Emulsified oil for hydraulic support and preparation method thereof

Abstract

The invention discloses an emulsified oil for hydraulic support and a preparation method thereof, and relates to the field of oil for hydraulic support, including the following raw materials by weight: 25-35 parts of base oil, 8-10 parts of oleic acid, 9-11 parts of triethanolamine, 5-7 parts of rust inhibitor, 5-7 parts of antioxidant, 1-3 parts of polyvinyl n-butyl ether, 0.6-0.8 parts of zinc cyclohexane, 0.4-0.6 parts of ethylene-vinyl acetate copolymer, 6-8 parts of ethylene oxide propylene oxide copolymer, 6-8 parts of dodecylphenol and 25-45 parts of distilled water. The synthesized rust inhibitor molecules include benzotriazole ring, imidazole ring, diquaternary ammonium salt, alkane long chain, rosin acid ester structure, which can quickly inhibit metal rust, and also help the emulsified oil system to play an emulsifying effect more uniformly and stably. The synthesized antioxidant molecules include hindered phenol, phosphite and thiophosphate structures, so that the emulsified oil has good antioxidant, corrosion resistance and lubricity.

Description

Technical Field

[0001] The invention relates to the field of oil for hydraulic supports, and in particular to emulsified oil for hydraulic supports and a preparation method thereof. Background Art

[0002] Emulsified oil for hydraulic supports is mainly used in coal mine hydraulic supports, single hydraulic props and other systems. As a power transmission medium, it needs to have good stability, rust resistance, corrosion resistance, oxidation resistance, lubricity and other properties to effectively protect the hydraulic system and extend its service life. The existing technology generally uses multiple powerful additives to improve the performance of emulsified oil. The addition of multiple additives will inevitably bring potential problems of poor compatibility, which is not conducive to maintaining the stability of the emulsified oil system. From the perspective of environmental protection and cost, it is worth more scholars to develop suitable additives to achieve the goal of multiple uses with one dose. Summary of the invention

[0003] In order to solve the above technical problems, the present invention provides an emulsified oil for a hydraulic support and a preparation method thereof.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] An emulsified oil for a hydraulic support, comprising the following raw materials in parts by weight: 25-35 parts of base oil, 8-10 parts of oleic acid, 9-11 parts of triethanolamine, 5-7 parts of rust inhibitor, 5-7 parts of antioxidant, 1-3 parts of polyvinyl n-butyl ether, 0.6-0.8 parts of zinc cyclohexane, 0.4-0.6 parts of ethylene-vinyl acetate copolymer, 6-8 parts of ethylene oxide propylene oxide copolymer, 6-8 parts of dodecylphenol and 25-45 parts of distilled water; the base oil is 7 # Base oil;

[0006] The preparation of the emulsified oil for hydraulic support comprises the following steps:

[0007] Heat the base oil to 55-65°C, add oleic acid, triethanolamine, rust inhibitor, antioxidant, polyvinyl n-butyl ether, zinc cyclohexaneate, ethylene-vinyl acetate copolymer, ethylene oxide propylene oxide copolymer, and dodecylphenol in sequence under stirring, continue to stir and react at a constant temperature for 5-6 hours after the addition is completed, finally add distilled water, stir for 1-1.5 hours, and adjust the pH of the system to 8.5-9 with 1 mol / L sodium hydroxide solution to obtain emulsified oil for hydraulic support;

[0008] The preparation of the rust inhibitor comprises the following steps:

[0009] Step A1: 1-(2-aminoethyl)-2-(cis-8-heptadecen-1-yl)imidazoline, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then 1-methyl-1H-1,2,3-benzotriazole-5-carbonyl chloride is added to dimethyl sulfoxide to obtain a mixed solution 2. The mixed solution 2 is slowly added dropwise to the mixed solution 1 in an ice-water bath at 0°C. After the addition is completed, the temperature is raised to 40°C, and the reaction is stirred at the constant temperature for 10 hours to obtain a heterocyclic product;

[0010] Further, the usage ratio of 1-(2-aminoethyl)-2-(cis-8-heptadecen-1-yl)imidazoline, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 75-85 mL; the usage ratio of 1-methyl-1H-1,2,3-benzotriazole-5-carbonyl chloride and dimethyl sulfoxide is 0.1 mol: 45-55 mL; the usage ratio of mixed solution 1 and mixed solution 2 is 80-90 mL: 50-60 mL;

[0011] During the reaction of step A1, the amino group of 1-(2-aminoethyl)-2-(cis-8-heptadecen-1-yl)imidazoline reacts with 1-methyl-1H-1,2,3-benzotriazole-5-carbonyl chloride to generate a heterocyclic product containing a carbon-carbon double bond, benzotriazole and an imidazole ring;

[0012] Step A2: Place the heterocyclic product and ethanol in a flask, start stirring, then add 1-chlorohexane, raise the temperature to 50-60° C., stir and react at constant temperature for 10-12 hours, rotary evaporate and recrystallize with acetone, and filter to obtain a diquaternary ammonium salt;

[0013] Further, the ratio of the heterocyclic product, ethanol, and 1-chlorohexane is 0.1 mol: 135-145 mL: 0.1 mol, and the volume fraction of ethanol is 95%;

[0014] During the reaction of step A2, the tertiary amine groups of the benzotriazole and imidazole rings of the heterocyclic product react with the chlorine atoms of 1-chlorohexane to form a diquaternary ammonium salt;

[0015] Step A3: Add diquaternary ammonium salt to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, stir and react at room temperature for 4-5 hours to obtain an epoxy product; in a nitrogen atmosphere, add rosin acid and toluene to a flask, heat to 45°C, add pyridine, start stirring, add the epoxy product to the flask, stir and react for 8-10 hours, then heat to 105-115°C, stir for 1-2 hours to obtain a rust inhibitor;

[0016] Further, the usage ratio of the diquaternary ammonium salt, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol: 150-160 mL: 0.1 mol; the usage ratio of rosin acid, toluene, pyridine and epoxy product is 30-35 g: 210-220 mL: 0.020-0.025 mol: 0.1 mol;

[0017] During the reaction process of step A3, the carbon-carbon double bond in the diquaternary ammonium salt is oxidized to an epoxy group to obtain an epoxy product; the carboxyl group of the rosin acid reacts with the epoxy group of the epoxy product to form a rust inhibitor.

[0018] The preparation of the antioxidant comprises the following steps:

[0019] Step B1: Add 3-(4-bromophenyl)-1-propene to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, stir and react at room temperature for 4-5 hours to obtain epoxidized product a; in a nitrogen atmosphere, add 3,5-di-tert-butyl-4-hydroxybenzoic acid and toluene to a flask, heat to 45°C, add pyridine, start stirring, add epoxidized product a to the flask, stir and react for 8-10 hours, then heat to 110-120°C, stir for 1-2 hours to obtain bromoaryl hydrocarbon;

[0020] Further, the usage ratio of 3-(4-bromophenyl)-1-propene, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol: 45-55 mL: 0.1 mol; the usage ratio of 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluene, pyridine and epoxidation product a is 0.1 mol: 100-110 mL: 0.010-0.015 mol: 0.1 mol;

[0021] During the reaction process of step B1, the carbon-carbon double bond in 3-(4-bromophenyl)-1-propylene is oxidized to an epoxy group to obtain an epoxy product a; the carboxyl group of 3,5-di-tert-butyl-4-hydroxybenzoic acid reacts with the epoxy group of the epoxy product a to form a brominated aromatic hydrocarbon containing an alcoholic hydroxyl group;

[0022] Step B2: Add diethyl cyanomethylphosphite to tetrahydrofuran, start stirring, add Raney nickel and Pd / C, introduce hydrogen, and react under normal pressure with stirring for 48 hours to obtain an amino product; add bromoaryl, amino product and methanol to a flask, add 2-dicyclohexylphosphine-2'-4'-6'-triisopropylbiphenyl, tris(dibenzylideneacetone)dipalladium and potassium carbonate, reflux and stir at 80°C under nitrogen protection for 4-5 hours, and vacuum dry at 50°C to obtain an alcohol hydroxyl product;

[0023] Further, the usage ratio of diethyl cyanomethylphosphite, tetrahydrofuran, Raney nickel and Pd / C is 0.1 mol: 40-50 mL: 0.01 mol: 0.01-0.015 mol; the usage ratio of bromoaryl hydrocarbon, amino product, methanol, 2-dicyclohexylphosphino-2'-4'-6'-triisopropylbiphenyl, tris(dibenzylideneacetone)dipalladium and potassium carbonate is 0.12 mol: 0.06 mol: 500-550 mL: 0.0025 g: 0.0025 g: 0.15-0.18 mol;

[0024] During the reaction of step B2, the cyano group of diethyl cyanomethylphosphite is reduced to an amino group to obtain an amino product; the aromatic bromination product and the amino product undergo a dehydrobromination coupling reaction to generate an alcohol hydroxyl product containing a hindered phenol and a phosphite structure;

[0025] Step B3: Add O,O-diethyl-O-(4-nitrophenyl)thiophosphate and toluene into a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring to react for 1 hour to obtain amino product b; add xylene into a four-necked flask, pass nitrogen, add amino product b and triphosgene successively at 75°C with stirring, and after the addition is complete, heat to 125°C and continue to react for 3.5 hours to obtain isocyanate;

[0026] Further, the amount ratio of O,O-diethyl-O-(4-nitrophenyl)thiophosphate, toluene, and sodium dithionite is 0.1 mol: 65-75 mL: 0.1 mol; the amount ratio of xylene, amino product b, and triphosgene is 110 mL: 0.1 mol: 0.1 mol;

[0027] During the reaction of step B3, the nitro group of O,O-diethyl-O-(4-nitrophenyl) thiophosphate is reduced to an amino group to obtain an amino product b; the amino group of the amino product b reacts with triphosgene to generate chloroamide, which is then heated to dehydrochlorinate to generate an isocyanate containing a thiophosphate structure;

[0028] Step B4: After mixing the alcohol hydroxyl product and isocyanate, add 20% by mass of dilute sulfuric acid solution and methanol, and react at 50° C. for 4 hours to obtain an antioxidant;

[0029] Furthermore, the amount ratio of the alcohol hydroxyl product, isocyanate, 20% by mass dilute sulfuric acid solution and methanol is 0.1 mol: 0.1 mol: 100 mL: 200 mL;

[0030] During the reaction of step B4, the alcoholic hydroxyl group of the alcoholic hydroxyl product reacts with isocyanate to obtain an antioxidant.

[0031] Beneficial effects of the invention: The invention discloses an emulsified oil for hydraulic support and a preparation method thereof, comprising the following raw materials: base oil, oleic acid, triethanolamine, rust inhibitor, antioxidant, etc. The synthesized rust inhibitor comprises a benzotriazole ring, an imidazole ring, a diquaternary ammonium salt, an alkane long chain, and a rosin acid ester structure in its molecule; the quaternary ammonium cation of the diquaternary ammonium salt can be quickly adsorbed on the metal surface, so that the metal surface is positively charged, and the like repels each other, preventing the approach of hydrogen ions, and the electrochemical corrosion reaction and the movement of charges are inhibited; the benzotriazole ring and the imidazole ring are complexed with the metal, so that the energy state of the metal surface tends to be stable, the activation energy of the corrosion reaction is increased, and the corrosion rate is reduced; the alkane long chain forms a hydrophobic protective film on the metal surface, which hinders the metal from chemically reacting with the corrosive medium or transferring substances; after the rosin acid forms a rosin acid ester, its oil solubility in the emulsified oil increases, so that the emulsified oil is mixed more evenly, is not easy to be stratified, and the stability of the emulsified oil system is maintained. Adding the synthesized rust inhibitor can quickly inhibit metal rust and also help the emulsified oil system to exert its emulsification effect more evenly and stably.

[0032] The synthesized antioxidant includes hindered phenol structure, phosphite structure and thiophosphate structure in its molecule; the hindered phenol structure reacts with peroxide free radicals to generate hydroperoxide, which terminates the free radical reaction in the oxidative degradation process, while the phosphite structure can reduce and decompose the hydroperoxide. The hindered phenol structure and the phosphite structure in the same molecule work together to form a thin film on the metal surface, isolating it from contact with oxygen or other corrosive substances, preventing the metal from catalyzing the oxidation reaction of the emulsified oil, and playing an anti-corrosion role; the thiophosphate structure has a good anti-wear effect because the sulfur contained can react with iron to generate an iron sulfide film under high temperature friction, and the phosphate contained in the phosphate reacts with steel to generate a low melting point and high plasticity phosphate mixture under the interaction of the thermal decomposition product under friction, both of which have anti-wear effects, thereby enhancing the lubricity of the emulsified oil. Adding a synthetic antioxidant can make the emulsified oil have good anti-oxidation properties and good lubricity. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Embodiment 1: A rust inhibitor, the preparation of which comprises the following steps:

[0035] Step A1: 1-(2-aminoethyl)-2-(cis-8-heptadecene-1-yl)imidazoline, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then 1-methyl-1H-1,2,3-benzotriazole-5-carbonyl chloride is added to dimethyl sulfoxide to obtain a mixed solution 2. In a 0°C ice-water bath, the mixed solution 2 is slowly added dropwise to the mixed solution 1. After the addition is completed, the temperature is raised to 40°C, and the reaction is stirred at the constant temperature for 10 hours. A heterocyclic product is obtained; the dosage ratio of 1-(2-aminoethyl)-2-(cis-8-heptadecen-1-yl)imidazoline, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 75 mL; the dosage ratio of 1-methyl-1H-1,2,3-benzotriazole-5-carbonyl chloride and dimethyl sulfoxide is 0.1 mol: 45 mL; the dosage ratio of mixed solution 1 and mixed solution 2 is 80-mL: 50 mL;

[0036] Step A2: placing the heterocyclic product and ethanol in a flask, stirring, then adding 1-chlorohexane, heating to 50°C, stirring at constant temperature for 10 hours, revolving and recrystallizing with acetone, filtering, and obtaining a diquaternary ammonium salt; the amount ratio of the heterocyclic product, ethanol, and 1-chlorohexane is 0.1 mol: 135 mL: 0.1 mol, and the volume fraction of ethanol is 95%;

[0037] Step A3: Add the diquaternary ammonium salt to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, stir and react at room temperature for 4 hours to obtain the epoxy product; in a nitrogen atmosphere, add rosin acid and toluene to a flask, heat to 45°C, add pyridine, start stirring, add the epoxy product to the flask, stir and react for 8-10 hours, then heat to 105°C, stir for 1 hour to obtain the rust inhibitor; the dosage ratio of the diquaternary ammonium salt, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol: 150 mL: 0.1 mol; the dosage ratio of rosin acid, toluene, pyridine and epoxy product is 30 g: 210 mL: 0.020 mol: 0.1 mol.

[0038] Embodiment 2: A rust inhibitor, the preparation of which comprises the following steps:

[0039] Step A1: 1-(2-aminoethyl)-2-(cis-8-heptadecene-1-yl)imidazoline, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then 1-methyl-1H-1,2,3-benzotriazole-5-carbonyl chloride is added to dimethyl sulfoxide to obtain a mixed solution 2. In a 0°C ice-water bath, the mixed solution 2 is slowly added dropwise to the mixed solution 1. After the addition is completed, the temperature is raised to 40°C and the reaction is stirred at the constant temperature for 10 hours. That is, a heterocyclic product is obtained; the usage ratio of 1-(2-aminoethyl)-2-(cis-8-heptadecen-1-yl)imidazoline, potassium carbonate and dimethyl sulfoxide is 0.1 mol:0.015 mol:80 mL; the usage ratio of 1-methyl-1H-1,2,3-benzotriazole-5-carbonyl chloride and dimethyl sulfoxide is 0.1 mol:50 mL; the usage ratio of mixed solution 1 and mixed solution 2 is 85 mL:55 mL;

[0040] Step A2: placing the heterocyclic product and ethanol in a flask, stirring, then adding 1-chlorohexane, heating to 55° C., stirring at constant temperature for 11 hours, revolving and recrystallizing with acetone, filtering, and obtaining a diquaternary ammonium salt; the amount ratio of the heterocyclic product, ethanol, and 1-chlorohexane is 0.1 mol: 140 mL: 0.1 mol, and the volume fraction of ethanol is 95%;

[0041] Step A3: Add diquaternary ammonium salt to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, stir and react at room temperature for 4.5 hours to obtain an epoxy product; in a nitrogen atmosphere, add rosin acid and toluene to a flask, heat to 45°C, add pyridine, start stirring, add the epoxy product to the flask, stir and react for 9 hours, then heat to 110°C, stir for 1.5 hours to obtain a rust inhibitor; the dosage ratio of diquaternary ammonium salt, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol: 155 mL: 0.1 mol; the dosage ratio of rosin acid, toluene, pyridine and epoxy product is 33 g: 215 mL: 0.023 mol: 0.1 mol.

[0042] Embodiment 3: A rust inhibitor, the preparation of which comprises the following steps:

[0043] Step A1: 1-(2-aminoethyl)-2-(cis-8-heptadecene-1-yl)imidazoline, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then 1-methyl-1H-1,2,3-benzotriazole-5-carbonyl chloride is added to dimethyl sulfoxide to obtain a mixed solution 2. In a 0°C ice-water bath, the mixed solution 2 is slowly added dropwise to the mixed solution 1. After the addition is completed, the temperature is raised to 40°C and the reaction is stirred at the constant temperature for 10 hours. That is, a heterocyclic product is obtained; the usage ratio of 1-(2-aminoethyl)-2-(cis-8-heptadecen-1-yl)imidazoline, potassium carbonate and dimethyl sulfoxide is 0.1 mol:0.015 mol:85 mL; the usage ratio of 1-methyl-1H-1,2,3-benzotriazole-5-carbonyl chloride and dimethyl sulfoxide is 0.1 mol:55 mL; the usage ratio of mixed solution 1 and mixed solution 2 is 90 mL:60 mL;

[0044] Step A2: placing the heterocyclic product and ethanol in a flask, stirring, then adding 1-chlorohexane, heating to 60°C, stirring at constant temperature for 12 hours, retorting and recrystallizing with acetone, filtering, and obtaining a diquaternary ammonium salt; the amount ratio of the heterocyclic product, ethanol, and 1-chlorohexane is 0.1 mol: 145 mL: 0.1 mol, and the volume fraction of ethanol is 95%;

[0045] Step A3: Add diquaternary ammonium salt to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, stir and react at room temperature for 5 hours to obtain an epoxy product; in a nitrogen atmosphere, add rosin acid and toluene to a flask, heat to 45°C, add pyridine, start stirring, add the epoxy product to the flask, stir and react for 10 hours, then heat to 115°C, stir for 2 hours to obtain a rust inhibitor; the dosage ratio of diquaternary ammonium salt, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol: 160 mL: 0.1 mol; the dosage ratio of rosin acid, toluene, pyridine and epoxy product is 35 g: 220 mL: 0.025 mol: 0.1 mol.

[0046] Example 4: An antioxidant, the preparation of which comprises the following steps:

[0047] Step B1: Add 3-(4-bromophenyl)-1-propene to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, stir and react at room temperature for 4 hours to obtain the epoxy product a; in a nitrogen atmosphere, add 3,5-di-tert-butyl-4-hydroxybenzoic acid and toluene to a flask, heat to 45°C, add pyridine, start stirring, add the epoxy product a to the flask, stir and react for 8 hours, then heat to 110°C, stir for 1 hour to obtain brominated aromatic hydrocarbons; the dosage ratio of 3-(4-bromophenyl)-1-propene, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol: 45 mL: 0.1 mol; the dosage ratio of 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluene, pyridine and epoxy product a is 0.1 mol: 100 mL: 0.010 mol: 0.1 mol;

[0048] Step B2: Add diethyl cyanomethylphosphite to tetrahydrofuran, start stirring, add Raney nickel and Pd / C, introduce hydrogen, and stir for 48 hours at normal pressure to obtain an amino product; add bromoaryl, amino product and methanol to a flask, add 2-dicyclohexylphosphine-2'-4'-6'-triisopropylbiphenyl, tris(dibenzylideneacetone)dipalladium and potassium carbonate, reflux and stir for 4 hours at 80°C under nitrogen protection, and vacuum dry at 50°C to obtain an alcohol hydroxyl product ; The dosage ratio of diethyl cyanomethylphosphite, tetrahydrofuran, Raney nickel and Pd / C is 0.1 mol: 40 mL: 0.01 mol: 0.01 mol; the dosage ratio of bromoaryl hydrocarbon, amino product, methanol, 2-dicyclohexylphosphino-2'-4'-6'-triisopropylbiphenyl, tris(dibenzylideneacetone)dipalladium and potassium carbonate is 0.12 mol: 0.06 mol: 500 mL: 0.0025 g: 0.0025 g: 0.15 mol;

[0049] Step B3: Add O,O-diethyl-O-(4-nitrophenyl) thiophosphate and toluene into a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring for reaction for 1h to obtain amino product b; add xylene into a four-necked flask, pass nitrogen, add amino product b and triphosgene successively under stirring at 75°C, after adding, heat to 125°C and continue to react for 3.5h to obtain isocyanate; the amount ratio of O,O-diethyl-O-(4-nitrophenyl) thiophosphate, toluene, and sodium dithionite is 0.1mol:65mL:0.1mol; the amount ratio of xylene, amino product b and triphosgene is 110mL:0.1mol:0.1mol;

[0050] Step B4: After mixing the alcohol hydroxyl product and isocyanate, add a 20% by mass solution of dilute sulfuric acid and methanol, and react at 50°C for 4 hours to obtain an antioxidant; the amount ratio of the alcohol hydroxyl product, isocyanate, a 20% by mass solution of dilute sulfuric acid and methanol is 0.1 mol: 0.1 mol: 100 mL: 200 mL.

[0051] Example 5: An antioxidant, the preparation of which comprises the following steps:

[0052] Step B1: Add 3-(4-bromophenyl)-1-propene to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, stir and react at room temperature for 4.5 hours to obtain epoxidized product a; in a nitrogen atmosphere, add 3,5-di-tert-butyl-4-hydroxybenzoic acid and toluene to a flask, heat to 45°C, add pyridine, start stirring, add epoxidized product a to the flask, stir and react for 9 hours, then heat to 115°C, stir for 1.5 hours to obtain brominated aromatic hydrocarbons; the dosage ratio of 3-(4-bromophenyl)-1-propene, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol: 50 mL: 0.1 mol; the dosage ratio of 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluene, pyridine and epoxidized product a is 0.1 mol: 105 mL: 0.013 mol: 0.1 mol;

[0053] Step B2: Add diethyl cyanomethylphosphite to tetrahydrofuran, start stirring, add Raney nickel and Pd / C, introduce hydrogen, and stir for 48 hours at normal pressure to obtain an amino product; add bromoaryl, amino product and methanol to a flask, add 2-dicyclohexylphosphine-2'-4'-6'-triisopropylbiphenyl, tris(dibenzylideneacetone)dipalladium and potassium carbonate, reflux and stir for 4.5 hours at 80°C under nitrogen protection, and vacuum dry at 50°C to obtain an alcohol hydroxyl product ; The usage ratio of diethyl cyanomethylphosphite, tetrahydrofuran, Raney nickel and Pd / C is 0.1mol:45mL:0.01mol:0.013mol; the usage ratio of bromoaryl hydrocarbon, amino product, methanol, 2-dicyclohexylphosphino-2'-4'-6'-triisopropylbiphenyl, tris(dibenzylideneacetone)dipalladium and potassium carbonate is 0.12mol:0.06mol:530mL:0.0025g:0.0025g:0.16mol;

[0054] Step B3: Add O,O-diethyl-O-(4-nitrophenyl) thiophosphate and toluene into a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring for reaction for 1 hour to obtain amino product b; add xylene into a four-necked flask, pass nitrogen, add amino product b and triphosgene successively under stirring at 75°C, after adding, heat to 125°C and continue to react for 3.5 hours to obtain isocyanate; the amount ratio of O,O-diethyl-O-(4-nitrophenyl) thiophosphate, toluene, and sodium dithionite is 0.1 mol:70 mL:0.1 mol; the amount ratio of xylene, amino product b and triphosgene is 110 mL:0.1 mol:0.1 mol;

[0055] Step B4: After mixing the alcohol hydroxyl product and isocyanate, add a 20% by mass solution of dilute sulfuric acid and methanol, and react at 50°C for 4 hours to obtain an antioxidant; the amount ratio of the alcohol hydroxyl product, isocyanate, a 20% by mass solution of dilute sulfuric acid and methanol is 0.1 mol: 0.1 mol: 100 mL: 200 mL.

[0056] Example 6: An antioxidant, the preparation of which comprises the following steps:

[0057] Step B1: Add 3-(4-bromophenyl)-1-propene to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, stir and react at room temperature for 5 hours to obtain the epoxy product a; in a nitrogen atmosphere, add 3,5-di-tert-butyl-4-hydroxybenzoic acid and toluene to a flask, heat to 45°C, add pyridine, start stirring, add the epoxy product a to the flask, stir and react for 10 hours, then heat to 120°C, stir for 2 hours to obtain brominated aromatic hydrocarbons; the dosage ratio of 3-(4-bromophenyl)-1-propene, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol: 55 mL: 0.1 mol; the dosage ratio of 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluene, pyridine and epoxy product a is 0.1 mol: 110 mL: 0.015 mol: 0.1 mol;

[0058] Step B2: Add diethyl cyanomethylphosphite to tetrahydrofuran, start stirring, add Raney nickel and Pd / C, introduce hydrogen, and react under normal pressure with stirring for 48 hours to obtain an amino product; add bromoaryl, amino product and methanol to a flask, add 2-dicyclohexylphosphine-2'-4'-6'-triisopropylbiphenyl, tris(dibenzylideneacetone)dipalladium and potassium carbonate, reflux and react under nitrogen protection at 80°C for 5 hours, and vacuum dry at 50°C to obtain an alcohol hydroxyl product; The usage ratio of diethyl cyanomethylphosphite, tetrahydrofuran, Raney nickel and Pd / C is 0.1 mol: 50 mL: 0.01 mol: 0.015 mol; the usage ratio of bromoaryl hydrocarbon, amino product, methanol, 2-dicyclohexylphosphino-2'-4'-6'-triisopropylbiphenyl, tris(dibenzylideneacetone)dipalladium and potassium carbonate is 0.12 mol: 0.06 mol: 550 mL: 0.0025 g: 0.0025 g: 0.18 mol;

[0059] Step B3: Add O,O-diethyl-O-(4-nitrophenyl) thiophosphate and toluene into a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring for reaction for 1h to obtain amino product b; add xylene into a four-necked flask, pass nitrogen, add amino product b and triphosgene successively under stirring at 75°C, after adding, heat to 125°C and continue to react for 3.5h to obtain isocyanate; the amount ratio of O,O-diethyl-O-(4-nitrophenyl) thiophosphate, toluene, and sodium dithionite is 0.1mol:75mL:0.1mol; the amount ratio of xylene, amino product b and triphosgene is 110mL:0.1mol:0.1mol;

[0060] Step B4: After mixing the alcohol hydroxyl product and isocyanate, add a 20% by mass solution of dilute sulfuric acid and methanol, and react at 50°C for 4 hours to obtain an antioxidant; the amount ratio of the alcohol hydroxyl product, isocyanate, a 20% by mass solution of dilute sulfuric acid and methanol is 0.1 mol: 0.1 mol: 100 mL: 200 mL.

[0061] Example 7: An emulsified oil for hydraulic support, comprising the following raw materials in parts by weight: 25 parts of base oil, 8 parts of oleic acid, 9 parts of triethanolamine, 5 parts of rust inhibitor, 5 parts of antioxidant, 1 part of polyvinyl n-butyl ether, 0.6 parts of zinc cyclohexane, 0.4 parts of ethylene-vinyl acetate copolymer, 6 parts of ethylene oxide propylene oxide copolymer, 6 parts of dodecylphenol and 25 parts of distilled water; the base oil is 7 # Base oil;

[0062] The preparation of the emulsified oil for hydraulic support comprises the following steps:

[0063] Heat the base oil to 55°C, and add oleic acid, triethanolamine, the rust inhibitor obtained in Example 1, the antioxidant obtained in Example 4, polyvinyl n-butyl ether, zinc cyclohexaneate, ethylene-vinyl acetate copolymer, ethylene oxide propylene oxide copolymer, and dodecylphenol in sequence under stirring. After the addition is completed, continue to stir and react at a constant temperature for 5 hours. Finally, add distilled water, stir for 1 hour, and adjust the pH of the system to 8.5 with 1 mol / L sodium hydroxide solution to obtain emulsified oil for hydraulic support.

[0064] Example 8: An emulsified oil for hydraulic support, comprising the following raw materials in parts by weight: 30 parts of base oil, 9 parts of oleic acid, 10 parts of triethanolamine, 6 parts of rust inhibitor, 6 parts of antioxidant, 2 parts of polyvinyl n-butyl ether, 0.7 parts of zinc cyclohexane, 0.5 parts of ethylene-vinyl acetate copolymer, 7 parts of ethylene oxide propylene oxide copolymer, 7 parts of dodecylphenol and 35 parts of distilled water; the base oil is 7 # Base oil;

[0065] The preparation of the emulsified oil for hydraulic support comprises the following steps:

[0066] Heat the base oil to 60°C, and add oleic acid, triethanolamine, the rust inhibitor obtained in Example 2, the antioxidant obtained in Example 5, polyvinyl n-butyl ether, zinc cyclohexaneate, ethylene-vinyl acetate copolymer, ethylene oxide propylene oxide copolymer, and dodecylphenol in sequence under stirring. After the addition is completed, continue to stir and react at a constant temperature for 5.5 hours. Finally, add distilled water, stir for 1.3 hours, and adjust the pH of the system to 8.7 with 1 mol / L sodium hydroxide solution to obtain emulsified oil for hydraulic support.

[0067] Example 9: An emulsified oil for hydraulic support, comprising the following raw materials in parts by weight: 35 parts of base oil, 10 parts of oleic acid, 11 parts of triethanolamine, 7 parts of rust inhibitor, 7 parts of antioxidant, 3 parts of polyvinyl n-butyl ether, 0.8 parts of zinc cyclohexane, 0.6 parts of ethylene-vinyl acetate copolymer, 8 parts of ethylene oxide propylene oxide copolymer, 8 parts of dodecylphenol and 45 parts of distilled water; the base oil is 7 # Base oil;

[0068] The preparation of the emulsified oil for hydraulic support comprises the following steps:

[0069] Heat the base oil to 65°C, and add oleic acid, triethanolamine, the rust inhibitor obtained in Example 3, the antioxidant obtained in Example 6, polyvinyl n-butyl ether, zinc cyclohexaneate, ethylene-vinyl acetate copolymer, ethylene oxide propylene oxide copolymer, and dodecylphenol in sequence under stirring. After the addition is completed, continue to stir and react at a constant temperature for 6 hours. Finally, add distilled water, stir for 1.5 hours, and adjust the pH of the system to 8.9 with 1 mol / L sodium hydroxide solution to obtain emulsified oil for hydraulic support.

[0070] Comparative Example 1: Compared with Example 9, the rust inhibitor was replaced with the diquaternary ammonium salt obtained in Example 3, and the rest was exactly the same as Example 9 to prepare emulsified oil for hydraulic support.

[0071] Comparative Example 2: Compared with Example 9, the antioxidant was replaced with the alcohol hydroxyl product obtained in Example 6, and the rest was exactly the same as Example 9 to prepare emulsified oil for hydraulic support.

[0072] Comparative Example 3: Compared with Example 9, the antioxidant was replaced with 3,5-di-tert-butyl-4-hydroxybenzoic acid, and the rest was exactly the same as Example 9 to prepare emulsified oil for hydraulic support.

[0073] The effect of the emulsified oil for hydraulic support prepared by the present invention is further tested, and the test results are as follows.

[0074] In order to test the emulsified oil for hydraulic support prepared by the present invention, the test was carried out according to the standard MT 76-2011 "Emulsified oil, concentrated oil and high water content hydraulic fluid for hydraulic support", and the results are recorded in Table 1;

[0075] Table 1: Test results

[0076]

[0077]

[0078] According to the data in Table 1, the emulsified oil for hydraulic support prepared by the present invention has good rust resistance, corrosion resistance, room temperature stability and lubricity. Comparison between Example 9 and Comparative Example 1 shows that the use of a rust inhibitor with a rosin acid ester structure not only makes the emulsified oil have good rust resistance, but also can more evenly and stably exert emulsification, and has good room temperature stability. Comparison between Example 9 and Comparative Example 2 shows that the use of an antioxidant with a thiophosphate ester not only has good corrosion resistance, but also has good lubricity. Comparison between Example 9 and Comparative Example 3 shows that the use of an antioxidant with a thiophosphate ester and a phosphite ester, the phosphite ester and the hindered phenol quickly synergize to improve the lubricity and corrosion resistance of the emulsified oil.

[0079] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. An emulsified oil for a hydraulic support, characterized in that: The invention comprises the following raw materials in parts by weight: 25-35 parts of base oil, 8-10 parts of oleic acid, 9-11 parts of triethanolamine, 5-7 parts of rust inhibitor, 5-7 parts of antioxidant, 1-3 parts of polyvinyl n-butyl ether, 0.6-0.8 parts of zinc cyclohexane, 0.4-0.6 parts of ethylene-vinyl acetate copolymer, 6-8 parts of ethylene oxide propylene oxide copolymer, 6-8 parts of dodecylphenol and 25-45 parts of distilled water; the base oil is 7 # Base oil; The preparation of the rust inhibitor comprises the following steps: Step A1: 1-(2-aminoethyl)-2-(cis-8-heptadecen-1-yl)imidazoline, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then 1-methyl-1H-1,2,3-benzotriazole-5-carbonyl chloride is added to dimethyl sulfoxide to obtain a mixed solution 2. The mixed solution 2 is slowly added dropwise to the mixed solution 1 in an ice-water bath at 0°C. After the addition is completed, the temperature is raised to 40°C, and the reaction is stirred at the constant temperature for 10 hours to obtain a heterocyclic product; Step A2: Place the heterocyclic product and ethanol in a flask, start stirring, then add 1-chlorohexane, raise the temperature to 50-60° C., stir and react at constant temperature for 10-12 hours, rotary evaporate and recrystallize with acetone, and filter to obtain a diquaternary ammonium salt; Step A3: Add diquaternary ammonium salt to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, stir and react at room temperature for 4-5 hours to obtain an epoxy product; in a nitrogen atmosphere, add rosin acid and toluene to a flask, heat to 45°C, add pyridine, start stirring, add the epoxy product to the flask, stir and react for 8-10 hours, then heat to 105-115°C, stir for 1-2 hours to obtain a rust inhibitor; The preparation of the antioxidant comprises the following steps: Step B1: Add 3-(4-bromophenyl)-1-propene to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, stir and react at room temperature for 4-5 hours to obtain epoxidized product a; in a nitrogen atmosphere, add 3,5-di-tert-butyl-4-hydroxybenzoic acid and toluene to a flask, heat to 45°C, add pyridine, start stirring, add epoxidized product a to the flask, stir and react for 8-10 hours, then heat to 110-120°C, stir for 1-2 hours to obtain bromoaryl hydrocarbon; Step B2: Add diethyl cyanomethylphosphite to tetrahydrofuran, start stirring, add Raney nickel and Pd / C, introduce hydrogen, and react under normal pressure with stirring for 48 hours to obtain an amino product; add bromoaryl, amino product and methanol to a flask, add 2-dicyclohexylphosphine-2'-4'-6'-triisopropylbiphenyl, tris(dibenzylideneacetone)dipalladium and potassium carbonate, reflux and stir at 80°C under nitrogen protection for 4-5 hours, and vacuum dry at 50°C to obtain an alcohol hydroxyl product; Step B3: Add O,O-diethyl-O-(4-nitrophenyl)thiophosphate and toluene into a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring to react for 1 hour to obtain amino product b; add xylene into a four-necked flask, pass nitrogen, add amino product b and triphosgene successively at 75°C with stirring, and after the addition is complete, heat to 125°C and continue to react for 3.5 hours to obtain isocyanate; Step B4: After mixing the alcohol hydroxyl product and isocyanate, add 20% by mass of dilute sulfuric acid solution and methanol, and react at 50° C. for 4 hours to obtain an antioxidant.

2. The emulsified oil for hydraulic support according to claim 1, characterized in that: In step A1, the usage ratio of 1-(2-aminoethyl)-2-(cis-8-heptadecen-1-yl)imidazoline, potassium carbonate and dimethyl sulfoxide is 0.1 mol:0.015 mol:75-85 mL; the usage ratio of 1-methyl-1H-1,2,3-benzotriazole-5-carbonyl chloride and dimethyl sulfoxide is 0.1 mol:45-55 mL; the usage ratio of mixed solution 1 and mixed solution 2 is 80-90 mL:50-60 mL.

3. The emulsified oil for hydraulic support according to claim 1, characterized in that: In step A2, the usage ratio of the heterocyclic product, ethanol and 1-chlorohexane is 0.1 mol: 135-145 mL: 0.1 mol, and the volume fraction of ethanol is 95%.

4. The emulsified oil for hydraulic support according to claim 1, characterized in that: In step A3, the usage ratio of diquaternary ammonium salt, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol: 150-160 mL: 0.1 mol; the usage ratio of rosin acid, toluene, pyridine and epoxy product is 30-35 g: 210-220 mL: 0.020-0.025 mol: 0.1 mol.

5. The emulsified oil for hydraulic support according to claim 1, characterized in that: In step B1, the usage ratio of 3-(4-bromophenyl)-1-propene, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol:45-55 mL:0.1 mol; the usage ratio of 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluene, pyridine and epoxidation product a is 0.1 mol:100-110 mL:0.010-0.015 mol:0.1 mol.

6. The emulsified oil for hydraulic support according to claim 1, characterized in that: In step B2, the usage ratio of diethyl cyanomethylphosphite, tetrahydrofuran, Raney nickel and Pd / C is 0.1 mol: 40-50 mL: 0.01 mol: 0.01-0.015 mol; the usage ratio of bromoaryl hydrocarbon, amino product, methanol, 2-dicyclohexylphosphino-2'-4'-6'-triisopropylbiphenyl, tris(dibenzylideneacetone)dipalladium and potassium carbonate is 0.12 mol: 0.06 mol: 500-550 mL: 0.0025 g: 0.0025 g: 0.15-0.18 mol.

7. The emulsified oil for hydraulic support according to claim 1, characterized in that: In step B3, the usage ratio of O,O-diethyl-O-(4-nitrophenyl)phosphorothioate, toluene, and sodium dithionite is 0.1 mol:65-75 mL:0.1 mol; the usage ratio of xylene, amino product b, and triphosgene is 110 mL:0.1 molg:0.1 mol.

8. The emulsified oil for hydraulic support according to claim 1, characterized in that: In step B4, the amount ratio of the alcohol hydroxyl product, isocyanate, 20% by mass dilute sulfuric acid solution and methanol is 0.1 mol: 0.1 mol: 100 mL: 200 mL.

9. The method for preparing emulsified oil for hydraulic support according to claim 1, characterized in that: The steps include: Heat the base oil to 55-65°C, and add oleic acid, triethanolamine, rust inhibitor, antioxidant, polyvinyl n-butyl ether, zinc cyclohexaneate, ethylene-vinyl acetate copolymer, ethylene oxide propylene oxide copolymer, and dodecylphenol in sequence under stirring. After the addition is completed, continue to stir and react at a constant temperature for 5-6 hours. Finally, add distilled water, stir for 1-1.5 hours, and adjust the pH of the system to 8.5-9 with 1 mol / L sodium hydroxide solution to obtain emulsified oil for hydraulic support.

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