WO2022052424A1 - 一种磷酸酯抗燃油 - Google Patents

一种磷酸酯抗燃油 Download PDF

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WO2022052424A1
WO2022052424A1 PCT/CN2021/077536 CN2021077536W WO2022052424A1 WO 2022052424 A1 WO2022052424 A1 WO 2022052424A1 CN 2021077536 W CN2021077536 W CN 2021077536W WO 2022052424 A1 WO2022052424 A1 WO 2022052424A1
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phosphate
tert
phosphate ester
ester fire
fire
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French (fr)
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鲁浩
詹烨
汪小龙
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安美科技股份有限公司
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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
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C—CHEMISTRY; METALLURGY
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • 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
    • 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
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • 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
    • C10M2223/041—Triaryl phosphates
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the invention relates to a phosphate ester fire-resistant oil, which can be widely used in the fields of electric power, machinery, chemical industry, energy, materials and the like, and is especially suitable for use as fire-resistant hydraulic oil for mechanical equipment.
  • Phosphate ester fire-resistant oil is a kind of synthetic oil. Compared with mineral oil, it has the characteristics of high self-ignition point, non-flammability and self-extinguishing. Applied to the steam turbine electro-hydraulic regulation system, it can greatly reduce the risk of fire caused by oil leakage, which is of great significance to ensure the safe operation of equipment.
  • the purpose of the present invention is to provide a phosphate ester fire-resistant oil, which has the characteristics of being difficult to ignite and self-extinguishing, and also has excellent oxidation stability, thermal stability, hydrolysis stability and good lubricity.
  • Another object of the present invention is to provide a method for preparing the phosphate ester fire-resistant oil.
  • a phosphoric acid ester fire-resistant oil which is prepared from the raw materials of the following components: tert-butyl phenyl diphenyl phosphate, tri-tert-butyl phenyl phosphate, triphenyl phosphate, Antioxidant, corrosion inhibitor, anti-emulsifier, anti-foaming agent.
  • the phosphate ester fire-resistant oil according to the first aspect is prepared from the raw materials of the following components in terms of mass percentage: 50-85 parts of tert-butyl benzene diphenyl phosphate, tri-tert-butyl phosphate 6-48.87 parts of phenyl phenyl ester, 1-5 parts of triphenyl phosphate, 0.1-1 part of antioxidant, 0.01-1 part of corrosion inhibitor, 0.01-1 part of anti-emulsifier, and 0.01-1 part of anti-foaming agent.
  • the antioxidants are 2,6-di-tert-butyl-p-cresol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,6-di-tert-butylphenol
  • 2,6-di-tert-butylphenol One or more combinations of di-tert-butyl- ⁇ -dimethylamino-p-cresol, N,N'-diisooctyldiphenylamine and N-phenyl- ⁇ -naphthylamine.
  • the corrosion inhibitor is one or several combinations of benzotriazole, methyl benzotriazole, benzotriazole derivatives, thiadiazoles, and thiadiazole derivatives.
  • the anti-emulsifier is one or more combinations of amine and epoxide condensate, ethylene oxide propylene block polyether, and polyethylene oxide-propylene oxide ether.
  • the antifoaming agent is one or more combinations of methyl silicone oil, acrylic acid and ether copolymer.
  • a preparation method of phosphate ester fire-resistant oil comprising the following steps:
  • the phosphate ester fire-resistant oil involved in the present invention has the synergistic effect of each component, so that the product has the characteristics of being difficult to ignite and self-extinguishing, and also has excellent oxidation stability, thermal stability, hydrolysis stability and good lubrication. It is a kind of fire-resistant hydraulic oil with excellent safety and long-life comprehensive performance.
  • the preparation process is simple, the reaction conditions are mild, the raw materials are readily available, and the yield is high.
  • a phosphate ester fire-resistant oil is prepared from the following raw materials by mass percentage: 50 parts of tert-butyl phenyl diphenyl phosphate, 48.87 parts of tri-tert-butyl phenyl phosphate, 1 part of triphenyl phosphate, 0.1 part of 2,6-di-tert-butyl-p-cresol, 0.01 part of benzotriazole, 0.01 part of amine and epoxide condensate, 0.01 part of methyl silicone oil.
  • a phosphate ester fire-resistant oil is prepared from the raw materials of the following components by mass percentage: 85 parts of tert-butyl phenyl diphenyl phosphate, 6 parts of tri-tert-butyl phenyl phosphate, 5 parts of triphenyl phosphate, 1 part of 4,4'-methylenebis(2,6-di-tert-butylphenol), 1 part of tolutriazole, 1 part of epoxide condensate, and 1 part of acrylic acid and ether copolymer.
  • a phosphate ester fire-resistant oil prepared by mass percentage of raw materials of the following components: 65 parts of tert-butyl phenyl diphenyl phosphate, 30 parts of tri-tert-butyl phenyl phosphate, 4 parts of triphenyl phosphate, 0.2 part of 2,6-di-tert-butyl- ⁇ -dimethylamino-p-cresol, 0.4 part of benzotriazole derivative, 0.3 part of ethylene oxide propane block polyether, 0.1 part of methyl silicone oil and acrylic acid and ether copolymer share.
  • a phosphate ester fire-resistant oil prepared by mass percentage of raw materials of the following components: 72 parts of tert-butyl phenyl diphenyl phosphate, 23 parts of tri-tert-butyl phenyl phosphate, 3.5 parts of triphenyl phosphate, 0.2 parts of N,N'-diisooctyl diphenylamine and N-phenyl- ⁇ -naphthylamine, 0.8 parts of thiadiazole and thiadiazole derivatives, ethylene oxide propylene block polyether and polyethylene oxide 0.3 part of alkane-propylene oxide ether, 0.2 part of methyl silicone oil and acrylic acid and ether copolymer.
  • a phosphate ester fire-resistant oil is prepared from the raw materials of the following components by mass percentage: 80 parts of tert-butyl phenyl diphenyl phosphate, 16 parts of tri-tert-butyl phenyl phosphate, 3.2 parts of triphenyl phosphate, 0.4 part of 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl- ⁇ -dimethylamino-p-cresol, 0.2 part of benzotriazole and benzotriazole derivative, amine and epoxide condensation 0.1 part of ethylene oxide propylene block polyether, methyl silicone oil and 0.1 part of acrylic acid and ether copolymer.
  • Example 1 On the basis of Example 1, 5 parts of tributyl phosphate were added, and the preparation method was the same as that of Example 1.
  • Example 2 On the basis of Example 2, 1 part of tolutriazole was removed, and the preparation method was the same as that of Example 2.
  • Example 4 On the basis of Example 4, the thiadiazole and thiadiazole derivatives were replaced by imidazoline derivatives, and the preparation method was the same as that of Example 4.
  • Example 5 On the basis of Example 5, dibutyl phenyl phosphate was used instead of triphenyl phosphate, and the preparation method was the same as that of Example 5.
  • the phosphate ester flame retardant oil prepared in the example has obvious synergistic effect between the phosphate ester components, and changing the phosphate ester component will significantly reduce the flame resistance of the phosphate ester flame retardant oil.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

本发明涉及一种磷酸酯抗燃油，可广泛用于电力、机械、化工、能源、材料等领域，尤其适合用作机械设备的抗燃液压油。本发明提供的磷酸酯抗燃油，由以下组分的原料制备而成：磷酸叔丁基苯二苯酯、磷酸三叔丁基苯酯、磷酸三苯酯、抗氧剂、腐蚀抑制剂、抗乳化剂、抗泡剂。本发明涉及的磷酸酯抗燃油，各组分之间协同作用，从而使得本产品具有难以点燃和自熄灭的特点，同时还具有优异的氧化安定性、热稳定性、水解安定性和良好的润滑性，是一种安全长寿命综合性能优异的抗燃液压油。其制备工艺简单，反应条件温和，原料易得，产率高。

Description

一种磷酸酯抗燃油 技术领域
本发明涉及一种磷酸酯抗燃油，可广泛用于电力、机械、化工、能源、材料等领域，尤其适合用作机械设备的抗燃液压油。
背景技术
随着电力工业的发展，高参数(高温、高压)大容量(300MW及以上)的汽轮机发电机组日益得到广泛应用。过热蒸汽已达到540℃以上，超临界机组的蒸汽温度甚至达到了600℃。汽轮机调节系统大多靠近过热蒸汽管道，而且系统油压最高可达到14.5MPa以上，如果采用矿物油(自然点只有350℃左右)作为调节系统的液压工作介质，一旦发生油泄露现象，发生火灾的危险性极大。
磷酸酯抗燃油是一种合成油，与矿物油相比，它具有自燃点高，不易燃和自熄灭等特点。应用于汽轮机电液调节系统，可以大幅降低因油泄漏而引起火灾的危险性，对保障设备安全运行具有重要的意义。
发明内容
本发的目的在于提供一种磷酸酯抗燃油，该磷酸酯抗燃油具有难以点燃和自熄灭的特点，同时还具有优异的氧化安定性、热稳定性、水解安定性和良好的润滑性。
本发的另一目的在于提供该磷酸酯抗燃油的制备方法。
根据本发明的第一个方面，提供了一种磷酸酯抗燃油，由以下组分的原料制备而成：磷酸叔丁基苯二苯酯、磷酸三叔丁基苯酯、磷酸三苯酯、抗氧剂、腐蚀抑制剂、抗乳化剂、抗泡剂。
根据本发明第二方面，按照第一个方面的磷酸酯抗燃油，按质量百分比计， 由以下组分的原料制备而成：磷酸叔丁基苯二苯酯50～85份、磷酸三叔丁基苯酯6～48.87份、磷酸三苯酯1～5份、抗氧剂0.1～1份、腐蚀抑制剂0.01～1份、抗乳化剂0.01～1份、抗泡剂0.01～1份。
作为上述技术方案的优选，所述的抗氧剂为2,6-二叔丁基对甲酚、4,4’-亚甲基双(2,6二叔丁基酚)、2,6-二叔丁基-α-二甲氨基对甲酚、N,N’-二异辛基二苯胺、N-苯基-α-萘胺的一种或几种组合。
作为上述技术方案的优选，所述的腐蚀抑制剂为苯三唑、甲基苯三唑、苯三唑衍生物、噻二唑、噻二唑衍生物的一种或几种组合。
作为上述技术方案的优选，所述的抗乳化剂为胺与环氧化物缩合物、环氧乙烷丙烷嵌段聚醚、聚环氧乙烷-环氧丙烷醚的一种或几种组合。
作为上述技术方案的优选，所述的抗泡剂为甲基硅油、丙烯酸与醚共聚物的一种或几种组合。
一种磷酸酯抗燃油的制备方法，包括以下步骤：
(1)将磷酸叔丁基苯二苯酯、磷酸三叔丁基苯酯、磷酸三苯酯依次加入反应釜，加入适量吸附剂，开启搅拌，控制搅拌速度为200～300r/min，控制反应釜内温度为65～75℃，搅拌60min。
(2)开启真空泵，控制反应釜内压力为-0.01～-0.04MPa，继续搅拌，脱气120min。
(3)用板框过滤器进行粗滤，滤液泵入调和釜，开启调和釜搅拌器，依次加入抗氧剂、腐蚀抑制剂、抗乳化剂、抗泡剂。
(4)用精密过滤器过滤到颗粒污染度为5级以下，制得磷酸酯抗燃油。
有益的技术效果
本发明涉及的磷酸酯抗燃油，各组分之间协同作用，从而使得本产品具有难以点燃和自熄灭的特点，同时还具有优异的氧化安定性、热稳定性、水解安定性和良好的润滑性，是一种安全长寿命综合性能优异的抗燃液压油。其制备工艺简单，反应条件温和，原料易得，产率高。
具体实施方式
实施例1：
一种磷酸酯抗燃油，按质量百分比计，由以下组分的原料制备而成：磷酸叔丁基苯二苯酯50份、磷酸三叔丁基苯酯48.87份、磷酸三苯酯1份、2,6-二叔丁基对甲酚0.1份、苯三唑0.01份、胺与环氧化物缩合物0.01份、甲基硅油0.01份。
其制备方法如下：
(1)将磷酸叔丁基苯二苯酯50份、磷酸三叔丁基苯酯48.87份、磷酸三苯酯1份依次加入反应釜，加入吸附剂，开启搅拌，控制搅拌速度为200～300r/min，控制反应釜内温度为65～75℃，搅拌60min。
(2)开启真空泵，控制反应釜内压力为-0.01～-0.04MPa，继续搅拌，脱气120min。
(3)用板框过滤器进行粗滤，滤液泵入调和釜，开启调和釜搅拌器，依次加入2,6-二叔丁基对甲酚0.1份、苯三唑0.01份、胺与环氧化物缩合物0.01份、甲基硅油0.01份。
(4)用精密过滤器过滤到颗粒污染度为5级以下，制得磷酸酯抗燃油。
实施例2：
一种磷酸酯抗燃油，按质量百分比计，由以下组分的原料制备而成：磷酸 叔丁基苯二苯酯85份、磷酸三叔丁基苯酯6份、磷酸三苯酯5份、4,4’-亚甲基双(2,6二叔丁基酚)1份、甲基苯三唑1份、环氧化物缩合物1份、丙烯酸与醚共聚物1份。
其制备方法如下：
(1)将磷酸叔丁基苯二苯酯85份、磷酸三叔丁基苯酯6份、磷酸三苯酯5份依次加入反应釜，加入吸附剂，开启搅拌，控制搅拌速度为200～300r/min，控制反应釜内温度为65～75℃，搅拌60min
(2)开启真空泵，控制反应釜内压力为-0.01～-0.04MPa，继续搅拌，脱气120min。
(3)用板框过滤器进行粗滤，滤液泵入调和釜，开启调和釜搅拌器，依次加入4,4’-亚甲基双(2,6二叔丁基酚)1份、甲基苯三唑1份、环氧化物缩合物1份、丙烯酸与醚共聚物1份。
(4)用精密过滤器过滤到颗粒污染度为5级以下，制得磷酸酯抗燃油。
实施例3：
一种磷酸酯抗燃油，按质量百分比计，由以下组分的原料制备而成：磷酸叔丁基苯二苯酯65份、磷酸三叔丁基苯酯30份、磷酸三苯酯4份、2,6-二叔丁基-α-二甲氨基对甲酚0.2份、苯三唑衍生物0.4份、环氧乙烷丙烷嵌段聚醚0.3份、甲基硅油以及丙烯酸与醚共聚物0.1份。
其制备方法如下：
(1)将磷酸叔丁基苯二苯酯65份、磷酸三叔丁基苯酯30份、磷酸三苯酯4份依次加入反应釜，加入吸附剂，开启搅拌，控制搅拌速度为200～300r/min，控制反应釜内温度为65～75℃，搅拌60min。
(2)开启真空泵，控制反应釜内压力为-0.01～-0.04MPa，继续搅拌，脱 气120min。
(3)用板框过滤器进行粗滤，滤液泵入调和釜，开启调和釜搅拌器，依次加入2,6-二叔丁基-α-二甲氨基对甲酚0.2份、苯三唑衍生物0.4份、环氧乙烷丙烷嵌段聚醚0.3份、甲基硅油以及丙烯酸与醚共聚物0.1份。
(4)用精密过滤器过滤到颗粒污染度为5级以下，制得磷酸酯抗燃油。
实施例4：
一种磷酸酯抗燃油，按质量百分比计，由以下组分的原料制备而成：磷酸叔丁基苯二苯酯72份、磷酸三叔丁基苯酯23份、磷酸三苯酯3.5份、N,N’-二异辛基二苯胺与N-苯基-α-萘胺0.2份、噻二唑与噻二唑衍生物0.8份、环氧乙烷丙烷嵌段聚醚与聚环氧乙烷-环氧丙烷醚0.3份、甲基硅油以及丙烯酸与醚共聚物0.2份。
其制备方法如下：
(1)将磷酸叔丁基苯二苯酯72份、磷酸三叔丁基苯酯23份、磷酸三苯酯3.5份依次加入反应釜，加入吸附剂，开启搅拌，控制搅拌速度为200～300r/min，控制反应釜内温度为65～75℃，搅拌60min。
(2)开启真空泵，控制反应釜内压力为-0.01～-0.04MPa，继续搅拌，脱气120min。
(3)用板框过滤器进行粗滤，滤液泵入调和釜，开启调和釜搅拌器，依次加入N,N’-二异辛基二苯胺与N-苯基-α-萘胺0.2份、噻二唑与噻二唑衍生物0.8份、环氧乙烷丙烷嵌段聚醚与聚环氧乙烷-环氧丙烷醚0.3份、甲基硅油以及丙烯酸与醚共聚物0.2份。
(4)用精密过滤器过滤到颗粒污染度为5级以下，制得磷酸酯抗燃油。
实施例5：
一种磷酸酯抗燃油，按质量百分比计，由以下组分的原料制备而成：磷酸叔丁基苯二苯酯80份、磷酸三叔丁基苯酯16份、磷酸三苯酯3.2份、2,6-二叔丁基对甲酚与2,6-二叔丁基-α-二甲氨基对甲酚0.4份、苯三唑与苯三唑衍生物0.2份、胺与环氧化物缩合物以及环氧乙烷丙烷嵌段聚醚0.1份、甲基硅油以及丙烯酸与醚共聚物0.1份。
其制备方法如下：
(1)将磷酸叔丁基苯二苯酯80份、磷酸三叔丁基苯酯16份、磷酸三苯酯3.2份依次加入反应釜，加入吸附剂，开启搅拌，控制搅拌速度为200～300r/min，控制反应釜内温度为65～75℃，搅拌60min。
(2)开启真空泵，控制反应釜内压力为-0.01～-0.04MPa，继续搅拌，脱气120min。
(3)用板框过滤器进行粗滤，滤液泵入调和釜，开启调和釜搅拌器，依次加入2,6-二叔丁基对甲酚与2,6-二叔丁基-α-二甲氨基对甲酚0.4份、苯三唑与苯三唑衍生物0.2份、胺与环氧化物缩合物以及环氧乙烷丙烷嵌段聚醚0.1份、甲基硅油以及丙烯酸与醚共聚物0.1份。
(4)用精密过滤器过滤到颗粒污染度为5级以下，制得磷酸酯抗燃油。
对照例1：
在实施例1的基础上，加入5份的磷酸三丁酯，制备方法同实施例1。
对照例2：
在实施例2基础上，将甲基苯三唑1份去除，制备方法同实施例2。
对照例3：
在实施例4的基础上，以咪唑啉衍生物代替噻二唑与噻二唑衍生物，制备方法同实施例4。
对照例4：
在实施例5的基础上，以磷酸二丁基苯基酯代替磷酸三苯酯，制备方法同实施例5。
性能测试：
1电厂用磷酸酯抗燃油的抗燃性
按照GB T 3536的试验方法，检测实施例及对照例中制得的磷酸酯抗燃油的闪点。按照DL/T 706的试验方法，检测实施例及对照例中制得的磷酸酯抗燃油的自燃点。结果列于表1。
表1 磷酸酯抗燃油的闪点和自燃点
  闪点(开口)，℃ 自燃点，℃
DL/T 571质量标准 ≥240 ≥530
实施例1 252 541
实施例2 255 545
实施例3 256 548
实施例4 252 542
实施例5 258 550
对照例1 226 464
对照例2 251 543
对照例3 253 543
对照例4 243 535
结果显示，实施例1～5中制得的磷酸酯抗燃油的闪点和自燃点均高于DL/T 571中新磷酸酯抗燃油的质量标准，具有良好的抗燃性。而对照例1中制得的磷酸酯抗燃油的闪点和自燃点不能够达到DL/T 571中新磷酸酯抗燃油的质量标准，而对照例4中制得的磷酸酯抗燃油的闪点和自燃点虽然能够达到DL/T 571中新磷酸酯抗燃油的质量标准，但性能不如实施例。由此可以看出，实施例中制得的磷酸酯抗燃油各磷酸酯组分之间的具有明显协同作用，改变磷酸酯组分会明显降低磷酸酯抗燃油的抗燃性能。
2磷酸酯抗燃油的氧化安定性
按照EN 14832的试验方法，检测实施例及对照例中制得的磷酸酯抗燃油的氧化安定性，结果列于表2。
表2 磷酸酯抗燃油的氧化安定性
Figure PCTCN2021077536-appb-000001
结果显示，实施例1～5中制得的磷酸酯抗燃油的氧化安定性试验各项指标均远优于DL/T 571中新磷酸酯抗燃油的质量标准，具有优异的氧化安定性。而对照例1不能满足DL/T 571的质量要求，对照例2～3虽然也可以满足DL/T 571的质量要求，但性能明显不如实施例。由此可以看出，实施例中制得的磷酸酯抗燃油各组分之间具有协同作用，改变其组分将明显降低磷酸酯抗燃油的氧化安定性。
3磷酸酯抗燃油的水解安定性
按照EN 14833的试验方法，检测实施例及对照例中制得的磷酸酯抗燃油的水解安定性，结果列于表3。
表3 电厂用磷酸酯抗燃油的水解安定性
Figure PCTCN2021077536-appb-000002
Figure PCTCN2021077536-appb-000003
结果显示，实施例1～5中制得的磷酸酯抗燃油的水解安定性试验指标远优于DL/T 571中新磷酸酯抗燃油的质量标准，具有优异的水解安定性。而对照例1不能满足DL/T 571的质量要求，对照例4虽然可以满足DL/T 571的质量要求，但性能不如实施例。由此可以看出，实施例中制得的磷酸酯抗燃油各磷酸酯组分之间的具有明显协同作用，改变磷酸酯组分会明显降低磷酸酯抗燃油的水解安定性能。
4磷酸酯抗燃油的润滑性
按照GB/T 3142的试验方法，检测实施例及对照例中制得的磷酸酯抗燃油的最大无卡咬负荷(P B)和烧结负荷(P D)，执行SHT 0189，检测实施例中制得的磷酸酯抗燃油的磨斑直径(D)。结果列于表4。
表4 磷酸酯抗燃油的最大无卡咬负荷(P B)、烧结负荷(P D)和磨斑直径(D)
  最大无卡咬负荷(P B)，N 烧结负荷(P D)，N 磨斑直径(D)，mm
实施例1 647 1568 0.527
实施例2 647 1568 0.521
实施例3 647 1568 0.516
实施例4 647 1568 0.520
实施例5 647 1568 0.531
对照例1 549 1235 0.612
对照例2 647 1568 0.511
对照例3 647 1568 0.523
对照例4 549 1235 0.603
结果显示，实施例1～5中制得的磷酸酯抗燃油的具有良好的润滑性。而对照例1和4中的磷酸酯抗燃油的润滑性能则明显实施例差。由此可以看出，实施例中制得的磷酸酯抗燃油各磷酸酯组分之间的具有明显协同作用，改变磷酸酯组分会明显降低磷酸酯抗燃油的润滑性能。
以上实施例仅为说明本发明的技术思想，不能以此限定本发明的保护范围，凡是按照本发明提出的技术思想，在技术方案基础上所做的任何改动，均落入本发明保护范围之内；本发明未涉及的技术均可通过现有技术加以实现。

Claims (7)

  1. 一种磷酸酯抗燃油，由以下组分的原料制备而成：磷酸叔丁基苯二苯酯、磷酸三叔丁基苯酯、磷酸三苯酯、抗氧剂、腐蚀抑制剂、抗乳化剂、抗泡剂。
  2. 如权利要求1所述的磷酸酯抗燃油，其特征在于：磷酸叔丁基苯二苯酯50～85份、磷酸三叔丁基苯酯6～48.87份、磷酸三苯酯1～5份、抗氧剂0.1～1份、腐蚀抑制剂0.01～1份、抗乳化剂0.01～1份、抗泡剂0.01～1份。
  3. 如权利要求1或2所述的磷酸酯抗燃油，所述的抗氧剂为2,6-二叔丁基对甲酚、4,4’-亚甲基双(2,6二叔丁基酚)、2,6-二叔丁基-α-二甲氨基对甲酚、N,N’-二异辛基二苯胺、N-苯基-α-萘胺的一种或几种组合。
  4. 如权利要求1或2所述的磷酸酯抗燃油，所述的腐蚀抑制剂为苯三唑、甲基苯三唑、苯三唑衍生物、噻二唑、噻二唑衍生物的一种或几种组合。
  5. 如权利要求1或2所述的磷酸酯抗燃油，所述的抗乳化剂为胺与环氧化物缩合物、环氧乙烷丙烷嵌段聚醚、聚环氧乙烷-环氧丙烷醚的一种或几种组合。
  6. 如权利要求1或2所述的磷酸酯抗燃油，所述的抗泡剂为甲基硅油、丙烯酸与醚共聚物的一种或几种组合。
  7. 一种制备权利要求1-6中任一项所述的电厂用磷酸酯抗燃油的方法，其步骤如下：
    (1)将磷酸叔丁基苯二苯酯、磷酸三叔丁基苯酯、磷酸三苯酯依次加入反应釜，加入适量吸附剂，开启搅拌，控制搅拌速度为200～300r/min，控制反应釜内温度为65～75℃，搅拌60min；
    (2)开启真空泵，控制反应釜内压力为-0.01--0.04MPa，继续搅拌，脱气120min；
    (3)用板框过滤器进行粗滤，滤液泵入调和釜，开启调和釜搅拌器，依次加入抗氧剂、腐蚀抑制剂、抗乳化剂、抗泡剂；
    (4)用精密过滤器过滤到颗粒无染度为5级以下，制得电厂用磷酸酯抗燃油。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103215105A (zh) * 2013-04-09 2013-07-24 天津市联瑞阻燃材料有限公司 以磷酸三甲苯酯做基础油的中压抗燃油及其生产方法
CN103215106A (zh) * 2013-04-09 2013-07-24 天津市联瑞阻燃材料有限公司 以磷酸三二甲苯酯做基础油的航空级高压抗燃油及其生产方法
CN103224829A (zh) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 清洗专用抗燃油及其制备方法
CN103224828A (zh) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 以磷酸三甲苯酯做基础油的航空级高压抗燃油及其生产方法
CN103224825A (zh) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 以磷酸三二甲苯酯做基础油的中压抗燃油及其生产方法
CN103897786A (zh) * 2013-04-09 2014-07-02 天津市联瑞阻燃材料有限公司 一种磷酸三甲苯酯作基础油的高压抗燃油及其生产方法
CN110305722A (zh) * 2019-07-12 2019-10-08 安徽中天石化股份有限公司 一种磷酸酯抗燃液压油
IN201831035181A (zh) * 2018-09-18 2020-03-20

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2903537C2 (de) * 1979-01-31 1985-03-07 Mobil Oil Corp., New York, N.Y. Schwer entflammbare Flüssigkeit
AU669184B2 (en) * 1992-06-11 1996-05-30 Solutia Inc. Functional fluid
JP5467843B2 (ja) * 2009-11-12 2014-04-09 Ｊｘ日鉱日石エネルギー株式会社 難燃性油圧作動油組成物
CN101812355A (zh) * 2009-12-18 2010-08-25 益田润石（北京）化工有限公司 一种新型合成型抗燃液压油组合物
CN102899133B (zh) * 2011-07-29 2015-02-25 中国石油化工股份有限公司 一种磷酸酯液压油组合物
CN103666663B (zh) * 2012-09-25 2016-01-20 中国石油化工股份有限公司 一种磷酸酯液压油组合物
CN110724582A (zh) * 2019-10-08 2020-01-24 山东瑞兴阻燃科技有限公司 一种叔丁基化磷酸三苯酯抗燃液压油及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103215105A (zh) * 2013-04-09 2013-07-24 天津市联瑞阻燃材料有限公司 以磷酸三甲苯酯做基础油的中压抗燃油及其生产方法
CN103215106A (zh) * 2013-04-09 2013-07-24 天津市联瑞阻燃材料有限公司 以磷酸三二甲苯酯做基础油的航空级高压抗燃油及其生产方法
CN103224829A (zh) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 清洗专用抗燃油及其制备方法
CN103224828A (zh) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 以磷酸三甲苯酯做基础油的航空级高压抗燃油及其生产方法
CN103224825A (zh) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 以磷酸三二甲苯酯做基础油的中压抗燃油及其生产方法
CN103897786A (zh) * 2013-04-09 2014-07-02 天津市联瑞阻燃材料有限公司 一种磷酸三甲苯酯作基础油的高压抗燃油及其生产方法
IN201831035181A (zh) * 2018-09-18 2020-03-20
CN110305722A (zh) * 2019-07-12 2019-10-08 安徽中天石化股份有限公司 一种磷酸酯抗燃液压油

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