Thermo-oxidative aging resistant environment-friendly concentrated solution and preparation method thereof

Abstract

The invention discloses a thermo-oxidative aging resistant environment-friendly concentrated solution and a preparation method thereof, and relates to the technical field of hydraulic support concentrated solutions. The thermo-oxidative aging resistant environment-friendly concentrated solution comprises the following raw materials in parts by weight: 10-14 parts of a modified surfactant, 5-7 parts of a modified antioxidant, 35-45 parts of base oil, 4-6 parts of an anti-rust preservative, 6-8 parts of a defoaming agent, 2-4 parts of a bacteriostatic agent and 130-150 parts of deionized water. The invention prepares a novel modified surfactant and an antioxidant which are used as auxiliaries of the concentrated solution for the hydraulic support, so that the hard water resistance and thermo-oxidative aging resistance of the concentrated solution for the hydraulic support are improved.

Description

Technical Field

[0001] The invention relates to the technical field of hydraulic support concentrated liquid, and in particular to an environmentally friendly concentrated liquid resistant to thermal oxidation aging and a preparation method thereof. Background Art

[0002] The concentrated liquid for hydraulic support is a kind of substance that can be dissolved in water to form a solution-type diluent. It is generally composed of water, water-soluble rust inhibitors, corrosion inhibitors, defoaming agents and other additives. It is mixed with mine water with a mass ratio of more than 95% to form a high-water hydraulic fluid as the transmission medium of the hydraulic support to realize the actions of hydraulic support lifting, lowering, pushing, sliding, and moving. At present, in the electro-hydraulic control system, due to the improvement of manufacturing precision, the tolerance is very small, and higher requirements are put forward for the cleanliness of the hydraulic fluid. Special technical treatment is required to achieve better stability and rust resistance; and the hardness of mine water often fluctuates greatly. When the hardness of mine water increases and exceeds the complexing capacity of the high-water hydraulic fluid of the hydraulic support, it will cause the high-water hydraulic fluid to precipitate soap, produce floccules and sediments, and then block the hydraulic system, causing the hydraulic support to fail to operate normally. Therefore, it is of great significance to develop a hydraulic support concentrate that is both resistant to hard water and resistant to thermal oxidation aging.

[0003] The Chinese invention patent with publication number CN103266004A discloses an environmentally friendly concentrated liquid for hydraulic supports, which includes the following components: composite lubricant, defoaming agent, defoaming agent, water treatment agent, composite anti-rust and corrosion agent, composite emulsifier, and deionized water. The concentrated liquid has good biodegradability, but its resistance to hard water and thermal oxidation aging is average. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention aims to provide an environmentally friendly concentrate resistant to thermal oxidation aging and a preparation method thereof.

[0005] To achieve the above object, the present invention is implemented through the following technical solutions: A heat-oxidative aging-resistant and environment-friendly concentrated liquid comprises the following raw materials in parts by weight: Modified surfactant: 10-14 parts, Modified antioxidant: 5-7 parts, Base oil: 35-45 parts, Antirust and anticorrosion agent: 4-6 parts, Defoaming agent: 6-8 parts, Antibacterial agent: 2-4 parts, Deionized water: 130-150 parts; The modified surfactant is prepared by the following method: S1: With toluene as solvent, 13-bromo-1-tridecene is polymerized under the action of azobisisobutyronitrile as initiator and Phillips catalyst to obtain a polymer with 13-bromo-1-tridecene as monomer. The reaction equation is as follows:

[0006] S2: Lauryl alcohol and epichlorohydrin react under the action of a catalyst, benzyltriethylammonium chloride, to obtain 1-chloro-3-(dodecyloxy)propan-2-ol, and the reaction equation is as follows:

[0007] S3: A dimethylamine aqueous solution and 1-chloro-3-(dodecyloxy)propan-2-ol react in anhydrous ethanol solvent to obtain 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol. The reaction equation is as follows:

[0008] S4: A polymer with 13-bromo-1-tridecene as a monomer and 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol are reacted in an ethyl acetate solvent to obtain a modified surfactant with a number average molecular weight of 6000-8000. The reaction equation is as follows:

[0009] The modified antioxidant is prepared by the following method: S5: A benzene solution of 4-vinylaniline and 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride reacts in a benzene solvent with K2CO3 as a catalyst to obtain 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl)propionamide. The reaction equation is as follows:

[0010] S6: Using toluene as solvent, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide is polymerized under the action of azobisisobutyronitrile as an initiator and Phillips catalyst to obtain a modified antioxidant with a number average molecular weight of 1500-1900. The reaction equation is as follows:

[0011] The feed mass ratio of toluene, 13-bromo-1-tridecene, azobisisobutyronitrile and Phillips catalyst is 40:(10-14):(0.04-0.08):(0.010-0.012).

[0012] The mass ratio of the lauryl alcohol, epichlorohydrin and catalyst benzyltriethylammonium chloride is (16-20):(8-10):(0.1-0.3).

[0013] The mass ratio of the anhydrous ethanol, the dimethylamine aqueous solution and the 1-chloro-3-(dodecyloxy)propan-2-ol is 80:(12-16):(26-30).

[0014] The mass ratio of ethyl acetate, the polymer with 13-bromo-1-tridecene as a monomer, and 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol is 30:(15-17):(4-8).

[0015] The feed mass ratio of benzene, 4-vinylaniline, benzene solution of 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride, and catalyst K2CO3 is 10:(2.5-3.5):(45-55):(2.6-2.8).

[0016] The feed mass ratio of toluene, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl)propionamide, azobisisobutyronitrile and Phillips catalyst is 40:(10-12):(0.02-0.06):(0.008-0.010).

[0017] The base oil is one of castor oil and palm oil; the defoaming agent is dimethyl silicone oil; and the antibacterial agent is one of s-triazine and isothiazolinone.

[0018] The anti-rust and anti-corrosion agent is a combination of S-carboxyethyl sulfosuccinic acid, diethanolamine and benzotriazole, with a mass ratio of (5-8):(7-14):(0.2-0.4).

[0019] A method for preparing an environmentally friendly concentrated liquid that resists thermal oxidation aging comprises the following steps: (1) Weigh by weight: 10-14 parts of modified surfactant, 5-7 parts of modified antioxidant, 35-45 parts of base oil, 4-6 parts of rust and corrosion inhibitor, 6-8 parts of defoaming agent, 2-4 parts of antibacterial agent, and 130-150 parts of deionized water; (2) Add the rust and corrosion inhibitor into deionized water, stir and mix well, and heat to 30-40°C; then add the modified surfactant, modified antioxidant, base oil, defoaming agent, and antibacterial agent in sequence, heat to 50-60°C, stir for 1-2 hours, and obtain an environmentally friendly concentrate that is resistant to thermal oxidation aging.

[0020] Due to the adoption of the above technical solution, the beneficial effects of the present invention include: (1) The present invention uses 13-bromo-1-tridecene as a monomer to react with a polymer and 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol to prepare a new modified surfactant; 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide is obtained by reacting 4-vinylaniline with 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride, and a new modified antioxidant is prepared by self-polymerization of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide.

[0021] (2) The modified surfactant used in the raw material of the hydraulic support concentrate of the present invention is an oligomeric cationic surfactant. Compared with the traditional single-chain cationic surfactant, its molecular structure has multiple hydrophilic groups and lipophilic carbon chains, which improves the rheological properties of the aqueous solution and exhibits excellent emulsification and dispersion properties; and the alkoxy group in the molecular structure is not easy to react with calcium and magnesium ions in water, has extremely high resistance to hard water, and will not produce soap precipitation, further enhancing the anti-hard water performance of the hydraulic support concentrate. At the same time, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide is obtained by the reaction of 4-vinylaniline and 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride, and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide is self-polymerized to prepare a low-molecular hindered phenol antioxidant, thereby increasing the relative molecular weight of the antioxidant, thereby increasing its volatility resistance and extraction resistance, and further improving the thermal oxidation aging resistance of the hydraulic support concentrate, so that it has the ability to maintain its properties and is not easily changed. DETAILED DESCRIPTION

[0022] The invention will be further described below in conjunction with the embodiments, but the invention is not limited to these embodiments.

[0023] Example 1 Preparation of modified surfactant: S1: 80g toluene, 20g 13-bromo-1-tridecene, 0.08g azobisisobutyronitrile, and 0.020g Phillips catalyst (CrO3 / SiO2 catalyst) were added into a reactor in sequence and mixed, and the mixture was heated and refluxed for 6.0h. After the reaction was completed, the mixture was distilled under reduced pressure at 50°C for 1h to remove the solvent, 300g methanol was added, the mixture was filtered, washed with 40g methanol, and dried under vacuum at 60°C for 2h to obtain a polymer with 13-bromo-1-tridecene as a monomer; S2: 16 g of lauryl alcohol was added to the reactor, the temperature was raised to 60° C., 0.1 g of catalyst benzyltriethylammonium chloride was added, the mixture was stirred, and 8 g of epichlorohydrin was added dropwise for 1 min, the temperature was raised to 90° C., the reaction was continued for 6 h, and the mixture was distilled at 60° C. under reduced pressure for 2 h to obtain a concentrated solution of 1-chloro-3-(dodecyloxy)propan-2-ol; S3: 80 g of anhydrous ethanol, 12 g of dimethylamine aqueous solution (33 wt%), and 26 g of 1-chloro-3-(dodecyloxy)propan-2-ol concentrate were added to the reactor in sequence and mixed, and allowed to stand for 10 h. The pH was adjusted to 9 with NaOH aqueous solution (1.5 mol / L), the temperature was raised to 60° C., the reaction was carried out for 5 h, the temperature was raised to 80° C., the reaction was carried out for 5 h, and the reduced pressure distillation at 50° C. was carried out for 3 h to obtain 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol concentrate; S4: 60g of ethyl acetate, 30g of a polymer with 13-bromo-1-tridecene as a monomer, and 8g of 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol concentrate were added to the reactor in sequence and mixed evenly. The mixture was heated to reflux for 25h. After the reaction was completed, the solvent was removed by distillation under reduced pressure for 30min. 100g of ethyl acetate was added, the mixture was filtered, washed with 15g of ethyl acetate, and dried under vacuum at 50°C for 3.5h to obtain a modified surfactant with a number average molecular weight of 6050.

[0024] Example 2 Preparation of modified surfactant: S1: 80g toluene, 24g 13-bromo-1-tridecene, 0.12g azobisisobutyronitrile, and 0.022g Phillips catalyst (CrO3 / SiO2 catalyst) were added into a reactor in sequence and mixed, and the mixture was heated and refluxed for 5.0h. After the reaction was completed, the mixture was distilled under reduced pressure at 50°C for 1h to remove the solvent, 300g methanol was added, the mixture was filtered, washed with 40g methanol, and dried under vacuum at 60°C for 2h to obtain a polymer with 13-bromo-1-tridecene as a monomer; S2: 18 g of lauryl alcohol was added to the reactor, the temperature was raised to 65°C, 0.2 g of catalyst benzyltriethylammonium chloride was added, the mixture was stirred, and 9 g of epichlorohydrin was added dropwise for 2 min, the temperature was raised to 95°C, the reaction was continued for 5 h, and the mixture was distilled under reduced pressure at 60°C for 1.5 h to obtain a concentrated solution of 1-chloro-3-(dodecyloxy)propan-2-ol; S3: 80 g of anhydrous ethanol, 14 g of dimethylamine aqueous solution (33 wt%), and 28 g of 1-chloro-3-(dodecyloxy)propan-2-ol concentrate were added to the reactor in sequence and mixed, and allowed to stand for 11 h. The pH was adjusted to 9.5 with NaOH aqueous solution (1 mol / L), and the temperature was raised to 65° C. and reacted for 4 h. The temperature was then raised to 85° C. and reacted for 4 h. The concentrated solution of 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol was obtained by vacuum distillation at 50° C. for 2.5 h. S4: 60g of ethyl acetate, 32g of a polymer with 13-bromo-1-tridecene as a monomer, and 12g of 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol concentrate were added to the reactor in sequence and mixed evenly. The mixture was refluxed at elevated temperature for 24h. After the reaction was completed, the solvent was removed by distillation under reduced pressure for 30min. 120g of ethyl acetate was added, the mixture was filtered, washed with 15g of ethyl acetate, and dried under vacuum at 55°C for 3h to obtain a modified surfactant with a number average molecular weight of 7080.

[0025] Example 3 Preparation of modified surfactant: S1: 80g toluene, 28g 13-bromo-1-tridecene, 0.16g azobisisobutyronitrile, and 0.024g Phillips catalyst (CrO3 / SiO2 catalyst) were added to the reactor in sequence and mixed, and the mixture was heated and refluxed for 4.0h. After the reaction was completed, the mixture was distilled under reduced pressure at 50°C for 1h to remove the solvent, 200g methanol was added, the mixture was filtered, washed with 40g methanol, and vacuum dried at 60°C for 2h to obtain a polymer with 13-bromo-1-tridecene as a monomer; S2: Add 20g of lauryl alcohol to the reactor, heat to 70°C, add 0.3g of catalyst benzyltriethylammonium chloride, stir, then drop 10g of epichlorohydrin for 2min, then heat to 100°C, react for 4h, and distill at 60°C under reduced pressure for 1h to obtain a concentrated solution of 1-chloro-3-(dodecyloxy)propan-2-ol; S3: 80 g of anhydrous ethanol, 16 g of dimethylamine aqueous solution (33 wt%), and 30 g of 1-chloro-3-(dodecyloxy)propan-2-ol concentrate were added to the reactor in sequence and mixed, and allowed to stand for 12 h. The pH was adjusted to 10 with NaOH aqueous solution (1.5 mol / L), the temperature was raised to 70° C., the reaction was continued for 3 h, the temperature was raised to 90° C., the reaction was continued for 3 h, and the reduced pressure distillation was carried out at 50° C. for 2 h to obtain 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol concentrate; S4: 60g of ethyl acetate, 34g of a polymer with 13-bromo-1-tridecene as a monomer, and 16g of 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol concentrate were added to the reactor in sequence and mixed evenly. The mixture was refluxed at elevated temperature for 23h. After the reaction was completed, the solvent was removed by distillation under reduced pressure for 30min. 150g of ethyl acetate was added, the mixture was filtered, washed with 20g of ethyl acetate, and dried under vacuum at 60°C for 3h to obtain a modified surfactant with a number average molecular weight of 7930.

[0026] Example 4 Preparation of modified antioxidant: S5: 10g benzene, 2.5g 4-vinylaniline, and 12.6g K2CO3 solution (2.6g dissolved in 10g deionized water) were added to the reactor in sequence and mixed evenly. The mixture was placed in an ice-water bath at 0°C, and 45g 3,5-di(tert-butyl)-4-hydroxyphenylpropionyl chloride benzene solution (15wt%) was slowly added dropwise. The mixture was added dropwise over 10 minutes. The mixture was heated to 35°C and nitrogen was protected. The mixture was reacted for 16 hours. The mixture was cooled to room temperature. The reaction solution was filtered and washed with deionized water for 3 times (10g deionized water was used each time). The mixture was dried under vacuum at 50°C for 2 hours to obtain 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide. S6: 80g toluene, 20g 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide, 0.04g azobisisobutyronitrile, and 0.016g Phillips catalyst (CrO3 / SiO2 catalyst) were added to the reactor in sequence, stirred, and refluxed for 4 hours. After the reaction was completed, the mixture was distilled under reduced pressure at 50°C for 1 hour to remove the solvent, 200g methanol was added, filtered, washed with 20g methanol, and vacuum dried at 60°C for 3 hours to obtain a modified antioxidant with a number average molecular weight of 1520.

[0027] Example 5 Preparation of modified antioxidant: S5: 10g benzene, 3g 4-vinylaniline, and 13.7g catalyst K2CO3 solution (2.7g dissolved in 11g deionized water) were added to the reactor in sequence and mixed evenly. The mixture was placed in an ice-water bath at 0°C, and 50g 3,5-di(tert-butyl)-4-hydroxyphenylpropionyl chloride benzene solution (15wt%) was slowly added dropwise. The mixture was added over 15 minutes. The mixture was heated to 40°C and nitrogen was protected. The mixture was reacted for 14 hours. The mixture was cooled to room temperature. The reaction solution was filtered and washed with deionized water for 3 times (10g deionized water was used each time). The mixture was dried under vacuum at 55°C for 2 hours to obtain 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide. S6: 80g toluene, 22g 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide, 0.08g azobisisobutyronitrile, and 0.018g Phillips catalyst (CrO3 / SiO2 catalyst) were added to the reactor in sequence, stirred, and refluxed for 3 hours. After the reaction was completed, the mixture was distilled at 50°C under reduced pressure for 1.5 hours to remove the solvent, 200g methanol was added, filtered, washed with 20g methanol, and vacuum dried at 65°C for 2 hours to obtain a modified antioxidant with a number average molecular weight of 1780.

[0028] Example 6 Preparation of modified oxidant: S5: 10g benzene, 3.5g 4-vinylaniline, and 14.8g K2CO3 solution (2.8g dissolved in 12g deionized water) were added to the reactor in sequence and mixed evenly. The mixture was placed in an ice-water bath at 0°C, and 55g 3,5-di(tert-butyl)-4-hydroxyphenylpropionyl chloride benzene solution (15wt%) was slowly added dropwise. The mixture was added over 20 minutes. The mixture was heated to 50°C and nitrogen was protected. The mixture was reacted for 12 hours. The mixture was cooled to room temperature. The reaction solution was filtered and washed with deionized water for 3 times (12g deionized water was used each time). The mixture was dried under vacuum at 60°C for 2 hours to obtain 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide. S6: 80g toluene, 24g 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide, 0.12g azobisisobutyronitrile, and 0.02g Phillips catalyst (CrO3 / SiO2 catalyst) were added into the reactor in sequence, stirred, and refluxed for 2h. After the reaction was completed, the mixture was distilled under reduced pressure at 50°C for 1h to remove the solvent, 200g methanol was added, filtered, washed with 20g methanol, and vacuum dried at 70°C for 1h to obtain a modified antioxidant with a number average molecular weight of 1880.

[0029] Example 7: Environmentally friendly concentrate with thermal oxidation resistance (1) Weigh 100 g of modified surfactant (prepared in Example 1), 50 g of modified antioxidant (prepared in Example 4), 350 g of base oil (palm oil), 40 g of rust and corrosion inhibitor (16.40 g of S-carboxyethyl sulfosuccinic acid, 22.95 g of diethanolamine and 0.65 g of benzotriazole), 60 g of defoamer (dimethyl silicone oil), 20 g of antibacterial agent (s-triazine), and 1300 g of deionized water; (2) Add the rust preventive and corrosion inhibitor into deionized water, stir to mix well, and heat to 30°C; then add the modified surfactant, modified antioxidant, base oil, defoaming agent, and antibacterial agent in sequence, heat to 50°C, and stir for 2 hours to obtain an environmentally friendly concentrate that is resistant to thermal oxidation aging.

[0030] Example 8: Environmentally friendly concentrate with thermal oxidation resistance (1) Weigh 120 g of modified surfactant (prepared in Example 2), 60 g of modified antioxidant (prepared in Example 5), 400 g of base oil (castor oil), 50 g of rust and corrosion inhibitor (18 g of S-carboxyethyl sulfosuccinic acid, 30 g of diethanolamine and 2 g of benzotriazole), 70 g of defoamer (dimethyl silicone oil), 30 g of antibacterial agent (1,2-benzisothiazolin-3-one), and 1400 g of deionized water; (2) Add the rust preventive and corrosion inhibitor into deionized water, stir to mix, and heat to 35°C; then add the modified surfactant, modified antioxidant, base oil, defoaming agent, and antibacterial agent in sequence, heat to 55°C, and stir for 1.5 hours to obtain an environmentally friendly concentrate that is resistant to heat and oxidation aging.

[0031] Example 9: Environmentally friendly concentrate with thermal oxidation resistance (1) Weigh 140 g of modified surfactant (prepared in Example 3), 70 g of modified antioxidant (prepared in Example 6), 450 g of base oil (palm oil), 60 g of rust and corrosion inhibitor (20 g of S-carboxyethyl sulfosuccinic acid, 38 g of diethanolamine and 2 g of benzotriazole), 80 g of defoamer (dimethyl silicone oil), 40 g of antibacterial agent (s-triazine), and 1500 g of deionized water; (2) Add the rust preventive and corrosion inhibitor into deionized water, stir to mix evenly, and heat to 40°C; then add the modified surfactant, modified antioxidant, base oil, defoaming agent, and antibacterial agent in sequence, heat to 60°C, and stir for 1 hour to obtain an environmentally friendly concentrate that is resistant to thermal oxidation aging.

[0032] Comparative Example 1 A heat-oxidative aging resistant and environment-friendly concentrated liquid, which has substantially the same raw materials and process as those of Example 8, except that the modified surfactant (prepared in Example 2) is replaced by an equal weight of a surfactant prepared by the following method.

[0033] The surfactant in this comparative example was prepared by the following method: S1: 42g toluene, 16g 13-bromo-1-tridecene, 0.09g azobisisobutyronitrile, and 0.013g Phillips catalyst (CrO3 / SiO2 catalyst) were added to the reactor in sequence and mixed evenly. The mixture was heated and refluxed for 4.5h. After the reaction was completed, the mixture was distilled under reduced pressure at 50°C for 1h to remove the solvent. 100g methanol was added, the mixture was filtered, washed with 20g methanol, and dried under vacuum at 60°C for 2h to obtain a polymer with 13-bromo-1-tridecene as a monomer. S4: 32 g of ethyl acetate, 19 g of a polymer with 13-bromo-1-tridecene as a monomer, and 9 g of 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol concentrate (prepared in Example 2) were added to the reactor in sequence and mixed evenly. The mixture was heated to reflux and reacted for 24 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure for 30 min. 100 g of ethyl acetate was added, the mixture was filtered, washed with 20 g of ethyl acetate, and dried under vacuum at 60°C for 4 h to obtain a modified surfactant with a number average molecular weight of 9250.

[0034] Comparative Example 2 A heat-oxidative aging resistant environmentally friendly concentrated liquid, the raw materials and process are basically the same as those of Example 8, the difference being that the modified antioxidant (prepared in Example 5) is replaced by an antioxidant prepared by the following method with an equal weight.

[0035] The antioxidant in this comparative example was prepared by the following method: S6: 42g toluene solvent, 14g 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide (prepared in Example 5), 0.07g azobisisobutyronitrile, and 0.011g Phillips catalyst (CrO3 / SiO2 catalyst) were added to the reactor in sequence and mixed evenly. The mixture was heated to reflux for 2.5h. After the reaction was completed, the mixture was distilled at 50°C under reduced pressure for 1h to remove the solvent. 200g methanol was added, the mixture was filtered, washed with 20g methanol, and dried under vacuum at 70°C for 1h to obtain a modified antioxidant with a number average molecular weight of 2270.

[0036] Comparative Example 3 A heat-oxidative aging resistant and environment-friendly concentrated liquid, whose raw material components and preparation method are basically the same as those of Example 8, except that no modified surfactant is added to the components of step (2).

[0037] Comparative Example 4 A heat-oxidative aging resistant and environment-friendly concentrated liquid, whose raw material components and preparation method are basically the same as those of Example 8, except that no modified oxidant is added to the components in step (2).

[0038] Comparative Example 5 A heat-oxidative aging resistant and environment-friendly concentrated liquid, whose raw material components and preparation method are basically the same as those of Example 8, except that no modified surfactant or modified oxidant is added to the components of step (2).

[0039] Comparative Example 6 A heat-resistant and oxidative aging-resistant environmentally friendly concentrated liquid, whose raw material components and preparation method are basically the same as those of Example 8, except that the modified surfactant added to the components of step (2) is replaced by an equal weight of N-carboxymethyl-N,N-dimethyldodecyl ammonium salt.

[0040] Comparative Example 7 A heat-oxidative aging resistant environmentally friendly concentrate, whose raw material components and preparation method are basically the same as those of Example 8, except that the modified surfactant added to the components of step (2) is replaced by an equal weight of a quaternary ammonium salt surfactant prepared by the following method: 30 g of ethyl acetate, 16 g of 13-bromo-1-tridecene, and 6 g of 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol concentrate (prepared in step S3 of Example 2) were added to the reactor in sequence and mixed evenly. The mixture was heated to reflux and reacted for 24 h. After the reaction was completed, the mixture was distilled under reduced pressure for 30 min, 60 g of ethyl acetate was added, the mixture was filtered, washed with 15 g of ethyl acetate, and dried under vacuum at 55 ° C for 2.5 h to obtain a quaternary ammonium surfactant.

[0041] Comparative Example 8 A heat-resistant and oxidative aging-resistant environmentally friendly concentrated liquid, whose raw material components and preparation method are basically the same as those of Example 8, except that the modified oxidant added to the components of step (2) is replaced by an equal weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride.

[0042] Comparative Example 9 A heat-oxidative aging-resistant and environment-friendly concentrated liquid, whose raw material components and preparation method are basically the same as those of Example 8, except that the modified oxidant added to the components of step (2) is replaced by an equal weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl)propionamide prepared in step S5 of Example 5.

[0043] Comparative Example 10 The raw material components and preparation method of a heat-resistant and oxidative aging-resistant environmentally friendly concentrated solution are basically the same as those in Example 8, except that the modified oxidant added to the components of step (2) is replaced by an equal weight of 2,4,6-tri-tert-butylphenol.

[0044] Comparative Example 11 The concentrated solution is prepared using the raw materials and method of Example 1 in publication number CN103266004A.

[0045] The castor oil used in the comparative examples and embodiments of the present application is cold-pressed castor oil, with a viscosity of 0.75 Pa.S at 25°C and a density of 0.959 g / cm 3 , purchased from Inner Mongolia Weiyu Biotechnology Co., Ltd.; the palm oil model is industrial grade 42 degrees, purchased from Jinan Juyang Chemical Technology Co., Ltd.; the dimethyl silicone oil is ZBH-201 dimethyl silicone oil, purchased from Qingdao Zhongbao Silicon Material Technology Co., Ltd.

[0046] The concentrated solutions prepared in Examples 7-9 and Comparative Examples 1-11 were evaluated for performance of high-water hydraulic fluids according to the coal industry standard MT / T 76-2011. The high-water hydraulic fluids of each sample were prepared at a mass concentration of 5%, and artificial hard water was used for preparation, with hardness levels of 10, 20, 30 and 40, respectively. The evaluation results of the high-water hydraulic fluids of Examples 7-9 and Comparative Examples 1-11 according to the hardness level of artificial hard water are shown in Table 1.

[0047] Determination of oxidation stability: the test method refers to GB / T 12581-2006; the evaluation index refers to GB11118.1-2011.

[0048] Table 1

[0049] It can be seen from Table 1 that the concentrated liquid prepared in the present application did not undergo soap precipitation under the test of artificial hard water hardness levels of 10-40, indicating that the concentrated liquid prepared in the present application has excellent hard water resistance; the acid value of its oxidative stability is below 0.05 mg / g, indicating that the concentrated liquid prepared in the present application has good resistance to thermal oxidative aging.

[0050] Comparative Example 1 of the present application is a concentrated solution using a modified surfactant with a number average molecular weight higher than 8000, which produces soap precipitation at an artificial hard water hardness level of 40 and has poor hard water resistance.

[0051] Comparative Example 2 of the present application is a concentrated solution using a modified oxidant having a number average molecular weight higher than 1900, and its oxidation stability acid value is 0.10 mg / g, and its thermal oxidation aging resistance is slightly reduced.

[0052] Comparative Example 3 of the present application is a concentrated solution without using a modified surfactant, and soap precipitation occurs in the test of artificial hard water hardness levels of 10-40.

[0053] Comparative Example 4 of the present application is a concentrated solution without using a modified oxidant, and its oxidation stability acid value is as high as 2.1 mg / g, exceeding 2.0 mg / g (quality indicator in the standard).

[0054] Comparative Example 5 of the present application is a concentrated solution without adding modified surfactant and modified oxidant. It undergoes soap precipitation under the test of artificial hard water hardness level of 10-40, and the acid value of the oxidative stability exceeds 2.0 mg / g (quality index in the standard).

[0055] Comparative Example 6 of the present application is different from Example 8, and its raw material components and preparation method are basically the same as those of Example 8. The difference lies in that the modified surfactant added in the step (2) component is replaced by an equal weight of N-carboxymethyl-N,N-dimethyldodecyl ammonium salt. Soap precipitation occurs when the artificial hard water hardness level is tested at 30 and 40, and the hard water resistance is poor.

[0056] Comparative Example 7 of the present application is different from Example 8. Its raw material components and preparation method are basically the same as those of Example 8. The difference is that the modified surfactant added in the step (2) component is replaced by an equal weight of a quaternary ammonium salt surfactant. Soap precipitation occurs when the artificial hard water hardness level is tested at 30 and 40, and the hard water resistance is poor.

[0057] Comparative Examples 8, 9, and 10 of the present application are different from Example 8, and their raw material components and preparation methods are basically the same as Example 8. The difference is that the modified antioxidant added to the components of step (2) is replaced by 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, and 2,4,6-tri-tert-butylphenol, respectively, and their oxidation stability acid value is higher than 0.10 mg / g, and their resistance to thermal oxidative aging is poor.

[0058] Comparative Example 11 is a concentrated liquid prepared using the raw materials and methods of Example 1 in Publication No. CN103266004A. It can be seen from the data in Table 1 that soap precipitation occurs under the test of artificial hard water hardness levels of 20, 30, and 40, indicating poor hard water resistance; the acid value of oxidation stability is 0.17 mg / g, and the thermal oxidation aging resistance is also poor.

[0059] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. However, any equivalent changes, modifications and evolutions made by ordinary technicians in the field without departing from the scope of the technical solution of the present invention by using the technical content disclosed above are all equivalent embodiments of the present invention. At the same time, any equivalent changes, modifications and evolutions made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the technical solution of the present invention.

Claims

1. An environmentally friendly concentrate that resists thermal oxidation aging, characterized in that: The invention comprises the following raw materials in parts by weight: Modified surfactant: 10-14 parts, Modified antioxidant: 5-7 parts, Base oil: 35-45 parts, Antirust and anticorrosion agent: 4-6 parts, Defoaming agent: 6-8 parts, Antibacterial agent: 2-4 parts, Deionized water: 130-150 parts; The modified surfactant is prepared by the following method: S1: Using toluene as solvent, 13-bromo-1-tridecene is polymerized in the presence of azobisisobutyronitrile as an initiator and Phillips catalyst to obtain a polymer with 13-bromo-1-tridecene as a monomer; S2: Lauryl alcohol and epichlorohydrin react under the action of a catalyst, benzyltriethylammonium chloride, to obtain 1-chloro-3-(dodecyloxy)propan-2-ol; S3: reacting a dimethylamine aqueous solution and 1-chloro-3-(dodecyloxy)propan-2-ol in anhydrous ethanol to obtain 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol; S4: a polymer with 13-bromo-1-tridecene as a monomer and 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol are reacted in ethyl acetate to obtain a modified surfactant with a number average molecular weight of 6000-8000; The modified antioxidant is prepared by the following method: S5: A benzene solution of 4-vinylaniline and 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride reacts in a benzene solvent with K2CO3 as a catalyst to obtain 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl)propionamide; S6: Using toluene as solvent, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl) propionamide is polymerized in the presence of azobisisobutyronitrile as an initiator and a Phillips catalyst to obtain a modified antioxidant having a number average molecular weight of 1500-1900.

2. The environmentally friendly concentrated liquid resistant to thermal oxidation aging according to claim 1, characterized in that: In step S1, the feed mass ratio of toluene, 13-bromo-1-tridecene, azobisisobutyronitrile and Phillips catalyst is 40:(10-14):(0.04-0.08):(0.010-0.012).

3. The environmentally friendly concentrated liquid resistant to thermal oxidation aging according to claim 1, characterized in that: In step S2, the mass ratio of lauryl alcohol, epichlorohydrin and catalyst benzyltriethylammonium chloride is (16-20):(8-10):(0.1-0.3).

4. The environmentally friendly concentrated liquid resistant to thermal oxidation aging according to claim 1, characterized in that: In step S3, the mass ratio of anhydrous ethanol, dimethylamine aqueous solution and 1-chloro-3-(dodecyloxy)propan-2-ol is 80:(12-16):(26-30).

5. The environmentally friendly concentrated liquid resistant to thermal oxidation aging according to claim 1, characterized in that: In step S4, the mass ratio of ethyl acetate, the polymer with 13-bromo-1-tridecene as a monomer, and 1-(dimethylamino)-3-(dodecyloxy)propan-2-ol is 30:(15-17):(4-8).

6. The environmentally friendly concentrated liquid resistant to thermal oxidation aging according to claim 1, characterized in that: In step S5, the feed mass ratio of benzene, 4-vinylaniline, benzene solution of 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride, and catalyst K2CO3 is 10:(2.5-3.5):(45-55):(2.6-2.8).

7. The environmentally friendly concentrated liquid resistant to thermal oxidation aging according to claim 1, characterized in that: In step S6, the feed mass ratio of toluene, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-vinylphenyl)propionamide, azobisisobutyronitrile, and Phillips catalyst is 40:(10-12):(0.02-0.06):(0.008-0.010).

8. The environmentally friendly concentrated liquid resistant to thermal oxidation aging according to claim 1, characterized in that: The base oil is one of castor oil and palm oil; the defoaming agent is dimethyl silicone oil; and the antibacterial agent is one of s-triazine and isothiazolinone.

9. The environmentally friendly concentrated liquid resistant to thermal oxidation aging according to claim 1, characterized in that: The anti-rust and anti-corrosion agent is a combination of S-carboxyethyl sulfosuccinic acid, diethanolamine and benzotriazole, with a mass ratio of (5-8):(7-14):(0.2-0.4).

10. A method for preparing the heat-oxidative aging resistant and environment-friendly concentrated solution according to any one of claims 1 to 9, characterized in that: The following steps are involved: (1) Weigh by weight: 10-14 parts of modified surfactant, 5-7 parts of modified antioxidant, 35-45 parts of base oil, 4-6 parts of rust and corrosion inhibitor, 6-8 parts of defoaming agent, 2-4 parts of antibacterial agent, and 130-150 parts of deionized water; (2) Add the rust and corrosion inhibitor into deionized water, stir and mix well, and heat to 30-40°C; then add the modified surfactant, modified antioxidant, base oil, defoaming agent, and antibacterial agent in sequence, heat to 50-60°C, stir for 1-2 hours, and obtain an environmentally friendly concentrate that is resistant to thermal oxidation aging.

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