WO2015027367A1 - 一种具有极性两端的高分子摩擦改进剂 - Google Patents

一种具有极性两端的高分子摩擦改进剂 Download PDF

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WO2015027367A1
WO2015027367A1 PCT/CN2013/001497 CN2013001497W WO2015027367A1 WO 2015027367 A1 WO2015027367 A1 WO 2015027367A1 CN 2013001497 W CN2013001497 W CN 2013001497W WO 2015027367 A1 WO2015027367 A1 WO 2015027367A1
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polar
friction modifier
friction
polymer
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李韶辉
汤正林
黄东升
崔海涛
赵治宇
官婷婷
狄泽超
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/12—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
    • 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
    • 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
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition

Definitions

  • the invention relates to a lubricating oil additive, in particular to a polymer friction improvement with polar ends
  • an organic friction modifier is a surfactant having a polar group at one end and a non-polar hydrocarbon group at the other end.
  • the friction modifier can form a directional adsorption film on the friction surface, thereby improving the lubrication condition of the friction pair, effectively reducing the friction and wear of the machine, and achieving the effects of reducing energy consumption and improving fuel economy.
  • the polar group of the friction modifier determines the bonding strength of the friction modifier to the surface, and is generally a compound containing a hetero atom such as nitrogen, oxygen, sulfur, phosphorus, or boron.
  • a frictional improvement containing one or more amide functional groups is disclosed in Chinese patent CN 102725385 A and US Pat. No. 20120283158 A1.
  • X is an oxygen atom or a sulfur atom
  • 1 2 are independently hydrogen or a hydrocarbon group presence.
  • the polar group of the friction modifier is an amide or thioamide and forms a composition with a functional fluid such as an engine oil for use while maintaining the stability, clarity and/or compatibility of the composition.
  • R 3 and R 4 may be hydrogen, but are not hydrogen at the same time, and wherein R 3 and/or R 4 may independently be a linear or branched hydrocarbon group having 1 to 34 carbon atoms, such that The total number of carbon atoms is about 11 to 35.
  • the polar group of the friction modifier is succinimide, and the base oil and additive composition constitutes a power transmission fluid having improved durability and improved friction properties.
  • US Patent No. 20100210487 A1 discloses a fatty acid sorbitan ester friction modifier:
  • n is an integer from 6 to 28.
  • the polar group of the friction modifier is a fatty acid sorbitan ester end and has a long-term antifriction property.
  • An object of the present invention is to provide a polymer friction modifier having polar ends which can achieve wear-free friction.
  • the technical solution of the present invention is: a polymer friction modifier having polar ends, wherein the friction modifier molecule is a linear polymer comprising the following structure:
  • R 2 is a methyl or hydrogen atom
  • m is an integer from 0 to 100
  • n is an integer from 0 to 100
  • ! with! ⁇ is an independently existing polar group containing a nitrogen, oxygen, sulfur, phosphorus, fluorine, boron or chlorine hetero atom;
  • the functionalized polar ends of the long chain of the friction modifier respectively coordinate with the metal of the friction pair surface, and the long chain completely separates the two metal surfaces of the friction pair.
  • the group shown by ⁇ represents an amino group, an ester group, a carboxyl group, a hydroxyl group, an amide group, a boronic acid group, a nitrile group, a thiol group or a phosphate group containing a hetero atom and a derivative thereof, or a derivative thereof, or Yuan and six-membered heterocycles and their derivatives.
  • the polar group as a five-membered heterocyclic ring represents furan, thiophene, tetrazole, triazole, pyrazole, pyrazolium, imidazole, oxazolidine, thiazolidine, pyrrolidine, pyrroline or pyrrole ring and their derivatives
  • the polar group as a six-membered heterocyclic ring means pyridine, pyrimidine, piperazine, pyrazine, thiomorpholine, thiazine, morpholine, oxazine or piperidine ring and derivatives thereof, but is not limited thereto Group.
  • Step 1 Preparation of styrene-isoprene copolymer: 0.5 mol of styrene, 0.5 mol of isoprene, 0.05 mol of hydroxybutyl ⁇ -bromoisobutyrate, 40 in a flask equipped with a thermometer Ml toluene, 0.05 mol of cuprous bromide CuBr, 0.015 mol of pentamethyldiethylenetriamine PMDETA, the system was evacuated under nitrogen, and the reaction was stirred at 60-65 Torr for 8 h. After the reaction is completed, the polymer is passed through an alumina chromatography column to remove the catalyst in the polymer. Then, using methanol as a precipitating agent, the polymer was precipitated and dried under vacuum, and the obtained styrene-isoprene copolymer had the following structure:
  • Step 2 Preparation of the hydroxystyrene-isoprene copolymer:
  • the styrene-isoprene copolymer synthesized in the step 1 was dissolved in dimethyl sulfoxide DMSO, and 30 times equivalent of triethylamine was added. And 20 times equivalent of ethanolamine, nitrogen gas, stirring reaction at room temperature for 48 h; after the reaction, using methanol as a precipitant, the obtained terminal hydroxystyrene-isoprene copolymer precipitated, vacuum drying, the resulting end
  • the structure of the hydroxyphenylethyl-isoprene copolymer is as follows:
  • Step 3 Preparation of a polymer friction modifier having polar imidazolinone groups:
  • the terminal hydroxystyrene-isoprene copolymer synthesized in step 2 is dissolved in dimethyl sulfoxide DMSO and dimethyl A mixed solvent of formamide DMF, which is mixed in a ratio of 3:1, and 2 times equivalent of 2-imidazolidinone-4-carboxylic acid is added while stirring, and then 1 equivalent of 4-dimethylaminopyridine DMAP is added.
  • a polymer friction modifier having both ends of a polar phosphate a terminal hydroxystyrene-isoprene copolymer synthesized in the second step of Example 1, 1.1 times equivalent of 1,8-diazo-bicyclo[ 5.4.0]-7-undecene DBU and 1 equivalent of 4-dimethylaminopyridine DMAP were dissolved in tetrahydrofuran THF and stirred to cool to 0 ° C; 2 times equivalent of dimethyl bromide was dissolved in In tetrahydrofuran THF, and dropwise added to the above solution under stirring and cooling, the reaction was stirred at room temperature for 24 h; after the reaction was completed, the polymer was washed and vacuum dried to obtain a polymer friction with polar phosphate ester ends.
  • the structure of the improver is as follows:
  • the experiments of low-speed friction tester (LVFA) and atomic force microscopy (AFM) prove that the polymer friction modifier with polar ends provided by the present invention can be combined with base oil and other required lubricating oil.
  • the additive constitutes a lubricating oil composition which exhibits an excellent antifriction and anti-wear lubrication effect and achieves wear-free friction.
  • the invention is characterized in that: compared with a conventional friction modifier molecule having a polar group at one end and a non-polar hydrocarbon at the other end, the polymer friction modifier having polar ends prepared by the invention has a length
  • the functionalized polar ends of the chain are respectively coordinated with the metal of the friction pair surface, and the long chain completely separates the two metal surfaces of the friction pair, preventing direct contact between the two friction surfaces, achieving wear-free friction, and being a lubricating oil. Provides excellent wear resistance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Lubricants (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本发明涉及一种具有极性两端的高分子摩擦改进剂；摩擦改进剂分子为直链高分子，包含式（I）或式（II）结构；其中，R1是苯基或环己烷基，R2是甲基或氢原子，m是0到100的整数，以及n是0到100的整数，P1和P2是独立存在的含有氮、氧、硫、磷、氟、硼或氯杂原子的极性基团；与传统的一端带有极性基团，另一端为非极性烃类的摩擦改进剂分子相比，其长链的功能化极性两端分别与摩擦副表面的金属配位，同时长链使摩擦副的两个金属表面完全隔开，防止两摩擦表面的直接接触，实现无磨损摩擦，可为润滑油提供极佳的抗磨损性能。

Description

-种具有极性两端的高分子摩擦改进剂 技术领域
本发明涉及一种润滑油添加剂，特别是一种具有极性两端的高分子摩擦改进
背景技术
通常， 有机摩擦改进剂是一种表面活性剂， 分子的一端带有极性基团， 另一 端为非极性的烃类基团。摩擦改进剂能在摩擦表面上形成定向吸附膜， 从而改善 摩擦副的润滑状况， 有效地减少机械的摩擦磨损， 达到降低能耗和提高燃油经济 性的作用。摩擦改进剂的极性基团决定摩擦改进剂与表面的结合强度， 一般为含 有氮、 氧、 硫、 磷、 硼等杂原子的化合物。
中国专利 CN 102725385 A和美国专利 US 20120283158 A1公开了一种含有 一个或多个酰胺官能团的摩擦改进 ：
Figure imgf000003_0001
其中， X为氧原子或硫原子， 和 1 2是独立存在的氢或烃基。 该摩擦改进 剂的极性基团为酰胺或硫代酰胺，且与一起使用的官能流体如发动机油形成组合 物， 同时保持组合物的稳定性、 澄清性和 /或相容性。
中国专利 CN 101323810 A和美国专利 US 20070293406 A1公开了一种琥珀 酰亚胺类摩擦改进剂：
Figure imgf000003_0002
其中， R3和 R4可以是氢， 但不同时为氢， 且其中的 R3和 /或 R4可独立地为直 链或支链的含有 1~34个碳原子的烃基， 使得 和1 4的碳原子总数为约 11〜35。 该摩擦改进剂的极性基团为琥珀酰亚胺，且与基础油和添加剂组合物组成一种具 有改进耐久性和提高摩擦性能的动力传递液。
美国专利 US 20100210487 A1公开了一种脂肪酸山梨醇酐酯类摩擦改进剂：
Figure imgf000004_0001
其中， n是 6到 28的整数。 该摩擦改进剂的极性基团为脂肪酸山梨醇酐酯 端， 且具有长时间的减摩性能。
经检索， 未见具有极性两端的高分子摩擦改进剂的相关报道。
发明内容
本发明的目的在于提供一种能实现无磨损摩擦的具有极性两端的高分子摩 擦改进剂。
本发明的技术解决方案是： 一种具有极性两端的高分子摩擦改进剂， 其特征 在于所述的摩擦改进剂分子为直链高分子， 包含下式结构：
Figure imgf000004_0002
Figure imgf000004_0003
其中， 是苯基或环己垸基， R2是甲基或氢原子， m是 0到 100的整数， 以及 n是 0到 100的整数， ？！和！^是独立存在的含有氮、 氧、 硫、 磷、 氟、 硼 或氯杂原子的极性基团；
所述的摩擦改进剂长链的功能化极性两端分别与摩擦副表面的金属配位，同 时长链使摩擦副的两个金属表面完全隔开。
作为！^和！^所示的基团， 表示氨基、 酯基、 羧基、 羟基、 酰胺基、 硼酸基、 腈基、硫醇基或磷酸酯基含有杂原子的极性基团及它们的衍生物， 或者是五元和 六元杂环及它们的衍生物。 其中， 作为五元杂环的极性基团表示呋喃、 噻吩、 四 唑、 三唑、 吡唑、 吡唑垸、 咪唑、 唑烷、 噻唑烷、 吡咯垸、 吡咯啉或吡咯环及它 们的衍生物， 作为六元杂环的极性基团表示吡啶、嘧啶、 哌嗪、吡嗪、硫代吗啉、 噻嗪、 吗啉、 噁嗪或哌啶环及它们的衍生物， 但不限于上述基团。
具体实施方式 以下给出本发明典型具有极性两端的高分子摩擦改进剂的实施例，但不限「 以下实施例中的原理、 工艺方法和使用的原料等。
实施例 1
第 1步进行苯乙烯 -异戊二烯共聚物的制备： 在装有温度计的烧瓶中加入 0.5 mol苯乙烯， 0.5 mol异戊二烯， 0.05 mol α-溴代异丁酸羟丁酯， 40 ml甲苯， 0.05 mol溴化亚铜 CuBr， 0.015 mol五甲基二亚乙基三胺 PMDETA, 将体系抽真空通 氮气， 在 60-65Ό下搅拌反应 8 h。 反应结束后， 将聚合物通过氧化铝层析柱， 以 脱除聚合物中的催化剂。 然后以甲醇为沉淀剂， 将聚合物沉淀析出， 真空干燥， 所得苯乙烯-异戊二烯共聚物的结构如下：
Figure imgf000005_0001
第 2步进行端羟基苯乙烯 -异戊二烯共聚物的制备： 将步骤 1 中合成的苯乙 烯-异戊二烯共聚物溶解于二甲基亚砜 DMSO, 并加入 30倍当量三乙胺和 20倍 当量乙醇胺， 通氮气， 在室温条件下搅拌反应 48 h; 反应结束后， 以甲醇为沉淀 剂， 将得到的端羟基苯乙烯-异戊二烯共聚物沉淀析出， 真空干燥， 所得端羟基 苯乙 -异戊二烯共聚物的结构如下：
Figure imgf000005_0002
第 3步进行具有极性咪唑啉酮基两端的高分子摩擦改进剂的制备： 将步骤 2 中合成的端羟基苯乙烯-异戊二烯共聚物溶解于二甲基亚砜 DMSO和二甲基甲酰 胺 DMF的混合溶剂， 两者之间按 3:1混合配制， 在搅拌的同时加入 2倍当量 2- 咪唑啉酮 -4-羧酸， 然后加入 1倍当量 4-二甲胺基吡啶 DMAP和 0.2倍当量乙基 二甲基胺丙基碳化二亚胺 EDC， 通氮气， 在室温条件下搅拌反应 24 h; 反应结 束后， 除去未反应的 2-咪唑啉酮 -4-羧酸和催化剂， 真空干燥， 所得具有极性咪 唑啉酮基两端的高分子摩擦改进剂， 具体结构如下： -
Figure imgf000006_0001
实施例 2
进行具有极性吡啶基两端的高分子摩擦改进剂的制备： 按实施例 1中的第 3 步操作， 区别是使用相应量的异烟酸替代 2-咪唑啉酮 -4-羧酸， 所得具有极性吡 剂的结构如下：
Figure imgf000006_0002
实施例 3
进行具有极性噻唑基两端的高分子摩擦改进剂的制备： 按实施例 1中的第 3 步操作， 区别是使用相应量的苯并噻唑 -6-羧酸替代 2-咪唑啉酮 -4-羧酸， 所得具 有极性噻唑基两端的高分子摩擦改进剂的结构如下：
Figure imgf000006_0003
实施例 4
进行具有极性磷酸酯两端的高分子摩擦改进剂的制备：将实施例 1中第 2步 合成的端羟基苯乙烯 -异戊二烯共聚物、 1.1倍当量 1,8-重氮 -双环 [5.4.0]-7-十一碳 烯 DBU和 1倍当量 4-二甲氨基吡啶 DMAP溶解于四氢呋喃 THF中， 并搅拌冷 却至 0°C ; 将 2倍当量二甲基溴代磷酸酯溶解于四氢呋喃 THF中， 并在搅拌冷 却条件下滴加至上述溶液中， 在室温条件下搅拌反应 24 h; 反应结束后， 将聚合 物清洗干净， 真空干燥， 所得具有极性磷酸酯两端的高分子摩擦改进剂的结构如 下：
Figure imgf000006_0004
通过低速摩擦试验机 （LVFA) 和原子力显微镜 （AFM) 的实验证明， 本发 明提供的具有极性两端的高分子摩擦改进剂可以与基础油及其它所需的润滑油 添加剂组成润滑油组合物， 示出优良的减摩抗磨损润滑效果， 并实现了无磨损 摩擦。
工业实用性
本发明的特点是： 与传统的一端带有极性基团， 另一端为非极性烃类的摩擦 改进剂分子相比， 本发明制备的具有极性两端的高分子摩擦改进剂， 其长链的功 能化极性两端分别与摩擦副表面的金属配位，同时长链使摩擦副的两个金属表面 完全隔开， 防止两摩擦表面的直接接触， 实现无磨损摩擦， 可为润滑油提供极佳 的抗磨损性能。

Claims

权 利 要 求 书
1 . 一种具有极性两端的卨分子摩擦改进剂， 其特征在于： 所述的摩擦改进 剂分子为直链高分子， 包含下式结构：
Pi P2
Figure imgf000008_0001
是苯基或环己垸基、 R2是甲基或氢原子、 m是 0到 100的整数、 n是 0到 100 的整数； ？1和？2是独立存在的含有氮、 氧、 硫、 磷、 氟、 硼或氯杂原子的 极性基团。
2. 根据权利要求 1所述的具有极性两端的高分子摩擦改进剂， 其特征在于： 所述的摩擦改进剂分子为直链高分子， 包含下式结构：
Figure imgf000008_0002
是苯基或环己垸基、 R2是甲基或氢原子、 m是 0到 100的整数、 n是 0到 100的整数； ？,和？2是独立存在的含有氮、 氧、 硫、 磷、 氟、 硼或氯杂原子的 极性基团。
3. 根据权利要求 1或 2所述的具有极性两端的高分子摩擦改进剂， 其特征 在于： 所述的摩擦改进剂长链的功能化极性两端分别与摩擦副表面的金属配位， 同时长链使摩擦副的两个金属表面完全隔开。
4. 根据权利要求 1或 2所述的具有极性两端的高分子摩擦改进剂， 其特征 在于： 所述的 Ρ^Π Ρ2所示的极性基团， 表示氨基、 酯基、 羧基、 羟基、 酰胺基、 硼酸基、 腈基、 硫醇基、 磷酸酯基含有杂原子的极性基团及它们的衍生物， 或五 元、 六元杂环的极性基团及它们的衍生物。
5. 根据权利要求 4所述的具有极性两端的高分子摩擦改进剂， 其特征在于： 作为五元杂环的极性基团， 表示呋喃、 噻吩、 四唑、 三唑、 吡唑、 吡唑烷、 咪唑、 唑烷、 噻唑垸、 吡咯垸、 吡咯啉或吡咯环及它们的衍生物。
6. 根据权利要求 4所述的具有极性两端的高分子摩擦改进剂， 其特征在于: 作为六元杂环的极性基团， 表示吡啶、 嘧啶、 哌嗪、 吡嗪、 硫代吗啉、 噻嗪、 吗 啉、 噁嗪或哌啶环及它们的衍生。
PCT/CN2013/001497 2013-08-30 2013-12-03 一种具有极性两端的高分子摩擦改进剂 Ceased WO2015027367A1 (zh)

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