CN107760412A - Boron molybdenum integration dispersant, its preparation method and application - Google Patents

Boron molybdenum integration dispersant, its preparation method and application Download PDF

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Publication number
CN107760412A
CN107760412A CN201610683031.0A CN201610683031A CN107760412A CN 107760412 A CN107760412 A CN 107760412A CN 201610683031 A CN201610683031 A CN 201610683031A CN 107760412 A CN107760412 A CN 107760412A
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dispersant
molybdenum
boron
reagent
preparation
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CN107760412B (en
Inventor
刘烨
蔡涛
商旺吉
张云潇
孙俪文
夏骏远
曾红玲
王声培
刘丹
刘升高
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JIANGXI FUEL & LUBRAICANT ADDITIVE Co.,Ltd.
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Jiangxi Fuel & Lubraicant Additive Co ltd
Ningbo Institute of Material Technology and Engineering of CAS
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The invention discloses a kind of boron molybdenum integration dispersant, its preparation method and application.The present invention contains boron element and molybdenum element simultaneously, and boron and molybdenum atom pass through B N keys and Mo N key connections.The preparation method of the present invention includes：At least by dispersant, addition or the diluent not added can be selected, borating agent and the mixing of molybdenum reagent carry out first stage reaction, remove the unreacted reactant that may be remained afterwards, then carry out second stage reaction, last post-treated acquisition target product.The present invention has the advantages of boron modification dispersant and molybdenum modifiers dispersants concurrently, act not only as the extreme pressure anti-wear additives of function admirable, friction improver uses, but also there is good additive effect with other functional additives, the present invention can also use directly as lubricant oil composite additive, without being aided with special formulation allocating technology, its simple production process is easy to operate, and controllability is high, aftertreatment technology is simple, and production cost is low.

Description

Boron molybdenum integration dispersant, its preparation method and application
Technical field
The present invention relates to a kind of Multi-functional dispersion agent and preparation method thereof, more particularly to a kind of boron molybdenum integration dispersant, Its preparation method and application.
Background technology
With the fast development of modern industry, lubricating oil that people are used plant equipment such as vehicle motor, internal combustion engines Performance requirement more and more higher, such as in internal combustion engine operation process, it is possible to create paint film, greasy filth and carbon deposit, cause oil circuit and filter The blocking of net, the abrasion of piston, piston ring bonds, so as to influence the service life of internal combustion engine.To solve these problems, from previous generation Recorded for five sixties, foreign study scholar prevents carbon deposit and oil using the method that dispersant is added in lubricating oil to reach Mud generates, and extends the oil draining period, saves the purpose of the energy and economic expenditure.
Dispersant has been carried out the dispersant principal item of industrialization as important one kind in lube oil additive at present Have：Succimide type, succinic acid ester type, Mannich (Manich) type, HMW type and boron modification type etc..
Wherein, succimide type dispersant be it is the most widely used at present it is a kind of without sulphur, it is without phosphorus, efficient, low into This ashless dispersant, it has good detergency and low temperature greasy filth dispersiveness, can suppress carbon distribution on engine piston and The generation of paint film.With the continuous lifting of improvement and the environmental requirement of engine performance, people change oil week to automobile oil Phase and fuel economy propose requirements at the higher level.But common succimide（The only succimide of linking group）By The reason in terms of the self structure, it has been difficult to meet these requirements.Thus, researcher is attempted in common succimide On the basis of, increase the function of product by introducing other functional group or inorganic functional elements, such as boron (B) or molybdenum (Mo), improve Properties of product and raising fuel economy etc..
It is boron modification succinimide dispersant that one of which, which typically improves product, its have good dispersive property and Antioxygenic property, especially because introducing boron element, its abrasion resistance is also improved, and can effectively prevent metal surface Pull and abrade, while the compatibility of dispersant and rubber seal can be reduced.
For example, EP0499384A1 and EP0499384B1 disclose the boron modification double focusing that a kind of Boron contents are 1.0 ~ 3.0wt% The product of isobutene succimide, its mainly by by double polyisobutene succinimides and boric acid, water at 177 ~ 260 DEG C React and formed.USP4554086 disclose it is a kind of there is the wear-resistant and boron modification dispersant of peptizaiton, the dispersant is one The boric acid ester compound of the succimide of kind hydrocarbon substitution, single or double, containing hydroxyl polyamine chain, mainly utilizes boron Acid reacts to be formed as borating agent with raw material.CN102925254A discloses the boron modification that a kind of Boron contents are 0.3 ~ 4.0wt% Dispersant, it is mainly by 85 ~ 95 DEG C, under atmosphere of inert gases, adds borating agent and mixed solvent, then 120 ~ 160 DEG C backflow 1 ~ 4h and obtain.
The wherein another typical product that improves is molybdenum modified succinimides dispersant, and its composition principle changes similar to boron Property succinimide dispersant, and molybdenum modified succinimides dispersant can also introduce sulphur source by post-cure.Molybdenum Modified succinimides dispersant, which has, to be added in lubricating oil and can obtain excellent antiwear and antifriction effect on a small quantity, is resisted with amine Oxidant compounding can also obtain high temperature synergistic antioxidative activities energy.
For example, USP8076275B2 discloses a kind of preparation method of molybdenum modifiers dispersants, it is mainly more by selecting Type（Mono-/bis-succimide type）Ashless dispersant as basic nitrogen compound, under conditions of temperature is no more than 120 DEG C with Molybdenum trioxide and the reaction of accelerator water, then it is post-treated and obtain target product.USP20120190864A1、 USP20130261313A1 discloses the preparation method of molybdenum modifiers dispersants, its mainly by select side chain molecular weight for 500 ~ 5000 ashless dispersant is pre-processed, then be no more than 150 DEG C of bar in temperature with acrylic acid afterwards as basic nitrogen compound React overnight then post-treated with molybdenum trioxide and accelerator water under part and obtain target product.
However, existing polyisobutene succinimide modification technology and the modification succinyl formed by these technologies are sub- Amine dispersant still suffers from many deficiencies, such as：First, when existing boron modification succinimide dispersant and molybdenum are modified succinyl When imine dispersants are using being the additives of product such as lubricant oil composite, generally require and be used cooperatively, but it is past each other It is past the problem of poor compatibility to be present, therefore also need to coordinate complicated formula allocating technology, operating difficulties, cost height；Second, nothing By being prepared by foregoing boron modification succinimide dispersant preparation technology or foregoing molybdenum modified succinimides dispersant Technique, the problems such as its generally existing technique is cumbersome and production cost is high.
The content of the invention
For different dispersant poor compatibilities in the prior art, formula allocating technology, cumbersome, operating difficulties, cost are high not Foot, it is a primary object of the present invention to propose a kind of boron molybdenum integration dispersant and preparation method thereof.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of boron molybdenum integration dispersant, it is characterised in that：Contain boron element and molybdenum element in the dispersant simultaneously, and boron and Molybdenum atom passes through B-N keys and Mo-N key connections.
Preferably, the boron molybdenum integration dispersant has following structural formula：
In the structural formula, R1、R2It is selected from
One or both of more than combination, wherein R is C2-C50Straight chained alkyl or the alkyl with side chain, m are 0-8's Integer, dp are at least any one of 1,2,3,4,5.
Present invention also offers a kind of preparation method of boron molybdenum integration dispersant, it includes：At least by dispersant, can be with Selection addition or the diluent not added, borating agent and the mixing of molybdenum reagent carry out first stage reaction, and removing afterwards can The unreacted reactant that can be remained, then second stage reaction is carried out, last post-treated acquisition target product.
Among some preferred embodiments, described preparation method can include：Dispersant is abundant with diluent After well mixed, property adds or is added portionwise borating agent, molybdenum reagent and can select what is added or do not add again Accelerator, and the borating agent and molybdenum reagent are to feed intake at the same time or separately, and first stage reaction is carried out, removing afterwards can The unreacted reactant that can be remained, then second stage reaction is carried out, last post-treated acquisition target product.
Among some more preferred embodiment, described preparation method can include：By dispersant and diluent It is sufficiently mixed uniformly under conditions of being 30 ~ 100 DEG C in temperature, boronation examination is added under conditions of being afterwards 50 ~ 120 DEG C in temperature It agent, molybdenum reagent and can select to add or the accelerator do not added, react 0.2 under conditions of being then 60 ~ 150 DEG C in temperature ~ 0.5h, then can select to add or do not add sulfiding reagent, temperature rising reflux reacts 4 ~ 10h, and then removing may remain not anti- Answer thing, then 0.5 ~ 5h of constant temperature holding under conditions of temperature is 80 ~ 200 DEG C at reduced pressure conditions, last post-treated acquisition mesh Mark product.
More preferable, the dispersant is selected from the dispersant containing basic nitrogen.
Further, the borating agent, molybdenum reagent can be respectively selected from boron-containing compound, molybdate compound.
Another free-revving engine of the present invention is the application for providing the boron molybdenum integration dispersant.
For example, providing a kind of lubricant oil composite in some case study on implementation, it includes described boron molybdenum integration point Powder.
Further, among some embodiments, the lubricant oil composite can also include other multiple additives.
Compared with prior art, advantages of the present invention includes：
（1）The boron molybdenum integration dispersant has expanded the category of dispersant, i.e. succinimide dispersant, high molecular weight dispersant And it can contain boron element and molybdenum element on the western dispersant of Manny simultaneously；
（2）The advantages of boron molybdenum integration dispersant has boron modification dispersant and molybdenum modifiers dispersants concurrently, acting not only as property The excellent extreme pressure anti-wear additives of energy, friction improver use, and also have in lubricating oil during application with other functional additives Good additive effect, it is a kind of multi-functional lube oil additive, for example, it resists in lubricating oil with alkylated diphenylamine class Oxidant has obvious collaboration antioxidation, has with zinc dialkyl dithiophosphate and well cooperates with antiwear and antifriction to act on, can Add dosage in lubricating oil to reduce similar additive, so as to reduce phosphorus content in lubricating oil product, be advantageous to improve entirety Fuel economy；
（3）The boron molybdenum integration dispersant can use directly as the additive of the products such as lubricant oil composite, match somebody with somebody without special Square allocating technology, can effectively solve the problems, such as boron modification dispersant and molybdenum modifiers dispersants while use poor compatibility, simplify It is formulated allocating technology；
（4）The simple production process of the boron molybdenum integration dispersant, it is easy to operate, and beneficial to aftertreatment technology is simplified, reduce production Cost；
More detailed explanation will hereafter be made to technical scheme.It is understood, however, that in the scope of the invention It is interior, can be mutual between above-mentioned each technical characteristic of the invention and each technical characteristic specifically described in below (eg embodiment) It is combined, so as to form new or preferable technical scheme.As space is limited, no longer tire out one by one herein and state.
Embodiment
As it was previously stated, in view of many deficiencies of prior art, inventor's in-depth study and a large amount of by long-term Practice, it is able to propose technical scheme, it is as detailed below.
One aspect of the present invention provides a kind of boron molybdenum integration dispersant, it is characterised in that：In the dispersant simultaneously Containing boron element and molybdenum element, and boron and molybdenum atom pass through B-N keys and Mo-N key connections.
Preferably, the boron molybdenum integration dispersant has following structural formula：
In the structural formula, R1、R2It is selected from
One or both of more than combination, wherein R is C2-C50Straight chained alkyl or the alkyl with side chain, m are 0-8's Integer, dp are at least any one of 1,2,3,4,5.
One aspect of the present invention provides a kind of preparation method of boron molybdenum integration dispersant, and it includes：It will at least divide Powder, addition or the diluent not added can be selected, borating agent and the mixing of molybdenum reagent carry out first stage reaction, it The unreacted reactant that may be remained is removed afterwards, then carries out second stage reaction, last post-treated acquisition target product.
Among some more specific embodiment, the preparation method can include：Dispersant is abundant with diluent After well mixed, property adds or is added portionwise borating agent, molybdenum reagent and can select what is added or do not add again Accelerator, and the borating agent and molybdenum reagent are to feed intake at the same time or separately, and first stage reaction is carried out, removing afterwards can The unreacted reactant that can be remained, then second stage reaction is carried out, last post-treated acquisition target product.
Preferably, the preparation method can include：Filled under conditions of being 30 ~ 100 DEG C in temperature by dispersant and diluent It is point well mixed, add borating agent, molybdenum reagent under conditions of being afterwards 50 ~ 120 DEG C in temperature and can select addition or The accelerator do not added, 0.2 ~ 0.5h is reacted under conditions of being then 60 ~ 150 DEG C in temperature, then can select to add or do not add Adding sulfiding reagent, temperature rising reflux reacts 4 ~ 10h, then removes the unreacted reactant that may be remained, then at reduced pressure conditions in temperature 0.5 ~ 5h, last post-treated acquisition target product are kept for constant temperature under conditions of 80 ~ 200 DEG C.
Further, the preparation method can also include：By dispersant and diluent under conditions of temperature is 50 ~ 80 DEG C Be sufficiently mixed uniformly after, temperature be 60 ~ 100 DEG C under conditions of add borating agent, molybdenum reagent and can select addition or The accelerator do not added, 0.2 ~ 0.5h is reacted under conditions of being then 60 ~ 110 DEG C in temperature, then can select to add or do not add Add sulfiding reagent, then temperature rising reflux to react 4 ~ 9h, then remove the unreacted reactant that may be remained, then at reduced pressure conditions in temperature 2 ~ 5h, last post-treated acquisition target product are kept for constant temperature under conditions of 120 ~ 155 DEG C.
Still more preferably, the reduced pressure refers to vacuum >=4kPa condition.
A kind of for example, boron molybdenum integration modified succinimides dispersant in a more typical case study on implementation of the invention Synthesis route see following formula：
。
Heretofore described dispersant, borating agent, molybdenum reagent and the definition of accelerator is people in the art What member had known.
More preferable, the dispersant uses the dispersant containing basic nitrogen.
It is more highly preferred to, it is sub- that the dispersant can be selected from single polyisobutene succinimide, double focusing isobutene succinyl Combination more than one or both of amine, mannich base, high molecular weight polyisobutylene succimide.
Further, the molecular weight of alkyl chain is 500 ~ 5000 in the dispersant.
More preferable, the molybdenum reagent is selected from molybdate compound, such as can preferably be selected from but be not limited to molybdenum dioxide, In molybdenum trioxide, the ammonium thiomolybdate of two water 13, four thio ammonium molybdate, sodium molybdate, ammonium molybdate, molybdic acid it is one or two kinds of with On combination.
More preferably, the mol ratio for the nitrogen that the dosage of the molybdenum reagent contains with the dispersant is 1:0.1~ 1:10。
More preferable, the borating agent be selected from boron-containing compound, for example, preferably oneself but be not limited to metaboric acid, boron Acid, pyroboric acid, boron chloride and organic boric acid ester in one or more kinds of combinations.
Further, the organic boric acid ester is preferably by C1~C12Alcohol and boric acid formed by esterification.
More preferable, the mol ratio for the nitrogen that the dosage of the borating agent contains with the dispersant is 1:0.1~ 1:10。
More preferable, the accelerator can be C1-C13Monohydric alcohol and/or polyalcohol and deionized water in one kind Or a variety of combinations, it can accelerate two phase reaction speed.
Further, the alcohol preferably from but be not limited to methanol, ethanol, n-butanol, isoamyl alcohol, n-octyl alcohol, isooctanol, One or more in propyl alcohol, isobutanol, ethylene glycol, cyclohexanol, cyclopentanol, the tert-butyl alcohol, sec-amyl alcohol.
It is further preferred that the dosage of the accelerator is 0.2 ~ 2 times of the borating agent and molybdenum reagent gross mass.
More preferable, the diluent may be selected from any one or two in hydrocarbon solvent, lube base oil, more cerebrols The combination of the kind above.
It is more highly preferred to, the hydrocarbon solvent may be selected from the low polar solvent that boiling range is 60 ~ 200 DEG C, and the hydrocarbon solvent includes It is any one in toluene, dimethylbenzene, pentane, n-hexane, hexamethylene, normal heptane, normal octane, isooctane, n-decane, petroleum ether Kind or two or more combinations.
Particularly preferably, the diluent includes n-hexane, petroleum ether, toluene, dimethylbenzene and lube base oil, more brains Any one in oil or two or more combinations.
It is further preferred that the dosage of the diluent is the reaction mass gross weight employed in the preparation method 0.1 ~ 3 times.
More preferable, the sulfiding reagent is preferably from carbon disulfide, sulfur dioxide, NaHS, active sulfur, vulcanization One or more in sodium, the concentrated sulfuric acid, sulfamic acid, phosphorus pentasulfide, lawesson reagent.
It is further preferred that the dosage of the sulfiding reagent is 0.1 ~ 2.5 times of the molybdenum reagent gross mass.
In the preparation process in accordance with the present invention, after the completion of reaction, unreacted raw material need to be removed, typically conventional method Including but not limited to：The methods of filtering, centrifugal filtration, decantation, is by unreacted solid material and impurity and required product It is separated.Filter aid such as diatomite (Celite) can be used, to improve separative efficiency.
Further, described post processing includes removing the water and solvent obtained in reaction product, is typically steamed by normal pressure Evaporate or be evaporated in vacuo and remove solvent and water.
For example, among a more specific case study on implementation, one kind prepares boron molybdenum integration modified succinimides and disperseed The method of agent can include：After the ashless dispersant of metering and solvent are mixed, 0.3h is stirred under conditions of temperature 70 C, is led to Optimization Mo/N and B/N ratio is crossed, the borating agent and/or molybdenum reagent and rush of metering are added under conditions of 80 DEG C of temperature Enter agent, then the mixture of formation is stirred into 0.3h under conditions of 120 DEG C of temperature, then temperature rising reflux reaction 8h；Continue to put into The molybdenum reagent and/or borating agent of metering, then back flow reaction 6h（Or under the same conditions disposably input borating agent and Molybdenum reagent）；The unreacted reactant that may be remained is removed, finally under conditions of vacuum >=4kPa, in 145 DEG C of condition of temperature Lower constant temperature keeps 4h, removes solvent and water, you can obtains target product.
Another aspect of the invention provides the purposes of the boron molybdenum integration dispersant.
For example, among some case study on implementation, the boron molybdenum integration dispersant and multiple additives can be compounded, adjusted With lubricant oil composite.And the boron molybdenum integration dispersant of the present invention has fine in lubricating oil with other functional additives Additive effect, be a kind of multi-functional lube oil additive.
Thus, present invention also offers a kind of lubricant oil composite, and it includes described boron molybdenum integration dispersant.
Further, among some embodiments, the lubricant oil composite can also include other multiple additives.
For example, the additive can be alkylated diphenylamine class antioxidant.Also, described boron molybdenum integration is ashless Dispersant has with alkylated diphenylamine class antioxidant cooperates with antioxidation well.
For example, the additive can be zinc dialkyl dithiophosphate（ZDDP）.Also, described boron molybdenum integration point Powder has with zinc dialkyl dithiophosphate cooperates with antiwear and antifriction to act on well.
Further, the lubricant oil composite can also include the one or more in following component, such as lubricate oil base Plinth oil, detergent-dispersant additive, antiwear additive, viscosity index improver, pour-point depressant, corrosion inhibitor, antirust agent, anti-foaming agent, benefit Fill friction improver or its mixture.
Technical scheme will be described in detail with reference to some embodiments as follows, but these embodiments are to pass through Expand what the mode that invention rather than limitation are invented proposed.
The preparation technology of some boron molybdenum integration modified succinimides dispersants is relate among following examples, its Employed in various reaction partners and process conditions be more typical example, but pass through inventor's lot of experiments Checking, is also applicable, and also reachable in the other types of reaction partner of those listed above and other process conditions The technique effect claimed into the present invention.If not in addition, illustrating, " % " addressed in following examples is " wt% ".
Embodiment 1 is by mono butonediimide ashless dispersant agent（Mono butonediimide ashless dispersant agent Mw=4002, poly- isobutyl Alkene Mn=1300, the mg KOH/g of base number=50.49）The 20 g and g of toluene 20 are launched into reaction bulb, 30 ~ 100 DEG C of stirring 0.5h, 50 ~ 100 DEG C of addition g of molybdenum trioxide 2.23,3.86 g distilled water, mixture stir 0.5h at 50 ~ 100 DEG C, then heated up back again 4 ~ 10h of stream reaction.It is filtered to remove the unreacted reactant that may be remained, finally under conditions of vacuum >=4kPa, 120 DEG C ~ 200 DEG C Under the conditions of constant temperature keep 2 ~ 4h, to remove toluene and water, obtain molybdenum modifiers dispersants intermediate；Take among the molybdenum modifiers dispersants Body 20g and toluene 20g is launched into reaction bulb, and 30 ~ 100 DEG C of stirring 0.5h, 50 ~ 100 DEG C add boric acid 2.97g, 1.49 g steaming Distilled water, then temperature rising reflux reacts 4 ~ 10h again.Pretreatment, it is filtered to remove the unreacted reactant that may be remained.In vacuum >=4kPa Under conditions of, constant temperature keeps 2 ~ 4h under the conditions of 120 DEG C ~ 200 DEG C, removes non-polar solven and water, and it is modified to obtain the integration of boron molybdenum Succinimide dispersant BM1, Boron contents 0.563%, molybdenum content 5.603%.
Embodiment 2 is by Mannich ashless dispersant（Mannich ashless dispersant Mw=3562, polyisobutene Mn=1300, alkali It is worth=56.98 mg KOH/g）The 20 g and g of dimethylbenzene 20 are launched into reaction bulb, and 30 ~ 100 DEG C of stirring 0.5h, 50 ~ 100 DEG C add Entering the g of ammonium molybdate 3.03,5.22 g distilled water, mixture stirs 0.5h at 50 ~ 100 DEG C, and then temperature rising reflux reacts 2 ~ 4h again, Boric acid 2.97g is added at such a temperature, and 1.49 g distilled water, then temperature rising reflux reacts 2 ~ 10h again.Pretreatment, is filtered to remove The unreacted reactant that may be remained.Under conditions of vacuum >=4kPa, constant temperature keeps 2 ~ 4h under the conditions of 120 DEG C ~ 200 DEG C, removes Non-polar solven and water, obtain the modified Mannich dispersant BM2 of boron molybdenum integration, Boron contents 0.273%, and molybdenum content is 5.048%。
Embodiment 3 is by mono butonediimide ashless dispersant agent（Mono butonediimide ashless dispersant agent Mw=4002, poly- isobutyl Alkene Mn=1300, the mg KOH/g of base number=50.49）The 20 g and g of toluene 20 are launched into reaction bulb, 30 ~ 100 DEG C of stirring 0.5h, 50 ~ 100 DEG C of addition g of molybdenum trioxide 2.23 and boric acid 2.97g, 5.35 g distilled water, mixture stir 0.5h at 50 ~ 100 DEG C, NaHS is subsequently added into, then temperature rising reflux reacts 2 ~ 10h, pretreatment, is filtered to remove the unreacted reactant that may be remained.In vacuum Under conditions of degree >=4kPa, constant temperature keeps 2 ~ 4h under the conditions of 120 DEG C ~ 200 DEG C, removes non-polar solven and water, obtains boron molybdenum one Body modified succinimides dispersant B M3, Boron contents 0.506%, molybdenum content 4.633%.
Embodiment 4 is by high molecular weight polyisobutylene Ashless butyl diimide dispersant（High molecular weight polyisobutylene succinyl Imines ashless dispersant Mw=15096, polyisobutene Mn=2300, the mg KOH/g of base number=32.56）The 20 g and g of petroleum ether 20 are thrown It is put into reaction bulb, 30 ~ 100 DEG C of stirring 0.5h, 50 ~ 100 DEG C add molybdenum trioxide 1.12g, 1.98 g distilled water, and mixture exists 50 ~ 100 DEG C of stirring 0.5h, then temperature rising reflux reacts 2 ~ 4h again, at such a temperature, adds boric acid 1.49g, then heats up back again 2 ~ 10h of stream reaction.Pretreatment, it is filtered to remove the unreacted reactant that may be remained.Under conditions of vacuum >=4kPa, 120 DEG C ~ Constant temperature keeps 2 ~ 4h under the conditions of 200 DEG C, removes non-polar solven and water, obtains boron molybdenum integration modified high-molecular amount polyisobutene Succinimide dispersant BM4, Boron contents 1.186%, molybdenum content 2.522%.
Embodiment 5 is by double Ashless butyl diimide dispersants（Double Ashless butyl diimide dispersant Mw=6537, poly- isobutyl Alkene Mn=1000, the mg KOH/g of base number=22.62）The 20 g and g of n-hexane 50 are launched into reaction bulb, 30 ~ 100 DEG C of stirrings 0.5h, 50 ~ 100 DEG C of addition g of ammonium molybdate 1.52,2.52 g distilled water, mixture stir 0.5h at 50 ~ 100 DEG C, then risen again Warm 2 ~ 4h of back flow reaction, at such a temperature, metaboric acid 1.49g is added, then temperature rising reflux reacts 2 ~ 10h again.Pretreatment, filtering Remove the unreacted reactant that may be remained.Under conditions of vacuum >=4kPa, constant temperature keeps 2 ~ 4h under the conditions of 120 DEG C ~ 200 DEG C, Non-polar solven and water are removed, obtains boron molybdenum integration modified succinimides dispersant B M5, Boron contents 1.834%, molybdenum contains Amount 1.221%.
Embodiment 6 is by double Ashless butyl diimide dispersants（Double Ashless butyl diimide dispersant Mw=6537, poly- isobutyl Alkene Mn=1000, the mg KOH/g of base number=22.62）20 g, n-hexane 20g and the g of toluene 20 are launched into reaction bulb, 30 ~ 100 DEG C Stir 0.5h, 50 ~ 100 DEG C of mixtures for adding the g of molybdenum trioxide 44.8 and pyroboric acid 12.66g, 22.4 g distilled water and methanol （Mass ratio 1:1）, mixture stirs 0.5h at 50 ~ 100 DEG C, is subsequently added into active sulfur 0.5g, then temperature rising reflux reacts 2 ~ 10h, Pretreatment, it is filtered to remove the unreacted reactant that may be remained.It is permanent under the conditions of 120 DEG C ~ 200 DEG C under conditions of vacuum >=4kPa Temperature keeps 2 ~ 4h, removes non-polar solven and water, obtains boron molybdenum integration modified succinimides dispersant B M6, Boron contents are 0.506%, molybdenum content 6.435%.
Embodiment 7 is by mono butonediimide ashless dispersant agent（Mono butonediimide ashless dispersant agent Mw=4002, poly- isobutyl Alkene Mn=1300, the mg KOH/g of base number=50.49）The 20 g and g of dimethylbenzene 20 are launched into reaction bulb, 30 ~ 100 DEG C of stirrings The mixture of 0.5h, 50 ~ 100 DEG C of addition g of molybdenum trioxide 0.45,1.27 g distilled water and n-butanol（Mass ratio 1:1）, mixing Thing stirs 0.5h at 50 ~ 100 DEG C, and then temperature rising reflux reacts 2 ~ 4h again, at such a temperature, adds butyl borate 0.185g, connects Again temperature rising reflux and react 2 ~ 10h.Pretreatment, it is filtered to remove the unreacted reactant that may be remained.In vacuum >=4kPa condition Under, constant temperature keeps 2 ~ 4h under the conditions of 120 DEG C ~ 200 DEG C, removes non-polar solven and water, obtains the modified succinyl of boron molybdenum integration Imine dispersants BM7, Boron contents 0.164%, molybdenum content 1.362%.
Comparative example 1 is by Ashless butyl diimide dispersant（Ashless butyl diimide dispersant Mw=4002, polyisobutene Mn= 1300, the mg KOH/g of base number=50.49）The 20 g and g of toluene 20 are launched into reaction bulb, 0.5h are stirred at 30 ~ 100 DEG C, 50 ~ 100 DEG C of addition g of molybdenum trioxide 2.0,3.44 g distilled water, mixture stir 0.5h at 50 DEG C ~ 100 DEG C, then heated up back again 4 ~ 10h of stream reaction.The unreacted reactant that may be remained is filtered to remove, under conditions of vacuum >=4KPa, in 120 DEG C ~ 200 DEG C bars Constant temperature keeps 2 ~ 4h under part, to remove non-polar solven and water, obtains molybdenum modified succinimides dispersant M1, molybdenum content is 5.834%。
The following performance that boron molybdenum integration dispersant is also obtained to embodiment 1-5 is tested, wherein the experiment used The additive sample of certain mass is is dissolved in the oil sample configured in base oil 150N by oil sample.
Anti-oxidant test（PDSC methods）：Performed according to SH/T 0719-2002（3.5 ± 0.2MPa of pressure, flow velocity 100 ± 10mL/min）, test result is shown in Table 1.
Antiwear and antifriction is tested（Four ball frictional testing machines）：Performed according to SH/T 0189-92（Rotating speed 1200rpm ± 60rpm, 75 DEG C ± 2 DEG C of temperature, time 60min ± 1min）.
Table 1：The collaboration that embodiment 1-2 and comparative example 1 obtain dispersant is anti-oxidant（PDSC methods）As a result
It can be seen that boron molybdenum integration dispersant of the invention is with after alkylated diphenylamine compounding, showing obvious adduction Antiopxidant effect；The result tested according to ICP, in the case where Mo contents are reduced, introduced on a small quantity in boron molybdenum one chemoattractant molecule Boron can improve system（Alkylated diphenylamine+molybdenum modifiers dispersants）Collaboration antioxidant effect（14% and 8%）.
Embodiment 2-5 and comparative example 1 obtain dispersant and zinc dialkyl dithiophosphate（ZDDP）Cooperate with antiwear and antifriction real Test result
It can be seen that boron molybdenum integration modified succinimides dispersant of the invention in base oil with dialkyl dithio phosphorus Sour zinc has collaboration antiwear and antifriction effect well, boron molybdenum integration modified succinimides dispersant and the result of ZDDP compoundings Molybdenum modifiers dispersants and the result of ZDDP compoundings are substantially better than, illustrate that B can improve system anti-wear and wear-resistant performance.
Described above is only the part preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art Member, under the premise without departing from the principles of the invention, can also make some variations in detail, these variations in detail also should be regarded as this hair Bright protection domain.

Claims (10)

  1. A kind of 1. boron molybdenum integration dispersant, it is characterised in that：Contain boron element and molybdenum element, and boron in the dispersant simultaneously Pass through B-N keys and Mo-N key connections with molybdenum atom.
  2. 2. boron molybdenum integration dispersant according to claim 1, it is characterised in that：The dispersant has following structural formula：
    In the structural formula, R1、R2It is selected from
    One or both of more than combination, wherein R is C2-C50Straight chained alkyl or the alkyl with side chain, m are 0-8's Integer, dp are at least any one of 1,2,3,4,5.
  3. 3. the preparation method of the boron molybdenum integration dispersant any one of claim 1-2, it is characterised in that：Including at least By dispersant, addition or the diluent not added can be selected, it is anti-that borating agent and the mixing of molybdenum reagent carry out the first stage Should, the unreacted reactant that may be remained is removed afterwards, then second stage reaction is carried out, last post-treated acquisition target product.
  4. 4. the preparation method of boron molybdenum integration dispersant according to claim 3, it is characterised in that：
    The preparation method includes：After dispersant and diluent are sufficiently mixed uniformly, property adds or is added portionwise boronation again Reagent, molybdenum reagent and it can select to add or the accelerator do not added, and the borating agent and molybdenum reagent are simultaneously Or feed intake respectively, and first stage reaction is carried out, the unreacted reactant that may be remained is removed afterwards, then second stage reaction is carried out, Last post-treated acquisition target product；
    Preferably, the preparation method includes：It is sufficiently mixed under conditions of being 30 ~ 100 DEG C in temperature by dispersant and diluent It is even, borating agent, molybdenum reagent are added under conditions of being afterwards 50 ~ 120 DEG C in temperature and can select what is added or do not add Accelerator, 0.2 ~ 0.5h is reacted under conditions of being then 60 ~ 150 DEG C in temperature, then can select to add or do not add vulcanization examination Agent, temperature rising reflux react 4 ~ 10h, then remove the unreacted reactant that may remain, then at reduced pressure conditions in temperature be 80 ~ 200 Constant temperature keeps 0.5 ~ 5h, last post-treated acquisition target product under conditions of DEG C；
    It is further preferred that the preparation method includes：It is fully mixed under conditions of being 50 ~ 80 DEG C in temperature by dispersant and diluent After closing uniformly, add borating agent, molybdenum reagent under conditions of being 60 ~ 100 DEG C in temperature and can select to add or do not add Accelerator, react 0.2 ~ 0.5h under conditions of being then 60 ~ 110 DEG C in temperature, then can select to add or not add vulcanization Reagent, temperature rising reflux react 4 ~ 9h, then remove the unreacted reactant that may remain, then at reduced pressure conditions in temperature be 120 ~ Constant temperature keeps 2 ~ 5h, last post-treated acquisition target product under conditions of 155 DEG C.
  5. 5. the preparation method of the boron molybdenum integration dispersant according to any one of claim 3-4, it is characterised in that：
    The dispersant is selected from the dispersant containing basic nitrogen；
    Preferably, the dispersant include single polyisobutene succinimide, double polyisobutene succinimides, mannich base, Combination more than one or both of high molecular weight polyisobutylene succimide；
    It is further preferred that the number-average molecular weight of alkyl chain is 500 ~ 5000 in the dispersant.
  6. 6. the preparation method of the boron molybdenum integration dispersant according to any one of claim 3-5, it is characterised in that：
    The mol ratio for the nitrogen that the dosage of the molybdenum reagent contains with the dispersant is 1:0.1~1:10；
    And/or the mol ratio of nitrogen that the dosage of the borating agent and the dispersant contain is 1:0.1~1:10.
  7. 7. the preparation method of the boron molybdenum integration dispersant according to any one of claim 3-6, it is characterised in that：
    The borating agent is selected from boron-containing compound, and the boron-containing compound includes the chlorination of metaboric acid, boric acid, pyroboric acid, boron Any one in thing and organic boric acid ester or two or more combinations；
    Preferably, the organic boric acid ester is mainly by C1~C12Alcohol formed with boric acid by esterification；
    And/or the molybdenum reagent is selected from molybdate compound, the molybdate compound includes molybdenum dioxide, molybdenum trioxide, two water Any one in 13 ammonium thiomolybdates, four thio ammonium molybdate, sodium molybdate, ammonium molybdate, molybdic acid or two or more combinations.
  8. 8. the preparation method of the boron molybdenum integration dispersant according to any one of claim 3-7, it is characterised in that：
    The accelerator includes C1-C13Monohydric alcohol and/or polyalcohol and deionized water in any one or it is two or more Combination, the alcohol include methanol, ethanol, n-butanol, isoamyl alcohol, n-octyl alcohol, isooctanol, propyl alcohol, isobutanol, ethylene glycol, ring Any one in hexanol, cyclopentanol, the tert-butyl alcohol, sec-amyl alcohol or two or more combinations；
    Preferably, the dosage of the accelerator is 0.2 ~ 2 times of the borating agent and molybdenum reagent gross mass；
    And/or the sulfiding reagent includes carbon disulfide, sulfur dioxide, NaHS, active sulfur, vulcanized sodium, the concentrated sulfuric acid, ammonia Combination more than one or both of base sulfonic acid, phosphorus pentasulfide, lawesson reagent；
    Preferably, the dosage of the sulfiding reagent is 0.1 ~ 2.5 times of the molybdenum reagent gross mass.
  9. 9. the preparation method of the boron molybdenum integration dispersant according to any one of claim 3-8, it is characterised in that：
    The diluent may be selected from any one or two or more combinations in hydrocarbon solvent, lube base oil, more cerebrols；
    Preferably, the hydrocarbon solvent may be selected from the low polar solvent that boiling range is 60 ~ 200 DEG C, and the hydrocarbon solvent includes toluene, diformazan Any one in benzene, pentane, n-hexane, hexamethylene, normal heptane, normal octane, isooctane, n-decane, petroleum ether or two kinds Combination above；
    Particularly preferably, the diluent is included in n-hexane, petroleum ether, toluene, dimethylbenzene and lube base oil, more cerebrols Any one or two or more combinations；
    It is further preferred that the dosage of the diluent is 0.1 ~ 3 of the reaction mass gross weight employed in the preparation method Times.
  10. A kind of 10. lubricant oil composite, it is characterised in that comprising the boron molybdenum integration dispersant described in claim 1-2 or according to Boron molybdenum integration dispersant prepared by the method described in claim 3-9.
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CN110128698A (en) * 2019-05-28 2019-08-16 佛山市三水金戈新型材料有限公司 A kind of environmental-protection 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

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CN102041137A (en) * 2009-10-12 2011-05-04 上海洗霸科技有限公司 Molybdate additive and polycrystalline silicon or monocrystalline silicon cutting fluid containing same
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CN110128698A (en) * 2019-05-28 2019-08-16 佛山市三水金戈新型材料有限公司 A kind of environmental-protection flame-retardant smoke suppressant and preparation method thereof
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

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