WO2025166998A1 - 摩擦改进剂及其制备方法、润滑油 - Google Patents

摩擦改进剂及其制备方法、润滑油

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Publication number
WO2025166998A1
WO2025166998A1 PCT/CN2024/106190 CN2024106190W WO2025166998A1 WO 2025166998 A1 WO2025166998 A1 WO 2025166998A1 CN 2024106190 W CN2024106190 W CN 2024106190W WO 2025166998 A1 WO2025166998 A1 WO 2025166998A1
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Prior art keywords
friction modifier
friction
lubricating oil
cor
formula
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PCT/CN2024/106190
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English (en)
French (fr)
Inventor
迟涵文
张德强
吴为理
张自立
刘鹏
梁东伟
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Guangzhou Automobile Group Co Ltd
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Guangzhou Automobile Group Co Ltd
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Application filed by Guangzhou Automobile Group Co Ltd filed Critical Guangzhou Automobile Group Co Ltd
Publication of WO2025166998A1 publication Critical patent/WO2025166998A1/zh
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    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—Amides; Imides
    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/16—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-nitrogen bond
    • 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
    • C10N2030/08—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
    • C10N2030/12—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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

Definitions

  • the present application belongs to the technical field of lubricating oil additives, and in particular relates to a friction modifier, a preparation method thereof, and lubricating oil.
  • Automotive lubricants are commonly found in engines and transmissions, used to reduce friction, save energy, dissipate heat, and maintain cleanliness.
  • electromechanical coupling transmission fluids for new energy vehicles must, in addition to the performance of traditional transmission fluids, possess suitable electrical properties, excellent corrosion protection, appropriate thermal management, compatibility with new materials, and friction properties that mitigate noise, vibration, and harshness (NVH) issues. If the clutch friction plates vibrate during starting and shifting, the driver will experience jerking or trembling as speed increases, which can negatively impact the overall vehicle's sensory quality and diminish the vehicle's brand image. Good friction properties are key to ensuring smooth operation of transmission gear components, reducing noise and extending lifespan.
  • the technical problem to be solved by the present application is: to provide a friction modifier, a preparation method thereof, and lubricating oil in response to the problem that the existing clutch using lubricating oil has dynamic jitter under speed difference.
  • the present application provides a friction modifier, the structure of which is shown in Formula I:
  • Ra includes one or more of alkanes, alkenes and derivatives thereof
  • Rb includes one or more of alkanes, alkenes and the formula -O-CH 2 CH 2 -COR', wherein -COR' is derived from a C2-C20 fatty acid.
  • the Ra is selected from one of C1-C10 alkanes, C1-C10 alkenes and derivatives thereof.
  • R b is selected from one or more of C5-C30 alkanes, C5-C30 alkenes, and -O-CH 2 CH 2 -COR', wherein -COR' is derived from a C2-20 fatty acid.
  • the number average molecular weight Mn of the friction modifier is 800-1200, and the molecular weight dispersion Mw/Mn of the friction modifier is 1.0-1.08.
  • the present application also provides a method for preparing the friction modifier as described above, comprising the following steps: mixing an imide compound, a metal cyanide, a halogenated phosphate compound, an auxiliary agent, and a solvent, reacting to obtain a crude product of the friction modifier, and purifying the crude product to obtain a friction modifier as shown in Formula I; the halogenated phosphate compound is shown in Formula II, and the imide compound is shown in Formula III.
  • Ra includes one or more alkanes, alkenes and their derivatives
  • Rb includes one or more alkanes, alkenes and the formula -O- CH2CH2 - COR ', wherein -COR' is derived from a C2-C20 fatty acid
  • X is selected from one or more of F, Cl, Br and I.
  • the metal cyanide comprises sodium cyanide.
  • the imide compound is added dropwise to a solvent containing the metal cyanide at 0-4° C. to obtain a mixed solution after the addition of the imide compound is completed, and the mixed solution is reacted at 40-60° C. for 6-7 hours;
  • the halogenated phosphate compound and the auxiliary agent are added dropwise to the mixed solution at 0-4° C., and after the addition is complete, the mixture is reacted at 40-60° C. for 7-8 hours.
  • the molar ratio of the imide compound, the metal cyanide, the halogenated phosphate compound and the auxiliary agent is (2-2.1):(2-2.1):1:(0.05-0.1).
  • the auxiliary agent includes a phenolic polymerization inhibitor, and the phenolic polymerization inhibitor includes hydroquinone.
  • the solvent includes one or more of tetrahydrofuran, diethyl ether and dioxane.
  • the present application also provides a lubricating oil comprising the friction modifier as described in any one of the above items or the friction modifier prepared by the method for preparing the friction modifier as described in any one of the above items.
  • the static friction coefficient change rate of the friction characteristics test of the lubricating oil is less than 7%.
  • the torque variation characteristic parameter of the lubricating oil in the NVH test is less than 10 N ⁇ m.
  • the torque variation characteristic parameter of the lubricating oil in the process of linear pressure variation from 0 to 12 bar is less than 2 N ⁇ m.
  • the phospholipid group of the friction modifier forms a polar clustering group with the imide structure, which improves the adsorption strength with the friction material.
  • the chain structure on the phospholipid and the chain structure on the imide form a polymer film layer between the shaft teeth, which improves the friction buffering effect and long-term stability of the lubricant.
  • the friction modifier has the properties of reducing wear, inhibiting copper corrosion, preventing rust, and emulsification stability. It is integrated with the additive system of existing lubricants, has little effect on other properties, and has good compatibility. It is used in new energy DHT electromechanical coupling transmission lubricants, has good low-temperature activity, can effectively solve the problem of dynamic jitter, and improve the problem of rapid decrease in static friction coefficient.
  • Figure 1 is a graph showing the coefficient of kinetic friction of the lubricating oil of Example 1 on an SAE No. 2 friction tester;
  • Figure 2 is a graph showing the static friction coefficient of the lubricating oil of Example 1 on an SAE No. 2 friction tester;
  • FIG4 is a graph showing the coefficient of kinetic friction of the lubricating oil of Example 1 on an SAE No. 2 friction tester;
  • FIG5 is a graph showing the static friction coefficient of the lubricating oil of Example 1 on an SAE No. 2 friction tester;
  • FIG6 is a graph showing ⁇ 0 / ⁇ d of the lubricating oil of Example 1 on a SAE No. 2 friction tester;
  • FIG7 is a diagram showing the vibration effect of the lubricating oil of Comparative Example 1 on a low-speed SAE No. 2 friction tester (rotation speed 20 r/min);
  • Figure 8 is a graph showing the vibration effect of the lubricating oil of Example 1 on a low-speed SAE No. 2 friction tester (rotation speed 100 r/min);
  • FIG9 is a diagram showing the vibration effect of the lubricating oil of Example 1 on a low-speed SAE No. 2 friction tester (rotation speed 20 r/min);
  • FIG11 is a diagram showing the torque jitter of the lubricating oil of Comparative Example 1 on a ZF dual-motor friction tester;
  • FIG12 is a diagram showing the torque jitter of the lubricating oil of Example 1 on a ZF dual-motor friction tester.
  • Ra includes one or more of alkanes, alkenes and derivatives thereof
  • Rb includes one or more of alkanes, alkenes and the formula -O-CH 2 CH 2 -COR', wherein -COR' is derived from a C2-C20 fatty acid.
  • the phospholipid groups of the friction modifier form polar clustering groups with the imide structure, enhancing adsorption strength with the friction material. Furthermore, the chain structures of the phospholipids and the imide form a polymer film between the shaft teeth, enhancing the friction cushioning effect and long-term stability of the lubricant.
  • This friction modifier also exhibits properties such as wear reduction, copper corrosion inhibition, rust prevention, and emulsion stability. It integrates well with existing lubricant additive systems, has minimal impact on other properties, and exhibits excellent compatibility. Used in new energy DHT electromechanical coupling transmission lubricants, it exhibits excellent low-temperature activity, effectively addressing dynamic vibration issues and improving the rapid decrease in the static friction coefficient.
  • the friction modifier Ra is selected from one of C1-C10 alkanes, C1-C10 alkenes and derivatives thereof, and the Rb is selected from C5-C30 alkanes, C5-C30 alkenes and compounds of the formula -O - CH2CH2 -COR'.
  • One or more of -COR', -COR' is derived from a C2-20 fatty acid.
  • the Ra is selected from a C2-C6 alkane
  • the Rb is selected from a C20-C25 alkene.
  • the friction modifier has a number average molecular weight (Mn) of 400-1500, and a molecular weight dispersion (Mw/Mn) of 1.0-1.2. Friction modifiers within this number average molecular weight and molecular weight dispersion range exhibit high friction cushioning and anti-shake effects. Specifically, Mw and Mn can be measured by any known method, typically by gel permeation chromatography (GPC).
  • the friction modifier has a number average molecular weight Mn of 800-1200 and a molecular weight dispersion Mw/Mn of 1.0-1.08. Within this molecular weight range, the phospholipid group and the imide structure form a polar clustering group, satisfying the structure shown in Formula I.
  • An embodiment of the present application further provides a method for preparing the friction modifier as described in the above embodiment, comprising the following steps:
  • Step 1 Mix an imide compound, a metal cyanide, a halogenated phosphate compound, an auxiliary agent, and a solvent to react to obtain a crude friction modifier.
  • the halogenated phosphate compound is shown in Formula II
  • the imide compound is shown in Formula III.
  • Ra includes one or more alkanes, alkenes and their derivatives
  • Rb includes one or more alkanes, alkenes and the formula -O- CH2CH2 - COR ', wherein -COR' is derived from a C2-C20 fatty acid
  • X is selected from one or more of F, Cl, Br and I.
  • the halogenated phosphate compound is selected from dichlorophosphate compounds.
  • the dichlorophosphate compounds include but are not limited to one or more of methyl dichlorophosphate, ethyl dichlorophosphate, and butyl dichlorophosphate
  • the imide compounds include but are not limited to one or more of 2-pentane-succinimide, 2-hexene-succinimide, 2-(ethoxypropionate) succinimide, and 2-pentacosyl-succinimide.
  • mixing the imide compound, the metal cyanide, the halogenated phosphate compound, the auxiliary agent, and the solvent specifically comprises the following steps:
  • the imide compound is added dropwise to a solvent containing a metal cyanide to obtain a mixed solution, and the mixed solution is reacted at 40-60° C. for 6-7 hours;
  • the halogenated phosphate compound and the auxiliary agent are added dropwise to the mixed solution at 0-4° C., and after the addition is complete, the mixture is reacted at 40-60° C. for 7-8 hours.
  • the imide compound is added dropwise to a solvent containing a metal cyanide at 0° C. to obtain a mixed solution after the addition of the imide compound is completed, and the mixed solution is reacted at 50° C. for 6 hours;
  • the halogenated phosphate compound and the auxiliary agent were added dropwise to the mixed solution at 0° C., and after the addition was completed, the mixture was reacted at 50° C. for 8 hours.
  • the metal cyanide includes but is not limited to sodium cyanide.
  • the molar ratio of the imide compound, the metal cyanide, the halogenated phosphate compound, and the auxiliary agent is (2-2.1):(2-2.1):1:(0.05-0.1).
  • the auxiliary agent includes a phenolic polymerization inhibitor, and the phenolic polymerization inhibitor includes hydroquinone, which prevents the halogenated phosphate compound from self-polymerizing.
  • the solvent includes one or more of tetrahydrofuran, diethyl ether, and dioxane.
  • Step 2 purifying the crude product to obtain a friction modifier as shown in Formula I.
  • the purification method uses column chromatography for separation and purification.
  • One embodiment of the present application further provides a lubricating oil, comprising the friction modifier as described in any one of the above items or the friction modifier prepared by the method for preparing the friction modifier as described in any one of the above items.
  • the content of the friction modifier is 0.2-0.4%.
  • the rate of change of the static friction coefficient of the lubricating oil friction characteristics test is less than 8%.
  • the friction characteristics test of the lubricating oil is conducted in accordance with JASO M348 standard "Road Vehicle Automatic Transmission Fluid Friction Characteristics Test Method" and is conducted for at least 10,000 cycles.
  • the torque variation characteristic parameter of the lubricant during NVH testing is less than 10 N ⁇ m.
  • the torque variation characteristic parameter refers to the torque variation of a friction plate coated with the lubricant at a predetermined speed difference during the NVH testing of the lubricant. Specifically, during the NVH testing of the lubricant, the torque variation of the friction plate coated with the lubricant at a speed difference of 20 rpm is less than 5 N ⁇ m, and the torque variation at a speed difference of 100 rpm is less than 10 N ⁇ m.
  • the NVH test of the lubricating oil was performed on a low-speed SAE No. 2 friction tester.
  • the lubricant In the dynamic pressure-torque test, the lubricant exhibited a torque variation characteristic parameter of less than 2 N ⁇ m during a linear pressure change from 0 to 12 bar.
  • the dynamic pressure-torque test operates within a pressure range of 0-12 bar, with the friction plate speed differential varying from ⁇ 20 r/min to ⁇ 100 r/min.
  • a speed differential such as ⁇ 20 r/min, is determined.
  • the pressure is then controlled to increase from 0 bar to 12 bar and then decrease from 12 bar to 0 bar, thereby determining the lubricant's torque variation characteristic parameter under varying pressure and speed differential conditions.
  • the preparation method of the friction modifier is as follows: at 0°C, an imide compound is added dropwise to a tetrahydrofuran solvent containing sodium cyanide to obtain a mixed solution after the addition of the imide compound is completed, and the mixed solution is reacted at 50°C for 6 hours; at 0°C, the halogenated phosphate compound and an auxiliary agent are added dropwise to the mixed solution, and after the addition is completed, the mixture is reacted at 50°C for 8 hours; the solvent and the auxiliary agent are removed by rotary evaporation, and then 200 mL of ether is added and mixed and stirred to wash the unreacted monomer components in the product, and the process is repeated three times; after washing, the ether is removed by rotary evaporation, and then ethyl acetate is used as an eluent, and the product is purified by alumina column chromatography to obtain the friction modifier.
  • the molar ratio of the imide compound, the sodium cyanide, the halogenated phosphate compound and the auxiliary agent is 2:2:1:0.05.
  • the halogenated phosphate compound is ethyl dichlorophosphate
  • the imide compound is 2-(5-eicosenyl)-succinimide.
  • the difference from Preparation Example 1 is that the imide compound is 2-pentacosyl-succinimide.
  • the difference from Preparation Example 1 is that the imide compound is 2-(ethoxyeicosanoate)-succinimide.
  • Lubricating oils were prepared according to the ingredients and ratios shown in Table 1.
  • the friction modifiers used in Examples 1-3 were the friction modifiers prepared in Preparation Examples 1-3, respectively.
  • Example 1-3 The difference from Example 1-3 is that the friction modifier is omitted, and the other ingredients and proportions are as shown in Table 1.
  • Base oil choose the three types of base oil commonly used on the market, Yubase produced by South Korea's SK, GTL produced by the Netherlands Shell, or CTL produced by Sinopec, which are universal.
  • Additives include dispersants, detergents, extreme pressure agents (typically containing boron and/or sulfur and/or phosphorus), antiwear agents, antioxidants (such as hindered phenols, amine antioxidants, or molybdenum compounds), corrosion inhibitors, friction modifiers, rubber swelling agents, and mixtures thereof.
  • Example 1 and Comparative Example 1 employed the widely available commercial additive package HiTec® R3491.
  • the antifoaming agent is a copolymer of ethyl acrylate, 2-ethylhexyl acrylate and optionally vinyl acetate, or polydimethylsiloxane.
  • the pour point depressant is polymethacrylate, polyacrylate or polyacrylamide.
  • the lubricating oils prepared in Comparative Example 1 and Examples 1-3 were subjected to performance testing, NVH testing, and dynamic pressure-torque testing, respectively.
  • Friction property test The lubricating oils of Comparative Example 1 and Examples 1-3 were tested on an SAE No. 2 friction tester according to the JASO M348 standard. The friction plate material was NW461E and the steel plate material was T903. The extended version was verified by 10,000 cycles.
  • the dynamic friction coefficient ⁇ d refers to the friction coefficient when the two contact surfaces have a relative motion speed, which represents the shift speed.
  • ⁇ 0 refers to the friction coefficient measured at the end of the shift or the final friction coefficient when the friction plate surface speed is relatively low, that is, when the friction plate engagement is completed. It is the maximum dynamic friction coefficient when the speed is less than 200 r/min. The ⁇ 0 / ⁇ d ratio affects the shift quality.
  • the static friction coefficient ⁇ s is calculated based on the maximum torque value after the start of dragging. It is the measured value when the two stationary contact surfaces just start to slide relative to each other under the action of load and represents the torque capacity.
  • the test results are entered in Table 2.
  • the test diagrams of Example 1 and Comparative Example 1 are shown in Figures 1 to 6.
  • Example 2 The test results of Example 2 are similar to those of Example 1, and the test chart and data thereof are not attached herewith.

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Abstract

一种摩擦改进剂及其制备方法、润滑油。该摩擦改进剂所述摩擦改进剂的结构如式I所示，其中，R a包括烷烃、烯烃及其衍生物中的一种或多种，R b包括烷烃、烯烃、式-O-CH2CH2-COR'中的一种或多种，-COR'衍生自C2-C20的脂肪酸。该摩擦改进剂中磷酯基团与酰亚胺结构形成极性簇拥集团，提高与摩擦材料的吸附强度，解决离合器动态抖动的问题。

Description

摩擦改进剂及其制备方法、润滑油
本申请要求于2024年02月06日提交中国专利局、申请号为202410170833.6、发明名称为“一种摩擦改进剂及其制备方法、润滑油”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
本申请属于润滑油添加剂技术领域，特别是涉及一种摩擦改进剂及其制备方法、润滑油。
背景技术
汽车润滑油多见于发动机和传动机构，用来减磨节能、散热清洁等，但新能源汽车的机电耦合变速器油，在传统的变速器油所具备的性能之外必须具有合适的电气特性、卓越的防腐性能、合适的热管理、与新材料的兼容性以及可减轻噪声、振动与声振粗糙度(Noise、Vibration、Harshness，NVH)问题的摩擦性能。汽车在起步和换档过程中，若是离合器摩擦片之间存在抖动现象，随着车速的提高，让驾驶员感受到顿挫或抖动的感觉，会影响整车感官品质，降低汽车品牌形象。良好的摩擦性是保证传动齿轮各件工作平顺的关键，并能降低噪声，延长寿命。
现有的润滑油使用过程中，在滑膜工况下，也就是连续滑动变矩离合器摩擦片在压紧力的连续变动时，扭矩不呈现线性相关性，出现高频的波动，也就是摩擦系数出现颤动。并且存在以下问题：1)在SAE No.2摩擦试验机上，整个生命周期的静摩擦系数下降较大，也就是扭矩容量变化大，不利于液压系统控制压力的分配；(2)在低速SAE No.2摩擦试验机上，NVH震动问题表现明显；(3)在采埃孚离合器性能试验机上，动态压力-扭矩在40℃时存在严重的抖动。
发明内容
本申请所要解决的技术问题是：针对现有的使用润滑油的离合器在速差下存在动态抖动的问题，提供一种摩擦改进剂及其制备方法、润滑油。
为解决上述技术问题，一方面，本申请提供了一种摩擦改进剂，所述摩擦改进剂的结构如式I所示，
其中，Ra包括烷烃、烯烃及其衍生物中的一种或多种，Rb包括烷烃、烯烃、式-O-CH2CH2-COR’中的一种或多种，-COR’衍生自C2-C20的脂肪酸。
可选地，所述Ra选自C1-C10的烷烃、C1-C10的烯烃及其衍生物中的一种。
可选地，所述Rb选自C5-C30的烷烃、C5-C30的烯烃和式-O-CH2CH2-COR’中的一种或多种，其中-COR’衍生自C2-20脂肪酸。
可选地，所述摩擦改进剂的数均分子量Mn为400-1500，所述摩擦改进剂的分子量分散度Mw/Mn为1.0-1.2。
可选地，所述摩擦改进剂的数均分子量Mn为800-1200，所述摩擦改进剂的分子量分散度Mw/Mn为1.0-1.08。
另一方面，本申请还提供一种如上所述的摩擦改进剂的制备方法，包括以下步骤：将酰亚胺化合物、金属氰化物、卤代磷酸酯化合物、助剂和溶剂混合，反应制得摩擦改进剂的粗产物，将所述粗产物纯化得到如式I所示的摩擦改进剂；所述卤代磷酸酯化合物如式II所示，所述酰亚胺化合物如式III所示，
其中，Ra包括烷烃、烯烃及其衍生物中的一种或多种，Rb包括烷烃、烯烃、式-O-CH2CH2-COR’中的一种或多种，-COR’衍生自C2-C20的脂肪酸，X选自F、Cl、Br、I中的一种或多种。
可选地，所述金属氰化物包括氰化钠。
可选地，在0-4℃下，将所述酰亚胺化合物滴加至含有所述金属氰化物的溶剂中，所述酰亚胺化合物滴加完毕后得到混合溶液，所述混合溶液在40-60℃下反应6-7h；
在0-4℃下，将所述卤代磷酸酯化合物和助剂滴加至所述混合溶液中，滴加完毕后，在40-60℃下反应7-8h。
可选地，所述酰亚胺化合物、所述金属氰化物、所述卤代磷酸酯化合物和所述助剂的物质的量的比为(2-2.1)：(2-2.1)：1：(0.05-0.1)。
可选地，所述助剂包括酚类阻聚剂，所述酚类阻聚剂包括对苯二酚。
可选地，所述溶剂包括四氢呋喃、二乙醚和二氧六环中的一种或多种。
另一方面，本申请还提供一种润滑油，包括如上任意一项所述的摩擦改进剂或由如上任意一项所述的摩擦改进剂的制备方法制备得到的摩擦改进剂。
可选地，所述润滑油的摩擦特性测试的静摩擦系数变化率小于7％。
可选地，所述润滑油的NVH测试的扭矩变化量特性参数小于10N·m。可选地，在动态压力-扭矩测试中，所述润滑油在压力0-12bar线性变化过程中的扭矩变化量特性参数小于2N·m。
在本申请中，摩擦改进剂的磷酯基团与酰亚胺结构形成极性簇拥基团，提高与摩擦材料的吸附强度，另外磷酯上的链状结构与酰亚胺上的链状结构在轴齿间形成聚合物膜层，提升润滑油的摩擦缓冲效果和长效稳定性。并且该摩擦改进剂具有减磨、抑制铜腐蚀、防锈蚀、乳化稳定性等性能，跟现有润滑油的添加剂体系相融合，对其他性能影响较小，配伍性良好。用于新能源DHT机电耦合变速器润滑油中，具有良好的低温活性，可有效解决动态抖动问题，改善静摩擦系数下降较快的问题。
附图说明
图1是对比例1的润滑油在SAE No.2摩擦试验机上的动摩擦系数表现图；
图2是对比例1的润滑油在SAE No.2摩擦试验机上的静摩擦系数表现图；
图3是对比例1的润滑油在SAE No.2摩擦试验机上的μ0/μd表现图；
图4是实施例1的润滑油在SAE No.2摩擦试验机上的动摩擦系数表现图；
图5是实施例1的润滑油在SAE No.2摩擦试验机上的静摩擦系数表现图；
图6是实施例1的润滑油在SAE No.2摩擦试验机上的μ0/μd表现图；
图7是对比例1的润滑油在低速SAE No.2摩擦试验机上抖动效果(转速20r/min)图；
图8是对比例1的润滑油在低速SAE No.2摩擦试验机上抖动效果(转速100r/min)图；
图9是实施例1的润滑油在在低速SAE No.2摩擦试验机上抖动效果(转速20r/min)图；
图10是实施例1的润滑油在低速SAE No.2摩擦试验机上抖动效果(转速100r/min)图；
图11是对比例1的润滑油在采埃孚双电机摩擦试验机上扭矩抖动情况图；
图12是实施例1的润滑油在采埃孚双电机摩擦试验机上扭矩抖动情况图。
具体实施方式
为了使本申请所解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请进行进一步的详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。
本申请实施例提供的摩擦改进剂，所述摩擦改进剂的结构如式I所示，
其中，Ra包括烷烃、烯烃及其衍生物中的一种或多种，Rb包括烷烃、烯烃、式-O-CH2CH2-COR’中的一种或多种，-COR’衍生自C2-C20的脂肪酸。
在本实施例中，摩擦改进剂的磷酯基团与酰亚胺结构形成极性簇拥基团，提高与摩擦材料的吸附强度，另外磷酯上的链状结构与酰亚胺上的链状结构在轴齿间形成聚合物膜层，提升润滑油的摩擦缓冲效果和长效稳定性。并且该摩擦改进剂具有减磨、抑制铜腐蚀、防锈蚀、乳化稳定性等性能，跟现有润滑油的添加剂体系相融合，对其他性能影响较小，配伍性良好。用于新能源DHT机电耦合变速器润滑油中，具有良好的低温活性，可有效解决动态抖动问题，改善静摩擦系数下降较快的问题。
在一些实施例中，所述摩擦改进剂Ra选自C1-C10的烷烃、C1-C10的烯烃及其衍生物中的一种，所述Rb选自C5-C30的烷烃、C5-C30的烯烃和式-O-CH2CH2-COR’中 的一种或多种，-COR’衍生自C2-20脂肪酸。在优选地实施例中，所述Ra选自C2-C6的烷烃，所述Rb选自C20-C25的烯烃。
在一些实施例中，所述摩擦改进剂的数均分子量Mn为400-1500，所述摩擦改进剂的分子量分散度Mw/Mn为1.0-1.2。该数均分子量和分子量分散度范围内的摩擦改进剂具有较高的摩擦缓冲效果和防抖动效果。具体地，Mw、Mn可以通过任何已知方法测量，通常通过凝胶渗透色谱(GPC)测量。
在优选地实施例中，所述摩擦改进剂的数均分子量Mn为800-1200，所述摩擦改进剂的分子量分散度Mw/Mn为1.0-1.08。在该分子量范围内的摩擦改进剂，磷酯基团与酰亚胺结构形成极性簇拥基团，满足式I所示结构。
本申请一实施例还提供了一种如上实施例所述的摩擦改进剂的制备方法，包括以下步骤：
步骤一、将酰亚胺化合物、金属氰化物、卤代磷酸酯化合物、助剂和溶剂混合，反应制得摩擦改进剂的粗产物。所述卤代磷酸酯化合物如式II所示，所述酰亚胺化合物如式III所示，
其中，Ra包括烷烃、烯烃及其衍生物中的一种或多种，Rb包括烷烃、烯烃、式-O-CH2CH2-COR’中的一种或多种，-COR’衍生自C2-C20的脂肪酸，X选自F、Cl、Br、I中的一种或多种。
在一些实施例中，卤代磷酸酯化合物选自二氯磷酸酯化合物。具体地，二氯磷酸酯化合物包括但不限于二氯磷酸甲酯、二氯磷酸乙酯、二氯磷酸丁酯中的一种或多种，酰亚胺化合物包括但不限于2-戊烷-琥珀酰亚胺、2-己烯-琥珀酰亚胺、2-(乙氧基丙酸酯基)琥珀酰亚胺、2-二十五烷基-琥珀酰亚胺中的一种或多种。
在一些实施例中，将酰亚胺化合物、金属氰化物、卤代磷酸酯化合物、助剂和溶剂混合具体包括以下步骤：
在0-4℃下，将所述酰亚胺化合物滴加至含有金属氰化物的溶剂中，所述酰亚胺化合物滴加完毕后得到混合溶液，所述混合溶液在40-60℃下反应6-7h；
在0-4℃下，将所述卤代磷酸酯化合物和助剂滴加至所述混合溶液中，滴加完毕后，在40-60℃下反应7-8h。
在优选实施例中，在0℃下，将所述酰亚胺化合物滴加至含有金属氰化物的溶剂中，所述酰亚胺化合物滴加完毕后得到混合溶液，所述混合溶液在50℃下反应6h；
在0℃下，将所述卤代磷酸酯化合物和助剂滴加至所述混合溶液中，滴加完毕后，在50℃下反应8h。
在一些实施例中，所述金属氰化物包括但不限于氰化钠。
在一些实施例中，所述酰亚胺化合物、所述金属氰化物、所述卤代磷酸酯化合物和所述助剂的物质的量的比为(2-2.1)：(2-2.1)：1：(0.05-0.1)。
在一些实施例中，所述助剂包括酚类阻聚剂，所述酚类阻聚剂包括对苯二酚，避免卤代磷酸酯化合物发生自聚。
在一些实施例中，所述溶剂包括四氢呋喃、二乙醚和二氧六环中的一种或多种。
步骤二，将所述粗产物纯化得到如式I所示的摩擦改进剂。
在一些实施例中，纯化方法采用柱层析法进行分离纯化。
本申请一实施例还提供一种润滑油，包括如上任意一项所述的摩擦改进剂或由如上任意一项所述的摩擦改进剂的制备方法制备得到的摩擦改进剂。
在一些实施例中，以润滑油的质量为100％计，摩擦改进剂的含量为0.2-0.4％。
在一些实施例中，所述润滑油摩擦特性测试的静摩擦系数变化率小于8％。润滑油的摩擦特性测试按照JASO M348标准《道路车辆自动变速器油液摩擦特性试验方法》进行至少10000次循环测试。
在一些实施例中，所述润滑油的NVH测试的扭矩变化量特性参数小于10N·m。扭矩变化量特性参数是指在润滑油的NVH测试中，涂有所述润滑油的摩擦片在预设转速差时扭矩变化量。具体地，在润滑油的NVH测试中，涂有所述润滑油的摩擦片在20rmp转速差时扭矩变化量小于5N·m，在100rmp转速差时扭矩变化量小于10N·m。
具体的，润滑油的NVH测试在低速SAE·No.2摩擦试验机上进行。
在动态压力-扭矩测试中，所述润滑油在压力0-12bar线性变化过程中的扭矩变化量特性参数小于2N·m。动态压力-扭矩测试的压力变化范围是0-12bar，摩擦片的速差变化范围为Δ20r/min-Δ100r/min，测试过程中先确定一速差，例如Δ20r/min，然后控制压力从0bar上升至12bar再从12bar下降至0bar，以活动润滑油在不同压力、不同速差条件下的扭矩变化量特性参数。
具体的，动态压力-扭矩测试在采埃孚双电机摩擦试验机上进行。
以下结合优选实施例，对本申请进行进一步的详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。
制备例1
摩擦改进剂的制备方法为：在0℃下，将酰亚胺化合物滴加至含有氰化钠的四氢呋喃溶剂中，所述酰亚胺化合物滴加完毕后得到混合溶液，所述混合溶液在50℃下反应6h；在0℃下，将所述卤代磷酸酯化合物滴和助剂加至所述混合溶液中，滴加完毕后，在50℃下反应8h；旋蒸除去溶剂和助剂，然后加入200mL乙醚混合搅拌洗涤产物中未反应的单体组分，重复三次；洗涤完后旋蒸除去乙醚，然后用乙酸乙酯做洗脱剂，采用氧化铝柱层析纯化产物，得到摩擦改进剂。
其中，所述酰亚胺化合物、所述氰化钠、所述卤代磷酸酯化合物和所述助剂的物质的量的比为2：2：1：0.05卤代磷酸酯化合物为二氯磷酸乙酯，酰亚胺化合物为2-(5-二十烯基)-琥珀酰亚胺。
制备例2
与制备例1的不同之处在于，酰亚胺化合物为2-二十五烷基-琥珀酰亚胺。
制备例3
与制备例1的不同之处在于，酰亚胺化合物为2-(乙氧基二十酸酯基)-琥珀酰亚胺。
实施例1-3
按表1所示成分及配比配制润滑油，实施例1-3所使用的摩擦改进剂分别为制备例1-3制备得到的摩擦改进剂。
对比例1
与实施例1-3不同之处在于省略摩擦改进剂，且其它成分及配比参照表1所示。
表1
表1中，除摩擦改进剂外的各成分说明如下：
基础油：选用市面上常用的三类基础油，韩国SK生产的Yubase、荷兰壳牌生产的GTL、或中石化石油公司的CTL，具有普适性。
黏指剂：成品油可以包含一种或多种黏度指数改进剂，不限于聚甲基丙烯酸酯、乙烯基芳族单体、聚α烯烃、聚异丁烯、苯乙烯-丁二烯的氢化共聚物、乙烯-丙烯共聚物、不饱和羧酸、酐或其衍生物的酯化共聚物等。实施例和对比例1采用传动系黏指剂○RR5008。
添加剂：包括分散剂、清净剂、极压剂(通常含硼和/或含硫和/或含磷)、抗磨剂、抗氧化剂(如受阻酚、胺类抗氧化剂或钼化合物)、腐蚀抑制剂、摩擦改进剂、橡胶溶胀剂、及其混合物。实施例和对比例1采用市场上广泛应用的市售复合添加剂包HiTec○R3491。
抗泡剂和降凝剂：抗泡剂采用丙烯酸乙酯和丙烯酸2-乙基己酯和任选乙酸乙烯酯的共聚物或聚二甲基硅氧烷。降凝剂采用聚甲基丙烯酸酯、聚丙烯酸酯或聚丙烯酰胺。
针对对比例1和实施例1-3制得的润滑油分别进行性能测试、NVH测试以及动态压力-扭矩测试。
(1)摩擦特性测试：将对比例1和实施例1-3的润滑油在SAE No.2摩擦试验机上按照JASO M348标准进行测试。摩擦片材料NW461E，钢片材料T903，进行10000次循环加长时间版验证。动摩擦系数μd是指当两个接触表面产生相对运动速度时的摩擦系数，代表换挡速度。μ0是指换档结束或最终的摩擦系数在摩擦片表面速度相对较低时测量即在摩擦片接合终了时测定的摩擦系数，转速小于200r/min时的最大动摩擦系数，μ0/μd比率影响着换挡品质。静摩擦系数μs是根据拖动开始后的最大扭矩值计算，是两个静止的接触表面在负荷的作用下刚刚发生相对滑动时候的测量值，代表扭矩容量。得到的测试结果填入表2。实施例1和对比例1的测试图如图1至图6所示。
表2
(2)润滑油的NVH测试：将对比例1和实施例1的润滑油在低速SAE No.2摩擦试验机上进行润滑油的NVH测试，摩擦片材料BW4329，钢片材料SPCC-1B，恒定转速为20或100r/min，油温40℃。结果如图7-10所示，可明显看到抖动效果的差异。
(3)动态压力-扭矩测试：将对比例1和实施例1的润滑油在采埃孚双电机摩擦试验机上进行摩擦片动态压力-扭矩测试，摩擦片材料BW4329，钢片材料SPCC-1B，油温40℃。双电机一侧转速1000r/min，另一侧转速第一次测试900r/min，第二次测试950r/min，第三次测试980r/min。压力从0bar匀速升到12bar再降回0bar的过程，形成转速差分别在Δ100r/min、Δ50r/min、Δ20r/min下的三个扭矩峰。结果如图11和图12所示。可明显看到抖动情况的差异，与低速SAE No.2的测试结果吻合。
实施例2的测试结果与实施例1相近，不再将其测试图及数据附上。
由图1-图6及表2可知，添加了摩擦改进剂的润滑油的动摩擦系数及静摩擦系数低于未添加摩擦改进剂的润滑油，且实施例1的静摩擦系数的变化率明显低于对比例1。由图7-图10中的扭矩变化可明显看出实施例1相对于对比例1的抖动明显得到了改善。图11和图12的测试图进一步验证了图7-图10的实验结果，证实了润滑油中添加本申请实施例的摩擦改进剂可有效解决动态抖动问题。
以上所述仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本申请的保护范围之内。

Claims (15)

  1. 一种摩擦改进剂，其特征在于，所述摩擦改进剂的结构如式I所示，
    其中，Ra包括烷烃、烯烃及其衍生物中的一种或多种，Rb包括烷烃、烯烃、式-O-CH2CH2-COR’中的一种或多种，-COR’衍生自C2-C20的脂肪酸。
  2. 根据权利要求1所述的摩擦改进剂，其特征在于，所述Ra选自C1-C10的烷烃、C1-C10的烯烃及其衍生物中的一种。
  3. 根据权利要求1所述的摩擦改进剂，其特征在于，所述Rb选自C5-C30的烷烃、C5-C30的烯烃和式-O-CH2CH2-COR’中的一种或多种，其中-COR’衍生自C2-20脂肪酸。
  4. 根据权利要求1所述的摩擦改进剂，其特征在于，所述摩擦改进剂的数均分子量Mn为400-1500，所述摩擦改进剂的分子量分散度Mw/Mn为1.0-1.2。
  5. 根据权利要求4所述的摩擦改进剂，其特征在于，所述摩擦改进剂的数均分子量Mn为800-1200，所述摩擦改进剂的分子量分散度Mw/Mn为1.0-1.08。
  6. 如权利要求1-5所述的摩擦改进剂的制备方法，其特征在于，包括以下步骤：将酰亚胺化合物、碱金属氰化物、卤代磷酸酯化合物、助剂和溶剂混合，反应制得摩擦改进剂的粗产物，将所述粗产物纯化得到如式I所示的摩擦改进剂；所述卤代磷酸酯化合物如式II所示，所述酰亚胺化合物如式III所示，
    其中，Ra包括烷烃、烯烃及其衍生物中的一种或多种，Rb包括烷烃、烯烃、式-O-CH2CH2-COR’中的一种或多种，-COR’衍生自C2-20脂肪酸，X选自F、Cl、Br、I中的一种或多种。
  7. 根据权利要求6所述的摩擦改进剂的制备方法，其特征在于，在0-4℃下，将所述酰亚胺化合物滴加至含有所述金属氰化物的溶剂中，所述酰亚胺化合物滴加完毕后得到混合溶液，所述混合溶液在40-60℃下反应6-7h；
    在0-4℃下，将所述卤代磷酸酯化合物滴加至所述混合溶液中，所述卤代磷酸酯化合物滴加完毕后，在40-60℃下反应7-8h。
  8. 根据权利要求6所述的摩擦改进剂的制备方法中，其特征在于，所述金属氰化物包括氰化钠。
  9. 根据权利要求6所述的摩擦改进剂的制备方法，其特征在于，所述酰亚胺化合物、所述金属氰化物、所述卤代磷酸酯化合物和所述助剂的物质的量的比为(2-2.1)：(2-2.1)：1：(0.05-0.1)。
  10. 根据权利要求6所述的摩擦改进剂的制备方法，其特征在于，所述助剂包括酚类阻聚剂，所述酚类阻聚剂包括对苯二酚。
  11. 根据权利要求6所述的摩擦改进剂的制备方法，其特征在于，所述溶剂包括四氢呋喃、二乙醚和二氧六环中的一种或多种。
  12. 一种润滑油，其特征在于，包括权利要求1-5任意一项所述的摩擦改进剂或由权利要求6-11任意一项所述的摩擦改进剂的制备方法制备得到的摩擦改进剂。
  13. 根据权利要求12所述的润滑油，其特征在于，所述润滑油的摩擦特性测试的静摩擦系数变化率小于7％。
  14. 根据权利要求12所述的润滑油，其特征在于，所述润滑油的NVH测试的扭矩变化量特性参数小于10N·m。
  15. 根据权利要求12所述的润滑油，其特征在于，在动态压力-扭矩测试中，所述润滑油在压力0-12bar线性变化过程中的扭矩变化量特性参数小于2N·m。
PCT/CN2024/106190 2024-02-06 2024-07-18 摩擦改进剂及其制备方法、润滑油 Pending WO2025166998A1 (zh)

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