CN107760412B - Boron-molybdenum integrated dispersant, preparation method and application thereof - Google Patents
Boron-molybdenum integrated dispersant, preparation method and application thereof Download PDFInfo
- Publication number
- CN107760412B CN107760412B CN201610683031.0A CN201610683031A CN107760412B CN 107760412 B CN107760412 B CN 107760412B CN 201610683031 A CN201610683031 A CN 201610683031A CN 107760412 B CN107760412 B CN 107760412B
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- boron
- dispersant
- integrated
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M165/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
Abstract
The invention discloses a boron-molybdenum integrated dispersant, a preparation method and application thereof. The invention contains boron and molybdenum at the same time, and the boron and molybdenum atoms are connected by a B-N bond and a Mo-N bond. The preparation method comprises the following steps: at least mixing a dispersant, a diluent which can be added or not added, a boronizing reagent and a molybdating reagent to carry out a first-stage reaction, then removing possible residual unreacted substances, carrying out a second-stage reaction, and finally carrying out post-treatment to obtain a target product. The invention has the advantages of both boron modified dispersant and molybdenum modified dispersant, not only can be used as extreme pressure antiwear agent and friction improver with excellent performance, but also has good addition effect with other functional additives.
Description
Technical Field
The invention relates to a multifunctional dispersant and a preparation method thereof, in particular to a boron-molybdenum integrated dispersant, a preparation method and application thereof.
Background
With the rapid development of modern industry, people have higher and higher requirements on the performance of lubricating oil used by mechanical equipment such as vehicle engines, internal combustion engines and the like, for example, in the running process of the internal combustion engines, paint films, oil sludge and carbon deposits can be formed to cause the blockage of oil passages and filter screens, the abrasion of pistons and the adhesion of piston rings, thereby influencing the service life of the internal combustion engines. To solve these problems, foreign researchers have used a method of adding a dispersant to lubricating oil to prevent carbon deposit and sludge formation, extend the oil change period, and save energy and economic expenditure since the fifties and sixties of the last century.
The dispersant is an important kind of lubricant additive, and the main varieties of dispersants which have been industrialized at present are: succinimide type, succinate type, mannich (mannich) type, high molecular weight type, boron-modified type, and the like.
The succinimide type dispersant is the most widely used ashless dispersant with no sulfur, no phosphorus, high efficiency and low cost at present, has good detergency and low-temperature oil sludge dispersibility, and can inhibit carbon deposition and paint film generation on an engine piston. With the improvement of the performance of the engine and the continuous improvement of the environmental protection requirement, people put higher requirements on the oil change period and the fuel economy of the lubricating oil for vehicles. However, it is difficult to satisfy these requirements for the conventional succinimide (only the linker group succinimide) due to its own structural aspect. Therefore, researchers have tried to increase the functions of products, improve the product properties, improve the fuel economy, etc. by introducing other functional groups or inorganic functional elements such as boron (B) or molybdenum (Mo) on the basis of general succinimide.
One typical improved product is a boron modified succinimide dispersant, which has good dispersing performance and oxidation resistance, especially, because of the introduction of boron, the wear resistance is also improved, the metal surface can be effectively prevented from being pulled and scratched, and the compatibility of the dispersant and a rubber sealing ring can be reduced.
For example, EP0499384A1 and EP0499384B1 disclose products of boron-modified bis-polyisobutylene succinimide with boron content of 1.0 to 3.0wt%, which is formed mainly by reacting bis-polyisobutylene succinimide with boric acid and water at 177 to 260 ℃. USP4554086 discloses a boron modified dispersant with antiwear and dispersing properties which is a hydrocarbyl substituted, mono-or di-containing, hydroxyl group containing polyamine chain succinimide borate ester compound formed by reacting a starting material with boric acid as the boronating agent. CN102925254A discloses a boron modified dispersant with a boron content of 0.3-4.0 wt%, which is obtained by adding a boronizing agent and a mixed solvent at 85-95 ℃ under an inert gas atmosphere, and then refluxing for 1-4 h at 120-160 ℃.
Another typical improved product is a molybdenum modified succinimide dispersant, which is synthesized according to a principle similar to that of a boron modified succinimide dispersant, and can also be introduced into a sulfur source through secondary vulcanization. The molybdenum modified succinimide dispersant can obtain excellent wear-resistant and friction-reducing effects by adding a small amount of the molybdenum modified succinimide dispersant into lubricating oil, and can obtain high-temperature synergistic oxidation resistance by compounding the molybdenum modified succinimide dispersant with an amine antioxidant.
For example, USP8076275B2 discloses a method for producing a molybdenum-modified dispersant, which is obtained by selecting various types (mono/bis-succinimide type) of ashless dispersants as alkali nitrogen compounds, reacting with molybdenum trioxide and promoter water at a temperature of not more than 120 ℃, and subjecting to a post-treatment. USP20120190864A1 and USP20130261313A1 disclose a preparation method of a molybdenum modified dispersant, which mainly comprises selecting an ashless dispersant with a side chain molecular weight of 500-5000 as an alkali nitrogen compound, pretreating with acrylic acid, reacting with molybdenum trioxide and accelerator water at a temperature of not more than 150 ℃ overnight, and post-treating to obtain a target product.
However, the existing polyisobutylene succinimide modification technologies and modified succinimide dispersants formed from these technologies still suffer from a number of deficiencies, such as: firstly, when the existing boron modified succinimide dispersant and molybdenum modified succinimide dispersant are applied as additives of products such as lubricating oil compositions and the like, the boron modified succinimide dispersant and the molybdenum modified succinimide dispersant are generally required to be matched for use, but the boron modified succinimide dispersant and the molybdenum modified succinimide dispersant have the problem of poor compatibility, so that a complex formula blending process is required to be matched, the operation is difficult, and the cost is high; secondly, the problems of complicated process, high production cost and the like generally exist in both the preparation process of the boron modified succinimide dispersant and the preparation process of the molybdenum modified succinimide dispersant.
Disclosure of Invention
Aiming at the defects of poor compatibility of different dispersants, complex formula preparation process, difficult operation and high cost in the prior art, the invention mainly aims to provide a boron-molybdenum integrated dispersant and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
a boron-molybdenum integrated dispersant is characterized in that: the dispersant contains boron and molybdenum simultaneously, and boron and molybdenum atoms are connected through a B-N bond and a Mo-N bond.
Preferably, the boron-molybdenum integrated dispersant has the following structural formula:
in the structural formula, R1、R2Is selected from
Wherein R is C2-C50A straight-chain alkyl group or an alkyl group having a branched chain, m is an integer of 0 to 8, and dp is at least any one of 1, 2, 3, 4, and 5.
The invention also provides a preparation method of the boron-molybdenum integrated dispersant, which comprises the following steps: at least mixing a dispersant, a diluent which can be added or not added, a boronizing reagent and a molybdating reagent to carry out a first-stage reaction, then removing possible residual unreacted substances, carrying out a second-stage reaction, and finally carrying out post-treatment to obtain a target product.
In some preferred embodiments, the preparation method may comprise: after fully and uniformly mixing the dispersant and the diluent, adding the boronizing agent, the molybdating agent and the accelerator which can be optionally added or not added in batches once or in batches, simultaneously or respectively feeding the boronizing agent and the molybdating agent, carrying out a first-stage reaction, removing unreacted substances which may remain, carrying out a second-stage reaction, and finally carrying out post-treatment to obtain a target product.
In some preferred embodiments, the preparation method may comprise: fully and uniformly mixing a dispersing agent and a diluent at the temperature of 30-100 ℃, then adding a boronizing agent, a molybdating agent and an optionally added accelerator at the temperature of 50-120 ℃, then reacting for 0.2-0.5 h at the temperature of 60-150 ℃, then optionally adding a vulcanizing agent, heating and refluxing for 4-10 h, then removing possibly residual unreacted substances, keeping the constant temperature for 0.5-5 h at the temperature of 80-200 ℃ under the reduced pressure condition, and finally performing post-treatment to obtain a target product.
More preferably, the dispersant is selected from dispersants containing basic nitrogen.
Further, the boronizing agent and the molybdating agent can be respectively selected from boron-containing compounds and molybdenum-containing compounds.
Another important object of the present invention is to provide the use of the boron-molybdenum integrated dispersant.
For example, in some embodiments, a lubricating oil composition is provided that includes the boron-molybdenum integral dispersant.
Further, in some embodiments, the lubricating oil composition may further comprise other additives.
Compared with the prior art, the invention has the advantages that:
(1) the boron-molybdenum integrated dispersant expands the category of the dispersant, namely, the succinimide dispersant, the high molecular weight dispersant and the Mannich dispersant can simultaneously contain boron and molybdenum;
(2) the boron-molybdenum integrated dispersant has the advantages of both a boron modified dispersant and a molybdenum modified dispersant, not only can be used as an extreme pressure antiwear agent and a friction modifier with excellent performance, but also has good addition effect with other functional additives when being applied to lubricating oil, is a multifunctional lubricating oil additive, for example, has obvious synergistic antioxidation with alkylated diphenylamine antioxidants in the lubricating oil, has good synergistic antiwear and antifriction effects with zinc dialkyl dithiophosphate, can reduce the addition amount of similar additives in the lubricating oil, thereby reducing the phosphorus content in the lubricating oil and being beneficial to improving the overall fuel economy;
(3) the boron-molybdenum integrated dispersant can be directly used as an additive of products such as lubricating oil compositions and the like, a special formula blending process is not needed, the problem that the boron modified dispersant and the molybdenum modified dispersant are poor in compatibility when used at the same time can be effectively solved, and the formula blending process is simplified;
(4) the production process of the boron-molybdenum integrated dispersant is simple and easy to operate, and is beneficial to simplifying the post-treatment process and reducing the production cost;
the technical solution of the present invention will be explained in more detail below. It is to be understood, however, that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with one another to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
As described above, in view of the disadvantages of the prior art, the present inventors have conducted extensive and intensive studies and extensive practices for a long time to propose a technical solution of the present invention, which will be described in detail below.
One aspect of the invention provides a boron-molybdenum integrated dispersant, which is characterized in that: the dispersant contains boron and molybdenum simultaneously, and boron and molybdenum atoms are connected through a B-N bond and a Mo-N bond.
Preferably, the boron-molybdenum integrated dispersant has the following structural formula:
in the structural formula, R1、R2Is selected from
Wherein R is C2-C50A straight-chain alkyl group or an alkyl group having a branched chain, m is an integer of 0 to 8, and dp is at least any one of 1, 2, 3, 4, and 5.
One aspect of the invention provides a preparation method of a boron-molybdenum integrated dispersant, which comprises the following steps: at least mixing a dispersant, a diluent which can be added or not added, a boronizing reagent and a molybdating reagent to carry out a first-stage reaction, then removing possible residual unreacted substances, carrying out a second-stage reaction, and finally carrying out post-treatment to obtain a target product.
In some more specific embodiments, the preparation method may comprise: after fully and uniformly mixing the dispersant and the diluent, adding the boronizing agent, the molybdating agent and the accelerator which can be optionally added or not added in batches once or in batches, simultaneously or respectively feeding the boronizing agent and the molybdating agent, carrying out a first-stage reaction, removing unreacted substances which may remain, carrying out a second-stage reaction, and finally carrying out post-treatment to obtain a target product.
Preferably, the preparation method may include: fully and uniformly mixing a dispersing agent and a diluent at the temperature of 30-100 ℃, then adding a boronizing agent, a molybdating agent and an optionally added accelerator at the temperature of 50-120 ℃, then reacting for 0.2-0.5 h at the temperature of 60-150 ℃, then optionally adding a vulcanizing agent, heating and refluxing for 4-10 h, then removing possibly residual unreacted substances, keeping the constant temperature for 0.5-5 h at the temperature of 80-200 ℃ under the reduced pressure condition, and finally performing post-treatment to obtain a target product.
Further, the preparation method can also comprise the following steps: fully and uniformly mixing a dispersing agent and a diluent at the temperature of 50-80 ℃, adding a boronizing agent, a molybdating agent and an optionally added accelerator at the temperature of 60-100 ℃, reacting for 0.2-0.5 h at the temperature of 60-110 ℃, optionally adding a vulcanizing agent, heating and refluxing for 4-9 h, removing possibly residual unreacted substances, keeping constant temperature at the temperature of 120-155 ℃ for 2-5 h under the reduced pressure condition, and finally performing post-treatment to obtain a target product.
More preferably, the reduced pressure condition is a condition that the degree of vacuum is not less than 4 kPa.
For example, in a more typical embodiment of the present invention, the process scheme for synthesizing a boron-molybdenum integrally modified succinimide dispersant can be found in the following formula:
the definitions of dispersants, borating agents, molybdating agents and promoters described herein are known to those skilled in the art.
Preferably, the dispersant is a dispersant containing basic nitrogen.
More preferably, the dispersant may be one or a combination of two or more selected from the group consisting of a mono-polyisobutylene succinimide, a di-polyisobutylene succinimide, a mannich base, and a high molecular weight polyisobutylene succinimide.
Furthermore, the molecular weight of an alkyl chain in the dispersing agent is 500-5000.
Preferably, the molybdating agent is selected from molybdenum-containing compounds, such as but not limited to, molybdenum dioxide, molybdenum trioxide, ammonium tridecylthiomolybdate dihydrate, ammonium tetrathiomolybdate, sodium molybdate, ammonium molybdate, and molybdic acid.
Preferably, the molar ratio of the amount of the molybdenum reagent to the nitrogen element contained in the dispersant is 1: 0.1-1: 10.
Preferably, the boronating agent is selected from boron-containing compounds, such as one or a combination of two or more selected from, but not limited to, metaboric acid, boric acid, pyroboric acid, boron chlorides and organic borates.
Further, the organic borate ester may preferably be composed of C1~C12The alcohol (b) and boric acid are formed by an esterification reaction.
Preferably, the molar ratio of the dosage of the boronizing agent to the nitrogen element contained in the dispersant is 1: 0.1-1: 10.
Preferably, the promoter may be C1-C13And/or a combination of one or more of monohydric alcohols and/or polyhydric alcohols and deionized water, which are capable of accelerating the two-phase reaction rate.
Further, the alcohol may be preferably selected from one or more of, but not limited to, methanol, ethanol, n-butanol, iso-pentanol, n-octanol, iso-octanol, propanol, iso-butanol, ethylene glycol, cyclohexanol, cyclopentanol, t-butanol, and sec-pentanol.
Further preferably, the dosage of the accelerator is 0.2-2 times of the total mass of the boronizing agent and the molybdating agent.
Preferably, the diluent may be selected from any one or a combination of two or more of hydrocarbon solvents, lubricant base oils, and naphtha.
More preferably, the hydrocarbon solvent may be selected from low polar solvents having a boiling range of 60 to 200 ℃, and the hydrocarbon solvent may include any one or a combination of two or more of toluene, xylene, n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, n-decane, and petroleum ether.
Particularly preferably, the diluent comprises any one or the combination of more than two of n-hexane, petroleum ether, toluene, xylene and lube base oil and naphtha.
Further preferably, the dosage of the diluent is 0.1-3 times of the total weight of the reaction materials adopted in the preparation method.
Preferably, the sulfuration reagent is one or more selected from carbon disulfide, sulfur dioxide, sodium hydrosulfide, active sulfur, sodium sulfide, concentrated sulfuric acid, sulfamic acid, phosphorus pentasulfide and lawson reagent.
More preferably, the amount of the vulcanizing agent is 0.1-2.5 times of the total mass of the molybdenum reagent.
In the preparation method of the present invention, after the completion of the reaction, unreacted raw materials are removed, and general methods include, but are not limited to: filtering, centrifuging, decanting, etc. to separate unreacted solid material and impurities from the desired product phase. Filter aids such as diatomaceous earth (Celite) may be used to improve the separation efficiency.
Further, the post-treatment comprises removing water and solvent from the obtained reaction product, typically by atmospheric distillation or vacuum distillation.
For example, in a more specific embodiment, a method of making a boron molybdenum integrally modified succinimide dispersant may comprise: mixing metered ashless dispersant and solvent, stirring for 0.3h at the temperature of 70 ℃, adding metered boronizing agent and/or molybdating agent and accelerator at the temperature of 80 ℃ by optimizing the ratio of Mo/N and B/N, stirring the formed mixture for 0.3h at the temperature of 120 ℃, and then heating and refluxing for 8 h; continuously adding the measured molybdenum reagent and/or the measured boron reagent, and then carrying out reflux reaction for 6h (or adding the boron reagent and the molybdenum reagent at one time under the same condition); removing possible residual unreacted substances, finally keeping the temperature for 4 hours at 145 ℃ under the condition that the vacuum degree is more than or equal to 4kPa, and removing the solvent and the water to obtain the target product.
In a further aspect of the invention, the use of the boron molybdenum integrated dispersant is provided.
For example, in some embodiments, the boron-molybdenum integral dispersant may be formulated with a variety of additives to formulate a lubricating oil composition. The boron-molybdenum integrated dispersant has good addition effect with other functional additives in lubricating oil, and is a multifunctional lubricating oil additive.
Thus, the present invention also provides a lubricating oil composition comprising the boron-molybdenum integrated dispersant.
Further, in some embodiments, the lubricating oil composition may further comprise other additives.
For example, the additive may be an alkylated diphenylamine type antioxidant. In addition, the boron-molybdenum integrated ashless dispersant and the alkylated diphenylamine antioxidant have good synergistic antioxidation effect.
For example, the additive may be zinc dialkyldithiophosphate (ZDDP). In addition, the boron-molybdenum integrated dispersing agent and the zinc dialkyl dithiophosphate have good synergistic anti-wear and anti-friction effects.
Further, the lubricating oil composition may further comprise one or more of such components as a lubricating oil base oil, detergent dispersants, antiwear agents, viscosity index improvers, pour point depressants, corrosion inhibitors, rust inhibitors, anti-foam agents, supplemental friction modifiers or mixtures thereof.
The technical solution of the present invention will be described in detail with reference to several examples, which are provided by way of expanding the invention and not limiting the invention.
Although the following examples relate to the preparation of boron-molybdenum integrally modified succinimide dispersants, the various reaction participants and process conditions used therein are typical examples, it is verified by the inventors that other types of reaction participants and other process conditions listed above are suitable and can achieve the claimed technical effects. In addition, "%" in the following examples is "wt%" unless otherwise specified.
Example 1 an ashless dispersant of mono-succinimide (ashless dispersant of mono-succinimide Mw =4002, polyisobutylene Mn =1300, base number =50.49 mg KOH/g) 20g and toluene 20g were put into a reaction flask, stirred at 30 to 100 ℃ for 0.5h, added with molybdenum trioxide 2.23 g and distilled water 3.86 g at 50 to 100 ℃, stirred at 50 to 100 ℃ for 0.5h, and then heated and refluxed for 4 to 10 h. Filtering to remove possible residual unreacted substances, and finally keeping the temperature of 120-200 ℃ for 2-4 h under the condition that the vacuum degree is more than or equal to 4kPa to remove toluene and water to obtain a molybdenum modified dispersant intermediate; and (2) putting 20g of the molybdenum modified dispersant intermediate and 20g of toluene into a reaction bottle, stirring for 0.5h at the temperature of 30-100 ℃, adding 2.97g of boric acid and 1.49g of distilled water at the temperature of 50-100 ℃, and then heating and carrying out reflux reaction for 4-10 h. Pre-treating, and filtering to remove unreacted substances possibly remaining. Keeping the temperature of 120-200 ℃ for 2-4 h under the condition that the vacuum degree is not less than 4kPa, removing the nonpolar solvent and water, and obtaining the boron-molybdenum integrated modified succinimide dispersant BM1, wherein the boron content is 0.563%, and the molybdenum content is 5.603%.
Example 2 mannich ashless dispersant (mannich ashless dispersant Mw =3562, polyisobutylene Mn =1300, base number =56.98 mg KOH/g) 20g and xylene 20g were put into a reaction flask, stirred at 30 to 100 ℃ for 0.5h, added with ammonium molybdate 3.03 g and distilled water 5.22 g at 50 to 100 ℃, stirred at 50 to 100 ℃ for 0.5h, heated and refluxed for 2 to 4h, added with boric acid 2.97g and distilled water 1.49g at the temperature, and heated and refluxed for 2 to 10 h. Pre-treating, and filtering to remove unreacted substances possibly remaining. Keeping the temperature of the mixture at 120-200 ℃ for 2-4 h under the condition that the vacuum degree is not less than 4kPa, and removing the nonpolar solvent and the water to obtain the boron-molybdenum integrated modified Mannich dispersant BM2, wherein the boron content is 0.273% and the molybdenum content is 5.048%.
Example 3 an ashless dispersant of mono-succinimide (ashless dispersant of mono-succinimide Mw =4002, polyisobutylene Mn =1300, base number =50.49 mg KOH/g) 20g and toluene 20g were charged into a reaction flask, stirred at 30 to 100 ℃ for 0.5h, added at 50 to 100 ℃ with 2.23 g of molybdenum trioxide and 2.97g of boric acid, 5.35 g of distilled water, the mixture was stirred at 50 to 100 ℃ for 0.5h, then added with sodium hydrosulfide, heated again for reflux reaction for 2 to 10h, pretreated, and filtered to remove unreacted materials that may remain. Keeping the temperature of 120-200 ℃ for 2-4 h under the condition that the vacuum degree is not less than 4kPa, removing the nonpolar solvent and water, and obtaining the boron-molybdenum integrated modified succinimide dispersant BM3, wherein the boron content is 0.506%, and the molybdenum content is 4.633%.
Example 4 an ashless dispersant (high molecular weight polyisobutylene succinimide ashless dispersant Mw =15096, polyisobutylene Mn =2300, base number =32.56 mg KOH/g) 20g and petroleum ether 20g were put into a reaction flask, stirred at 30-100 ℃ for 0.5h, added at 50-100 ℃ with 1.12g of molybdenum trioxide and 1.98 g of distilled water, and the mixture was stirred at 50-100 ℃ for 0.5h, then heated to reflux for 2-4 h, added at this temperature with 1.49g of boric acid, and then heated to reflux for 2-10 h. Pre-treating, and filtering to remove unreacted substances possibly remaining. Keeping the temperature of 120-200 ℃ for 2-4 h under the condition that the vacuum degree is not less than 4kPa, removing the nonpolar solvent and water, and obtaining the boron-molybdenum integrated modified high molecular weight polyisobutylene succinimide dispersant BM4, wherein the boron content is 1.186% and the molybdenum content is 2.522%.
Example 5 20g of a bissuccinimide ashless dispersant (bissuccinimide ashless dispersant Mw =6537, polyisobutylene Mn =1000, base number =22.62 mg KOH/g) and 50 g of n-hexane were charged into a reaction flask, stirred at 30 to 100 ℃ for 0.5 hour, and added with 1.52 g of ammonium molybdate and 2.52 g of distilled water at 50 to 100 ℃, and the mixture was stirred at 50 to 100 ℃ for 0.5 hour, followed by heating and refluxing for 2 to 4 hours, and at this temperature, 1.49g of metaboric acid was added, followed by heating and refluxing for 2 to 10 hours. Pre-treating, and filtering to remove unreacted substances possibly remaining. Keeping the temperature of 120-200 ℃ for 2-4 h under the condition that the vacuum degree is not less than 4kPa, removing the nonpolar solvent and water, and obtaining the boron-molybdenum integrated modified succinimide dispersant BM5, wherein the boron content is 1.834%, and the molybdenum content is 1.221%.
Example 6 an ashless dispersant for bissuccinimide (ashless dispersant for bissuccinimide Mw =6537, polyisobutylene Mn =1000, base number =22.62 mg KOH/g) 20g, n-hexane 20g and toluene 20g were charged into a reaction flask, stirred at 30 to 100 ℃ for 0.5 hour, a mixture of molybdenum trioxide 44.8 g, pyroboric acid 12.66g, distilled water 22.4 g and methanol (mass ratio 1: 1) was added at 50 to 100 ℃, stirred at 50 to 100 ℃ for 0.5 hour, then, active sulfur 0.5g was added, the mixture was heated again and refluxed for 2 to 10 hours, pretreated, and filtered to remove possible residual unreacted materials. Keeping the temperature of 120-200 ℃ for 2-4 h under the condition that the vacuum degree is not less than 4kPa, removing the nonpolar solvent and water, and obtaining the boron-molybdenum integrated modified succinimide dispersant BM6, wherein the boron content is 0.506%, and the molybdenum content is 6.435%.
Example 7 an ashless dispersant of mono-succinimide (ashless dispersant of mono-succinimide Mw =4002, polyisobutylene Mn =1300, base number =50.49 mg KOH/g) 20g and xylene 20g were charged into a reaction flask, stirred at 30 to 100 ℃ for 0.5 hour, and a mixture of molybdenum trioxide 0.45 g and 1.27 g of distilled water and n-butanol (mass ratio 1: 1) was added at 50 to 100 ℃, stirred at 50 to 100 ℃ for 0.5 hour, and then heated under reflux for 2 to 4 hours, and at this temperature, butyl borate 0.185g was added, and then heated under reflux for 2 to 10 hours. Pre-treating, and filtering to remove unreacted substances possibly remaining. Keeping the temperature of 120-200 ℃ for 2-4 h under the condition that the vacuum degree is not less than 4kPa, removing the nonpolar solvent and water, and obtaining the boron-molybdenum integrated modified succinimide dispersant BM7, wherein the boron content is 0.164%, and the molybdenum content is 1.362%.
Comparative example 120 g of ashless dispersant succinimide (ashless dispersant succinimide Mw =4002, polyisobutylene Mn =1300, base number =50.49 mg KOH/g) and 20g of toluene were charged into a reaction flask, stirred at 30 to 100 ℃ for 0.5h, added with 2.0 g of molybdenum trioxide and 3.44 g of distilled water at 50 to 100 ℃, stirred at 50 to 100 ℃ for 0.5h, and then heated to reflux for 4 to 10 h. Filtering to remove possible residual unreacted substances, and keeping the temperature of 120-200 ℃ for 2-4 h under the condition that the vacuum degree is more than or equal to 4KPa to remove the nonpolar solvent and water to obtain the molybdenum modified succinimide dispersant M1 with the molybdenum content of 5.834%.
The performances of the boron-molybdenum integrated dispersants obtained in examples 1 to 5 were also tested as follows, wherein the experimental oil samples used were those prepared by dissolving a certain mass of additive sample in 150N of base oil.
Antioxidant test (PDSC method): performed according to SH/T0719-.
Anti-wear and anti-friction test (four-ball friction tester): performed according to SH/T0189-92 (rotation speed 1200rpm +/-60 rpm, temperature 75 +/-2 ℃ and time 60min +/-1 min).
Table 1: results of synergistic Oxidation resistance (PDSC method) of the dispersants obtained in examples 1-2 and comparative example 1
It can be seen that the boron-molybdenum integrated dispersant of the invention shows obvious additive antioxidant effect after being compounded with alkylated diphenylamine; according to the results of ICP tests, the incorporation of a small amount of boron into the boron-molybdenum integrated molecule can improve the synergistic antioxidant effect (14% and 8%) of the system (alkylated diphenylamine + molybdenum modified dispersant) with a reduced Mo content.
Results of experiments on the dispersant obtained in examples 2 to 5 and comparative example 1, which was used in combination with zinc dialkyldithiophosphate (ZDDP) for anti-wear and anti-friction
It can be seen that the boron-molybdenum integrated modified succinimide dispersant of the invention has good synergistic wear-resistant and antifriction effects with zinc dialkyl dithiophosphate in base oil, and the compounding result of the boron-molybdenum integrated modified succinimide dispersant and ZDDP is obviously superior to the compounding result of the molybdenum modified dispersant and ZDDP, which shows that B can improve the system antifriction and antiwear performance.
The foregoing is only a partial preferred embodiment of this invention and it should be noted that numerous changes in detail can be made therein by those skilled in the art without departing from the principles of the invention and such changes in detail are deemed to be within the scope of the invention.
Claims (16)
1. A boron-molybdenum integrated dispersant is characterized in that:
the dispersant has the following structural formula:
in the structural formula, R1、R2Is selected from
Wherein R is C2-C50A straight-chain alkyl group or a branched-chain alkyl group, m is an integer of 0 to 8 and is not 0, dp is at least any one of 1, 2, 3, 4, 5.
2. The method for preparing the boron-molybdenum integrated dispersant of claim 1, characterized in that:
the preparation method comprises the following steps: fully and uniformly mixing a dispersing agent and a diluent, then adding a boronizing agent, a molybdating agent and an accelerator which can be optionally added or not added in batches at one time, simultaneously or respectively feeding the boronizing agent and the molybdating agent, carrying out a first-stage reaction, then removing unreacted substances which may remain, keeping the temperature of the unreacted substances at 80-200 ℃ for 0.5-5 h under a reduced pressure condition, and finally carrying out post-treatment to obtain a target product;
the dispersant comprises one or the combination of more than two of single polyisobutylene succinimide, double polyisobutylene succinimide, Mannich base and high molecular polyisobutylene succinimide;
the boronizing agent is selected from boron-containing compounds, and the boron-containing compounds comprise any one or a combination of more than two of metaboric acid, boric acid, pyroboric acid, boron chloride and organic borate;
the molybdenum reagent is selected from molybdenum-containing compounds, and the molybdenum-containing compounds comprise any one or the combination of more than two of molybdenum dioxide, molybdenum trioxide, ammonium tridecylthiomolybdate dihydrate, ammonium tetrathiomolybdate, sodium molybdate, ammonium molybdate and molybdic acid.
3. The method for preparing the boron-molybdenum integrated dispersant according to claim 2, characterized in that:
the preparation method comprises the following steps: fully and uniformly mixing a dispersing agent and a diluent at the temperature of 30-100 ℃, then adding a boronizing agent, a molybdating agent and an optionally added accelerator at the temperature of 50-120 ℃, then reacting for 0.2-0.5 h at the temperature of 60-150 ℃, then optionally adding a vulcanizing agent, heating and refluxing for 4-10 h, then removing possibly residual unreacted substances, keeping the constant temperature for 0.5-5 h at the temperature of 80-200 ℃ under the reduced pressure condition, and finally performing post-treatment to obtain a target product.
4. The method for preparing the boron-molybdenum integrated dispersant according to claim 2, characterized in that:
the preparation method comprises the following steps: fully and uniformly mixing a dispersing agent and a diluent at the temperature of 50-80 ℃, adding a boronizing agent, a molybdating agent and an optionally added accelerator at the temperature of 60-100 ℃, reacting for 0.2-0.5 h at the temperature of 60-110 ℃, optionally adding a vulcanizing agent, heating and refluxing for 4-9 h, removing possibly residual unreacted substances, keeping constant temperature at the temperature of 120-155 ℃ for 2-5 h under the reduced pressure condition, and finally performing post-treatment to obtain a target product.
5. The method for producing a boron-molybdenum integrated dispersant according to any one of claims 2 to 4, characterized in that:
the molar ratio of the consumption of the molybdenum reagent to the nitrogen element contained in the dispersant is 1: 0.1-1: 10.
6. The method for producing a boron-molybdenum integrated dispersant according to any one of claims 2 to 4, characterized in that:
the molar ratio of the dosage of the boronizing agent to the nitrogen element contained in the dispersant is 1: 0.1-1: 10.
7. The method for preparing the boron-molybdenum integrated dispersant according to claim 2, characterized in that:
the organic boric acid ester is composed of C1~C12Is formed by esterification with boric acid.
8. The method for producing a boron-molybdenum integrated dispersant according to any one of claims 2 to 4, characterized in that:
the accelerator comprises C1-C13The monohydric alcohol and/or the polyhydric alcohol and deionized water, wherein the alcohol comprises any one or the combination of more than two of methanol, ethanol, n-butanol, isoamyl alcohol, n-octanol, isooctanol, propanol, isobutanol, ethylene glycol, cyclohexanol, cyclopentanol, tertiary butanol and secondary pentanol.
9. The method for producing a boron-molybdenum integrated dispersant according to any one of claims 2 to 4, characterized in that:
the dosage of the accelerator is 0.2-2 times of the total mass of the boronizing agent and the molybdenation agent.
10. The method for preparing a boron-molybdenum integrated dispersant according to any one of claim 3, characterized in that:
the sulfuration reagent comprises one or the combination of more than two of carbon disulfide, sulfur dioxide, sodium hydrosulfide, active sulfur, sodium sulfide, concentrated sulfuric acid, sulfamic acid, phosphorus pentasulfide and Lawson reagent.
11. The method for preparing the boron-molybdenum integrated dispersant according to claim 10, characterized in that:
the dosage of the vulcanizing reagent is 0.1-2.5 times of the total mass of the molybdenum reagent.
12. The method for producing a boron-molybdenum integrated dispersant according to any one of claims 2 to 4, characterized in that:
the diluent is selected from any one or the combination of more than two of hydrocarbon solvent and lubricant base oil.
13. The method for preparing the boron-molybdenum integrated dispersant of claim 12, wherein:
the hydrocarbon solvent is selected from low-polarity solvents with a boiling range of 60-200 ℃, and comprises any one or a combination of more than two of toluene, xylene, n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, n-decane and petroleum ether.
14. The method for preparing the boron-molybdenum integrated dispersant of claim 12, wherein:
the diluent comprises any one or the combination of more than two of n-hexane, petroleum ether, toluene and xylene.
15. The method for preparing the boron-molybdenum integrated dispersant of claim 12, wherein:
the dosage of the diluent is 0.1-3 times of the total weight of the reaction materials adopted in the preparation method.
16. A lubricating oil composition characterized by comprising the boron-molybdenum integrated dispersant of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610683031.0A CN107760412B (en) | 2016-08-18 | 2016-08-18 | Boron-molybdenum integrated dispersant, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610683031.0A CN107760412B (en) | 2016-08-18 | 2016-08-18 | Boron-molybdenum integrated dispersant, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107760412A CN107760412A (en) | 2018-03-06 |
| CN107760412B true CN107760412B (en) | 2020-09-01 |
Family
ID=61261360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610683031.0A Active CN107760412B (en) | 2016-08-18 | 2016-08-18 | Boron-molybdenum integrated dispersant, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107760412B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128698B (en) * | 2019-05-28 | 2021-01-01 | 佛山金戈新材料股份有限公司 | Environment-friendly flame-retardant smoke suppressant and preparation method thereof |
| CN113025408A (en) * | 2021-02-25 | 2021-06-25 | 任明洁 | Biodegradable lubricating oil and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8507417B2 (en) * | 2006-03-07 | 2013-08-13 | Exxonmobil Research And Engineering Company | Organomolybdenum-boron additives |
| CN102041137B (en) * | 2009-10-12 | 2013-07-10 | 上海洗霸科技股份有限公司 | Polycrystalline silicon or monocrystalline silicon cutting fluid |
| SG10201504239SA (en) * | 2014-06-02 | 2016-01-28 | Infineum Int Ltd | Lubrication oil compositions |
| CN105062623A (en) * | 2015-08-11 | 2015-11-18 | 王严绪 | Molybdenum alloy lubricant additive and preparation method thereof |
-
2016
- 2016-08-18 CN CN201610683031.0A patent/CN107760412B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107760412A (en) | 2018-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1305521A (en) | Lubricating oil compositions | |
| WO2015114920A1 (en) | Lubricating oil composition | |
| CN111088101B (en) | Gasoline engine oil composition and preparation method thereof | |
| TW201406946A (en) | Lubricating oil composition and preparation method therefor | |
| AU2007233234A1 (en) | Lubricant oil additive compositions | |
| FR2515185A1 (en) | ||
| CN107760412B (en) | Boron-molybdenum integrated dispersant, preparation method and application thereof | |
| CN113046159A (en) | Engine lubricating oil and preparation method thereof | |
| US9217117B2 (en) | Friction modifier and their use in lubricants and fuels | |
| CN106566617A (en) | Preparation method for energy-saving and environment-friendly diesel engine oil | |
| JP3650635B2 (en) | Molybdenum containing friction reducing additive | |
| US9200229B2 (en) | Friction modifier and their use in lubricants and fuels | |
| CN111088092B (en) | Heavy-load diesel engine oil composition and preparation method thereof | |
| CN100460490C (en) | Lubricating oil oxidation stability additive composition and preparation method thereof | |
| CN1181168C (en) | Engine lubricating oil composition | |
| US6638898B2 (en) | Process of preparing multi-functional amino di(alkylcyclohexyl) phosphordithioate additive for lubricant composition from saturated cashew nut shell liquid | |
| CN112694936B (en) | Diesel engine oil composition and preparation method thereof | |
| RU2266912C2 (en) | Organomolybdenum complexes, addition agent for lubricant material, method for reducing friction coefficient | |
| CN110016380B (en) | Diesel engine oil composition | |
| EP3013927A1 (en) | Lubricating oil additive and lubricating oil composition | |
| CN117917466A (en) | Lubricating oil composition for hybrid automobile engine and preparation method thereof | |
| CN111088100B (en) | Diesel engine oil composition and preparation method thereof | |
| CN113512451A (en) | Lubricating oil composition for internal combustion engine and preparation method thereof | |
| CN109679707B (en) | Gas engine lubricating oil composition and preparation method thereof | |
| CN117363395A (en) | Energy-saving type gasoline and oil complexing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210528 Address after: 330000 Room 101, 1st floor, R & D center, no.665, Changbei Avenue, Nanchang Economic and Technological Development Zone, Nanchang City, Jiangxi Province Patentee after: JIANGXI FUEL & LUBRAICANT ADDITIVE Co.,Ltd. Address before: 330000 room 316, Guanshan management office, Nanchang Economic and Technological Development Zone, Nanchang City, Jiangxi Province Patentee before: JIANGXI FUEL & LUBRAICANT ADDITIVE Co.,Ltd. Patentee before: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right |