CN113174283A - High-performance phosphate flame-retardant hydraulic oil - Google Patents
High-performance phosphate flame-retardant hydraulic oil Download PDFInfo
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- CN113174283A CN113174283A CN202110361559.7A CN202110361559A CN113174283A CN 113174283 A CN113174283 A CN 113174283A CN 202110361559 A CN202110361559 A CN 202110361559A CN 113174283 A CN113174283 A CN 113174283A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/0405—Phosphate esters used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/049—Phosphite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
Abstract
The invention discloses a high-performance phosphate flame-retardant hydraulic oil which comprises the following components in parts by weight: the feed comprises the following raw materials in parts by weight: phosphate ester base oil, a demulsifier, benzonaphthalene thiophene, a non-silicon type anti-foaming agent, a benzotriazole derivative, an antioxidant, a preservative and a flame retardant; heating the solution A to 105 ℃ and stirring for 3h, after the reaction is finished, carrying out reduced pressure distillation, removing toluene, adding ethyl acetate for dissolving, washing with deionized water, and then distilling to remove ethyl acetate; obtaining phosphate ester base oil; adding the demulsifier, the benzonaphthalene thiophene, the non-silicon type anti-foaming agent, the benzotriazole derivative, the antioxidant, the preservative and the flame retardant into the phosphate base oil according to the weight parts, and mixing and stirring to obtain the high-performance phosphate anti-flaming hydraulic oil; the invention has the characteristics of high spontaneous combustion point, good oxidation stability and high-temperature wear resistance and the like, and can meet the use requirements of a high-temperature hydraulic system.
Description
Technical Field
The invention belongs to the technical field of hydraulic oil, relates to phosphate flame-retardant hydraulic oil, and particularly relates to high-performance phosphate flame-retardant hydraulic oil.
Background
The phosphate fire-resistant hydraulic pressure is widely applied to electric power, military and airplane hydraulic systems, has extremely strong fire-resistant performance, and has an irreplaceable position in hydraulic systems which are in contact with high-temperature heat sources and naked flames.
With the use of a large amount of high-capacity and high-parameter steam turbine units, the single-machine capacity of a thermal power plant reaches over 800MW, and the steam temperature reaches over 565 ℃, which puts higher requirements on the flame resistance, high-temperature wear resistance, high-temperature oxidation resistance and the like of phosphate flame-resistant hydraulic oil. The phosphate flame-retardant hydraulic oil widely used at present has poor flame-retardant performance, and the natural point is generally below 550 ℃. The wear is large and the service life of the equipment is short when the device is used at high temperature; the antioxidant performance is poor, the phosphate flame-retardant hydraulic oil is quick to age and deteriorate, and the oil change period is short. In order to solve the defects of the phosphate flame-retardant hydraulic oil, the invention provides the high-performance phosphate flame-retardant hydraulic oil which has the characteristics of high spontaneous combustion point, oxidation stability, high-temperature abrasion resistance, and the like, and can meet the use requirements of a high-temperature hydraulic system.
Disclosure of Invention
The invention aims to solve the problems that the single-machine capacity of a thermal power plant reaches more than 800MW and the steam temperature reaches more than 565 ℃ along with the heavy use of a large-capacity and high-parameter steam turbine set, which puts higher requirements on the flame resistance, the high-temperature wear resistance, the high-temperature oxidation resistance and the like of phosphate flame-resistant hydraulic oil. The phosphate flame-retardant hydraulic oil widely used at present has poor flame-retardant performance, and the natural point is generally below 550 ℃. The wear is large and the service life of the equipment is short when the device is used at high temperature; the phosphate flame-retardant hydraulic oil has poor oxidation resistance, rapid aging and deterioration of the phosphate flame-retardant hydraulic oil and short oil change period, and the high-performance phosphate flame-retardant hydraulic oil is provided.
The purpose of the invention can be realized by the following technical scheme:
a high-performance phosphate flame-retardant hydraulic oil: the feed comprises the following raw materials in parts by weight: 95-99.5 parts of phosphate base oil, 0-0.5 part of demulsifier, 0.01-5 parts of benzonaphthalene thiophene, 0-0.1 part of non-silicon type anti-foaming agent, 0.01-5 parts of benzotriazole derivative, 2-5 parts of antioxidant, 2-5 parts of preservative and 2-5 parts of flame retardant;
the preparation process of the phosphate flame-retardant hydraulic oil comprises the following steps:
the first step is as follows: under the protection of nitrogen, base oil, triethylamine and anhydrous toluene are mixed, and then PCI is dripped3Diluting the toluene solution to obtain solution A; wherein, the base oil contains glycerol with the mass fraction of 5 percent;
the second step is that: heating the solution A to 105 ℃ and stirring for 3h, after the reaction is finished, carrying out reduced pressure distillation, removing toluene, adding ethyl acetate for dissolving, washing with deionized water, and then distilling to remove ethyl acetate; obtaining phosphate ester base oil;
the third step: adding the demulsifier, the benzonaphthalene thiophene, the non-silicon type anti-foaming agent, the benzotriazole derivative, the antioxidant, the preservative and the flame retardant into the phosphate base oil according to the weight parts, and mixing and stirring to obtain the high-performance phosphate anti-flaming hydraulic oil.
Preferably, the base oil, triethylamine, anhydrous toluene and PCI are controlled3The mass ratio of the toluene solution is 100-150: 50-80:500-600: 20-40 parts of; PCI3From PCI3And toluene according to the mass ratio of 3-8: 20-50.
Preferably, the preparation process of the antioxidant comprises the following steps:
the first step is as follows: adding copper sulfate pentahydrate and sodium chloride into deionized water, stirring and dissolving, adding copper powder and hydrochloric acid, reacting at 80 ℃ for 20min to obtain a mixed solution A, mixing the mixed solution A with the deionized water, hydrolyzing, filtering, washing a filter cake with the deionized water, then washing with absolute ethyl alcohol, and drying the filter cake in a drying box to obtain a cuprous chloride solid;
the second step is that: mixing and dissolving a piperidinol free radical and deionized water, and adding cuprous chloride solid and an acetaldehyde aqueous solution with the volume fraction of 40% to obtain a mixed solution B; adding hydrogen peroxide into the mixed solution B, and stirring and mixing for 30min at the temperature of 600 ℃; and after the reaction is finished, cooling, filtering, adjusting the pH value of the filtrate to 8, extracting with ethyl acetate to obtain an organic phase, washing the organic phase with a sodium borohydride solution, washing with a sodium chloride saturated solution for 3 times, and performing rotary evaporation to obtain the antioxidant.
Preferably, the mass ratio of the copper sulfate pentahydrate to the sodium chloride to the deionized water to the copper powder to the hydrochloric acid is controlled to be 10-15:50-80:200-300:2-5: 2-5; the mass ratio of the mixed solution A to the deionized water is 1: 4-5; the mass ratio of the piperidinol free radical, the deionized water, the cuprous chloride solid, the 40% volume fraction acetaldehyde aqueous solution and the hydrogen peroxide is controlled to be 60-80:150-200:1-3:80-100: 80-100.
Preferably, the preparation process of the preservative comprises the following steps:
quinoline and nitrogen heterocyclic compound are mixed and stirred, after the temperature is raised to 130 ℃, benzyl chloride is dripped, and the mixture reacts for 4 hours at the temperature of 148 ℃, so that the preservative is obtained.
Preferably, the dosage ratio of the quinoline to the nitrogen heterocyclic compound to the benzyl chloride is controlled to be 1-1.4 mol: 15-20 mL:1 mol.
Preferably, the preparation process of the flame retardant comprises the following steps:
mixing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane and triethylamine under the protection of nitrogen to obtain a solution a; and (3) adding 3-isocyanate propyl triethoxysilane into the solution a, stirring for 20h, performing rotary evaporation to remove dichloromethane after the reaction is finished, and performing vacuum drying to obtain the flame retardant.
Preferably, the amount ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the methylene chloride, the triethylamine and the 3-isocyanatopropyltriethoxysilane is controlled to be 1 mol: 70-100 mL: 5-10mL, 1-1.2 mol.
Preferably, the demulsifying agent is one or more of T1001 and DL 32; the non-silicon type anti-foaming agent is Kantai KT 903A; the benzotriazole derivative is a Mannich reaction product of benzotriazole, formaldehyde and diamine, wherein the molar ratio of benzotriazole, formaldehyde and diamine is 2:2: 1.
Compared with the prior art, the invention has the beneficial effects that: the phosphite ester is an auxiliary antioxidant, can generate a good synergistic effect with a hindered phenol antioxidant, and improves the color, heat-resistant stability and weather resistance of the polymer; the antioxidant effect of the phosphite antioxidant on the polymer is related to the substituent R' of the phosphite antioxidant; when R' is a hindered phenol substituted unit, the polymer is stabilized;
the antioxidant prepared by the invention generates oxidation resistance mainly by capturing free radicals; first, HALS is oxidized under the conditions of heat, light and the like to be converted into stable nitroxyl radical, the nitroxyl radical reacts with R < - > and RO < - > in the polymer to lose the activity, and the generated ester and peroxyester react with R < - >, RO < - > and R00 < - > to be recovered into the nitroxyl radical; in this way, nitroxyl radicals are continuously regenerated to promote the mutual combination of radicals in the polymer, thereby achieving the effect of stabilizing the polymer;
therefore, under the synergistic cooperation effect of the phosphate base oil and the antioxidant, the base oil has good oxidation resistance;
the quaternary nitrogen cation in the quinoline quaternary ammonium salt preservative is a nitrogen atom, has a center of a hydrophilic group with good surface activity, and can be separated in an acid solution of the quaternary nitrogen cation and chloride ions with constant concentration; since the hydrophobic group which can be efficiently formed prevents corrosion of the anode and reaction of the cathode, thereby preventing corrosion and effectively preventing charge transfer; the quinoline quaternary ammonium salt preservative has good high-temperature resistance, so that the quinoline quaternary ammonium salt preservative has good corrosion resistance by being added into the phosphate base oil;
the flame retardant is a derivative of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide synthesized by 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 3-isocyanatopropyl triethoxysilane, as the molecules of the derivative of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide contain biphenyl ring and phenanthrene ring structures, therefore, the flame retardant has good thermal stability and chemical stability, so that the flame retardant of the derivative of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added into the phosphate base oil to ensure that the flame retardant has good flame retardant property;
the high-performance phosphate ester flame-retardant hydraulic oil provided by the invention has the advantages of high spontaneous combustion point (higher than 550 ℃), strong oxidation resistance, strong acid capture capacity, inhibition of acid value increase, maintenance of stable volume resistivity of the hydraulic oil, remarkable improvement of abrasion resistance, and effective increase of the service life of equipment, and the diameter of a wear scar is only 30-40% of that of commonly used phosphate ester flame-retardant hydraulic oil.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A high-performance phosphate flame-retardant hydraulic oil: the feed comprises the following raw materials in parts by weight: 95 parts of phosphate base oil, 0.01 part of demulsifier, 0.3 part of benzonaphthalene thiophene, 0.001 part of non-silicon type anti-foaming agent, 0.5 part of benzotriazole derivative, 2 parts of antioxidant, 2 parts of preservative and 2 parts of flame retardant;
the preparation process of the phosphate flame-retardant hydraulic oil comprises the following steps:
the first step is as follows: under the protection of nitrogen, base oil, triethylamine and anhydrous toluene are mixed, and then PCI is dripped3Diluting the toluene solution to obtain solution A; wherein, the base oil contains glycerol with the mass fraction of 5 percent;
the second step is that: heating the solution A to 105 ℃ and stirring for 3h, after the reaction is finished, carrying out reduced pressure distillation, removing toluene, adding ethyl acetate for dissolving, washing with deionized water, and then distilling to remove ethyl acetate; obtaining phosphate ester base oil;
the third step: adding the demulsifier, the benzonaphthalene thiophene, the non-silicon type anti-foaming agent, the benzotriazole derivative, the antioxidant, the preservative and the flame retardant into the phosphate base oil according to the weight parts, and mixing and stirring to obtain the high-performance phosphate anti-flaming hydraulic oil.
Control of base oil, Triethylamine, Anhydrous toluene and PCI3The mass ratio of the toluene solution is 100: 50:500: 20; PCI3From PCI3And toluene according to the mass ratio of 3: 20.
The preparation process of the antioxidant comprises the following steps:
the first step is as follows: adding copper sulfate pentahydrate and sodium chloride into deionized water, stirring and dissolving, adding copper powder and hydrochloric acid, reacting at 80 ℃ for 20min to obtain a mixed solution A, mixing the mixed solution A with the deionized water, hydrolyzing, filtering, washing a filter cake with the deionized water, then washing with absolute ethyl alcohol, and drying the filter cake in a drying box to obtain a cuprous chloride solid;
the second step is that: mixing and dissolving a piperidinol free radical and deionized water, and adding cuprous chloride solid and an acetaldehyde aqueous solution with the volume fraction of 40% to obtain a mixed solution B; adding hydrogen peroxide into the mixed solution B, and stirring and mixing for 30min at the temperature of 600 ℃; and after the reaction is finished, cooling, filtering, adjusting the pH value of the filtrate to 8, extracting with ethyl acetate to obtain an organic phase, washing the organic phase with a sodium borohydride solution, washing with a sodium chloride saturated solution for 3 times, and performing rotary evaporation to obtain the antioxidant.
Controlling the mass ratio of copper sulfate pentahydrate to sodium chloride to deionized water to copper powder to hydrochloric acid to be 10:50:200:2: 2; the mass ratio of the mixed solution A to the deionized water is 1: 4; the mass ratio of the piperidinol free radical, the deionized water, the cuprous chloride solid, the 40% volume fraction acetaldehyde aqueous solution and the hydrogen peroxide is controlled to be 60:150:1:80: 80.
The preparation process of the preservative comprises the following steps:
quinoline and nitrogen heterocyclic compound are mixed and stirred, after the temperature is raised to 130 ℃, benzyl chloride is dripped, and the mixture reacts for 4 hours at the temperature of 148 ℃, so that the preservative is obtained.
Controlling the dosage ratio of quinoline to nitrogen heterocyclic compound to benzyl chloride to be 1 mol: 15mL of: 1 mol.
The preparation process of the flame retardant comprises the following steps:
mixing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane and triethylamine under the protection of nitrogen to obtain a solution a; and (3) adding 3-isocyanate propyl triethoxysilane into the solution a, stirring for 20h, performing rotary evaporation to remove dichloromethane after the reaction is finished, and performing vacuum drying to obtain the flame retardant.
Controlling the use ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane, triethylamine and 3-isocyanate propyl triethoxysilane to be 1 mol: 70mL of: 5mL:1 mol.
The demulsifying agent is one or more of T1001 and DL 32; the non-silicon type anti-foaming agent is Kantai KT 903A; the benzotriazole derivative is a Mannich reaction product of benzotriazole, formaldehyde and diamine, wherein the molar ratio of benzotriazole, formaldehyde and diamine is 2:2: 1.
Example 2
A high-performance phosphate flame-retardant hydraulic oil: the feed comprises the following raw materials in parts by weight: 96 parts of phosphate base oil, 0.01 part of demulsifier, 3 parts of benzonaphthalene thiophene, 0.001 part of non-silicon type anti-foaming agent, 2 parts of benzotriazole derivative, 3 parts of antioxidant, 3 parts of preservative and 3 parts of flame retardant;
the preparation process of the phosphate flame-retardant hydraulic oil comprises the following steps:
the first step is as follows: under the protection of nitrogen, base oil, triethylamine and anhydrous toluene are mixed, and then PCI is dripped3Diluting the toluene solution to obtain solution A; wherein, the base oil contains glycerol with the mass fraction of 5 percent;
the second step is that: heating the solution A to 105 ℃ and stirring for 3h, after the reaction is finished, carrying out reduced pressure distillation, removing toluene, adding ethyl acetate for dissolving, washing with deionized water, and then distilling to remove ethyl acetate; obtaining phosphate ester base oil;
the third step: adding the demulsifier, the benzonaphthalene thiophene, the non-silicon type anti-foaming agent, the benzotriazole derivative, the antioxidant, the preservative and the flame retardant into the phosphate base oil according to the weight parts, and mixing and stirring to obtain the high-performance phosphate anti-flaming hydraulic oil.
Control of base oil, Triethylamine, Anhydrous toluene and PCI3The mass ratio of the toluene solution is 110: 60:520: 25; PCI3From PCI3And toluene according to the mass ratio of 4: 30.
The preparation process of the antioxidant comprises the following steps:
the first step is as follows: adding copper sulfate pentahydrate and sodium chloride into deionized water, stirring and dissolving, adding copper powder and hydrochloric acid, reacting at 80 ℃ for 20min to obtain a mixed solution A, mixing the mixed solution A with the deionized water, hydrolyzing, filtering, washing a filter cake with the deionized water, then washing with absolute ethyl alcohol, and drying the filter cake in a drying box to obtain a cuprous chloride solid;
the second step is that: mixing and dissolving a piperidinol free radical and deionized water, and adding cuprous chloride solid and an acetaldehyde aqueous solution with the volume fraction of 40% to obtain a mixed solution B; adding hydrogen peroxide into the mixed solution B, and stirring and mixing for 30min at the temperature of 600 ℃; and after the reaction is finished, cooling, filtering, adjusting the pH value of the filtrate to 8, extracting with ethyl acetate to obtain an organic phase, washing the organic phase with a sodium borohydride solution, washing with a sodium chloride saturated solution for 3 times, and performing rotary evaporation to obtain the antioxidant.
Controlling the mass ratio of copper sulfate pentahydrate to sodium chloride to deionized water to copper powder to hydrochloric acid to be 11:60:220:3: 3; the mass ratio of the mixed solution A to the deionized water is 1: 4-5; the mass ratio of the piperidinol free radical, the deionized water, the cuprous chloride solid, the 40% volume fraction acetaldehyde aqueous solution and the hydrogen peroxide is controlled to be 65:160:2:85: 85.
The preparation process of the preservative comprises the following steps:
quinoline and nitrogen heterocyclic compound are mixed and stirred, after the temperature is raised to 130 ℃, benzyl chloride is dripped, and the mixture reacts for 4 hours at the temperature of 148 ℃, so that the preservative is obtained.
Controlling the dosage ratio of the quinoline to the nitrogen heterocyclic compound to the benzyl chloride to be 1.2 mol: 16mL of: 1 mol.
The preparation process of the flame retardant comprises the following steps:
mixing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane and triethylamine under the protection of nitrogen to obtain a solution a; and (3) adding 3-isocyanate propyl triethoxysilane into the solution a, stirring for 20h, performing rotary evaporation to remove dichloromethane after the reaction is finished, and performing vacuum drying to obtain the flame retardant.
Controlling the use ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane, triethylamine and 3-isocyanate propyl triethoxysilane to be 1 mol: 80mL of: 6mL:1.1 mol.
The demulsifying agent is one or more of T1001 and DL 32; the non-silicon type anti-foaming agent is Kantai KT 903A; the benzotriazole derivative is a Mannich reaction product of benzotriazole, formaldehyde and diamine, wherein the molar ratio of benzotriazole, formaldehyde and diamine is 2:2: 1.
Example 3
A high-performance phosphate flame-retardant hydraulic oil: the feed comprises the following raw materials in parts by weight: 98 parts of phosphate base oil, 0.01 part of demulsifier, 0.5 part of benzonaphthalene thiophene, 0.001 part of non-silicon type anti-foaming agent, 1.0 part of benzotriazole derivative, 4 parts of antioxidant, 4 parts of preservative and 4 parts of flame retardant;
the preparation process of the phosphate flame-retardant hydraulic oil comprises the following steps:
the first step is as follows: under the protection of nitrogen, base oil, triethylamine and anhydrous toluene are mixed, and then PCI is dripped3Diluting the toluene solution to obtain solution A; wherein, the base oil contains glycerol with the mass fraction of 5 percent;
the second step is that: heating the solution A to 105 ℃ and stirring for 3h, after the reaction is finished, carrying out reduced pressure distillation, removing toluene, adding ethyl acetate for dissolving, washing with deionized water, and then distilling to remove ethyl acetate; obtaining phosphate ester base oil;
the third step: adding the demulsifier, the benzonaphthalene thiophene, the non-silicon type anti-foaming agent, the benzotriazole derivative, the antioxidant, the preservative and the flame retardant into the phosphate base oil according to the weight parts, and mixing and stirring to obtain the high-performance phosphate anti-flaming hydraulic oil.
Control of base oil, Triethylamine, Anhydrous toluene and PCI3The mass ratio of the toluene solution is 120: 70:540: 30, of a nitrogen-containing gas; PCI3From PCI3And toluene according to the mass ratio of 6: 40.
The preparation process of the antioxidant comprises the following steps:
the first step is as follows: adding copper sulfate pentahydrate and sodium chloride into deionized water, stirring and dissolving, adding copper powder and hydrochloric acid, reacting at 80 ℃ for 20min to obtain a mixed solution A, mixing the mixed solution A with the deionized water, hydrolyzing, filtering, washing a filter cake with the deionized water, then washing with absolute ethyl alcohol, and drying the filter cake in a drying box to obtain a cuprous chloride solid;
the second step is that: mixing and dissolving a piperidinol free radical and deionized water, and adding cuprous chloride solid and an acetaldehyde aqueous solution with the volume fraction of 40% to obtain a mixed solution B; adding hydrogen peroxide into the mixed solution B, and stirring and mixing for 30min at the temperature of 600 ℃; and after the reaction is finished, cooling, filtering, adjusting the pH value of the filtrate to 8, extracting with ethyl acetate to obtain an organic phase, washing the organic phase with a sodium borohydride solution, washing with a sodium chloride saturated solution for 3 times, and performing rotary evaporation to obtain the antioxidant.
Controlling the mass ratio of copper sulfate pentahydrate to sodium chloride to deionized water to copper powder to hydrochloric acid to be 13:70:250:4: 4; the mass ratio of the mixed solution A to the deionized water is 1: 5; the mass ratio of the piperidinol free radical, the deionized water, the cuprous chloride solid, the 40% volume fraction acetaldehyde aqueous solution and the hydrogen peroxide is controlled to be 75:180:2:90: 95.
The preparation process of the preservative comprises the following steps:
quinoline and nitrogen heterocyclic compound are mixed and stirred, after the temperature is raised to 130 ℃, benzyl chloride is dripped, and the mixture reacts for 4 hours at the temperature of 148 ℃, so that the preservative is obtained.
Controlling the dosage ratio of the quinoline to the nitrogen heterocyclic compound to the benzyl chloride to be 1.3 mol: 18mL of: 1 mol.
The preparation process of the flame retardant comprises the following steps:
mixing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane and triethylamine under the protection of nitrogen to obtain a solution a; and (3) adding 3-isocyanate propyl triethoxysilane into the solution a, stirring for 20h, performing rotary evaporation to remove dichloromethane after the reaction is finished, and performing vacuum drying to obtain the flame retardant.
Controlling the use ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane, triethylamine and 3-isocyanate propyl triethoxysilane to be 1 mol: 90mL of: 8mL:1.2 mol.
The demulsifying agent is one or more of T1001 and DL 32; the non-silicon type anti-foaming agent is Kantai KT 903A; the benzotriazole derivative is a Mannich reaction product of benzotriazole, formaldehyde and diamine, wherein the molar ratio of benzotriazole, formaldehyde and diamine is 2:2: 1.
Example 4
A high-performance phosphate flame-retardant hydraulic oil: the feed comprises the following raw materials in parts by weight: 99.5 parts of phosphate base oil, 0.01 part of demulsifier, 3 parts of benzonaphthalene thiophene, 0.001 part of non-silicon type anti-foaming agent, 3 parts of benzotriazole derivative, 5 parts of antioxidant, 5 parts of preservative and 5 parts of flame retardant;
the preparation process of the phosphate flame-retardant hydraulic oil comprises the following steps:
the first step is as follows: under the protection of nitrogen, base oil, triethylamine and anhydrous toluene are mixed, and then PCI is dripped3Diluting the toluene solution to obtain solution A; wherein, the base oil contains glycerol with the mass fraction of 5 percent;
the second step is that: heating the solution A to 105 ℃ and stirring for 3h, after the reaction is finished, carrying out reduced pressure distillation, removing toluene, adding ethyl acetate for dissolving, washing with deionized water, and then distilling to remove ethyl acetate; obtaining phosphate ester base oil;
the third step: adding the demulsifier, the benzonaphthalene thiophene, the non-silicon type anti-foaming agent, the benzotriazole derivative, the antioxidant, the preservative and the flame retardant into the phosphate base oil according to the weight parts, and mixing and stirring to obtain the high-performance phosphate anti-flaming hydraulic oil.
Control of base oil, Triethylamine, Anhydrous toluene and PCI3Mass ratio of toluene solution (2)Is 150: 80:600: 40; PCI3From PCI3And toluene according to the mass ratio of 8: 50.
The preparation process of the antioxidant comprises the following steps:
the first step is as follows: adding copper sulfate pentahydrate and sodium chloride into deionized water, stirring and dissolving, adding copper powder and hydrochloric acid, reacting at 80 ℃ for 20min to obtain a mixed solution A, mixing the mixed solution A with the deionized water, hydrolyzing, filtering, washing a filter cake with the deionized water, then washing with absolute ethyl alcohol, and drying the filter cake in a drying box to obtain a cuprous chloride solid;
the second step is that: mixing and dissolving a piperidinol free radical and deionized water, and adding cuprous chloride solid and an acetaldehyde aqueous solution with the volume fraction of 40% to obtain a mixed solution B; adding hydrogen peroxide into the mixed solution B, and stirring and mixing for 30min at the temperature of 600 ℃; and after the reaction is finished, cooling, filtering, adjusting the pH value of the filtrate to 8, extracting with ethyl acetate to obtain an organic phase, washing the organic phase with a sodium borohydride solution, washing with a sodium chloride saturated solution for 3 times, and performing rotary evaporation to obtain the antioxidant.
Controlling the mass ratio of copper sulfate pentahydrate to sodium chloride to deionized water to copper powder to hydrochloric acid to be 15:80:300:5: 5; the mass ratio of the mixed solution A to the deionized water is 1: 4-5; the mass ratio of the piperidinol free radical, the deionized water, the cuprous chloride solid, the 40% volume fraction acetaldehyde aqueous solution and the hydrogen peroxide is controlled to be 80:200:3:100: 100.
The preparation process of the preservative comprises the following steps:
quinoline and nitrogen heterocyclic compound are mixed and stirred, after the temperature is raised to 130 ℃, benzyl chloride is dripped, and the mixture reacts for 4 hours at the temperature of 148 ℃, so that the preservative is obtained.
Controlling the dosage ratio of the quinoline to the nitrogen heterocyclic compound to the benzyl chloride to be 1.4 mol: 20mL of: 1 mol.
The preparation process of the flame retardant comprises the following steps:
mixing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane and triethylamine under the protection of nitrogen to obtain a solution a; and (3) adding 3-isocyanate propyl triethoxysilane into the solution a, stirring for 20h, performing rotary evaporation to remove dichloromethane after the reaction is finished, and performing vacuum drying to obtain the flame retardant.
Controlling the use ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane, triethylamine and 3-isocyanate propyl triethoxysilane to be 1 mol: 100mL of: 10mL:1.2 mol.
The demulsifying agent is one or more of T1001 and DL 32; the non-silicon type anti-foaming agent is Kantai KT 903A; the benzotriazole derivative is a Mannich reaction product of benzotriazole, formaldehyde and diamine, wherein the molar ratio of benzotriazole, formaldehyde and diamine is 2:2: 1.
Comparative example 1
The hydraulic oil of comparative example 1 was a commercially available product;
the examples 1 to 4 and comparative example 1 were subjected to a performance test:
the high-performance phosphate ester flame-retardant hydraulic oil provided by the invention has the advantages of high spontaneous combustion point (higher than 550 ℃), strong oxidation resistance, strong acid capture capacity, inhibition of acid value increase, maintenance of stable volume resistivity of the hydraulic oil, remarkable improvement of abrasion resistance, and effective increase of the service life of equipment, and the diameter of a wear scar is only 30-40% of that of commonly used phosphate ester flame-retardant hydraulic oil.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. A high-performance phosphate flame-retardant hydraulic oil is characterized in that: the feed comprises the following raw materials in parts by weight: 95-99.5 parts of phosphate base oil, 0-0.5 part of demulsifier, 0.01-5 parts of benzonaphthalene thiophene, 0-0.1 part of non-silicon type anti-foaming agent, 0.01-5 parts of benzotriazole derivative, 2-5 parts of antioxidant, 2-5 parts of preservative and 2-5 parts of flame retardant;
the preparation process of the phosphate flame-retardant hydraulic oil comprises the following steps:
the first step is as follows: under the protection of nitrogen, base oil, triethylamine and anhydrous toluene are mixed, and then PCI is dripped3Diluting the toluene solution to obtain a solution A, wherein the base oil contains glycerol with the mass fraction of 5%;
the second step is that: heating the solution A to 105 ℃ and stirring for 3h, after the reaction is finished, carrying out reduced pressure distillation, removing toluene, adding ethyl acetate for dissolving, washing with deionized water, and then distilling to remove ethyl acetate; obtaining phosphate ester base oil;
the third step: adding the demulsifier, the benzonaphthalene thiophene, the non-silicon type anti-foaming agent, the benzotriazole derivative, the antioxidant, the preservative and the flame retardant into the phosphate base oil according to the weight parts, and mixing and stirring to obtain the high-performance phosphate anti-flaming hydraulic oil.
2. The high-performance phosphate ester flame-retardant hydraulic oil as claimed in claim 1, wherein the control base oil, triethylamine, anhydrous toluene and PCI3The mass ratio of the toluene solution is 100-150: 50-80:500-600: 20-40 parts of; PCI3From PCI3And toluene according to the mass ratio of 3-8: 20-50.
3. The high-performance phosphate flame-retardant hydraulic oil as claimed in claim 1, wherein the preparation process of the antioxidant comprises the following steps:
the first step is as follows: adding copper sulfate pentahydrate and sodium chloride into deionized water, stirring and dissolving, adding copper powder and hydrochloric acid, reacting at 80 ℃ for 20min to obtain a mixed solution A, mixing the mixed solution A with the deionized water, hydrolyzing, filtering, washing a filter cake with the deionized water, then washing with absolute ethyl alcohol, and drying the filter cake in a drying box to obtain a cuprous chloride solid;
the second step is that: mixing and dissolving a piperidinol free radical and deionized water, and adding cuprous chloride solid and an acetaldehyde aqueous solution with the volume fraction of 40% to obtain a mixed solution B; adding hydrogen peroxide into the mixed solution B, and stirring and mixing for 30min at the temperature of 600 ℃; and after the reaction is finished, cooling, filtering, adjusting the pH value of the filtrate to 8, extracting with ethyl acetate to obtain an organic phase, washing the organic phase with a sodium borohydride solution, washing with a sodium chloride saturated solution for 3 times, and performing rotary evaporation to obtain the antioxidant.
4. The high-performance phosphate ester flame-retardant hydraulic oil as claimed in claim 3, wherein the mass ratio of copper sulfate pentahydrate, sodium chloride, deionized water, copper powder and hydrochloric acid is controlled to be 10-15:50-80:200-300:2-5: 2-5; the mass ratio of the mixed solution A to the deionized water is 1: 4-5; the mass ratio of the piperidinol free radical, the deionized water, the cuprous chloride solid, the 40% volume fraction acetaldehyde aqueous solution and the hydrogen peroxide is controlled to be 60-80:150-200:1-3:80-100: 80-100.
5. The high-performance phosphate flame-retardant hydraulic oil as claimed in claim 1, wherein the preparation process of the preservative comprises the following steps:
quinoline and nitrogen heterocyclic compound are mixed and stirred, after the temperature is raised to 130 ℃, benzyl chloride is dripped, and the mixture reacts for 4 hours at the temperature of 148 ℃, so that the preservative is obtained.
6. The high-performance phosphate flame-retardant hydraulic oil as claimed in claim 5, wherein the dosage ratio of quinoline to the nitrogen heterocyclic compound to the benzyl chloride is controlled to be 1-1.4 mol: 15-20 mL:1 mol.
7. The high-performance phosphate flame-retardant hydraulic oil as claimed in claim 1, wherein the preparation process of the flame retardant comprises the following steps:
mixing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane and triethylamine under the protection of nitrogen to obtain a solution a; and (3) adding 3-isocyanate propyl triethoxysilane into the solution a, stirring for 20h, performing rotary evaporation to remove dichloromethane after the reaction is finished, and performing vacuum drying to obtain the flame retardant.
8. The high-performance phosphate flame-retardant hydraulic oil as claimed in claim 7, wherein the use ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane, triethylamine and 3-isocyanatopropyltriethoxysilane is controlled to be 1 mol: 70-100 mL: 5-10mL, 1-1.2 mol.
9. The high-performance phosphate flame-retardant hydraulic oil as claimed in claim 1, wherein the demulsifier is one or more of T1001 and DL 32; the non-silicon type anti-foaming agent is Kantai KT 903A; the benzotriazole derivative is a Mannich reaction product of benzotriazole, formaldehyde and diamine, wherein the molar ratio of benzotriazole, formaldehyde and diamine is 2:2: 1.
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