Special agent for chlorine-free high-base-number calcium sulfonate-based lubricating grease and preparation method thereof

Abstract

The invention discloses a special agent for chlorine-free high-base-number calcium sulfonate-based lubricating grease and a preparation method thereof, and mainly relates to the technical field of sulfonic acid. The special agent for the chlorine-free high-base-number calcium sulfonate-based lubricating grease comprises the following components: base oil, calcium hydroxide, n-butyl alcohol, an accelerant, sulfonic acid, neutral salt, n-butyl alcohol, an accelerant, an amine substance, a synergist, inorganic salt and carbon dioxide, the amine substance is one or a mixture of two of ethylenediamine, diethylenetetramine and ammonium carbonate, and the synergist is one or a mixture of more of graphene, graphene oxide, modified graphene, hydroxy propyl distarch phosphate and polyphenylene sulfide. Compared with the prior art, the composite calcium sulfonate-based lubricating grease additive is used for producing composite calcium sulfonate-based lubricating grease, and the high temperature resistance, mechanical stability, extreme pressure property and wear resistance of the composite calcium sulfonate-based lubricating grease are jointly improved.

Description

Technical Field

[0001] The invention relates to the technical field of sulfonic acid, and in particular to a special agent for chlorine-free high-alkalinity calcium sulfonate-based grease and a preparation method thereof. Background Art

[0002] The high polarity of chloride ions promotes the occurrence of corrosion reactions, and they have strong penetrability, easily penetrating the protective film on the metal surface, causing local corrosion. Since calcium sulfonate-based grease is mainly used in steel mills, metallurgy, automobiles, textiles, aerospace and other fields, the presence of chloride ions in the application will promote corrosion, shorten the service life of the equipment, and affect the service life. In the prior art, the source of chloride ions can be replaced or reduced in the basic formula, the use of chloride ions in the grease can be reduced, the risk of corrosion can be reduced, and the service life of the equipment can be increased.

[0003] In the prior art, specific additives such as antioxidants, anti-wear agents, extreme pressure agents and corrosion inhibitors can be added to prepare calcium sulfonate-based grease to improve application performance. The improvement of water resistance can prevent the grease from being lost or degraded in a humid environment, while the enhancement of corrosion resistance can protect against corrosion and extend the service life of the equipment. The improvement of anti-friction performance can reduce friction and wear, improve mechanical efficiency, reduce energy consumption, and reduce maintenance costs.

[0004] CN101928239A discloses a method for preparing high-base calcium sulfonate, which uses alkylbenzene sulfonate and / or petroleum sulfonic acid as raw materials, low molecular alcohol as a promoter, calcium oxide and / or calcium hydroxide as a calcification agent, firstly performs a neutralization reaction to generate calcium sulfonate, then performs two carbonation reactions, then adds a post-treatment agent to react, and finally removes alcohol, water, solvent and solid residue to obtain a product. The product obtained by the invention is particularly suitable for preparing lubricating grease. The preparation of lubricating grease with the product can shorten the crystal transformation time of calcium sulfonate and improve the high temperature performance and water resistance of the lubricating grease.

[0005] CN104531306A discloses a wear reducer and a preparation method thereof, wherein the wear reducer comprises the following components: (a) composite calcium sulfonate grease; (b) extreme pressure anti-wear agent; (c) antioxidant; (d) solid additive; based on the mass of the composite calcium sulfonate grease (a) as 100%, the addition amount of the extreme pressure anti-wear agent (b) is 0.5-5% by mass; the addition amount of the antioxidant (c) is 0.1-3% by mass; and the addition amount of the solid additive (d) is 1-10% by mass. The wear reducer of the invention has a low friction coefficient and outstanding extreme pressure anti-wear properties, has strong wide temperature adaptability, oxidation stability, colloidal stability and corrosion resistance, has excellent comprehensive performance, is suitable for modern rail transit lubrication; and has a simple preparation process and is easy to industrialize and control.

[0006] The solutions reported in the above patent documents can solve the problems of water resistance, oxidation stability, colloidal stability, friction reduction and corrosion resistance, but do not improve the water resistance, corrosion resistance and wear reduction performance at the same time. Summary of the invention

[0007] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to provide a special grease additive for composite calcium sulfonate-based grease, which can improve its water resistance, corrosion resistance and wear reduction performance.

[0008] To achieve the above object, the present invention provides a special agent for chlorine-free high-alkalinity calcium sulfonate-based grease and a preparation method thereof.

[0009] The preparation method of the chlorine-free high-base calcium sulfonate-based grease special agent comprises the following steps:

[0010] (1) adding base oil, calcium hydroxide, n-butanol and accelerator into a reaction kettle at one time, controlling the temperature at 60-65° C., adding sulfonic acid dropwise for 80-90 minutes, and after the addition of sulfonic acid, controlling the temperature at 65-70° C., keeping the temperature constant for 1-2 hours, flashing in a flash tank, adding 3-5 times the weight of the total amount of filter aid, filtering, and obtaining neutral salt;

[0011] (2) neutral salt, n-butanol, accelerator, amine substance and synergist are put into the reactor again, the temperature of the reactor is raised to 45-50° C., inorganic salt is added, carbon dioxide is introduced for 4-5 hours, after the carbonation reaction is completed, flash treatment is carried out in a flash tank, and 3-5 times the weight of the total amount of filter aid is added for filtration to obtain the chlorine-free high-base calcium sulfonate based grease special agent.

[0012] The mass percentages of base oil, calcium hydroxide, n-butanol, accelerator and sulfonic acid in step (1) are as follows: 30-35% base oil, 3-5% calcium hydroxide, 5-8% n-butanol, 2-4% accelerator and 48-60% sulfonic acid.

[0013] The mass percentages of the neutral salt, n-butanol, accelerator, amine substance, synergist, inorganic salt and carbon dioxide in step (2) are as follows: 31-53% of neutral salt, 15-25% of n-butanol, 2-4% of accelerator, 1-2% of amine substance, 1-2% of synergist, 16-20% of inorganic salt and 12-16% of carbon dioxide.

[0014] In the step (1), the base oil is one of 150SN and 400SN or a mixture of the two.

[0015] The promoter in step (1) and step (2) is one of methanol and ethylene glycol or a mixture of the two.

[0016] In the step (1), the sulfonic acid is a mixture of one or more of linear heavy alkylbenzene sulfonic acid, long-chain linear alkylbenzene sulfonic acid and dodecylbenzene sulfonic acid.

[0017] The amine substance in step (2) is one of ethylenediamine, diethylenetetramine, and ammonium carbonate, or a mixture of the two.

[0018] The inorganic salt in step (2) is one of calcium hydroxide and calcium oxide, or a mixture of the two.

[0019] The filter aid in step (1) and step (2) is diatomaceous earth filter aid; specifically, the amount of the filter aid in step (1) is 3-5 times by weight of the total amount of base oil, calcium hydroxide, n-butanol, promoter, and sulfonic acid; the amount of the filter aid in step (2) is 3-5 times by weight of the total amount of neutral salt, n-butanol, promoter, amine substance, synergist, inorganic salt, and carbon dioxide.

[0020] The synergist in step (2) is a mixture of one or more of graphene, graphene oxide, modified graphene, hydroxypropyl distarch phosphate, and polyphenylene sulfide.

[0021] The preparation method of the modified graphene in step (2) is as follows, in parts by weight:

[0022] Add 0.4-1 parts of graphene oxide to 15-30 parts of water and disperse for 10-30 minutes, add 0.05-0.2 parts of 1-aminoethyl-3-methylimidazolium tetrafluoroborate and 0.01-0.02 parts of sodium hydroxide and stir for 0.5-1 hour, reflux at 80-100° C. for 24 hours, cool to 20-40° C. and centrifuge, wash the filter cake with water 2-4 times to obtain modified graphene.

[0023] In the chlorine-free high-alkalinity calcium sulfonate-based grease special agent of the present invention, base oil is the main lubricating component to improve the lubricity and fluidity of the grease, and reduce friction and wear during the lubrication process; calcium hydroxide reacts with sulfonic acid to form calcium salt, which is a key component for forming calcium sulfonate-based grease and can also improve the thermal stability of the grease; n-butanol as a solvent can effectively dissolve many non-polar or weakly polar organic or inorganic substances; accelerators methanol and ethylene glycol can accelerate the reaction of sulfonic acid and calcium hydroxide and improve the reaction efficiency; dodecylbenzene sulfonic acid can react with alkali to form salts with excellent surface activity and lubrication properties; inorganic salts help enhance the water resistance and thermal stability of the grease. Carbon dioxide reacts to form calcium carbonate, which helps to improve the base value and corrosion resistance of the grease; diatomaceous earth filter aid is used to improve the filtration efficiency during the filtration process and ensure the purity of the grease; the synergist jointly improves the overall lubricity, water resistance, corrosion resistance, friction reduction, etc. of the chlorine-free high-alkalinity calcium sulfonate-based grease special agent in the grease through the synergistic effect of each component. The present invention uses amine substances to replace traditional calcium chloride as a component of the calcium sulfonate-based grease special agent, thereby avoiding the introduction of chloride ions, helping to reduce the risk of pollution in water and soil environments, and reducing the occurrence of corrosion caused by chloride ions.

[0024] Beneficial effects of the present invention:

[0025] Compared with the prior art, the chlorine-free high-alkalinity calcium sulfonate-based grease special agent of the present invention replaces the calcium chloride in the previous calcium sulfonate-based grease special agent with amine substances. The obtained product not only does not contain chloride ions, but also can better meet the market requirements of composite calcium sulfonate-based grease. The chlorine-free high-alkalinity calcium sulfonate-based grease special agent of the present invention also adds a synergist composed of one or more mixed compounds of graphene, graphene oxide, modified graphene, hydroxypropyl distarch phosphate, and polyphenylene sulfide. Through the synergistic effect of each component, it is used as an additive for the production of composite calcium sulfonate-based grease to jointly improve its high temperature resistance, mechanical stability, extreme pressure resistance and wear resistance. DETAILED DESCRIPTION

[0026] The parameters of the specific chemical substances used in the examples are from the following sources:

[0027] 150SN base oil: purity is 99.9%.

[0028] 400SN base oil: purity is 99.9%.

[0029] Linear heavy alkylbenzene sulfonic acid: The manufacturer is Shanghai Myrel Biochemical Technology Co., Ltd., and the product number is M75424.

[0030] Long-chain linear alkylbenzene sulfonic acid: The manufacturer is Jinzhou Chenghua New Materials Co., Ltd., model number is T106B.

[0031] Dodecylbenzenesulfonic acid: CAS number is 27176-87-0.

[0032] Hydroxypropyl distarch phosphate: The manufacturer is Jiangsu Yihaotian Biotechnology Co., Ltd., and the product number is 001.

[0033] Graphene: The manufacturer is Hubei Wande Chemical Co., Ltd., and the product number is WD3378.

[0034] Graphene oxide: The manufacturer is Shanghai Myrrel Biochemical Technology Co., Ltd., and the product number is M33420.

[0035] 1-aminoethyl-3-methylimidazolium tetrafluoroborate: CAS is 143314-16-3.

[0036] Diatomaceous earth filter aid: specific surface area is 3.1m 2 / g, loose density is 0.3-0.5g / cm 3 , pH value is 7, manufacturer is Hebei McMahon Mineral Products Co., Ltd., model is Y7965.

[0037] Comparative Example 1

[0038] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0039] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0040] (2) 424 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, and 12 g of calcium chloride were again added to the reactor, the temperature of the reactor was raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide were added, and 150 g of carbon dioxide was introduced for 4.5 hours. After the carbonation reaction was completed, the mixture was flash-evaporated in a flash tank, and 4 kg of diatomaceous earth filter aid was added for filtration to obtain the chlorine-free high-base calcium sulfonate-based grease special agent.

[0041] Example 1

[0042] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0043] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0044] (2) 424 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, and 12 g of ethylenediamine were again added to the reactor, the temperature of the reactor was raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide were added, and 150 g of carbon dioxide was introduced for 4.5 hours. After the carbonation reaction was completed, the mixture was flash-evaporated in a flash tank, and 4 kg of diatomaceous earth filter aid was added for filtration to obtain the chlorine-free high-base calcium sulfonate-based grease special agent.

[0045] Example 2

[0046] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0047] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0048] (2) 424 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, and 12 g of diethylenetetramine were again added to the reactor, the temperature of the reactor was raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide were added, and 150 g of carbon dioxide was introduced for 4.5 hours. After the carbonation reaction was completed, the mixture was flash-evaporated in a flash tank, and 4 kg of diatomaceous earth filter aid was added for filtration to obtain the chlorine-free high-base calcium sulfonate-based grease special agent.

[0049] Example 3

[0050] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0051] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0052] (2) 424 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, and 12 g of ammonium carbonate were again added to the reactor, the temperature of the reactor was raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide were added, and 150 g of carbon dioxide was introduced for 4.5 hours. After the carbonation reaction was completed, the mixture was flash-evaporated in a flash tank, and 4 kg of diatomaceous earth filter aid was added for filtration to obtain the chlorine-free high-base calcium sulfonate-based grease special agent.

[0053] Example 4

[0054] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0055] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0056] (2) 424 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, 6 g of ethylenediamine, and 6 g of diethylenetetramine were again added to the reactor, the temperature of the reactor was raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide were added, and 150 g of carbon dioxide was introduced for 4.5 hours. After the carbonation reaction was completed, the mixture was flash-evaporated in a flash tank, and 4 kg of diatomaceous earth filter aid was added for filtration to obtain the chlorine-free high-base calcium sulfonate-based grease special agent.

[0057] Example 5

[0058] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0059] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0060] (2) 424 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, 6 g of ethylenediamine, and 6 g of ammonium carbonate were again added to the reactor, the temperature of the reactor was raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide were added, and 150 g of carbon dioxide was introduced for 4.5 hours. After the carbonation reaction was completed, the mixture was flash-evaporated in a flash tank, and 4 kg of diatomaceous earth filter aid was added for filtration to obtain the chlorine-free high-base calcium sulfonate-based grease special agent.

[0061] Example 6

[0062] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0063] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0064] (2) 424 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, 6 g of diethylenetetramine, and 6 g of ammonium carbonate were again added to the reactor, the temperature of the reactor was raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide were added, and 150 g of carbon dioxide was introduced for 4.5 hours. After the carbonation reaction was completed, the mixture was flash-evaporated in a flash tank, and 4 kg of diatomaceous earth filter aid was added for filtration to obtain the chlorine-free high-base calcium sulfonate-based grease special agent.

[0065] Example 7

[0066] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0067] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0068] (2) 412 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, 6 g of diethylenetetramine, 6 g of ammonium carbonate, and 12 g of graphene are again put into the reactor, the temperature of the reactor is raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide are added, and 150 g of carbon dioxide is introduced for 4.5 hours. After the carbonation reaction is completed, the mixture is flash-evaporated in a flash tank, and 4 kg of diatomaceous earth filter aid is added for filtration to obtain the chlorine-free high-base calcium sulfonate-based grease special agent.

[0069] Example 8

[0070] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0071] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0072] (2) 412 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, 6 g of diethylenetetramine, 6 g of ammonium carbonate, and 12 g of graphene oxide were put into the reactor again, the temperature of the reactor was raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide were added, and 150 g of carbon dioxide was introduced for 4.5 hours. After the carbonation reaction was completed, the reaction mixture was flash-evaporated in a flash tank, and 4 kg of diatomaceous earth filter aid was added for filtration to obtain the chlorine-free high-base calcium sulfonate grease special agent.

[0073] Example 9

[0074] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0075] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0076] (2) 412 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, 6 g of diethylenetetramine, 6 g of ammonium carbonate, 4 g of graphene, and 8 g of hydroxypropyl distarch phosphate were put into the reactor again, the temperature of the reactor was raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide were added, and 150 g of carbon dioxide was introduced for 4.5 hours. After the carbonation reaction was completed, the mixture was flash-evaporated in a flash tank, and then 4 kg of diatomaceous earth filter aid was added for filtration to obtain the chlorine-free high-base calcium sulfonate-based grease special agent.

[0077] Example 10

[0078] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0079] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0080] (2) 412 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, 6 g of diethylenetetramine, 6 g of ammonium carbonate, 4 g of graphene, and 8 g of polyphenylene sulfide were put into the reactor again, the temperature of the reactor was raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide were added, and 150 g of carbon dioxide was introduced for 4.5 hours. After the carbonation reaction was completed, the mixture was flash-evaporated in a flash tank, and then 4 kg of diatomaceous earth filter aid was added for filtration to obtain the chlorine-free high-alkali calcium sulfonate-based grease special agent.

[0081] Embodiment 11

[0082] A method for preparing a special agent for a chlorine-free high-base calcium sulfonate-based grease comprises the following steps:

[0083] (1) 140 g of 150SN base oil, 200 g of 400SN base oil, 39 g of calcium hydroxide, 65 g of n-butanol, 18 g of methanol, and 18 g of ethylene glycol are put into a reactor at one time, the temperature is controlled at 63° C., 390 g of linear heavy alkylbenzene sulfonic acid, 104 g of long-chain linear alkylbenzene sulfonic acid, and 26 g of dodecylbenzene sulfonic acid are added dropwise, and the dodecylbenzene sulfonic acid dropping time is 90 minutes. After the dodecylbenzene sulfonic acid dropping is completed, the temperature is controlled at 68° C., and the temperature is kept constant for 1.5 hours. After flash treatment in a flash tank, 4 kg of diatomaceous earth filter aid is added, and filtration is performed to obtain a neutral salt;

[0084] (2) 412 g of neutral salt, 200 g of n-butanol, 12 g of methanol, 12 g of ethylene glycol, 6 g of diethylenetetramine, 6 g of ammonium carbonate, 2 g of modified graphene, 4 g of graphene, and 6 g of hydroxypropyl distarch phosphate were put into the reactor again, the temperature of the reactor was raised to 48° C., 11 g of calcium hydroxide and 8 g of calcium oxide were added, and 150 g of carbon dioxide was introduced for 4.5 hours. After the carbonation reaction was completed, the mixture was flash-evaporated in a flash tank, and then 4 kg of diatomaceous earth filter aid was added for filtration to obtain the chlorine-free high-base calcium sulfonate grease special agent.

[0085] The preparation method of modified graphene oxide in step (2) is as follows:

[0086] 5 g of graphene oxide was added to 200 g of water and dispersed for 20 minutes. 1 g of 1-aminoethyl-3-methylimidazolium tetrafluoroborate and 0.1 g of sodium hydroxide were added and stirred for 0.5 hours. The mixture was refluxed at 90° C. for 24 hours, cooled to 35° C. and centrifuged. The filter cake was washed with water for 3 times to obtain modified graphene.

[0087] Test Example 1

[0088] The chlorine-free high-alkalinity calcium sulfonate-based grease special agent obtained by the preparation method of Example 1-11 was tested for water resistance. The test method was based on the industry standard SH / T 0643-1997 "Determination of water spray resistance of grease". 1g of the chlorine-free high-alkalinity calcium sulfonate-based grease special agent of Example 1-11 was added to 15g of calcium sulfonate-based grease to obtain the corresponding test sample. The test principle is as follows: by applying the test sample of the calcium sulfonate-based grease corresponding to Example 1-11 on a stainless steel plate, spraying water for 5 minutes at a temperature of 38°C and a pressure of 276kPa, the spray weight loss percentage of the test sample of the calcium sulfonate-based grease corresponding to Example 1-11 was measured as a measure of water spray resistance. The smaller the value, the better the water resistance of the grease; 3 groups of tests were set for each example, and the test data were averaged and summarized as shown in Table 1. The calculation formula is as follows:

[0089] x={(m 2 -m 3 ) / (m 2 -m 1 )}×100%

[0090] Where:

[0091] m 1 ——The initial mass of the clean stainless steel plate, g;

[0092] m 2 ——The mass of grease added to the stainless steel plate before spraying, g;

[0093] m 3 ——The mass of grease added to the stainless steel plate after spraying, g.

[0094] Table 1 Water resistance test results

[0095]

[0096]

[0097] The reason for the difference in water resistance data of Examples 1-11 is the difference in amine substances and synergists. Different amine substances are added in Examples 1-6, and different synergists are added in Examples 7-11. The synergistic enhancement of each component improves the water resistance. The high specific surface area and surface energy of graphene form a strong interaction between it and water molecules, resulting in the adsorption and spreading of water molecules on the graphene surface, thereby enhancing its water resistance; the number of oxygen-containing functional groups on the surface of graphene oxide increases, and the hydrogen bonding effect is enhanced, thereby improving its water resistance; the contact angle of the modified graphene surface to water increases, and the rolling angle decreases, thereby enhancing its water resistance; the addition of hydroxypropyl distarch phosphate may form a protective film on the surface of the grease to reduce the infiltration of water, and the hydrophobicity of polyphenylene sulfide helps to improve the water resistance of the grease. In Example 11, the overall water resistance is optimized by compounding modified graphene, graphene and hydroxypropyl distarch phosphate.

[0098] Test Example 2

[0099] The anti-corrosion performance of the chlorine-free high-base calcium sulfonate-based grease special agent obtained by the preparation method of Comparative Example 1 and Examples 6-11 was tested. The test method was based on the national standard GB / T 7326-1987 "Copper Sheet Corrosion Test Method for Grease". The test temperature was 100°C, the test time was 24 hours, and the anti-corrosion degree was determined by the classification of the copper sheet corrosion standard color plate. Each example has 3 groups of tests, and the test data are averaged and summarized as shown in Table 3. The classification is as follows: Grade 1: Mild discoloration is light orange or dark orange, Grade 2: Moderate discoloration is purple, lavender, silvery white, multi-color, brass or golden yellow, Grade 3: Deep discoloration is magenta, peacock green, Grade 4: Corrosion is black, dark gray or brown with slight peacock green.

[0100] Table 2 Anticorrosion performance test results

[0101]

[0102]

[0103] In Test Example 2, the grease-specific agent of Comparative Example 1 exhibits worse anti-corrosion performance than that of Examples 6-11. The main reason is that calcium chloride is used in Comparative Example 1 without adding any synergist. Example 6-1 replaces the calcium chloride of Comparative Example 1 with amine substances diethylenetetramine and ammonium carbonate. Calcium chloride, as a salt, is easily dissolved in water and releases chloride ions. These chloride ions promote the corrosion of metals, resulting in the corrosion level of copper sheets reaching level 4, that is, black, dark gray or brown with slight malachite green, indicating that the corrosion is more serious. In Example 6-11, on the basis of Comparative Example 1, not only amine substances but also different synergist combinations are added, and the anti-corrosion effect is jointly improved by the combination of different synergists. Graphene and graphene oxide can form a protective film on the metal surface, reduce the contact between the metal and the corrosive medium, thereby improving the anti-corrosion performance of the grease, and hydroxypropyl distarch phosphate and polyphenylene sulfide can indirectly improve its anti-corrosion performance by enhancing the adhesion of the grease and forming a stable adsorption film. Example 11 forms a more uniform and stable protective film by adding a composite synergist of modified graphene, graphene and hydroxypropyl distarch phosphate, thereby improving the anti-corrosion performance of the grease.

[0104] Test Example 3

[0105] The chlorine-free high-alkalinity calcium sulfonate-based grease special agent obtained by the preparation method of Examples 6-11 was tested for friction reduction performance. The test method calculated the four-ball load capacity load of the test sample according to the national standard GB / T 3142-2019 "Determination of Lubricant Load Capacity Four-Ball Method", and 1g of the chlorine-free high-alkalinity calcium sulfonate-based grease special agent of Examples 6-11 was added to 15g of calcium sulfonate-based grease to obtain the corresponding test sample. Three groups of tests were set for each example, and the test data were averaged and summarized as shown in Table 3.

[0106] Table 3 Anti-friction performance test results

[0107] Example Four-ball bearing capacity load P / N Example 6 1055 Example 7 1340 Example 8 1335 Example 9 1198 Example 10 1302 Embodiment 11 1406

[0108] In the anti-friction performance test of Test Example 3, Examples 6-11 added amine substances diethylenetetramine and ammonium carbonate. Diethylenetetramine forms a stable adsorption film with the metal surface, thereby improving the anti-wear performance of the grease. Ammonium carbonate, as an alkaline substance, can neutralize the acidic components in the grease and reduce corrosion to the metal, thereby indirectly improving the anti-friction performance. The difference in the anti-friction performance of Examples 6-11 mainly comes from the difference in enhancers. The graphene enhancer added in Example 7 can form a protective layer on the metal surface and significantly improve the anti-friction performance; although the improvement of the anti-friction performance by graphene oxide in Example 8 is not as obvious as that of graphene; Examples 9-10 respectively add hydroxypropyl distarch phosphate and polyphenylene sulfide to Example 7 for compounding and reducing costs. The phosphate group of hydroxypropyl distarch phosphate can form an adsorption film with the metal surface, reducing direct contact between metals, thereby reducing wear, and the anti-friction effect of polyphenylene sulfide added in Example 10 is The result is lower than that of hydroxypropyl distarch phosphate; the modified graphene, graphene and hydroxypropyl distarch phosphate are added to the special agent for chlorine-free high-alkali calcium sulfonate grease in Example 11, and a more uniform and stable protective film is formed through the synergistic effect of the compounding of the components in the synergist on the metal surface, wherein the modified graphene modified with terminal amine ion liquid is obtained by the liquid phase method of 1-aminoethyl-3-methylimidazolium tetrafluoroborate ionic liquid, and the compounding with graphene and hydroxypropyl distarch phosphate synergizes to make the synergist play a better role, and the wear rate is lower than that of Example 9 without adding modified graphene. Compared with Example 6 without adding synergist, Examples 7-11 of the present invention reduce direct contact and reduce wear rate during friction.

[0109] The preferred specific embodiments of the present invention are described in detail above. It should be understood that a person skilled in the art can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solution that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A method for preparing a special agent for chlorine-free high-base calcium sulfonate-based grease, characterized in that: The following steps are involved: (1) adding base oil, calcium hydroxide, n-butanol and accelerator into a reaction kettle at one time, controlling the temperature at 60-65° C., adding sulfonic acid dropwise for 80-90 minutes, and after the addition of sulfonic acid, controlling the temperature at 65-70° C., keeping the temperature constant for 1-2 hours, flashing in a flash tank, adding 3-5 times the weight of the total amount of filter aid, filtering, and obtaining neutral salt; (2) neutral salt, n-butanol, accelerator, amine substance and synergist are put into the reactor again, the temperature of the reactor is raised to 45-50° C., inorganic salt is added, carbon dioxide is introduced for 4-5 hours, after the carbonation reaction is completed, flash treatment is carried out in a flash tank, and 3-5 times the weight of the total amount of filter aid is added for filtration to obtain the chlorine-free high-base calcium sulfonate based grease special agent; The mass percentages of base oil, calcium hydroxide, n-butanol, accelerator and sulfonic acid in step (1) are as follows: 30-35% base oil, 3-5% calcium hydroxide, 5-8% n-butanol, 2-4% accelerator and 48-60% sulfonic acid; The mass percentages of the neutral salt, n-butanol, accelerator, amine substance, synergist, inorganic salt and carbon dioxide in step (2) are as follows: 31-53% of neutral salt, 15-25% of n-butanol, 2-4% of accelerator, 1-2% of amine substance, 1-2% of synergist, 16-20% of inorganic salt and 12-16% of carbon dioxide.

2. The method for preparing the chlorine-free high-base calcium sulfonate-based grease special agent according to claim 1, characterized in that: In the step (1), the base oil is one of 150SN and 400SN or a mixture of the two.

3. The method for preparing the special agent for chlorine-free high-base calcium sulfonate-based grease according to claim 1, characterized in that: The promoter in step (1) and step (2) is one of methanol and ethylene glycol or a mixture of the two.

4. The method for preparing the special agent for non-chlorine high-base calcium sulfonate-based grease according to claim 1, characterized in that: In the step (1), the sulfonic acid is a mixture of one or more of linear heavy alkylbenzene sulfonic acid, long-chain linear alkylbenzene sulfonic acid and dodecylbenzene sulfonic acid.

5. The method for preparing the special agent for chlorine-free high-base calcium sulfonate-based grease according to claim 1, characterized in that: The amine substance in step (2) is one of ethylenediamine, diethylenetetramine, and ammonium carbonate, or a mixture of the two.

6. The method for preparing the special agent for non-chlorine high-base calcium sulfonate-based lubricating grease according to claim 1, characterized in that: The inorganic salt in step (2) is one of calcium hydroxide and calcium oxide, or a mixture of the two.

7. The method for preparing the special agent for non-chlorine high-base calcium sulfonate-based lubricating grease according to claim 1, characterized in that: The filter aid in the steps (1) and (2) is diatomaceous earth filter aid.

8. The method for preparing the special agent for chloride-free high-base calcium sulfonate-based grease according to claim 1, characterized in that: The synergist in step (2) is a mixture of one or more of graphene, graphene oxide, modified graphene, hydroxypropyl distarch phosphate, and polyphenylene sulfide.

9. The method for preparing the special agent for non-chlorine high-base calcium sulfonate-based lubricating grease according to claim 8, characterized in that: The preparation method of the modified graphene in step (2) is as follows, in parts by weight: Add 0.4-1 parts of graphene oxide to 15-30 parts of water and disperse for 10-30 minutes, add 0.05-0.2 parts of 1-aminoethyl-3-methylimidazolium tetrafluoroborate and 0.01-0.02 parts of sodium hydroxide and stir for 0.5-1 hour, reflux at 80-100° C. for 24 hours, cool to 20-40° C. and centrifuge, wash the filter cake with water 2-4 times to obtain modified graphene.

10. A special agent for chlorine-free high-base calcium sulfonate-based grease, characterized in that: Prepared by the method according to any one of claims 1 to 9.

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