WO2025007453A1 - 一种硼化脂肪酸甘油酯抗磨添加剂及其制备方法 - Google Patents

一种硼化脂肪酸甘油酯抗磨添加剂及其制备方法 Download PDF

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WO2025007453A1
WO2025007453A1 PCT/CN2023/126781 CN2023126781W WO2025007453A1 WO 2025007453 A1 WO2025007453 A1 WO 2025007453A1 CN 2023126781 W CN2023126781 W CN 2023126781W WO 2025007453 A1 WO2025007453 A1 WO 2025007453A1
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fatty acid
preparation
formula
added
glycerol
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French (fr)
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范丰奇
周康
于海
吕会英
王玉玲
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Petrochina Co Ltd
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Petrochina Co Ltd
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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • 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
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/74—Esters of polyhydroxy 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C10M2227/062—Cyclic esters
    • 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

Definitions

  • the invention belongs to the field of lubricating oil additives and relates to a boronated fatty acid glyceride anti-wear additive and a preparation method thereof.
  • boron additives are gaining more and more attention due to their unique chemical properties.
  • Boron additives can be divided into inorganic borates and organic borates from the perspective of chemical structure. Borate additives not only have excellent thermal oxidation stability and sealing adaptability, no corrosion to copper at high temperatures, and good anti-rust properties for steel, but also help improve the operating environment, have excellent load-bearing capacity and anti-friction and anti-wear properties, and have been widely used in engine oils and industrial gear oils.
  • Patents US4394277, US4465605, and US4486323 report sulfur-containing borate esters. These borate esters are generally formed by the reaction of S-containing monohydroxy compounds or polyhydroxy compounds with boric acid to form esters.
  • Patents US4555353, US4536306, US4557844, and US006228818 respectively disclose borate compounds containing phosphoric acid ester structures.
  • the above research work has improved the performance of borate additives in different aspects, but the introduction of some active elements has limited the application of additives to a certain extent.
  • the development of oil technology has put forward new requirements for additives. Engine oil has made stricter restrictions on the S and P elements of additives.
  • GF-6 engine oil requires that the S element is not more than 0.5% and the P element is not more than 0.08%.
  • High-end industrial gear oils are increasingly concerned about the odor, biodegradability, and whether they meet food grade certification requirements of additives.
  • the development of low-sulfur, low-phosphorus biodegradable borate additives will be a way to meet the needs of new oil products.
  • the molecular adjustability of fatty acid glycerides is strong, triglycerides have good thermal stability, and the molecules of monoglycerides and diesters contain adsorption groups such as ester bonds and hydroxyls, which have good lubrication properties.
  • Patents US4734211, US4764296 and CN105658779 disclose the use of boronized oleic acid glycerides in engine oils.
  • Patents US004507216 and US005006276 disclose the use of hindered phenols and hydroxyl-containing esters reacted with boric acid to generate a mixed borate ester.
  • Patent US5759965 discloses a method for preparing boronized fatty acid glycerides using boric acid and fatty acid glycerides.
  • the above patents mainly use boric acid as a boronating agent to prepare boronized fatty acid glycerides.
  • the purpose of the present invention is to provide a boronated fatty acid glyceride anti-wear additive and a preparation method thereof and a lubricating oil, wherein the anti-wear additive has excellent anti-wear performance and good thermal stability, and has no adverse effect on the corrosion performance of the lubricating oil.
  • the present invention provides a boronated fatty acid glyceride anti-wear additive, which comprises: a compound shown in formula I, a compound shown in formula II, and a compound shown in formula III;
  • R 1 , R 2 and R 3 are the same or different and are independently selected from C 3 -C 24 hydrocarbon groups;
  • R is selected from a C 3 -C 24 hydrocarbon group, and R 5 is selected from a C 4 -C 24 alkyl group and a C 6 -C 18 aryl group;
  • R 5 is selected from C 4 -C 24 alkyl, C 6 -C 18 aryl; R 4 and R 6 are the same or different, and are independently selected from Wherein, R7 and R8 are the same or different and are independently selected from C3 - C24 hydrocarbon groups.
  • the mass ratio of the compound represented by formula I, the compound represented by formula II, and the compound represented by formula III is (8-12): (46-52): (36-46).
  • the present invention also provides a method for preparing the boronated fatty acid glyceride anti-wear additive, which comprises the following steps:
  • step (2) mixing a boronating agent and a solvent, adding the fatty acid glyceride mixture obtained in step (1), an inert gas with water, heating to 60-150° C., reacting for 3-8 hours, to obtain the boronated fatty acid glyceride anti-wear additive;
  • the boronating agent is an alkyl boric acid and/or an aryl boric acid.
  • step (1) glycerol is mixed with a solid acid catalyst, a C 4 -C 24 fatty acid is added dropwise, an esterification reaction is carried out, and an inert gas is introduced with water to obtain a fatty acid glyceride mixture.
  • the molar ratio of the C 4 -C 25 fatty acid and glycerol calculated based on carboxyl groups and hydroxyl groups is 1:3-2.5:3.
  • the molar ratio of the C 4 -C 24 fatty acid to glycerol calculated based on carboxyl groups to hydroxyl groups is 1:3-2.5:3.
  • the molar ratio of the C 4 -C 25 fatty acid and glycerol calculated based on carboxyl groups and hydroxyl groups is 1.1:3-1.8:3.
  • the molar ratio of the C 4 -C 24 fatty acid to glycerol calculated based on carboxyl groups and hydroxyl groups is 1.1:3-1.8:3.
  • the reaction temperature is 80-160° C.
  • the reaction time is 3-10 h.
  • the solid acid catalyst comprises one or a combination of two or more of Al2O3 , Al2O3 - SiO2 , metal salts (such as sulfates, phosphates), molecular sieve ZSM-5, and MCM-41.
  • the amount of the solid acid catalyst added is 0.05 wt% to 1.2 wt% of the total mass of the C 4 -C 25 fatty acid and glycerol.
  • the amount of the solid acid catalyst added is 0.05 wt% to 1.2 wt% of the total mass of the C 4 -C 24 fatty acid and glycerol.
  • the boronating agent has a structure shown in Formula IV:
  • R 5 is selected from C 4 -C 24 alkyl and C 6 -C 18 aryl.
  • the molar amount of the boronating agent added is [(3a-b)/2] to (3a-b), wherein a is the molar amount of glycerol added, and b is the molar amount of C 4 -C 25 fatty acid added.
  • the molar amount of the boronating agent added is [(3a-b)/2] to (3a-b), wherein a is the molar amount of glycerol added, and b is the molar amount of C 4 -C 24 fatty acid added.
  • the solvent is one or a combination of two or more of petroleum ether, benzene, toluene, cyclohexane, n-heptane, n-octane and xylene.
  • the amount of solvent added is 50 wt%-150 wt% of the total mass of the fatty acid glyceride mixture.
  • the inert gas is nitrogen and/or helium.
  • the present invention also provides a lubricating oil, which includes the boronized fatty acid glyceride anti-wear additive.
  • the boronized fatty acid glyceride anti-wear additive can be used alone as a lubricating oil anti-wear and friction reducing additive, or can be used in combination with other lubricating oil additives.
  • the boronated fatty acid glyceride anti-wear additive is added to the base oil in an amount of 0.2 wt% to 10 wt%.
  • the above preparation method comprises the following specific steps:
  • step (2) adding a certain amount of one or more boronating agents of alkyl boronic acid or aryl boronic acid with a specific structure and a solvent into a reactor, stirring and mixing evenly, adding the fatty acid glyceride mixture obtained in step (1), inert gas with water, heating to 60-150° C., continuing the reaction for 3-8 hours, and removing the solvent by reduced pressure distillation to obtain a boronated fatty acid glyceride anti-wear additive.
  • the present invention firstly utilizes the reaction of fatty acid and glycerol to prepare a fatty acid glyceride mixture of a specific composition, and then synthesizes a boronized fatty acid glyceride by a one-step esterification reaction of the fatty acid glyceride and a boronized reagent in a certain proportion.
  • the agent has a simple production process, is easy to operate, safe and environmentally friendly, has a simple post-processing process, and has a low production cost.
  • Different series of anti-wear additive products can be prepared according to specific needs. The product has excellent anti-wear performance and good thermal stability, and will not have adverse effects on the corrosion performance of lubricating oil.
  • FIG1 is a gel chromatogram of boronated olein.
  • This embodiment provides a boronized fatty acid glyceride anti-wear additive, and the preparation method thereof is as follows:
  • This embodiment provides a boronized fatty acid glyceride anti-wear additive, and the preparation method thereof is as follows:
  • step (1) 142.2 g of octylboric acid (0.9 mol) and 300 g of toluene were added to a reaction vessel, stirred and mixed evenly, and glyceryl isooctanoate in step (1) was added, nitrogen was passed through with water, the temperature was raised to 90° C., the reaction was continued for 5 hours, and the solvent was removed by reduced pressure distillation to obtain boronized glyceryl isooctanoate anti-wear additive B.
  • This embodiment provides a boronized fatty acid glyceride anti-wear additive, and the preparation method thereof is as follows:
  • This embodiment provides a boronized fatty acid glyceride anti-wear additive, and the preparation method thereof is as follows:
  • This comparative example provides a boronized fatty acid glyceride anti-wear additive, and its preparation method is as follows:
  • This comparative example provides a boronized fatty acid glyceride anti-wear additive, and its preparation method is as follows:
  • This comparative example provides a boronized fatty acid monoglyceride anti-wear additive, and the preparation method thereof is as follows:
  • the boronated oleic acid glycerides prepared in the examples and comparative examples were characterized by gel chromatography, wherein the gel chromatography of Example 1 is shown in FIG1 , and the component content ratios of the examples and comparative examples are shown in Table 1.
  • the boronated fatty acid glyceride anti-wear additive obtained in the examples and comparative examples was added to GL-5 gear oil in an amount of 1.0wt%.
  • the wear spot diameter, sintering load (PD value), friction coefficient and copper sheet corrosion performance of the lubricating oil under a load of 392N were then measured. The results are shown in Table 1.
  • the maximum no-seizure load (PD value) was determined according to the method of GB/T 3142-1982, the wear spot diameter of the steel ball was determined according to the method of NB/SH/T0189-2017, the friction coefficient was determined according to the method of SH/T 0762-2005, and the copper sheet corrosion was determined according to the method of GB/T 5096-2017.
  • the anti-wear additive of the present invention has excellent anti-wear and friction reduction properties, and has no adverse effect on the corrosion properties of the lubricating oil.

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

Abstract

本发明提供了一种硼化脂肪酸甘油酯抗磨添加剂及其制备方法，该抗磨添加剂组成包括：式（Ⅰ）所示化合物、式（Ⅱ）所示化合物、式（Ⅲ）所示化合物：式（Ⅰ）中，R1、R2和R3相同或不同，各自独立地选自C3-C24的烃基；式（Ⅱ）中，R选自C3-C24的烃基，R5选自C4-C24的烷基、C6-C18的芳基；式（Ⅲ）中，R5选自C4-C24的烷基、C6-C18的芳基；R4和R6相同或不同，各自独立地选自式（A），式（B），其中，R7和R8相同或不同，各自独立地选自C3-C24的烃基。该抗磨添加剂具有优异的抗磨性能和良好的热稳定性、且对润滑油的腐蚀性能不会产生不良影响。

Description

一种硼化脂肪酸甘油酯抗磨添加剂及其制备方法 技术领域
本发明属于润滑油添加剂领域，涉及一种硼化脂肪酸甘油酯抗磨添加剂及其制备方法。
背景技术
作为一类新型环境友好型润滑油添加剂，硼系添加剂以其独特的化学特性受到人们越来越多的重视。硼系添加剂从化学结构来看，可分为无机硼酸盐类和有机硼酸酯类，硼酸酯类添加剂不仅具有优良的热氧化安定性和密封适应性、在高温下对铜无腐蚀作用，对钢铁具有良好的防锈性能，同时利于改善操作环境，具备优异的承载能力和减摩抗磨性能，已在发动机油、工业齿轮油中得到广泛应用。
近年来为了提高硼酸酯润滑油添加剂的性能，将N、S、P等活性元素引入到硼酸酯分子中成为研究的热点。在硼酸酯的分子结构中引入氮原子，使氮原子与硼原子形成B-N配位键是目前用来改善硼酸酯水解稳定性的一种有效的方法，专利US4204972、US5084194、CN114605460、CN100350025均介绍了含胺基硼酸酯，这类硼酸酯一般是由含羟基的长链胺直接与硼酸反应成酯，这些含胺基的硼酸酯大多具有好的减摩性能和高的热氧化稳定性。专利US4394277、US4465605、US4486323报道了含硫硼酸酯，这类硼酸酯一般是用含S单羟基化合物或多羟基化合物与硼酸反应成酯。专利US4555353、US4536306、US4557844、US006228818分别公开了含磷酸酯结构的硼酸酯化合物。上述研究工作均在不同方面提升了硼酸酯添加剂的性能，但一些活性元素引入又在一定程度上限制了添加剂的应用，油品技术发展对添加剂提出了新的要求，发动机油对添加剂的S、P元素做出了更严格的限制，GF-6发动机油要求S元素不大于0.5％，P元素不大于0.08％；高端工业齿轮油越来越关注添加剂的气味、可生物降解性、是否满足食品级认证要求等，开发低硫、低磷的可生物降解型硼酸酯添加剂将是满足新型油品需求的一种思路。
酯肪酸甘油酯的分子可调节性强，甘油三酯热稳定性好，甘油单酯和双酯的分子中包含酯键、羟基等吸附基团，具有良好的润滑性能。专利US4734211、US4764296和CN105658779公开了硼化油酸甘油酯在发动机油中的应用。专利US004507216、US005006276公开了用位阻酚及含羟基酯再与硼酸反应生成一种混合硼酸酯。专利US5759965公开了用硼酸与脂肪酸甘油酯制备硼化脂肪酸甘油酯的方法。上述专利主要是应用硼酸作为硼化试剂制备硼化脂肪酸甘油酯。
发明内容
为了解决上述问题，本发明的目的在于提供一种硼化脂肪酸甘油酯抗磨添加剂及其制备方法与一种润滑油，该抗磨添加剂具有优异的抗磨性能和良好的热稳定性，且对润滑油的腐蚀性能不会产生不良影响。
为了达到上述目的，本发明提供了一种硼化脂肪酸甘油酯抗磨添加剂，其组成包括：式Ⅰ所示化合物、式Ⅱ所示化合物、式Ⅲ所示化合物；
式Ⅰ中，R1、R2和R3相同或不同，各自独立地选自C3-C24的烃基；
式Ⅱ中，R选自C3-C24的烃基，R5选自C4-C24的烷基、C6-C18的芳基；
式Ⅲ中，R5选自C4-C24的烷基、C6-C18的芳基；R4和R6相同或不同，各自独立地选自其中，R7和R8相同或不同，各自独立地选自C3-C24的烃基。
根据本发明的具体实施方案，优选地，式Ⅰ所示化合物、式Ⅱ所示化合物、式Ⅲ所示化合物三者的质量比为(8-12)：(46-52)：(36-46)。
本发明还提供了上述硼化脂肪酸甘油酯抗磨添加剂的制备方法，其包括以下步骤：
(1)将甘油与固体酸催化剂混合，滴加C4-C25的脂肪酸，进行酯化反应，通入惰性气体带水，得到脂肪酸甘油酯混合物；
(2)将硼化试剂和溶剂混合，加入步骤(1)所得脂肪酸甘油酯混合物，惰性气体带水，升温至60-150℃，反应3-8小时，得到所述硼化脂肪酸甘油酯抗磨添加剂；所述硼化试剂为烷基硼酸和/或芳基硼酸。
根据本发明的具体实施方案，优选地，步骤(1)中，将甘油与固体酸催化剂混合，滴加C4-C24的脂肪酸，进行酯化反应，通入惰性气体带水，得到脂肪酸甘油酯混合物。
根据本发明的具体实施方案，优选地，步骤(1)中，所述C4-C25的脂肪酸和甘油以羧基与羟基计算的摩尔比为1:3-2.5:3。
根据本发明的具体实施方案，优选地，步骤(1)中，所述C4-C24的脂肪酸和甘油以羧基与羟基计算的摩尔比为1:3-2.5:3。
根据本发明的具体实施方案，优选地，步骤(1)中，所述C4-C25的脂肪酸和甘油以羧基与羟基计算的摩尔比为1.1:3-1.8:3。
根据本发明的具体实施方案，优选地，步骤(1)中，所述C4-C24的脂肪酸和甘油以羧基与羟基计算的摩尔比为1.1:3-1.8:3。
根据本发明的具体实施方案，优选地，步骤(1)中，反应温度为80-160℃，反应时间为3-10h。
根据本发明的具体实施方案，优选地，步骤(1)中，所述固体酸催化剂包括Al2O3、Al2O3-SiO2、金属盐类(例如硫酸盐、磷酸盐)、分子筛ZSM-5、MCM-41中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，步骤(1)中，所述固体酸催化剂的加入量为所述C4-C25的脂肪酸和甘油的总质量的0.05wt％-1.2wt％。
根据本发明的具体实施方案，优选地，步骤(1)中，所述固体酸催化剂的加入量为所述C4-C24的脂肪酸和甘油的总质量的0.05wt％-1.2wt％。
根据本发明的具体实施方案，优选地，步骤(2)中，所述硼化试剂具有式Ⅳ所示的结构：
式Ⅳ中，R5选自C4-C24的烷基、C6-C18的芳基。
根据本发明的具体实施方案，优选地，步骤(2)中，所述硼化试剂加入摩尔量为[(3a-b)/2]至(3a-b)，其中，a为甘油加入的摩尔量，b为C4-C25脂肪酸加入的摩尔量。
根据本发明的具体实施方案，优选地，步骤(2)中，所述硼化试剂加入摩尔量为[(3a-b)/2]至(3a-b)，其中，a为甘油加入的摩尔量，b为C4-C24脂肪酸加入的摩尔量。
根据本发明的具体实施方案，优选地，步骤(2)中，所述溶剂为石油醚、苯、甲苯、环己烷、正庚烷、正辛烷、二甲苯中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，步骤(2)中，所述溶剂加入量为所述脂肪酸甘油酯混合物总质量的50wt％-150wt％。
根据本发明的具体实施方案，优选地，所述惰性气体为氮气和/或氦气。
本发明还提供了一种润滑油，其包括上述硼化脂肪酸甘油酯抗磨添加剂。所述硼化脂肪酸甘油酯抗磨添加剂可作为润滑油抗磨和减磨添加剂单独使用，也可以和其它润滑油添加剂复合使用。
根据本发明的具体实施方案，优选地，所述硼化脂肪酸甘油酯抗磨添加剂在基础油中的添加量为0.2wt％-10wt％。
根据本发明的具体实施方案，上述制备方法包括以下具体步骤：
(1)以C4-C25直链或支链的一元脂肪酸和甘油为原料，一定量的固体酸催化剂；将所述甘油与所述固体酸催化剂一次性投入反应器中，滴加脂肪酸，升温进行反应，通入惰性气体带水，当反应体系无水产生时，停止反应过滤，得到脂肪酸甘油酯混合物；
(2)将一定量的特定结构的烷基硼酸或芳基硼酸中的一种或多种硼化试剂和溶剂加入反应器中，搅拌混合均匀，加入步骤(1)所得脂肪酸甘油酯混合物，惰性气体带水，升温至60-150℃，持续反应3-8小时后，减压蒸馏除去溶剂，得到硼化脂肪酸甘油酯抗磨添加剂。
本发明首先利用脂肪酸与甘油反应制备特定组成的脂肪酸甘油酯混合物，然后按一定比例将脂肪酸甘油酯与硼化试剂通过一步酯化反应合成一种硼化脂肪酸甘油酯添加 剂，其生产工艺简单易操作、安全环保、后处理工艺简单、生产成本低，生产可根据具体需要制备不同系列的抗磨添加剂产品，该产品具有优异的抗磨性能和良好的热稳定性，且对润滑油的腐蚀性能不会产生不良影响。
附图说明
图1为硼化油酸甘油酯凝胶色谱图。
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硼化脂肪酸甘油酯抗磨添加剂，其制备方法如下：
(1)将92.1g甘油(1摩尔)和2.16g Al2O3-SiO2催化剂加入到反应器中，搅拌混合均匀，滴加入339g的油酸(1.2摩尔)，升温至150℃，氮气带水，持续反应5小时，体系无水产生时，停止反应过滤，得到油酸甘油酯；
(2)将121.9g苯硼酸(1摩尔)和400g石油醚加入反应容器中，搅拌混合均匀，加入步骤(1)中油酸甘油酯，通氮气带水，升温至95℃，持续反应4小时后，减压蒸馏除去溶剂，得到硼化油酸甘油酯抗磨添加剂A。
实施例2
本实施例提供了一种硼化脂肪酸甘油酯抗磨添加剂，其制备方法如下：
(1)将92.1g甘油(1摩尔)和0.22g ZSM-5催化剂加入到反应器中，搅拌混合均匀，滴加入187.5g的异辛酸(1.3摩尔)，升温至130℃，氮气带水，持续反应4.5小时，体系无水产生时，停止反应过滤，得到异辛酸甘油酯；
(2)将142.2g辛基硼酸(0.9摩尔)和300g甲苯加入反应容器中，搅拌混合均匀，加入步骤(1)中异辛酸甘油酯，通氮气带水，升温至90℃，持续反应5小时后，减压蒸馏除去溶剂，得到硼化异辛酸甘油酯抗磨添加剂B。
实施例3
本实施例提供了一种硼化脂肪酸甘油酯抗磨添加剂，其制备方法如下：
(1)将92.1g甘油(1摩尔)和3.6g MCM-41催化剂加入到反应器中，搅拌混合均匀，滴加入356.2g的十六烯酸(1.4摩尔)，升温至160℃，氮气带水，持续反应4小时，体系无水产生时，停止反应过滤，得到十六烯酸甘油酯；
(2)将136g对甲基苯硼酸(1摩尔)和300g二甲苯加入反应容器中，搅拌混合均 匀，加入步骤(1)中十六烯酸甘油酯，通氮气带水，升温至105℃，持续反应6小时后，减压蒸馏除去溶剂，得到硼化十六烯酸甘油酯抗磨添加剂C。
实施例4
本实施例提供了一种硼化脂肪酸甘油酯抗磨添加剂，其制备方法如下：
(1)将46.1g甘油(0.5摩尔)和2.16g K2SO4催化剂加入到反应器中，搅拌混合均匀，滴加入226g的油酸(0.8摩尔)，升温至155℃，工业氦气带水，持续反应8小时，体系无水产生时，停止反应过滤，得到油酸甘油酯；
(2)将54.4g对甲基苯硼酸(0.4摩尔)和200g甲苯加入反应容器中，搅拌混合均匀，加入步骤(1)中油酸甘油酯，通氦气带水，升温至110℃，持续反应8小时后，减压蒸馏除去溶剂，得到硼化油酸甘油酯抗磨添加剂D。
对比例1
本对比例提供了一种硼化脂肪酸甘油酯抗磨添加剂，其制备方法如下：
(1)将92.1g甘油(1摩尔)和2.16g Al2O3-SiO2催化剂加入到反应器中，搅拌混合均匀，滴加入339g的油酸(1.2摩尔)，升温至150℃，氮气带水，持续反应5小时，体系无水产生时，停止反应过滤，得到油酸甘油酯；
(2)将61.83g硼酸(1摩尔)和400g石油醚加入反应容器中，搅拌混合均匀，加入步骤(1)中油酸甘油酯，氮气带水，升温至95℃，持续反应4小时后，减压蒸馏除去溶剂，得到硼化油酸甘油酯抗磨添加剂E。
对比例2
本对比例提供了一种硼化脂肪酸甘油酯抗磨添加剂，其制备方法如下：
将61.83g硼酸(1摩尔)和400g石油醚加入反应容器中，搅拌混合均匀，加入213.9g甘油单油酸脂(0.6摩尔)，通氮气带水，升温至95℃，持续反应4小时后，减压蒸馏除去溶剂，得到硼化甘油单油酸脂抗磨添加剂F。
对比例3
本对比例提供了一种硼化脂肪酸单甘油酯抗磨添加剂，其制备方法如下：
将136g对甲基苯硼酸(1摩尔)和400g石油醚加入反应容器中，搅拌混合均匀，加入164.3g甘油单十六烯酸酯(0.5摩尔)，通氮气带水，升温至105℃，持续反应6小时后，减压蒸馏除去溶剂，得到硼化十六烯酸单甘油酯抗磨添加剂G。
对实施例和对比例制备的硼化油酸甘油酯进行了凝胶色谱的表征，其中实施例1的凝胶色谱见图1，各实施例和对比例的组分含量比见表1。
将实施例、对比例得到的硼化脂肪酸甘油酯抗磨添加剂以1.0wt％的添加量调入GL-5齿轮油中，随后对该润滑油在392N载荷下的磨斑直径、烧结负荷(PD值)、392N载荷下的摩擦系数和铜片腐蚀性能进行了测定，结果见表1。
依据GB/T 3142-1982的方法测定了最大无卡咬负荷(PD值)，依据NB/SH/T0189-2017的方法测定了钢球的磨斑直径，依据SH/T 0762-2005的方法进行摩擦系数的测定，依据GB/T 5096-2017的方法进行铜片腐蚀的测定。
表1硼化脂肪酸甘油酯抗磨添加剂性能评价
结果表明本发明抗磨添加剂具有优异的抗磨和减摩性能，同时对润滑油的腐蚀性能无不良影响。

Claims (20)

  1. 一种硼化脂肪酸甘油酯抗磨添加剂，其组成包括：式Ⅰ所示化合物、式Ⅱ所示化合物、式Ⅲ所示化合物；
    式Ⅰ中，R1、R2和R3相同或不同，各自独立地选自C3-C24的烃基；
    式Ⅱ中，R选自C3-C24的烃基，R5选自C4-C24的烷基、C6-C18的芳基；
    式Ⅲ中，R5选自C4-C24的烷基、C6-C18的芳基；R4和R6相同或不同，各自独立地选自其中，R7和R8相同或不同，各自独立地选自C3-C24的烃基。
  2. 根据权利要求1所述的硼化脂肪酸甘油酯抗磨添加剂，其中，式Ⅰ所示化合物、式Ⅱ所示化合物、式Ⅲ所示化合物三者的质量比为(8-12)：(46-52)：(36-46)。
  3. 权利要求1或2所述的硼化脂肪酸甘油酯抗磨添加剂的制备方法，其包括以下步骤：
    (1)将甘油与固体酸催化剂混合，滴加C4-C25的脂肪酸，进行酯化反应，通入惰 性气体带水，得到脂肪酸甘油酯混合物；
    (2)将硼化试剂和溶剂混合，加入步骤(1)所得脂肪酸甘油酯混合物，惰性气体带水，升温至60-150℃，反应3-8小时，得到所述硼化脂肪酸甘油酯抗磨添加剂；
    所述硼化试剂为烷基硼酸和/或芳基硼酸。
  4. 根据权利要求3所述的制备方法，其中，所述制备方法包括以下步骤：
    (1)将甘油与固体酸催化剂混合，滴加C4-C24的脂肪酸，进行酯化反应，通入惰性气体带水，得到脂肪酸甘油酯混合物；
    (2)将硼化试剂和溶剂混合，加入步骤(1)所得脂肪酸甘油酯混合物，惰性气体带水，升温至60-150℃，反应3-8小时，得到所述硼化脂肪酸甘油酯抗磨添加剂；
    所述硼化试剂为烷基硼酸和/或芳基硼酸。
  5. 根据权利要求3所述的制备方法，其中，步骤(1)中，所述C4-C25的脂肪酸和甘油以羧基与羟基计算的摩尔比为1:3-2.5:3。
  6. 根据权利要求3所述的制备方法，其中，步骤(1)中，所述C4-C24的脂肪酸和甘油以羧基与羟基计算的摩尔比为1:3-2.5:3。
  7. 根据权利要求5所述的制备方法，其中，步骤(1)中，所述C4-C25的脂肪酸和甘油以羧基与羟基计算的摩尔比为1.1:3-1.8:3。
  8. 根据权利要求6所述的制备方法，其中，步骤(1)中，所述C4-C24的脂肪酸和甘油以羧基与羟基计算的摩尔比为1.1:3-1.8:3。
  9. 根据权利要求3所述的制备方法，其中，步骤(1)中，反应温度为80-160℃，反应时间为3-10h。
  10. 根据权利要求3所述的制备方法，其中，步骤(1)中，所述固体酸催化剂包括Al2O3、Al2O3-SiO2、金属盐类、分子筛ZSM-5、MCM-41中的一种或两种以上的组合。
  11. 根据权利要求3所述的制备方法，其中，步骤(1)中，所述固体酸催化剂的加入量为所述C4-C25的脂肪酸和甘油的总质量的0.05wt％-1.2wt％。
  12. 根据权利要求3所述的制备方法，其中，步骤(1)中，所述固体酸催化剂的加入量为所述C4-C24的脂肪酸和甘油的总质量的0.05wt％-1.2wt％。
  13. 根据权利要求3所述的制备方法，其中，步骤(2)中，所述硼化试剂具有式Ⅳ所示的结构：
    式Ⅳ中，R5选自C4-C24的烷基、C6-C18的芳基。
  14. 根据权利要求3所述的制备方法，其中，步骤(2)中，所述硼化试剂加入摩尔量为[(3a-b)/2]至(3a-b)，其中，a为甘油加入的摩尔量，b为C4-C25脂肪酸加入的摩尔量。
  15. 根据权利要求3所述的制备方法，其中，步骤(2)中，所述硼化试剂加入摩尔量为[(3a-b)/2]至(3a-b)，其中，a为甘油加入的摩尔量，b为C4-C24脂肪酸加入的摩尔量。
  16. 根据权利要求3所述的制备方法，其中，步骤(2)中，所述溶剂为石油醚、苯、甲苯、环己烷、正庚烷、正辛烷、二甲苯中的一种或两种以上的组合。
  17. 根据权利要求3所述的制备方法，其中，步骤(2)中，所述溶剂加入量为所述脂肪酸甘油酯混合物总质量的50wt％-150wt％。
  18. 根据权利要求3所述的制备方法，其中，所述惰性气体为氮气和/或氦气。
  19. 一种润滑油，其包括权利要求1或2所述的硼化脂肪酸甘油酯抗磨添加剂。
  20. 根据权利要求19所述的润滑油，其中，所述硼化脂肪酸甘油酯抗磨添加剂在基础油中的添加量为0.2wt％-10wt％。
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CN119931741A (zh) * 2023-11-02 2025-05-06 中国石油天然气股份有限公司 复合硼化甘油酸酯极压抗磨添加剂及制备方法和应用
CN119931741B (zh) * 2023-11-02 2025-10-17 中国石油天然气股份有限公司 复合硼化甘油酸酯极压抗磨添加剂及制备方法和应用

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