (AR, Tianjin Damao Chemical Reagent Factory), xylene (AR, Tianjin Damao Chemical Reagent Factory), dichloromethane (99%, Beijing Inokai Technology Co., Ltd.), ethyl acetate (99%, Beijing Inokai Technology Co., Ltd.), anhydrous sodium sulfate (98%, Shanghai Maclean Biochemical Technology Co., Ltd.), sodium bicarbonate (98%, Shanghai Maclean Biochemical Technology Co., Ltd.), sodium chloride (98%, Shanghai Maclean Biochemical Technology Co., Ltd.), V81 (4,4-di-tert-octyl diphenylamine) (Vanderbilt Company), T706 (benzotriazole) (Nanjing Ningjiang Chemical Plant), 9PE-8 polyol ester base oil (self-made in the laboratory).

[0045] The reaction equation for preparing the 9PE-8 polyol ester base oil is as follows:

[0046]

[0047] The preparation method of the 9PE-8 polyol ester base oil is as follows:

[0048] Dipentaerythritol (180.05g, 0.7106mol, 1eq), valeric acid (260.5336g, 2.551mol, 3.6eq), hexanoic acid (118.5297g, 1.0204mol, 1.44eq), heptanoic acid (66.4178g, 0.5102mol, 0.72eq), octanoic acid (147.1533g, 1.0204mol, 1.44eq), p-toluenesulfonic acid (7.12g) were added sequentially to a 1000ml reaction bottle with mechanical stirring, nitrogen conduit, thermometer, spherical condenser and water separator. The temperature was gradually raised to 200°C, the water output was observed and recorded, and the water separator was heated until no condensed water appeared. Stirring and heating were stopped, the mixture was cooled to room temperature, filtered, the filtrate was collected, and the excess acid was removed by vacuum distillation. The solution was washed with KOH aqueous solution of appropriate concentration, residual alkali solution was removed by water washing, and the solution was dehydrated and decolorized to prepare 9PE-8 polyol ester base oil.

[0049] Taking isooctyl alcohol as an example, the reaction equation for preparing phosphate ester is as follows:

[0050]

[0051] After the above reaction, the reaction product of the phosphate ester prepared by the present invention includes product A, product B, product C, and product D, which is a mixture. This mixture can be used for the next reaction without separation.

[0052] Taking 1,1,3,3-tetramethylbutylamine and the above product as examples, the reaction equation for preparing phosphate amine salts of the present invention is as follows:

[0053]

[0054] Example 1

[0055] The main raw materials include: methylene diphosphoric acid, 2-ethylhexanol, triethylamine, 4-dimethylaminopyridine, dicyclohexylcarbodiimide, dichloromethane, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0056] The reaction steps for preparing phosphate compounds are as follows:

[0057] Disperse methylene diphosphoric acid (1 g, 5.68 mmol, 1.0 eq) in 30 ml of dry dichloromethane, add to the reaction bottle, introduce N2 protection, stir, ice-water bath to 0-5°C, add dicyclohexylcarbodiimide (4.8075 g, 23.30 mmol, 4.1 eq), stir at 0-5°C for 30 min, add 2-ethylhexanol (3.0337 g, 23.30 mmol, 4.1 eq), 4-dimethylaminopyridine (0.4270 g, 3.495 mmol, 0.15 eq), triethylamine (0.3537 g, 3.495 mmol, 0.15 eq), maintain stirring at 0-5 ° C for 1 h, and then continue to stir and react at room temperature for 24 h. During the reaction, white solid (dicyclohexylurea) is continuously precipitated from the clear and transparent reaction solution. After the reaction is completed, the white solid is filtered out, the reaction solution is washed with saturated sodium bicarbonate solution, and the liquid is extracted with ethyl acetate. The organic phase is collected, washed with saturated brine, and dried with anhydrous sodium sulfate. The solvent and residual 2-ethylhexanol are filtered and evaporated to obtain product 1 as a light yellow liquid.

[0058] Structural characterization of product 1 in Example 1

[0059] The product 1 was analyzed by mass spectrometry. Figure 1 .

[0060] The mass spectrometry conditions were as follows:

[0061] Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS), model Bruker SolariX XR, magnetic field strength 15T. Experimental conditions are: injection rate 120μL / h, electrospray ion source, positive ion mode (ESI+), capillary voltage 4500V, nebulizer 1bar, drying gas flow rate 4.0L / min, dryer temperature 200℃, TOF 0.6ms, Q1 mass 150u, RF 800Vpp, front and rear baffle voltage 1.8V, SEP (Sweep Excitation Power) 15, mass-to-charge ratio (m / z) detection range 50-1500, and cumulative scanning 64 times during sampling. Sample preparation: Prepare about 0.1mg / mL sample with chromatographic pure methanol.

[0062] The relative molecular mass of tetra-isooctyl methylene diphosphate is 624.46, and the relative molecular mass of tri-isooctyl methylene diphosphate is 512.34. Figure 1 The mass spectrometry absorption peak with a mass-to-charge ratio of 625.47204 is the product 1 containing tetra-isooctyl methylene diphosphate combined with one H + The mass spectrometry absorption peak with a mass-to-charge ratio of 647.453985 is the product 1 tetraisooctyl methylene diphosphate combined with a Na +The molecular ion peak (Na + from the mass spectrometry ion source); the mass spectrometry absorption peak with a mass-to-charge ratio of 513.34684 is the product 1 tri-isooctyl methylene diphosphate combined with one H + The mass spectrometry absorption peak with a mass-to-charge ratio of 535.328784 is the product 1 tri-isooctyl methylene diphosphate combined with a Na + The molecular ion peak (Na + from the mass spectrometer ion source).

[0063] In summary, product 1 is a mixture of two compounds shown in the following formula.

[0064]

[0065] Comparative Example 1

[0066] The main raw materials include: methylphosphonic acid, 2-ethylhexanol, 4-dimethylaminopyridine, dicyclohexylcarbodiimide, dichloromethane, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0067] The reaction steps for preparing the comparative phosphate ester compounds are as follows:

[0068] Disperse methylphosphoric acid (2 g, 22.828 mmol, 1.0 eq) in 60 ml dry dichloromethane, add to the reaction bottle, introduce N2 protection, stir, ice-water bath to 0-5°C, add dicyclohexylcarbodiimide (4.5123 g, 21.8694 mmol, 1.05 eq), stir at 0-5°C for 30 min, add 2-ethylhexanol (5.6960 g, 43.7388 mmol, 2.1 eq), 4-dimethylaminopyridine (0.3817 g, 5.207 mmol, 0.15 eq), Triethylamine (0.5269 g, 5.207 mmol, 0.15 eq) was added, stirring was maintained at 0-5°C for 1 h, and then stirring was continued at room temperature for 24 h. During the reaction, white solid (dicyclohexylurea) was continuously precipitated from the clear and transparent reaction solution. After the reaction, the white solid was filtered out, and the reaction solution was washed with saturated sodium bicarbonate solution. The liquid was extracted with ethyl acetate, and the organic phase was collected. The organic phase was washed with saturated brine, and the organic phase was dried with anhydrous sodium sulfate. The organic phase was filtered, and the solvent and residual 2-ethylhexanol were removed by rotary evaporation to obtain product 2 as a light yellow liquid.

[0069] Characterization of Product 2 in Comparative Example 1

[0070] The product 2 was analyzed by mass spectrometry. Figure 2 The mass spectrometry conditions were the same as those for product 1.

[0071] The relative molecular mass of 2-ethylhexyl methylphosphonate is 208.12, and the relative molecular mass of 2-ethylhexyl methylphosphonate is 320.25. Figure 2 The mass spectrometry absorption peak with a mass-to-charge ratio of 209.130108 is the product 2 containing isooctyl methylphosphonate combined with one H + The mass spectrometry absorption peak with a mass-to-charge ratio of 231.112052 is the product 2 of isooctyl methylphosphonate combined with a Na + The mass spectrometry absorption peak with a mass-to-charge ratio of 321.255309 is the product 2 of diisooctyl methylphosphonate combined with one H + The mass spectrometry absorption peak with a mass-to-charge ratio of 343.237253 is the product 2 of diisooctyl methylphosphonate combined with a Na + In summary, product 2 is a mixture of two compounds shown in the following formula.

[0072]

[0073] Example 2

[0074] The main raw materials include: methylene diphosphoric acid, p-methylphenol, triethylamine, 4-dimethylaminopyridine, dicyclohexylcarbodiimide, dichloromethane, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0075] The reaction steps for preparing the phosphate compounds of the present invention are as follows:

[0076] Disperse methylene diphosphoric acid (1 g, 5.68 mmol, 1.0 eq) in 40 ml of dry dichloromethane, add to the reaction bottle, introduce N2 protection, stir, ice-bath to 0-5°C, add dicyclohexylcarbodiimide (4.8075 g, 23.30 mmol, 4.1 eq), stir at 0-5°C for 30 min, add p-methylphenol (2.4884 g, 23.01 mmol, 4.05 eq), 4-dimethylaminopyridine (0.4270 g, 3.495 mmol, 0.15 eq) and 4-dimethylaminopyridine (0.4270 g, 3.495 mmol, 0.15 eq). ), triethylamine (0.3537 g, 3.495 mmol, 0.15 eq), stirring was maintained at 0-5°C for 1 h, and then stirring was continued at room temperature for 24 h. During the reaction, white solids were continuously precipitated from the clear and transparent reaction solution. After the reaction, the white solids were filtered out, the reaction solution was washed with saturated sodium bicarbonate solution, and the liquid was separated by extraction with ethyl acetate. The organic phase was collected, washed with saturated brine, and dried with anhydrous sodium sulfate. The solvent and residual p-methylphenol were removed by filtration and rotary evaporation to obtain product 3 as a light yellow liquid.

[0077] Characterization of Product 3 in Example 2

[0078] The product 3 was analyzed by mass spectrometry. Figure 3 The mass spectrometry conditions were the same as those for product 1.

[0079] The relative molecular mass of tetracresol methylene diphosphate is 536.15, and the relative molecular mass of tricresol methylene diphosphate is 446.10. Figure 3 The mass spectrometry absorption peak with a mass-to-charge ratio of 537.160235 is the product 3 containing tetramethyl methylene diphosphate combined with one H + The mass spectrometry absorption peak with a mass-to-charge ratio of 559.141312 is the product 3 of tetramethyl methylene diphosphate combined with a Na + The mass spectrometry absorption peak with a mass-to-charge ratio of 447.112808 is the product 3 of trimethylol methylene diphosphate combined with one H + The mass spectrometry absorption peak with a mass-to-charge ratio of 469.094106 is the product 3 of trimethylol methylene diphosphate combined with a Na + In summary, product 3 is a mixture of two compounds shown in the following formula.

[0080]

[0081] Comparative Example 2

[0082] The main raw materials include: methylphosphonic acid, p-methylphenol, 4-dimethylaminopyridine, dicyclohexylcarbodiimide, dichloromethane, ethyl acetate, anhydrous sodium sulfate, sodium chloride, and sodium bicarbonate.

[0083] The reaction steps for preparing the comparative phosphate ester compounds are as follows:

[0084] Disperse methylphosphoric acid (1 g, 11.41 mmol, 1.0 eq) in 40 ml of dry dichloromethane, add to the reaction bottle, introduce N2 protection, stir, ice-water bath to 0-5°C, add dicyclohexylcarbodiimide (4.5123 g, 21.8694 mmol, 2.1 eq), stir at 0-5°C for 30 min, add p-methylphenol (2.3650 g, 21.87 mmol, 2.1 eq), 4-dimethylaminopyridine (0.1907 g, 1.5615 mmol, 0.15 eq), triethylamine (0.200 g, 1.5 eq), 4-nitropropene (0.200 g, 1.5 eq), 1.2-naphthene (0.200 g, 1.5 eq), 1.6 ... Amine (0.1580 g, 1.5615 mmol, 0.15 eq) was added and stirred at 0-5 °C for 1 h, and then stirred at room temperature for 24 h. During the reaction, white solid (dicyclohexylurea) was continuously precipitated from the clear and transparent reaction solution. After the reaction, the white solid was filtered out and the reaction solution was washed with saturated sodium bicarbonate solution. The liquid was extracted with ethyl acetate, the organic phase was collected, washed with saturated brine, dried with anhydrous sodium sulfate, filtered and evaporated to remove the solvent and residual p-methylphenol to obtain product 4 as a light yellow liquid.

[0085] Characterization of Product 4 in Comparative Example 2

[0086] The product 4 was analyzed by mass spectrometry. Figure 4 The mass spectrometry conditions were the same as those for product 1.

[0087] The relative molecular mass of di-p-cresyl methylphosphonate is 276.09, and the relative molecular mass of p-cresyl methylphosphonate is 186.15. Figure 4 The mass spectrometry absorption peak with a mass-to-charge ratio of 277.098988 is the product 4 containing di-p-cresol methylphosphonate combined with one H + The mass spectrometry absorption peak with a mass-to-charge ratio of 299.080302 is the product 4 of di-p-cresol methylphosphonate combined with a Na + The mass spectrometry absorption peak with a mass-to-charge ratio of 187.156032 is the product 4 of methylphosphonic acid p-cresol ester combined with one H + The mass spectrometry absorption peak with a mass-to-charge ratio of 209.157901 is the product 4 of methylphosphonic acid p-cresol ester combined with a Na + In summary, product 4 is a mixture of two compounds shown in the following formula.

[0088]

[0089] Example 3

[0090] The main raw materials include: product 1, 1,1,3,3-tetramethylbutylamine and xylene.

[0091] The reaction steps for preparing the phosphate amine salt compound of the present invention are as follows:

[0092] The product 1 (1 g) was dispersed in 30 ml of xylene solution and added to a reaction bottle equipped with magnetic stirring, nitrogen conduit, spherical condenser and constant pressure dropping funnel; a xylene (5 ml) solution containing 1,1,3,3-tetramethylbutylamine (0.4654 g, 3.60 mmol) was prepared and poured into a constant pressure dropping funnel; the reaction bottle was placed in a 40°C constant temperature oil bath, magnetic stirring was turned on and N2 protection was introduced, and the xylene solution of 1,1,3,3-tetramethylbutylamine was added dropwise thereto. After the dropwise addition, the mixture was stirred at this temperature for 2 h, then the temperature was raised to 90°C and stirred at this temperature for 4 h, and the xylene was removed from the mixture after the reaction by rotary evaporation to obtain the product 5. The acid value determination results in Table 3 below show that the product is a mixture of tri-isooctyl methylene diphosphate-1,1,3,3-tetramethylbutylamine salt and tetra-isooctyl methylene diphosphate as shown in the following formula, which is a light yellow viscous liquid.

[0093]

[0094] Comparative Example 3

[0095] The main raw materials include: product 2, 1,1,3,3-tetramethylbutylamine, and xylene.

[0096] The reaction steps for preparing the comparative phosphate amine salt compound are as follows:

[0097] The product 2 (1 g) was dispersed in 30 ml of xylene solution and added to a reaction bottle equipped with magnetic stirring, nitrogen conduit, spherical condenser and constant pressure dropping funnel; a xylene (15 ml) solution of 1,1,3,3-tetramethylbutylamine (0.1891 g, 1.463 mmol) was prepared and poured into a constant pressure dropping funnel; the reaction bottle was placed in a 40°C constant temperature oil bath, magnetic stirring was turned on and N2 protection was introduced, and the xylene solution of 1,1,3,3-tetramethylbutylamine was added dropwise thereto. After the dropwise addition, the mixture was stirred at this temperature for 2 h, then the temperature was raised to 90°C and stirred at this temperature for 4 h, and the xylene was removed from the mixture after the reaction by rotary evaporation to obtain the product 6. The acid value determination results in Table 3 below show that the product is a mixture of methylphosphonic acid isooctyl ester-1,1,3,3-tetramethylbutylamine salt and methylphosphonic acid diisooctyl ester as shown in the following formula, which is a light yellow viscous liquid.

[0098]

[0099] Example 4

[0100] The main raw materials include: product 3, 1,1,3,3-tetramethylbutylamine, and xylene.

[0101] The reaction steps for preparing the phosphate amine salt compound of the present invention are as follows:

[0102] The product 3 (1 g) was dispersed in 30 ml of xylene solution and added to a reaction bottle equipped with magnetic stirring, nitrogen conduit, spherical condenser and constant pressure dropping funnel; a xylene solution of 1,1,3,3-tetramethylbutylamine (0.3185 g, 2.46 mmol) (5 ml) was prepared and poured into the constant pressure dropping funnel; the reaction bottle was placed in a 40°C constant temperature oil bath, magnetic stirring was turned on and N2 protection was introduced, and the xylene solution of 1,1,3,3-tetramethylbutylamine was added dropwise thereto. After the dropwise addition, the mixture was stirred at this temperature for 2 h, then the temperature was raised to 90°C and stirred at this temperature for 4 h, and the xylene was removed from the mixture after the reaction by rotary evaporation to obtain the product 7. The acid value determination results in Table 3 below show that the product is a mixture of methylene diphosphate trimethylol ester-1,1,3,3-tetramethylbutylamine salt and methylene diphosphate tetramethylol ester as shown in the following formula, which is a light yellow viscous liquid.

[0103]

[0104] Comparative Example 4

[0105] The main raw materials include: product 4, 1,1,3,3-tetramethylbutylamine, and xylene.

[0106] The reaction steps for preparing the comparative phosphate amine salt compound are as follows:

[0107] The product 4 (1 g) was dispersed in 30 ml of xylene solution and added to a reaction bottle equipped with magnetic stirring, nitrogen conduit, spherical condenser and constant pressure dropping funnel; a xylene (15 ml) solution of 1,1,3,3-tetramethylbutylamine (0.7637 g, 5.91 mmol) was prepared and poured into a constant pressure dropping funnel; the reaction bottle was placed in a 40°C constant temperature oil bath, magnetic stirring was turned on and N2 protection was introduced, and the xylene solution of 1,1,3,3-tetramethylbutylamine was added dropwise thereto. After the dropwise addition, the mixture was stirred at this temperature for 2 h, then the temperature was raised to 90°C and stirred at this temperature for 4 h, and the xylene was removed from the mixture after the reaction by rotary evaporation to obtain the product 8. The acid value determination results in Table 3 below show that the product is a mixture of methylphosphonic acid p-cresol ester-1,1,3,3-tetramethylbutylamine salt and methylphosphonic acid dicresol ester as shown in the following formula, which is a light yellow viscous liquid.

[0108]

[0109] Performance evaluation test

[0110] The lubricating effects of products 1, 3, 5, and 7 in 9PE-8 polyol ester base oil were evaluated using a four-ball testing machine (GB / T3142-2019, NB / SH / T 0189-2017), and products 2, 4, 6, and 8 were used as comparison agents.

[0111] Products 1, 3, 5, 7 were blended with V9317 (aniline antioxidant) and 9PE-8 polyol ester base oil to obtain lubricating oil composition examples I-1 to I-4; products 2, 4, 6, 8 were blended with V9317 (aniline antioxidant) and 9PE-8 polyol ester base oil to obtain lubricating oil composition comparative examples DI-1 to DI-4. The physical and chemical properties of the 9PE-8 polyol ester base oil are shown in Table 1.

[0112] Table 1 Physical and chemical properties of 9PE-8 polyol ester base oil

[0113]

[0114] The numbers and compositions of the above lubricating oil compositions are shown in Table 2. The maximum no-seizure load (P B The results of wear spot diameter (WSD) and average coefficient of friction (COF) are shown in Table 2.

[0115] Table 2 Lubricating oil composition and performance evaluation results

[0116]

[0117] By comparing the examples with the comparative examples in Table 2, it can be seen that the methylene phosphonate and the amine salt compound thereof of the present invention have better anti-wear performance, friction reduction performance and extreme pressure performance.

[0118] Corrosion resistance evaluation test

[0119] Products 1, 3, 5, and 7 were dissolved in 9PE-8 polyol ester base oil to determine the acid value of the modulated oil sample, wherein products 1, 3, 5, and 7 accounted for 0.5% of the total weight of the oil sample, respectively, to evaluate its corrosion resistance; products 2, 4, 6, and 8 were dissolved in 9PE-8 polyol ester base oil as comparative additives to determine the acid value of the modulated oil sample, wherein products 2, 4, 6, and 8 accounted for 0.5% of the total weight of the oil sample, respectively, as a comparative example to compare the corrosion resistance. The composition and acid value evaluation results of the modulated oil sample are shown in Table 3.

[0120] Table 3 Oil sample composition and acid value evaluation results (acid value unit is mgKOH / g)

[0121]

[0122] It can be seen from the acid value data in Table 3 that the synthesized products 1 and 3 are acidic methylene phosphates, and the products 5 and 7 generated after neutralization with organic amines are neutral methylene phosphate amine salts. The synthesized products 1, 3, 5, and 7 have lower acid values ​​than the corresponding comparative examples, respectively, indicating that the methylene phosphate and methylene phosphate amine salt of the present invention have better corrosion resistance.

[0123] The above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, a person of ordinary skill in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features thereof may be replaced by equivalents.

Claims

1. Phosphate and / or amine salt of phosphate, the structure of which is shown in formula (I): In formula (I), each R1 group is independently selected from H, C1 to C 30 Straight or branched alkyl, C3~C 30 Cycloalkyl, C7~C 30 Alkylphenyl, C7~C 30 Alkoxyphenyl, R2 group is selected from C8~C 30 wherein n is any number between 0 and 4.4; and wherein m R1 groups in formula (I) are independently selected from C1 to C 30 Straight or branched alkyl, C3~C 30 Cycloalkyl, C7~C 30 Alkylphenyl, C7~C 30 The alkoxyphenyl group is an alkoxyphenyl group, wherein m is any number between 1 and 4.

2. The phosphoric acid ester and / or phosphoric acid ester amine salt according to claim 1, characterized in that: n is any number between 1 and 4.

3. The phosphoric acid ester and / or phosphoric acid ester amine salt according to claim 1, characterized in that: C7~C 30 The alkylphenyl group is selected from the following groups: 4-eicosylphenyl, 4-nonadecylphenyl, 4-octadecylphenyl, 4-heptadecylphenyl, 4-hexadecylphenyl, 4-pentadecylphenyl, 4-tetradecylphenyl, 4-tridecylphenyl, 4-dodecylphenyl, 4-undecylphenyl, 4-decylphenyl, 4-nonylphenyl, 4-octylphenyl, 4-heptylphenyl, 4-hexylphenyl, 4-pentylphenyl, 4-butylphenyl, 4-propylphenyl, 4-ethylphenyl, 4-methylphenyl, 4-sec-octylphenyl; the C7-C 30 The alkoxyphenyl group is selected from the following groups: 4-icosyloxyphenyl, 4-nonadecyloxyphenyl, 4-octadecyloxyphenyl, 4-heptadecyloxyphenyl, 4-hexadecyloxyphenyl, 4-pentadecyloxyphenyl, 4-tetradecyloxyphenyl, 4-tridecyloxyphenyl, 4-dodecyloxyphenyl, 4-undecyloxyphenyl, 4-decyloxyphenyl, 4-nonyloxyphenyl, 4-octyloxyphenyl, 4-heptyloxyphenyl, 4-hexyloxyphenyl, 4-pentyloxyphenyl, 4-butoxyphenyl, 4-propoxyphenyl, 4-ethoxyphenyl, 4-methoxyphenyl; the R2 group is selected from tert-butyl, tert-hexyl, 1,1,3,3-tetramethylbutyl, 2-decyltetradecyl.

4. The phosphoric acid ester and / or phosphoric acid ester amine salt according to claim 1, characterized in that: The phosphate ester and / or phosphate amine salt is any one of the following compounds in group (a), group (b), group (c), and group (d), or a composition obtained by combining them in any proportion: (a) (b) (c) (d) 5. The method for preparing the phosphate ester and / or phosphate amine salt according to claim 1, comprising the following step (1) and optional step (2): (1) allowing methylene diphosphoric acid to undergo an esterification reaction with R1OH, and collecting the esterification product; wherein the R1 group is selected from C1 to C 30 Straight or branched alkyl, C3~C 30 Cycloalkyl, C7~C 30 Alkylphenyl, C7~C 30 Alkoxyphenyl; (2) subjecting the esterification product of step (1) to an amination reaction with H2N-R2, and collecting the product; wherein the R2 group is selected from C8 to C 30 A straight chain or branched chain alkyl group.

6. The preparation method according to claim 5, characterized in that: In step (1), the molar ratio of methylene diphosphoric acid to R1OH is 1:1.1-4.1; the temperature for the esterification reaction of methylene diphosphoric acid and R1OH is -30°C-50°C; and the time for the esterification reaction of methylene diphosphoric acid and R1OH is 2-24 hours.

7. The preparation method according to claim 5, characterized in that: In step (1), a catalyst is added to the esterification reaction of the methylene diphosphoric acid and R1OH, and the catalyst is one or more of concentrated sulfuric acid, p-toluenesulfonic acid, pyridine, picoline, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.

8. The preparation method according to claim 5, characterized in that: In step (2), the molar ratio between the esterification product of step (1) and H2N-R2 is 1:1 to 4.1; the temperature for the amination reaction between the esterification product of step (1) and H2N-R2 is 40 to 120°C; the time for the amination reaction between the esterification product of step (1) and H2N-R2 is 0.5 to 20 hours.

9. The preparation method according to claim 5, characterized in that: The R1OH is selected from C1~C 30 Fatty alcohols, C7~C 30 Aromatic alcohols, C7~C 30 Alkoxy aromatic alcohol; the H2N-R2 is selected from C8~C 30 Straight chain or branched chain alkylamine.

10. The preparation method according to claim 5, characterized in that: The reaction of step (1) and / or step (2) is carried out under the protection of inert gas.

11. Use of the phosphate ester and / or phosphate amine salt according to any one of claims 1 to 4 or the phosphate ester and / or phosphate amine salt prepared by the preparation method according to any one of claims 5 to 10 as an extreme pressure antiwear agent for lubricating oil.

12. A lubricating oil composition comprising a base oil, a phosphoric acid ester and / or a phosphoric acid ester amine salt according to any one of claims 1 to 4, or a phosphoric acid ester and / or a phosphoric acid ester amine salt prepared by the preparation method according to any one of claims 5 to 10.

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