CN108728206B - Gear oil composition and method of making the same - Google Patents

Abstract

其中各基团的定义见说明书。本发明的齿轮油组合物具有优良的清净分散、抗磨、抗氧性能，能够满足GL‑5及以上极压重负荷齿轮油规格的要求。The present invention provides a gear oil composition and a manufacturing method thereof. The gear oil composition of the present invention includes a polyetheramine compound, an antioxidant, an antiwear agent, a metal corrosion inhibitor and the balance of lubricating oil base oil, and the structure of the polyetheramine compound is:

The definition of each group is shown in the specification. The gear oil composition of the invention has excellent cleaning and dispersing, anti-wear and anti-oxidative properties, and can meet the requirements of GL-5 and above extreme pressure and heavy load gear oil specifications.

Description

Gear oil composition and method of making the same

technical field

The present invention relates to a lubricating oil composition, in particular to a gear oil composition.

Background technique

Gear oil is used for gears, bearings and other parts of mechanical transmission, drive axle and steering gear, and can play the role of lubrication, cooling, rust prevention and buffering. Due to the complex working conditions of automobile gears, high contact pressure, fast peripheral speed, high sliding speed and high oil temperature, higher requirements are put forward for the performance of gear oil. In particular, the working conditions of the hyperbolic gear transmission mechanism are more severe. If the appropriate gear oil cannot be selected during use, the normal lubrication of the gear cannot be guaranteed, which will easily lead to early wear and abrasion of the gear, and even cause major vehicle and personal accidents.

With the development of the automobile industry, the volume of the gearbox becomes smaller, the load increases, and the operating conditions are more severe, resulting in an increase in the temperature of the gear oil. Therefore, the gear oil is required to have better thermal stability, oxidation stability, detergency and dispersion and inhibition of deposition. Therefore, the gears rotate more smoothly, reduce gear wear, prolong the life of the gearbox, and reduce unnecessary maintenance costs. In order to meet the industrial demands of automotive gear machinery and increasingly harsh working conditions, the development of gear oils with good sediment dispersion properties has become a new research focus.

At present, the gear oil compositions produced by using the prior art detergency and dispersants can no longer fully meet the requirements of higher specification gear oil products. Therefore, there is still a need for a gear oil composition in the prior art, which can not only meet the increasingly stringent requirements for detergency and dispersing properties of today's higher specification products, but also have more excellent anti-oxidation and anti-wear properties.

Unsaturated olefins, aromatic hydrocarbons and a small amount of sulfur-containing compounds in fuel oil can easily react with oxygen to form colloids, and eventually form carbon deposits, especially in key parts such as intake valves, nozzles, and combustion chambers, which will accelerate engine deposits. It will seriously affect the working performance of the engine, resulting in problems such as difficulty in starting the engine, unstable idling, poor drivability, poor acceleration, and serious power loss. In order to suppress the formation of such deposits in engines, a number of detergents have been developed in the prior art.

US 5112364 discloses a process for the amination of nonylphenol polyoxybutylene ethers in the presence of nickel-containing catalysts to produce polyetheramines useful as fuel oil detergents. However, the manufacturing method of this prior art has the disadvantage that the manufacturing cost of the polyetheramine is high, and the polyetheramine cannot be said to be sufficient in terms of the deposit formation inhibitory performance when used as a fuel oil detergent.

SUMMARY OF THE INVENTION

The present invention provides a gear oil composition and a manufacturing method thereof.

The gear oil composition of the present invention includes a polyetheramine compound, an antioxidant, an antiwear agent, a metal corrosion inhibitor and the balance of lubricating oil base oil, and the structure of the polyetheramine compound is:

(其中，q个基团R8彼此相同或不同，各自独立地选自C_1-40亚烃基，优选C_1-40直链或支链亚烷基，更优选C_1-20直链或支链亚烷基，进一步优选C_2-6直链或支链亚烷基；q个基团R₉彼此相同或不同，各自独立地选自氢和C_1-10烃基(优选C_1-6直链或支链烷基，进一步优选C_1-4直链或支链烷基)；基团R₁₀选自氢和C_1-10烃基(优选C_1-6直链或支链烷基，进一步优选C_1-4直链或支链烷基)；q为1至50之间的整数，优选1至10之间的整数，更优选1、2、3或4)；a为1至10之间的整数，优选1至4之间的整数，更优选1、2或3；a个基团R'彼此相同或不同，各自独立地选自单键和C_1-10亚烃基(优选C_1-6直链或支链亚烷基，进一步优选C_1-4直链或支链亚烷基，更优选亚甲基或亚乙基)；基团R₅选自氢和C_1-10烃基(优选C_1-6直链或支链烷基，进一步优选C_1-4直链或支链烷基)。wherein the group R ₀ is selected from hydrogen atom, C _1-40 hydrocarbon group, preferably selected from hydrogen atom, C _1-20 straight or branched chain alkyl group, more preferably selected from hydrogen atom, C _5-15 straight chain or branched chain Alkyl; the y groups Ru are the same or different from each other, each independently selected from C _2-24 linear or branched alkylene, preferably each independently selected from C _2-12 linear or branched alkylene, More preferably, each is independently selected from C _2-6 linear or branched alkylene, more preferably each is independently selected from -CH ₂ -CH ₂ - and -CH ₂ -CH(CH ₃ )-; y represents polyether The average degree of polymerization of the segment -O-Ru-, selected from any value between 1 and 200, preferably any value between 1 and 100, more preferably any value between 1 and 50, more preferably between 1 and 30 Any value between; the groups R ₁ and R ₂ are the same or different from each other, each independently selected from hydrogen and C _1-10 hydrocarbon groups (preferably C _1-6 straight or branched chain alkyl, more preferably C _1-4 straight chain or branched alkyl); a group R ₃ or a group R ₄ are the same or different from each other, each independently selected from hydrogen and C _1-10 hydrocarbyl (preferably C _1-6 straight or branched chain alkanes a group R ₆ or a group R ₇ are the same or different from each other, each independently selected from hydrogen, optionally substituted _{C 1-10} Hydrocarbyl (preferably optionally substituted C _1-6 straight or branched chain alkyl, further preferably optionally substituted C _1-4 straight or branched alkyl) and

(wherein, the q groups R8 are the same or different from each other, each independently selected from C _1-40 alkylene groups, preferably C _1-40 linear or branched alkylene groups, more preferably C _1-20 linear or branched chain Alkylene, further preferably C _2-6 straight or branched chain alkylene; q groups R ₉ are the same or different from each other, each independently selected from hydrogen and C _1-10 hydrocarbon group (preferably C _1-6 straight chain or branched chain alkyl group, further preferably C _1-4 straight chain or branched chain alkyl group); group R ₁₀ is selected from hydrogen and C _1-10 hydrocarbon group (preferably C _1-6 straight chain or branched chain alkyl group, further preferred C _1-4 straight or branched chain alkyl); q is an integer between 1 and 50, preferably an integer between 1 and 10, more preferably 1, 2, 3 or 4); a is between 1 and 10 an integer between 1 and 4, preferably an integer between 1 and 4, more preferably 1, 2 or 3; a group R' is the same or different from each other, each independently selected from a single bond and a C _1-10 hydrocarbylene group (preferably C _{1- 6} straight-chain or branched alkylene, further preferably C _1-4 straight _- chain or branched alkylene, more preferably methylene or ethylene); group R is selected from hydrogen and C _1-10 hydrocarbon group ( Preference is given to C _1-6 straight-chain or branched chain alkyl groups, more preferred C _1-4 straight-chain or branched chain alkyl groups).

The preparation method of the polyetheramine compound includes:

1) react the hydroxyl-containing polyether with an alkenyl compound to generate an alkenyl polymer;

2) reacting the product of step 1) with an oxidant;

3) The oxidation product of step 2) is reacted with an aminating agent, and the product is collected.

所述烯基化合物优选

其中基团R₀选自氢原子、C_1-40烃基，优选C_1-20直链或支链烷基，更优选C_5-15直链或支链烷基。作为所述基团R₀，具体比如可以举出十二烷基苯基或者壬基苯基。The hydroxyl-containing polyether described in step 1) is preferably

The alkenyl compound is preferably

wherein the group R ₀ is selected from a hydrogen atom, a C _1-40 hydrocarbon group, preferably a C _1-20 straight chain or branched chain alkyl group, more preferably a C _5-15 straight chain or branched chain alkyl group. Specific examples of the group R ₀ include dodecylphenyl and nonylphenyl.

The y groups Ru are the same or different from each other, each independently selected from C _2-24 straight-chain or branched alkylene, preferably each independently selected from C _2-12 straight or branched alkylene, more Preferably each is independently selected from C _2-6 linear or branched alkylene groups, more preferably each is independently selected from -CH ₂ -CH ₂ - and -CH ₂ -CH(CH ₃ )-, more preferably -CH ₂ -CH( _CH3 )-.

Wherein, group G represents a functional group capable of reacting with -OH to remove compound GH, preferably halogen (more preferably chlorine) or hydroxyl; groups R ₁ and R ₂ are the same or different from each other, each independently selected from hydrogen and C _{1 -10} hydrocarbon groups (preferably C _1-6 straight or branched chain alkyl groups, more preferably C _1-4 straight or branched chain alkyl groups); a group R ₃ or a group R ₄ are the same or different from each other, Each is independently selected from hydrogen and C _1-10 hydrocarbon group (preferably C _1-6 straight or branched chain alkyl group, more preferably C _1-4 straight chain or branched chain alkyl group); a is an integer between 1 and 10 , preferably an integer between 1 and 4, more preferably 1, 2 or 3; a group R' is the same or different from each other, each independently selected from single bonds and C _1-10 hydrocarbylene (preferably C _1-6 straight chain or branched alkylene, further preferably C _1-4 straight or branched chain alkylene, more preferably methylene or ethylene) _; group R is selected from hydrogen and C _1-10 hydrocarbyl (preferably C _1-6 linear or branched chain alkyl, more preferably C _1-4 linear or branched alkyl).

Examples of the alkenyl compound include allyl halide, 3-butene-1-halogen, 3-butene-2-halogen, 3-methyl-3-butene-1-halogen, and 4-pentene- 1-Halo, 4-Pentene-2-Halo, 4-Pentene-3-Halo, 3-Methyl 4-Pentene 1-Halo, 2-Methyl 4-Pentene 1-Halo, 3-Ethyl 4-pentene 1-halogen, 2-ethyl 4-pentene 1-halogen, 3-isobutyl 4-pentene 1-halogen, 2-isobutyl 4-pentene 1-halogen, 2,3- Dimethyl 4-pentene 1-halogen, 2,2-dimethyl 4-pentene 1-halogen, 3,3-dimethyl 4-pentene 1-halogen, 5-hexene-1-halogen, 4-Methyl-5-hexene halide, 3-methyl-5-hexene halide, 2-methyl-5-hexene halide, 3-ethyl-5-hexene halide, 5-hexene-2 -Halo, 5-hexene-3-halo, 5-hexene-4-halo, 6-heptene-1-halo, 2-methyl-6-heptene-1-halo, 3-methyl-6 -heptene-1-halo, 4-methyl-6-heptene-1-halo, 5-methyl-6-heptene-1-halo, 2-ethyl-6-heptene-1-halo, 3-Ethyl-6-heptene-1-halo, 4-ethyl-6-heptene-1-halo, 5-ethyl-6-heptene-1-halo, 2-methyl-7-octene -1-halo, 3-methyl-7-octene-1-halo, 4-methyl-7-octene-1-halo, 5-methyl-7-octene-1-halo, 6-methyl-7 Octene-1-halo, 3-ethyl-7-octene-1-halo, 9-decene-1-halo, 10-undecene-1-halo, 11-dodecene-1-halo, 5 -Chloro-1,3-pentadiene, 6-chloro-1,3-hexadiene, 5-chloro-1,3-hexadiene, 6-chloro-2,4-hexadiene and 5-chloro- - One or more of 2,4-hexadiene.

According to the present invention, the molar ratio of the hydroxyl-containing polyether to the alkenyl compound is generally 1:1-1.5, preferably 1:1-1.2, the reaction temperature is generally 50-150°C, and the reaction pressure is generally normal pressure, The reaction time is generally 2-10h.

In the step 1), a catalyst can be used as required. Examples of the catalysts include those commonly used by those skilled in the art for this purpose, specific examples include basic catalysts, and more specific examples include alkali metals, alkali metal alkoxides, and alkali metal hydroxides , especially potassium hydroxide and sodium methoxide. When used, the molar ratio of the catalyst to the alkenyl compound is generally 1-2:1, preferably 1-1.5:1, most preferably 1-1.1:1.

In the step 1), a solvent may or may not be used. When used, examples of the solvent include C _1-6 monohydric alcohols, and more specific examples include methanol, ethanol, isopropanol, and n-butanol. These solvents may be used alone or in combination of two or more.

In step 2), the oxidant is preferably oxygen, ozone, hydrogen peroxide, metal oxide, metal peroxide, dichromic acid or its salt, permanganic acid or its salt, peracid or its salt, hypohalous acid or its salt. Salts, organic hydroperoxides and organic peroxides, more specifically, for example, hydrogen peroxide, organic hydroperoxides and peroxygenated organic acids, especially hydrogen peroxide, sodium hypochlorite, ammonium peroxodisulfate, benzoyl peroxide , N-methyl morpholine oxide, methyl rhenium trioxide, osmium tetroxide, hypochlorous acid, KMnO ₄ , K ₂ Cr ₂ O ₇ , KNO ₃ , Na ₂ O ₂ , MnO ₂ , ozone and oxygen. Here, as the organic hydroperoxide, for example, tert-butyl hydroperoxide can be mentioned more specifically. As the peroxyorganic acid, more specifically, for example, _{C3-12 peroxyorganic} acid can be mentioned, preferably peroxyformic acid, peroxyacetic acid, peroxypropionic acid, peroxybutyric acid, peroxybenzoic acid or m-chloroperoxyacid oxybenzoic acid. As the oxidizing agent, meta-chloroperoxybenzoic acid and peroxyacetic acid are particularly preferable, and meta-chloroperoxybenzoic acid is most preferable. These oxidizing agents may be used alone or in combination of two or more.

In step 2), the molar ratio of the alkenyl compound to the oxidant in step 1) is generally 1:1-100, preferably 1:10-40, and the reaction temperature is generally 100-200°C, preferably 100-150 °C, most preferably 100-120 °C, reaction pressure is generally 1-5 kg, preferably 1-3 kg, most preferably 1-2 kg, reaction time is generally 3-20h, preferably 3-11h.

In step 2), a catalyst can be used as required. Examples of the catalysts include those commonly used by those skilled in the art for this purpose, specific examples include basic catalysts, and more specific examples include alkali metals, alkali metal alkoxides, and alkali metal hydroxides , especially potassium hydroxide and sodium methoxide. These catalysts may be used alone or in combination of two or more. When used, the molar ratio of the catalyst to the alkenyl compound is generally 1-2:1, preferably 1-1.5:1, most preferably 1-1.1:1. According to the present invention, in step 2), a solvent may or may not be used. When used, examples of the solvent include C _1-6 monohydric alcohols, and more specific examples include methanol, ethanol, isopropanol, and n-butanol. These solvents may be used alone or in combination of two or more.

全部胺化为基团

According to the present invention, in step 3), the oxidation product obtained in step 2) is subjected to an amination reaction with an aminating agent, and the group

All aminated to groups

In step 3), as the aminating agent, for example, the aminating agent represented by the following formula (II) can be mentioned, and specific examples include ammonia, C ₁ -C ₃₀ primary amine, C ₃ -C ₃₀ secondary amine Amines, alcohol amines and polyene polyamines, preferably ammonia and C ₁ -C ₃₀ primary amines, and more specific examples include ammonia, ethylamine, propylamine, ethylenediamine, ethanolamine and triethylenetetramine. These aminating agents may be used alone or in combination of two or more.

在此，作为所述C_1-10烃基，比如可以举出C_1-10直链或支链烷基、C_2-10直链或支链烯基和C_2-10直链或支链炔基，优选C_1-6直链或支链烷基，进一步优选C_1-4直链或支链烷基。In formula (II), the groups R ₆ and R ₇ are the same or different from each other, each independently selected from hydrogen, optionally substituted C _1-10 hydrocarbyl and

Here, as the C _1-10 hydrocarbon group, for example, a C _1-10 straight-chain or branched chain alkyl group, a C _2-10 straight-chain or branched chain alkenyl group, and a C _2-10 straight-chain or branched chain alkyne can be mentioned. group, preferably a C _1-6 straight-chain or branched chain alkyl group, more preferably a C _1-4 straight-chain or branched chain alkyl group.

中，存在q个基团R₈。在此，所述q个基团R₈彼此相同或不同，各自独立地选自C_1-40亚烃基。作为所述C_1-40亚烃基，比如可以举出C_1-40直链或支链亚烷基、C_2-40直链或支链亚烯基和C_2-40直链或支链亚炔基，优选C_1-40直链或支链亚烷基，更优选C_1-20直链或支链亚烷基，进一步优选C_2-6直链或支链亚烷基。According to the present invention, in the formula

In , there are q groups R ₈ . Here, the q groups R ₈ are the same or different from each other, and are each independently selected from C _1-40 hydrocarbylene groups. As the C _1-40 alkylene group, for example, a C _1-40 linear or branched alkylene group, a C _2-40 linear or branched alkenylene group, and a C _2-40 linear or branched alkylene group can be cited. Alkynyl, preferably C _1-40 straight or branched chain alkylene, more preferably C _1-20 straight or branched alkylene, further preferably C _2-6 straight or branched alkylene.

中，存在q个基团R₉。在此，所述q个基团R₉彼此相同或不同，各自独立地选自氢和C_1-10烃基。在此，作为所述C_1-10烃基，比如可以举出C_1-10直链或支链烷基、C_2-10直链或支链烯基和C_2-10直链或支链炔基，优选C_1-6直链或支链烷基，进一步优选C_1-4直链或支链烷基。According to the present invention, in the formula

In , there are q groups R ₉ . Here, the q groups R ₉ are the same or different from each other, and are each independently selected from hydrogen and C _1-10 hydrocarbon groups. Here, as the C _1-10 hydrocarbon group, for example, a C _1-10 straight-chain or branched chain alkyl group, a C _2-10 straight-chain or branched chain alkenyl group, and a C _2-10 straight-chain or branched chain alkyne can be mentioned. group, preferably a C _1-6 straight-chain or branched chain alkyl group, more preferably a C _1-4 straight-chain or branched chain alkyl group.

中，基团R₁₀选自氢和C_1-10烃基。在此，作为所述C_1-10烃基，比如可以举出C_1-10直链或支链烷基、C_2-10直链或支链烯基和C_2-10直链或支链炔基，优选C_1-6直链或支链烷基，进一步优选C_1-4直链或支链烷基。According to the present invention, in the formula

, the group R ₁₀ is selected from hydrogen and C _1-10 hydrocarbon groups. Here, as the C _1-10 hydrocarbon group, for example, a C _1-10 straight-chain or branched chain alkyl group, a C _2-10 straight-chain or branched chain alkenyl group, and a C _2-10 straight-chain or branched chain alkyne can be mentioned. group, preferably a C _1-6 straight-chain or branched chain alkyl group, more preferably a C _1-4 straight-chain or branched chain alkyl group.

中，q为1至50之间的整数，优选1至10之间的整数，更优选1、2、3或4。According to the present invention, in the formula

wherein, q is an integer between 1 and 50, preferably an integer between 1 and 10, and more preferably 1, 2, 3 or 4.

为计)的摩尔比一般为1-4:1，优选为1-2:1，最优选1-1.5:1。According to the present invention, in step 3), the aminating agent and the oxidation product (with the group

The molar ratio is generally 1-4:1, preferably 1-2:1, most preferably 1-1.5:1.

According to the present invention, in step 3), the reaction temperature is generally 100-180 °C, preferably 100-150 °C, most preferably 120-150 °C, and the reaction pressure is generally 1-5 kg, preferably 1-3 kg, most preferably 1 -2 kg, the reaction time is generally 1h-8h, preferably 2h-6h, most preferably 2h-5h.

According to the present invention, in step 3), a solvent may or may not be added. Specific examples of the solvent include C ₁ -C ₈ alcohols, and more specific examples include n-propanol, n-butanol, and n-hexanol.

According to the present invention, in step 3), a catalyst may or may not be added. Examples of the catalyst include tertiary amines and phenolic substances, and tertiary amines are preferred. Examples of the tertiary amines include trihydrocarbyl tertiary amines with a molecular weight of 10-500 and amine derivatives thereof, and more specific examples include trimethylamine, triethylamine, tripropylamine, N,N-dimethylethylamine Amine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, N,N-diethylpropylamine, N,N-dipropyl-1-propylamine, N,N-diethylbutylamine Amine, N,N-dimethyl-1,2-ethylenediamine, N,N-dimethyl-1,3-propanediamine, N,N-dimethylpentylamine, N,N-dimethylamine N,N-dimethylheptylamine, N,N-dimethylheptylamine, N,N-dimethyloctylamine, N,N-dimethylnonylamine, N,N-dimethyldecylamine, triphenylamine and N,N -2-methylbenzylamine, preferably trimethylamine, triethylamine and N,N'-2methylbenzylamine, most preferably trimethylamine and/or triethylamine. These tertiary amines may be used alone or in combination of two or more. As the phenolic substances, for example, monobasic, dibasic, polyhydric phenol or sodium phenate with molecular weight of 20-500 can be mentioned, and electron donating groups such as alkoxy, phenyl, and alkyl groups can be connected to the benzene ring. More specific examples of the phenolic substances include phenol, sodium phenolate, hydroquinone, sodium hydroquinone, o-cresol, sodium o-cresol, m-cresol, sodium m-cresol, and p-cresol. and sodium p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, ethylphenol, sodium ethylphenate, 2,4-diethylphenol, 2,4,6-triethylphenol methoxyphenol, p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, sodium p-methoxyphenol, sodium m-methoxyphenol, sodium o-methoxyphenol, sodium phenylphenol in phenylphenol , preferably phenol and/or sodium phenate, most preferably sodium phenate. These phenolic substances may be used alone or in combination of two or more.

为计)的摩尔比为0.1-1:1，优选0.1-0.5:1，最优选0.3-0.5:1。According to the present invention, in step 3), when in use, the catalyst is combined with the oxidation product (with the group

The molar ratio is 0.1-1:1, preferably 0.1-0.5:1, most preferably 0.3-0.5:1.

According to the present invention, after the production process of the polyetheramine is completed, the polyetheramine is obtained after removing the catalyst and possibly the solvent from the finally obtained reaction mixture by any means conventionally known. The polyetheramines of the present invention are particularly suitable for the manufacture of detergents (detergent main agents), such as fuel oil detergents, especially gasoline detergents. The detergent exhibits excellent deposit formation inhibiting properties.

According to the present invention, in order to manufacture the detergent, a diluent may be further added to the polyetheramine. Here, as the diluent, for example, mineral base oils, polyolefins, and polyethers can be mentioned. These diluents may be used alone or in combination of two or more.

According to the present invention, it further relates to a gear oil composition comprising any of the aforementioned polyetheramine compounds of the present invention or polyetheramine compounds manufactured according to the aforementioned manufacturing methods of the present invention, antioxidants, antiwear agents, metal corrosion inhibitors agent and the balance of lubricating base oil.

The antioxidant is selected from one or more of phenolic antioxidants, aromatic amine antioxidants, phenolic ester antioxidants and thiophenolic ester antioxidants (preferably phenolic ester antioxidants). ), the antiwear agent is selected from one or more of phosphoric acid esters, sulfurized olefins, dialkyldithiocarbamates and dialkyldithiophosphates (preferably phosphoric acid esters, sulfurized olefins and dialkyldithiophosphates) The composition of alkyl dithiophosphate), the metal corrosion inhibitor is selected from one or more of benzotriazole derivatives, thiazole derivatives and thiadiazole derivatives (preferably benzotriazole derivatives) .

In terms of mass, the polyetheramine compound accounts for 0.01%-20% (preferably 0.02%-16%, more preferably 0.1%-15%) of the total mass of the gear oil composition; the antioxidant accounts for the gear oil 0.01-10% (preferably 0.1%-0.5%, more preferably 0.2%-3%) of the total mass of the composition; the anti-wear agent accounts for 0.1%-10% (preferably 0.2%) of the total mass of the gear oil composition ～8%, more preferably 0.5%～5%); the metal corrosion inhibitor accounts for 0.01%～5% of the total mass of the gear oil composition (preferably 0.02%～4%, more preferably 0.05%～3%) .

The manufacturing method of the gear oil composition is characterized by comprising the step of mixing the polyetheramine compound, antioxidant, antiwear agent, metal corrosion inhibitor and lubricating oil base oil.

The gear oil composition of the invention has excellent cleaning and dispersing, anti-wear and anti-oxidative properties, and can meet the requirements of GL-5 and above extreme pressure and heavy load gear oil specifications.

Detailed ways

The deposit formation inhibiting properties related to Examples and Comparative Examples were evaluated as follows.

The simulation test method for gasoline engine intake valve deposits (GB19592-2004) was adopted.

Specifically, use xylene and n-heptane to clean the pipeline, oil circuit and sample bottle respectively; replace the sponge at the injection port in the sample bottle, add the sample, insert the deposition plate into the groove and clamp it, insert the thermocouple, and count the time. Set it to 70min; when the temperature rises to 165°C, open the air shut-off valve, control the air flow at 700L/h, and the air pressure at 80kPa; when it reaches 175°C, open the fuel valve, firstly discharge air bubbles until there is no wheezing sound, and the float is stable at the index "30"; control the sample to be sprayed within 70-75min; close the fuel valve and air valve, keep at 175 ℃, after re-timing for 10min, turn off the heating, cool naturally; soak the deposition plate in n-heptane for 6min, take out Constant weight, weighing, and the difference between the blank plate is the amount of sediment generated.

The sediment drop rate is an important index for evaluating the detergency of detergents, and the larger the value, the stronger the detergency. Based on the amount of sediment formation (m _IVD , mg) measured by the gasoline engine intake valve sediment simulation test method (GB19592-2004), the sediment drop rate (%) was calculated according to the following formula:

Among them, m _IVD,0 and m _IVD are the simulated intake valve deposits of blank gasoline and gasoline with detergent, respectively, and the unit is mg.

Example 1

1) Preparation of polyether. The mixture of 220g of nonylphenol and 2.0g of potassium hydroxide was added to the reactor, the air in the reactor was replaced with nitrogen, the reactor was sealed and heated to 110 ° C, the pressure was reduced to 2000 Pa, after the water was evaporated. , feed nitrogen into the reactor to restore normal pressure, raise the temperature to about 140°C, and continuously press 696g of propylene oxide into the reactor to react until the pressure no longer changes. After the reaction was completed, the reactant was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. The water and volatile matter are evaporated under reduced pressure to obtain the nonylphenol polyether product.

The chemical formula of the obtained polyether is:

2) Add 59 g of sodium methoxide to 898 g of polyether obtained in step 1) to react to generate sodium polyether alkoxide, then add 76.5 g of allyl chloride, the reaction time is 2-10 h, the reaction temperature is 50-150 ° C, and the reaction is carried out. After completion, the unreacted allyl chloride is removed under reduced pressure, and the crude product is purified. The structure of the obtained alkenyl-terminated polyether is as follows:

3) Epoxidation of alkenyl-terminated polyethers. Under nitrogen protection, 939g of polyether and 75g of formic acid were added to the four-necked flask, the temperature was raised to 60°C, 453g of hydrogen peroxide was mixed and added dropwise to the four-necked flask within two hours, and the reaction was performed for 2-8 hours. Washing with water to pH=7.0 or so and then washing three times with water, drying and rotary evaporation to obtain epoxy polyether. The chemical formula of the obtained epoxy polyether is:

4) The above-mentioned treated material was poured into the amination reactor, 60 g of ethylenediamine and 10 g of n-butanol were added, and the reaction temperature was 150° C. for 2-6 hours to obtain a crude polyetheramine product. The polyetheramine product is obtained after the product is washed and rotary evaporated, the nitrogen content of the product is 2.15%, and the total conversion rate is 77%. The chemical formula of the obtained polyetheramine is:

Example 2

1) Preparation of polyether. The mixture of 220g of nonylphenol and 2.0g of potassium hydroxide was added to the reactor, the air in the reactor was replaced with nitrogen, the reactor was sealed and heated to 110 ° C, the pressure was reduced to 2000 Pa, and the water was evaporated. , nitrogen was introduced into the reactor to restore normal pressure, the temperature was raised to about 140°C, and 864 g of butylene oxide was continuously pressed into the reactor for reaction until the pressure no longer changed. After the reaction was completed, the reactant was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. The water and volatile matter are evaporated under reduced pressure to obtain the nonylphenol polyether product.

2) Add 44 g of sodium hydroxide to 1066 g of polyether obtained in step 1) to react to generate sodium polyether alkoxide, then add 76.5 g of allyl chloride, the reaction time is 2-10 h, and the reaction temperature is 50-150 ° C, After the reaction is completed, the unreacted allyl chloride is removed under reduced pressure, and the crude product is purified.

3) Epoxidation of alkenyl-terminated polyethers. Under nitrogen protection, 1121 g of alkenyl-terminated polyether was added to the four-necked flask. 172.57g of m-chloroperoxybenzoic acid was added dropwise to the four-necked flask within two hours, and the reaction was carried out for 2-8 hours. The product was successively washed with 5% _NaSO solution and ₅ % NaHCO solution, and then washed 5-6 times with water. To pH=7.0 or so, after drying and rotary evaporation, epoxy polyether is obtained.

4) The above-mentioned treated material was poured into the amination reactor, 61 g of ethanolamine and 10 g of triethylamine were added, and the reaction temperature was 150° C. for 2-6 hours to obtain a crude polyetheramine product. The polyetheramine product is obtained after the product is washed with water and rotary evaporated. The nitrogen content of the product was 0.98%, and the total conversion was 83%.

Example 3

1) Preparation of polyether. The mixture of 220g of nonylphenol and 2.0g of potassium hydroxide was added to the reactor, the air in the reactor was replaced with nitrogen, the reactor was sealed and heated to 110 ° C, the pressure was reduced to 2000 Pa, after the water was evaporated. , feed nitrogen into the reactor to restore normal pressure, raise the temperature to about 140°C, and continuously press 696g of propylene oxide into the reactor to react until the pressure no longer changes. After the reaction was completed, the reactant was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. The moisture and volatile matter are evaporated under reduced pressure to obtain the nonylphenol polyether product,

2) 59g of sodium methoxide was added to 898g of polyether obtained in step 1) to react to generate sodium polyetherate, and then 103.5g of 5-chloro-1,3-pentadiene was added, the reaction time was 2-10h, and the reaction temperature At 50-150°C, after the completion of the reaction, the unreacted allyl chloride should be removed under reduced pressure, and the crude product should be purified. The structure of the obtained alkenyl-terminated polyether is as follows:

3) Epoxidation of alkenyl-terminated polyethers. Under nitrogen protection, 966g of polyether and 150g of formic acid were added to the four-necked flask, the temperature was raised to 60°C, 906g of hydrogen peroxide was mixed and added dropwise to the four-necked flask within two hours, and the reaction was performed for 2-8 hours. Washing with water to pH=7.0 or so and then washing three times with water, drying and rotary evaporation to obtain epoxy polyether.

4) The above-mentioned treated material was poured into the amination reactor, 120 g of ethylenediamine and 20 g of n-butanol were added, and the reaction temperature was 150° C. for 2-6 hours to obtain a crude polyetheramine product. The polyetheramine product is obtained after the product is washed and rotary evaporated, the nitrogen content of the product is 3.96%, and the total conversion rate is 79%. The chemical formula of the obtained polyetheramine is:

Comparative Example 1

1) Preparation of polyether. The mixture of 1.5g potassium hydroxide was put into the reactor, the air in the reactor was nitrogen, the temperature was raised to about 140 ° C, and about 696g of propylene oxide was continuously pressed into the reactor to react until the pressure no longer changed, and The mixture was continued to react at 140°C until the pressure no longer changed. After the reaction was completed, the reactant was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. The water and volatile matter were evaporated under reduced pressure to obtain a polyether product, the polyether hydroxyl value of the product was 136 mgKOH/g, and the molecular weight was 696.

2) In a 1L autoclave, put into the polyether obtained in step 1), 45g of modified Raney nickel catalyst and 60g of ethylenediamine, charge hydrogen to the initial pressure of 10.0-14.0Mpa, and start heating, at the reaction temperature Keep the temperature at 200-240°C for several hours, complete the reaction, cool down to room temperature, empty the gas in the kettle, open the kettle, discharge the material, filter to remove the catalyst, then, the liquid is distilled under reduced pressure to remove water and excess liquid ammonia to obtain the product Polyetheramine. After analysis, the nitrogen content of the product is 3.51%, the conversion rate is 93%, and its structural formula is:

Comparative Example 2

1) Preparation of polyether. The mixture of 1.5g potassium hydroxide was put into the reactor, the air in the reactor was nitrogen, the temperature was raised to about 140 ° C, and about 696g of propylene oxide was continuously pressed into the reactor to react until the pressure no longer changed, and The mixture was continued to react at 140°C until the pressure ceased to change. After the reaction was completed, the reactant was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. The water and volatile matter are evaporated under reduced pressure to obtain a polyether product. The product polyether has a hydroxyl value of 136 mgKOH/g and a molecular weight of 696.

2) In a 1L autoclave, put into the polyether obtained in step 1), 45g of modified Raney nickel catalyst and two kilograms of ammonia gas, then fill with hydrogen to an initial pressure of 10.0-14.0Mpa, and start heating, and the reaction At a temperature of 200-240 ° C, the temperature is kept for several hours, the reaction is completed, the temperature is lowered to room temperature, the gas in the kettle is evacuated, the kettle is opened, the material is discharged, and the catalyst is filtered to remove the catalyst. Then, the liquid is distilled under reduced pressure to remove water and excess liquid ammonia to obtain The product polyetheramine. After analysis, the nitrogen content of the product is 3.77%, the conversion rate is 98.43%, and its structural formula is:

Comparative Example 3

1) Preparation of polyether. The mixture of 1.5g potassium hydroxide was put into the reactor, the air in the reactor was nitrogen, the temperature was raised to about 140 ° C, and about 696g of propylene oxide was continuously pressed into the reactor to react until the pressure no longer changed, and The mixture was continued to react at 140°C until the pressure ceased to change. After the reaction was completed, the reactant was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. The water and volatile matter are evaporated under reduced pressure to obtain a polyether product. The product polyether has a hydroxyl value of 136 mgKOH/g and a molecular weight of 696.

2) In a 1L autoclave, put into the polyether prepared in step 1), 45g of modified Raney nickel catalyst and 30g of ethylenediamine, fill with hydrogen to an initial pressure of 10.0-14.0Mpa, and start heating, at the reaction temperature Keep the temperature at 200-240°C for several hours, complete the reaction, cool down to room temperature, empty the gas in the kettle, open the kettle, discharge the material, filter to remove the catalyst, then, the liquid is distilled under reduced pressure to remove water and excess liquid ammonia to obtain the product Polyetheramine. After analysis, the nitrogen content of the product is 1.12%, the conversion rate is 58%, and its structural formula is:

According to the present invention, in order to manufacture the gear oil composition, the aforementioned polyetheramine compound of the present invention, antioxidant, antiwear agent, metal corrosion inhibitor, lubricating oil base oil are mixed uniformly according to a predetermined ratio or addition amount, that is, Can.

Some of the lubricating oil additives used are as follows:

Antioxidant, 2,2'-thiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid ethyl ester], produced by Beijing Coupling Technology Company;

Anti-wear agent, sulfided isobutylene, produced by Liaoning Tianhe Fine Chemical Co., Ltd.;

Anti-wear agent, di-n-butyl phosphite, produced by Beijing Coupling Technology Company;

Antiwear agent, antimony dibutyldithiocarbamate, Yueqing Laiyi Chemical Trade Co., Ltd.;

Metal corrosion inhibitor, benzotriazole, produced by Liaoning Tianhe Fine Chemical Co., Ltd.;

Lubricant base oil, Ⅱ base oil 100N, produced by Dalian Petrochemical Company;

Lubricant base oil, Ⅱ base oil 150BS, produced by Dalian Petrochemical Company.

According to the formula composition in Table 1, Examples 4-6 and Comparative Examples 4-6 of the gear oil composition were obtained.

Engine crankcase coking simulation tests to simulate piston deposits were performed on these gear oil compositions. The method is to add 300mL sample sample into the coke plate simulator, heat it to 150°C, splash oil on the aluminum plate with a temperature of 310°C in a continuous manner, and weigh the amount of coke generated on the aluminum plate after 6 hours to simulate the piston. on the sediments. The higher the amount of coke formation, the worse the piston cleanliness of the test sample.

A high-frequency reciprocating friction tester was used to conduct the anti-wear test of the gear oil composition. The test conditions were: load 400g, frequency 20Hz, temperature 60°C, and test time 60min. The anti-oxidation performance test of the oil product was carried out on the gear oil composition by high pressure differential scanning calorimetry (PDSC), and the test temperature was 170°C.

The test results of the coking plate test, the anti-wear test and the anti-oxidation test of each gear oil composition are shown in Table 1.

Table 1

Claims (16)

1. A gear oil composition, comprising a polyetheramine compound, an antioxidant, an antiwear agent, a metal corrosion inhibitor and a balance of lubricating oil base oil, the structure of the polyetheramine compound is:

Wherein group R ₀ is selected from hydrogen atom, C _1-20 straight or branched chain alkyl; y groups Ru are the same or different from each other, each independently selected from C _2-24 straight or branched alkylene; y represents the average degree of polymerization of the polyether segment -O-Ru-, selected from any number between 1 and 200; the groups R ₁ and R ₂ are the same or different from each other, each independently selected from hydrogen and C _1-6 Linear or branched alkyl; a group _R3 or a group _R4 the same or different from each other, each independently selected from hydrogen and _C1-6 linear or branched alkyl; a group R ₆ or a of the groups R ₇ are the same or different from each other, each independently selected from hydrogen, optionally substituted C _1-6 straight or branched chain alkyl and

Wherein q groups R ₈ are the same or different from each other, each independently selected from C _1-40 linear or branched alkylene; q groups R ₉ are the same or different from each other, each independently selected from hydrogen and C _{1 -6} straight or branched chain alkyl; group R ₁₀ is selected from hydrogen and C _1-6 straight or branched chain alkyl; q is an integer between 1 and 50; a is an integer between 1 and 10; a group R' is the same or different from each other, each independently selected from single bond and C _1-6 straight or branched alkylene _; group R is selected from hydrogen and C _1-6 straight or branched alkane base. 2. The gear oil composition according to claim 1, wherein the group R ₀ is selected from a hydrogen atom, a C _5-15 straight or branched chain alkyl group; the y groups Ru are each independently selected from C _2-12 straight or branched chain alkylene; y is selected from any value between 1 and 100; groups R ₁ and R ₂ are each independently selected from hydrogen and C _1-4 straight or branched chain alkyl ; Group R ₃ or group R ₄ is each independently selected from hydrogen and C _1-4 straight or branched chain alkyl; Group R ₆ or group R ₇ is each independently selected from hydrogen, optionally substituted C _1-4 straight or branched chain alkyl and

wherein the groups R ₈ are the same or different from each other and are each independently selected from C _1-20 straight or branched chain alkylene; the groups R ₉ are each independently selected from hydrogen and C _1-4 straight or branched chain alkyl; The group R ₁₀ is selected from hydrogen and C _1-4 straight or branched chain alkyl; q is an integer between 1 and 10; a is an integer between 1 and 4; the groups R' are each independently selected from mono bond and C _1-4 linear or branched alkylene; group R ₅ is selected from hydrogen and C _1-4 linear or branched alkyl. 3 . The gear oil composition according to claim 2 , wherein a is 1, 2 or 3. 4 . 4 . The gear oil composition according to claim 1 , wherein the R ₀ is selected from C _5-15 straight or branched chain alkyl groups. 5 . 5. The gear oil composition according to claim 1, wherein the preparation method of the polyetheramine compound comprises: 1) react the hydroxyl-containing polyether with an alkenyl compound to generate an alkenyl polymer; 2) reacting the product of step 1) with an oxidant; 3) react the oxidation product of step 2) with aminating agent, and collect the product; The hydroxyl-containing polyether described in step 1) is

The alkenyl compound is

wherein the group R ₀ is selected from a hydrogen atom or a C _1-20 straight or branched chain alkyl group. 6. The gear oil composition according to claim 5, wherein the y groups Ru are the same or different from each other, and are independently selected from C _2-24 straight or branched chain alkylene groups; groups G represents a functional group capable of reacting with -OH to remove the compound GH; the groups R ₁ and R ₂ are the same or different from each other, each independently selected from hydrogen and C _1-6 straight or branched chain alkyl; a group R ₃ or a group R ₄ are the same or different from each other, each independently selected from hydrogen and C _1-6 straight or branched chain alkyl; a is an integer between 1 and 10; a group R' is each other The same or different, each is independently selected from a single bond and a C _1-6 straight or branched chain alkylene group; the group R ₅ is selected from hydrogen and a C _1-6 straight or branched chain alkyl group. 7. The gear oil composition according to claim 6, wherein the group G is halogen or hydroxyl. 8. The gear oil composition according to claim 6, wherein the group G is chlorine or hydroxyl. 9. The gear oil composition according to claim 5, wherein the alkenyl compound is selected from the group consisting of allyl halide, 3-butene-1-halogen, 3-butene-2-halogen, 3- Methyl-3-butene-1-halo, 4-pentene-1-halo, 4-pentene-2-halo, 4-pentene-3-halo, 3-methyl-4-pentene 1-halo , 2-methyl 4-pentene 1-halogen, 3-ethyl 4-pentene 1-halogen, 2-ethyl 4-pentene 1-halogen, 3-isobutyl 4-pentene 1-halogen, 2-Isobutyl 4-pentene 1-halogen, 2,3-dimethyl 4-pentene 1-halogen, 2,2-dimethyl 4-pentene 1-halogen, 3,3-dimethyl 4-Pentene 1-halogen, 5-hexene-1-halogen, 4-methyl-5-hexene halide, 3-methyl-5-hexene halide, 2-methyl-5-hexene halide, 3-ethyl-5-hexene halide, 5-hexene-2-halogen, 5-hexene-3-halogen, 5-hexene-4-halogen, 6-heptene-1-halogen, 2-methyl yl-6-heptene-1-halo, 3-methyl-6-heptene-1-halo, 4-methyl-6-heptene-1-halo, 5-methyl-6-heptene-1 -halo, 2-ethyl-6-heptene-1-halo, 3-ethyl-6-heptene-1-halo, 4-ethyl-6-heptene-1-halo, 5-ethyl- 6-heptene-1-halo, 2-methyl-7-octene-1-halo, 3-methyl-7-octene-1-halo, 4-methyl-7-octene-1-halo, 5- Methyl-7-octene-1-halo, 6-methyl-7-octene-1-halo, 3-ethyl-7-octene-1-halo, 9-decene-1-halo, 10-undecene Alkene-1-halo, 11-dodecene-1-halo, 5-chloro-1,3-pentadiene, 6-chloro-1,3-hexadiene, 5-chloro-1,3-hexadiene One or more of alkene, 6-chloro-2,4-hexadiene and 5-chloro-2,4-hexadiene. 10. The gear oil composition according to claim 5, wherein the molar ratio of the hydroxyl-containing polyether to the alkenyl compound in step 1) is 1:1-1.5, and the reaction temperature is 50-150 ℃, the reaction time is 2-10h; in step 2), the oxidant is selected from oxygen, ozone, hydrogen peroxide, metal oxides, metal peroxides, dichromic acid or its salts, permanganic acid or its salts, permanganic acid or its salts. One or more of acid or its salt, hypohalous acid or its salt and organic peroxide; in step 2), the molar ratio of alkenyl compound and said oxidant in said step 1) is 1:1 -100, the reaction temperature is 100-200°C, and the reaction time is 3-20h; in step 3), the oxidation product obtained in step 2) is aminated with an aminating agent, and the group

All aminated to groups

In step 3), the aminating agent is selected from the aminating agent represented by the following formula (II):

In formula (II), the groups R ₆ and R ₇ are the same or different from each other, each independently selected from hydrogen, optionally substituted C _1-6 straight or branched chain alkyl and

in

, there are q R ₈ , q R ₉ , and 1 R ₁₀ , the groups R ₈ are the same or different from each other, and each is independently selected from C _1-40 straight or branched chain alkylene; the group The groups R ₉ are the same or different from each other, and each is independently selected from hydrogen and C _1-6 straight or branched chain alkyl; the group R ₁₀ is selected from hydrogen and C _1-6 straight or branched chain alkyl; q is 1 an integer between 50 and 50; in step 3), the molar ratio of the aminating agent to the oxidation product is 1-4:1, the reaction temperature is 100-180° C., and the reaction time is 1h-8h. 11. The gear oil composition according to claim 10, wherein the oxidant in step 2) is an organic hydroperoxide. 12. The gear oil composition according to claim 10, wherein a catalyst is added in step 3), the catalyst is selected from tertiary amines and phenolic substances, and the molar ratio of the catalyst to the oxidation product is 0.1-1:1, the number of moles of the oxidation product is in groups

to calculate. 13. The gear oil composition according to claim 1, wherein the antioxidant is selected from the group consisting of phenolic antioxidants, aromatic amine antioxidants, phenolic ester antioxidants and thiophenolic esters One or more of antioxidants selected from one or more of phosphoric acid esters, sulfurized olefins, dialkyldithiocarbamates and dialkyldithiophosphates , the metal corrosion inhibitor is selected from one or more of benzotriazole derivatives, thiazole derivatives and thiadiazole derivatives. 14. The gear oil composition according to claim 1, wherein the antioxidant is selected from phenolic ester type antioxidants, and the antiwear agent is selected from phosphoric acid esters, sulfurized olefins and dialkyl disulfides A phosphate-substituting composition, wherein the metal corrosion inhibitor is selected from benzotriazole derivatives. 15 . The gear oil composition according to claim 1 , wherein the polyetheramine compound accounts for 0.01% to 20% of the total mass of the gear oil composition by mass; the antioxidant accounts for 0.01% to 20% of the total mass of the gear oil composition. 0.01-10% of the total mass of the gear oil composition; the anti-wear agent accounts for 0.1-10% of the total mass of the gear oil composition; the metal corrosion inhibitor accounts for 0.01% of the total mass of the gear oil composition % to 5%. 16. A method of manufacturing a gear oil composition, characterized in that it comprises making the polyetheramine compound, antioxidant, antiwear agent, metal corrosion inhibitor and lubricating oil base described in one of claims 1 to 15 Oil mixing steps.