WO2025007447A1 - 一种无灰防锈剂及其制备方法 - Google Patents

一种无灰防锈剂及其制备方法 Download PDF

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WO2025007447A1
WO2025007447A1 PCT/CN2023/125587 CN2023125587W WO2025007447A1 WO 2025007447 A1 WO2025007447 A1 WO 2025007447A1 CN 2023125587 W CN2023125587 W CN 2023125587W WO 2025007447 A1 WO2025007447 A1 WO 2025007447A1
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Prior art keywords
preparation
rust inhibitor
acid
oil
ashless rust
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English (en)
French (fr)
Inventor
张雪涛
张孟佳
曾凯
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Petrochina Co Ltd
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Petrochina Co Ltd
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Priority to DE112023003499.0T priority Critical patent/DE112023003499T5/de
Publication of WO2025007447A1 publication Critical patent/WO2025007447A1/zh
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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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • 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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C10M157/06—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a sulfur-, selenium- or tellurium-containing compound
    • 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
    • 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
    • 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • 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
    • 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
    • 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
    • C10M2215/02—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
    • 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the invention relates to an ashless rust inhibitor and a preparation method thereof, belonging to the technical field of rust inhibitor preparation.
  • Ash-containing additives containing metal ions will affect the filterability of oil. Therefore, it is necessary to add ashless rust inhibitors to the oil.
  • oil-soluble ashless rust inhibitors include organic carboxylic acids/esters, organic amines, nitrogen-containing compounds and heterocyclic compounds.
  • patent US4409411 discloses the preparation of an alkyl succinic acid polyol ester ashless rust inhibitor for rust prevention of fuel oil and lubricating oil
  • patent US5055230 discloses an ashless rust inhibitor containing hydroxyl, ester and carboxylic acid groups, which can be used for water-based or oil-based products.
  • Patent US4165292 discloses the preparation of an ashless rust inhibitor of alkyl succinic acid amine, which is used for rust prevention of lubricating oil.
  • Patent US5275749 discloses an ashless rust inhibitor of acylated aspartic acid derivatives.
  • Patent US5254277 discloses an ashless rust inhibitor of bis(hydroxyethyl) animal fatty amine and its carboxylic acid ester, which is used for rust prevention of polyol esters.
  • the purpose of the present invention is to provide an ashless rust inhibitor and a preparation method thereof, wherein the ashless rust inhibitor has excellent rust prevention performance and has a good synergistic effect with an extreme pressure anti-wear agent.
  • the present invention first provides a method for preparing an ashless rust inhibitor, which comprises the following steps:
  • the polyene polyamine and the mixed acid A are mixed in a molar ratio of 0.5-2.0:1, and deionized water and methanol are added to react until the pH value of the solution is neutral;
  • Methyl methacrylate and base oil are added to the system after the reaction, and the temperature is raised for distillation, and then the reduced pressure distillation is performed until no obvious distillate is produced, thereby obtaining the ashless rust inhibitor.
  • the molar ratio of dinonylnaphthalenesulfonic acid to dodecenylsuccinic acid is 1:4-4:1.
  • the molar amount of mixed acid A is based on the sum of the molar amounts of dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid.
  • the non-polar solvent includes one or a combination of two or more of n-heptane, dioxane, and toluene.
  • the polyene polyamine includes one or a combination of two or more of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.
  • the molar ratio of the deionized water to the polyene polyamine is 0.5-1.5:1.
  • the molar ratio of methanol to polyene polyamine is 1.0-2.0: 1.
  • the present invention attempts to replace methanol with anhydrous ethanol and n-butanol, but the desired effect of the present invention cannot be obtained.
  • the reaction after adding deionized water and methanol is carried out at a temperature of 70 ⁇ 5°C.
  • the molar ratio of methyl methacrylate to polyene polyamine is 0.05-0.15:1.
  • the base oil is added in an amount such that the ratio of the total mass of the mixed acid A and the polyene polyamine to the mass of the base oil is 40:60-70:30.
  • the base oil includes one or a combination of two or more of industrial white oil, mineral oil, hydrogenated oil, and PAO base oil.
  • the temperature of the temperature-raising distillation is 145 ⁇ 5°C.
  • the temperature-raising distillation is carried out until no obvious fraction is distilled out, at which point most of the non-polar solvent and its azeotrope with water are replaced by the base oil.
  • the pressure of the reduced pressure distillation is 2 ⁇ 1 kPa.
  • the above preparation method can be carried out according to the following specific steps: in a non-polar solvent, dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid are mixed in a molar ratio of 0.5-2.0:1 to obtain a mixed acid A; further, polyene polyamine and the mixed acid A are mixed in a molar ratio of 0.5-2.0:1, and a small amount of deionized water is added.
  • the invention also provides an ashless rust inhibitor, which is prepared by the above preparation method.
  • the present invention also provides an oil product, wherein the oil product contains more than 0.02wt% of an ashless rust inhibitor and 0.01-0.03% of an extreme pressure anti-wear agent; the ashless rust inhibitor is the above-mentioned ashless rust inhibitor provided by the present invention.
  • the prior art does not involve an ashless rust inhibitor of a mixed acid amine of dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid.
  • the ashless rust inhibitor of the present invention is a single agent, the anion part of which is a mixed acid of dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid, and the cation part is polyene polyamine.
  • the ashless rust inhibitor of the present invention integrates the advantages of dinonylnaphthalenesulfonic acid group and dodecenylsuccinic acid group at the molecular level, has better rust prevention, and has good synergistic effect with extreme pressure anti-wear agent.
  • the present invention is characterized in that the reaction conditions are mild, the amination reaction is gel-free, the polyene polyamine can fully participate in the reaction, and no post-treatment is required, thereby achieving 100% utilization rate.
  • This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:
  • This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:
  • This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:
  • This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:
  • This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:
  • This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:
  • This comparative example provides a method for preparing an ashless rust inhibitor.
  • the specific steps are the same as those in Example 1, except that stearic acid is used, and the obtained ashless rust inhibitor is AAR-a.
  • This comparative example provides a method for preparing an ashless rust inhibitor.
  • the specific steps are the same as those in Example 1, except that oleic acid is used, and the obtained ashless rust inhibitor is AAR-b.
  • test oil was blended according to the blending scheme in Table 1, and the liquid phase corrosion performance of the ashless rust inhibitor AAR-1 and its effect on extreme pressure and anti-wear properties were tested. The results are shown in Table 1.
  • the manufacturer of extreme pressure anti-wear agent IR353 is BASF;
  • Liquid phase corrosion (B method) is carried out in accordance with ASTM D665B;
  • the wear spot diameter is tested in accordance with ASTM D4172.
  • AAR-1 has excellent anti-rust performance, and only 0.02% of the dosage is required to achieve liquid phase corrosion compliance, and it has a very good synergistic effect with the extreme pressure anti-wear agent, so that the extreme pressure anti-wear agent exhibits excellent extreme pressure anti-wear performance at a very low dosage.
  • 0.03% of the dosage is required for liquid phase corrosion compliance, and it will have a negative impact on extreme pressure anti-wear performance. It is necessary to add 0.03% of extreme pressure anti-wear agent to achieve the performance level of AAR-1.
  • stearic acid or oleic acid instead of dodecenylsuccinic acid and dinonylnaphthalenesulfonic acid for compounding cannot obtain qualified antirust performance.
  • the ashless rust inhibitors of Examples 2 to 6 were evaluated using the same evaluation scheme, and similar results were obtained, indicating that the ashless rust inhibitor of the present invention has excellent antirust performance, has very good synergy with the extreme pressure antiwear agent, and can significantly reduce the dosage of the extreme pressure antiwear agent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Lubricants (AREA)

Abstract

本发明提供了一种无灰防锈剂及其制备方法。该制备方法包括以下步骤：在非极性溶剂中，将二壬基萘磺酸和十二烯基丁二酸混合，得到混合酸A；将多烯多胺与混合酸A按0.5-2.0：1的摩尔比混合，加入去离子水和甲醇进行反应，直至溶液PH值为中性；向反应后的体系中加入甲基丙烯酸甲酯和基础油，升温蒸馏，然后再进行减压蒸馏，直至无明显蒸馏物产生，既得所述无灰防锈剂。本发明还提供了上述方法制备的无灰防锈剂。本发明的无灰防锈剂在分子层面整合了二壬基萘磺酸基团和十二烯基丁二酸基团的优点，防锈性更好，而且，该无灰防锈剂与极压抗磨剂有很好的协同作用。

Description

一种无灰防锈剂及其制备方法
交叉引用信息
本申请要求于2023年7月3日提交中国专利局、申请号为202310805380.5、发明名称为“一种无灰防锈剂及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种无灰防锈剂及其制备方法，属于防锈剂制备技术领域。
背景技术
为了满足苛刻工况的要求，工业油品中一般都要加入含有活性硫成分的极压抗磨剂。活性硫元素的引入，对系统中的铜、钢部件会产生腐蚀作用，而且因为工作过程中不可避免地会有水进入油品，将会加剧对钢部件的锈蚀，所以为了更好地保护机械部件，需要在油品中加入一定量的防锈剂。
另外，随着零部件的精密度越来越高，对油品的过滤性要求也越来越高，而含金属离子的有灰型添加剂会影响油品的过滤性，因此，需要在油品中加入无灰防锈剂。目前常用的油溶性无灰型防锈剂包括有机羧酸/酯类、有机胺及含氮化合物类及杂环化合物类。
众所周知，同时包含羧酸基和羟基官能团的化合物可用作无灰防锈剂，比如：专利US4409411公开了一种烷基丁二酸多元醇酯无灰防锈剂的制备，用于燃料油和润滑油的防锈；专利US5055230公开了一种包含羟基、酯基和羧酸基的无灰防锈剂，可用于水基或油基产品。
专利US4165292公开了一种烷基丁二酸胺无灰防锈剂的制备，用于润滑油的防锈。专利US5275749公开了一种酰化天冬氨酸衍生物无灰防锈剂。专利US5254277公开了一种双(羟乙基)动物脂肪胺及其羧酸酯的无灰防锈剂，用于多元醇酯的防锈。
另外，由于相互间存在竞争吸附，很多防锈剂会对极压抗磨剂的性能会产生不利影响，因此需要特别关注防锈剂与极压抗磨剂之间的复配，然而目前还缺少能够与极压抗磨剂实现良好配合的防锈剂。
发明内容
为解决上述技术问题，本发明的目的在于提供一种无灰防锈剂及其制备方法，该无灰防锈剂既具有优秀的防锈性能，而且与极压抗磨剂有很好的协同作用。
为达到上述目的，本发明首先提供了一种无灰防锈剂的制备方法，其包括以下步骤：
在非极性溶剂中，将二壬基萘磺酸和十二烯基丁二酸混合，得到混合酸A；
将多烯多胺与混合酸A按0.5-2.0：1的摩尔比混合，加入去离子水和甲醇进行反应，直至溶液PH值为中性；
向反应后的体系中加入甲基丙烯酸甲酯和基础油，升温蒸馏，然后再进行减压蒸馏，直至无明显蒸馏物产生，既得所述无灰防锈剂。
在上述制备方法中，优选地，所述二壬基萘磺酸和十二烯基丁二酸的摩尔比为1:4-4:1。
在上述制备方法中，计算多烯多胺与混合酸A的摩尔比时，混合酸A的摩尔量以二壬基萘磺酸和十二烯基丁二酸的摩尔量之和为基准。
在上述制备方法中，优选地，所述非极性溶剂包括正庚烷、二氧六环、甲苯中的一种或者两种以上的组合。
在上述制备方法中，优选地，所述多烯多胺包括二乙烯三胺、三乙烯四胺、四乙烯五胺的一种或者两种以上的组合。
在上述制备方法中，优选地，所述去离子水与多烯多胺的摩尔比为0.5-1.5：1。
在上述制备方法中，优选地，所述甲醇与多烯多胺的摩尔比为1.0-2.0：1。本发明尝试以无水乙醇、正丁醇替代甲醇，无法获得本发明所需要的效果。
在上述制备方法中，优选地，加入去离子水和甲醇之后的反应在70±5℃的温度下进行。
在上述制备方法中，优选地，所述甲基丙烯酸甲酯与多烯多胺的摩尔比为0.05-0.15：1。
在上述制备方法中，优选地，所述基础油的添加量为：混合酸A和多烯多胺的总质量与基础油的质量的比为40：60-70：30。
在上述制备方法中，优选地，所述基础油包括工业白油、矿物油、加氢油、PAO基础油的一种或者两种以上的组合。
在上述制备方法中，优选地，所述升温蒸馏的温度为145±5℃。
在上述制备方法中，优选地，所述升温蒸馏是进行至无明显馏分馏出，此时大部分非极性溶剂及其与水的共沸物被基础油取代。
在上述制备方法中，优选地，所述减压蒸馏的压力为2±1kPa。
根据本发明的具体实施方案，优选地，上述制备方法可以按照以下具体步骤进行：在非极性溶剂中，将二壬基萘磺酸和十二烯基丁二酸0.5-2.0：1的摩尔比混合，得到混合酸A；进一步地，将多烯多胺与混合酸A按0.5-2.0：1的摩尔比混合，加入少量去离 子水和甲醇，在70±5℃下反应，直至溶液PH值为中性；向体系中加入少量甲基丙烯酸甲酯和适量基础油，升温至145±5℃蒸馏，直至大部分溶剂及其与水的共沸物被基础油取代；随后在2±1kPa下减压蒸馏，直至无明显蒸馏物产生，既得本发明所述无灰防锈剂。
本发明还提供了一种无灰防锈剂，其是由上述制备方法制备的。
本发明还提供了一种油品，其中，该油品含有0.02wt％以上的无灰防锈剂和0.01-0.03％的极压抗磨剂；所述无灰防锈剂为本发明所提供的上述无灰防锈剂。
现有技术均未涉及二壬基萘磺酸和十二烯基丁二酸的混合酸胺无灰防锈剂。
本发明的无灰防锈剂为单剂，其阴离子部分为二壬基萘磺酸和十二烯基丁二酸的混合酸，阳离子部分为多烯多胺。本发明的无灰防锈剂在分子层面整合了二壬基萘磺酸基团和十二烯基丁二酸基团的优点，防锈性更好，而且，该无灰防锈剂与极压抗磨剂有很好的协同作用。本发明的特点在于反应条件温和，胺化反应无凝胶，多烯多胺能够完全参加反应，无需后处理，从而实现100％的利用率。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
实施例1
本实施例提供了一种无灰防锈剂的制备方法，具体包括以下步骤：
向配备回流冷凝管的250ml三口烧瓶中加入57g正庚烷，将37g二壬基萘磺酸、5.7g十二烯基丁二酸先后加入到烧瓶中，开启搅拌；
将14.6g三乙烯四胺缓慢滴加到烧瓶中，10分钟内加料完毕；
随后向烧瓶中加入3.2g甲醇和2.7g去离子水；
缓慢升温至70±5℃，反应1-2小时，直至溶液PH值为中性；
随后向体系中加入1.0g甲基丙烯酸甲酯和57g矿物基础油150SN，缓慢升温至145±5℃蒸馏，直至大部分溶剂及其与水的共沸物被基础油取代；
最后在2±1kPa下减压蒸馏，直至无明显蒸馏物产生，既得无灰防锈剂AAR-1。
实施例2
本实施例提供了一种无灰防锈剂的制备方法，具体包括以下步骤：
向配备回流冷凝管的250ml三口烧瓶中加入42g甲苯，将9.2g二壬基萘磺酸、22.7g十二烯基丁二酸先后加入到烧瓶中，开启搅拌；
将9.5g四乙烯五胺缓慢滴加到烧瓶中，10分钟内加料完毕；
随后向烧瓶中加入1.6g甲醇和1.4g去离子水；
缓慢升温至70±5℃，反应1-2小时，直至溶液PH值为中性；
随后向体系中加入0.5g甲基丙烯酸甲酯和28g辽河10号基础油，缓慢升温至145±5℃蒸馏，直至大部分溶剂及其与水的共沸物被基础油取代；
最后在2±1kPa下减压蒸馏，直至无明显蒸馏物产生，既得无灰防锈剂AAR-1。
实施例3
本实施例提供了一种无灰防锈剂的制备方法，具体包括以下步骤：
向配备回流冷凝管的250ml三口烧瓶中加入58g二氧六环，将23g二壬基萘磺酸、14g十二烯基丁二酸先后加入到烧瓶中，开启搅拌；
将21g二乙烯三胺缓慢滴加到烧瓶中，10分钟内加料完毕；
随后向烧瓶中加入6.4g甲醇和5.4g去离子水；
缓慢升温至70±5℃，反应1-2小时，直至溶液PH值为中性；
随后向体系中加入2g甲基丙烯酸甲酯和86g加氢基础油150N，缓慢升温至145±5℃蒸馏，直至大部分溶剂及其与水的共沸物被基础油取代；
最后在2±1kPa下减压蒸馏，直至无明显蒸馏物产生，既得无灰防锈剂AAR-3。
实施例4
本实施例提供了一种无灰防锈剂的制备方法，具体包括以下步骤：
向配备回流冷凝管的250ml三口烧瓶中加入56g正庚烷，将27.6g二壬基萘磺酸、11.4g十二烯基丁二酸先后加入到烧瓶中，开启搅拌；
将16.7g三乙烯四胺和四乙烯五胺的混合物缓慢滴加到烧瓶中，10分钟内加料完毕；
随后向烧瓶中加入3.2g甲醇和2.7g去离子水；
缓慢升温至70±5℃，反应1-2小时，直至溶液PH值为中性；
随后向体系中加入1g甲基丙烯酸甲酯和56g加氢基础油Yubase 4，缓慢升温至145±5℃蒸馏，直至大部分溶剂及其与水的共沸物被基础油取代；
最后在2±1kPa下减压蒸馏，直至无明显蒸馏物产生，既得无灰防锈剂AAR-4。
实施例5
本实施例提供了一种无灰防锈剂的制备方法，具体包括以下步骤：
向配备回流冷凝管的250ml三口烧瓶中加入48g二氧六环，将18.4g二壬基萘磺酸、17.0g十二烯基丁二酸先后加入到烧瓶中，开启搅拌；
将12.5g三乙烯四胺和二乙烯三胺的混合物缓慢滴加到烧瓶中，10分钟内加料完毕；
随后向烧瓶中加入3.2g甲醇和2.7g去离子水；
缓慢升温至70±5℃，反应1-2小时，直至溶液PH值为中性；
随后向体系中加入1g甲基丙烯酸甲酯和21g工业白油W1-100，缓慢升温至145±5℃蒸馏，直至大部分溶剂及其与水的共沸物被基础油取代；
最后在2±1kPa下减压蒸馏，直至无明显蒸馏物产生，既得无灰防锈剂AAR-5。
实施例6
本实施例提供了一种无灰防锈剂的制备方法，具体包括以下步骤：
向配备回流冷凝管的250ml三口烧瓶中加入52g甲苯，将23g二壬基萘磺酸、14.2g十二烯基丁二酸先后加入到烧瓶中，开启搅拌；
将14.6g二乙烯三胺、三乙烯四胺和四乙烯五胺的混合物缓慢滴加到烧瓶中，10分钟内加料完毕；
随后向烧瓶中加入3.2g甲醇和2.7g去离子水；
缓慢升温至70±5℃，反应1-2小时，直至溶液PH值为中性；
随后向体系中加入1g甲基丙烯酸甲酯和35g恒力10号基础油，缓慢升温至145±5℃蒸馏，直至大部分溶剂及其与水的共沸物被基础油取代；
最后在2±1kPa下减压蒸馏，直至无明显蒸馏物产生，既得无灰防锈剂AAR-6。
对比例1
本对比例提供了一种无灰防锈剂的制备方法，具体步骤与实施例1相同，不同之处在于采用硬脂酸，所得无灰防锈剂为AAR-a。
对比例2
本对比例提供了一种无灰防锈剂的制备方法，具体步骤与实施例1相同，不同之处在于采用油酸，所得无灰防锈剂为AAR-b。
测试例：
按照表1的调合方案调合试验油品，测试无灰防锈剂AAR-1的液相锈蚀性能以及对极压抗磨性的影响，结果见表1所示。
表1无灰防锈剂的性能评价

其中：极压抗磨剂IR353的生产厂家为巴斯夫；
液相锈蚀(B法)按照ASTM D665B的规定进行；
磨斑直径按照ASTM D4172的规定进行测试。
从表1中可以看出，AAR-1的防锈性能优异，只需0.02％的加剂量即可实现液相锈蚀合格，并且与极压抗磨剂具有非常好的协同效应，使极压抗磨剂在非常低的加剂量下表现出优异的极压抗磨性。而对于市售产品(巴斯夫的IRGACOR L844)，需要0.03％的加剂量液相锈蚀才合格，并且会对极压抗磨性带来负面影响，需要添加0.03％的极压抗磨剂才能达到AAR-1的性能水平。
采用硬脂酸、油酸替代十二烯基丁二酸与二壬基萘磺酸进行复配也无法获得合格的防锈性能。
采用相同的评价方案评价实施例2-实施例6的无灰防锈剂，可得到类似的结果。说明本发明的无灰防锈剂的防锈性能优越，与极压抗磨剂的协同性非常好，可明显降低极压抗磨剂的加剂量。
以上为本发明的典型实施例，并不用于限制本发明，凡在本发明的原则之内所做的任何修改、等同替换和改进等，均应在本发明的保护范围之内。

Claims (17)

  1. 一种无灰防锈剂的制备方法，其包括以下步骤：
    在非极性溶剂中，将二壬基萘磺酸和十二烯基丁二酸混合，得到混合酸A；
    将多烯多胺与混合酸A按0.5-2.0：1的摩尔比混合，加入去离子水和甲醇进行反应，直至溶液PH值为中性；
    向反应后的体系中加入甲基丙烯酸甲酯和基础油，升温蒸馏，然后再进行减压蒸馏，直至无明显蒸馏物产生，既得所述无灰防锈剂。
  2. 根据权利要求1所述的制备方法，其中，所述二壬基萘磺酸和十二烯基丁二酸的摩尔比为1:4-4:1。
  3. 根据权利要求1所述的制备方法，其中，所述非极性溶剂包括正庚烷、二氧六环、甲苯中的一种或者两种以上的组合。
  4. 根据权利要求1所述的制备方法，其中，所述多烯多胺包括二乙烯三胺、三乙烯四胺、四乙烯五胺的一种或者两种以上的组合。
  5. 根据权利要求1所述的制备方法，其中，所述去离子水与多烯多胺的摩尔比为0.5-1.5：1。
  6. 根据权利要求1所述的制备方法，其中，所述甲醇与多烯多胺的摩尔比为1.0-2.0：1。
  7. 根据权利要求1所述的制备方法，其中，加入去离子水和甲醇之后的反应在70±5℃的温度下进行。
  8. 根据权利要求1所述的制备方法，其中，所述甲基丙烯酸甲酯与多烯多胺的摩尔比为0.05-0.15：1。
  9. 根据权利要求1所述的制备方法，其中，所述基础油的添加量为：混合酸和多烯多胺的总质量与基础油的质量的比为40：60-70：30。
  10. 根据权利要求1所述的制备方法，其中，所述基础油包括工业白油、矿物油、加氢油、PAO基础油的一种或者两种以上的组合。
  11. 根据权利要求9所述的制备方法，其中，所述基础油包括工业白油、矿物油、加氢油、PAO基础油的一种或者两种以上的组合。
  12. 根据权利要求1所述的制备方法，其中，所述升温蒸馏的温度为145±5℃。
  13. 根据权利要求1所述的制备方法，其中，所述升温蒸馏是进行至无明显馏分馏出。
  14. 根据权利要求12所述的制备方法，其中，所述升温蒸馏是进行至无明显馏分馏出。
  15. 根据权利要求1所述的制备方法，其中，所述减压蒸馏的压力为2±1kPa。
  16. 一种无灰防锈剂，其是由权利要求1-15任一项所述的制备方法制备的。
  17. 一种油品，其中，该油品含有0.02wt％以上的无灰防锈剂和0.01-0.03％的极压抗磨剂；
    所述无灰防锈剂为权利要求16所述的无灰防锈剂。
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CN119955560B (zh) * 2023-11-08 2025-11-18 中国石油天然气股份有限公司 含混合酸多胺的无灰防锈剂组合物及制备方法

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