CN105968140A - High-activity organic molybdenum compound and preparation and use method thereof - Google Patents

High-activity organic molybdenum compound and preparation and use method thereof Download PDF

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CN105968140A
CN105968140A CN201610368013.3A CN201610368013A CN105968140A CN 105968140 A CN105968140 A CN 105968140A CN 201610368013 A CN201610368013 A CN 201610368013A CN 105968140 A CN105968140 A CN 105968140A
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molybdenum
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文万军
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic System compounds without a metal-carbon linkage
    • 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
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
    • 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
    • C10N2030/54—Fuel economy
    • 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
    • C10N2030/76—Reduction of noise, shudder, or vibrations
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Abstract

A high-activity organic molybdenum compound is characterized in that the organic molybdenum compound with a chemical general formula (1) is formed by conducting grafting and interior building on S=C-S groups and molybdenum Mo in molecules; in the general formula, molybdenum Mo serves as a nucleophilic center, and the two S=C-S groups are grafted on the periphery of Mo, so the product molecule structure has the characteristics of -S-Mo-S- similar to the structural morphology and characteristics of molybdenum disulfide; multi-amidocyanogen multi-thiocarboxylic acid molybdenum is formed by conducting grafting and interior building on S=C-S groups and molybdenum Mo in the molecules, more S=C-S polar groups are grafted on the multi-amidocyanogen multi-thiocarboxylic acid molybdenum, the adsorption force on metal is higher, and thermal stability is higher. When a large quantity of beneficial polar groups are manufactured by the compound in the use process of an engine, the lubricating performance is further enhanced and improved, and the whole process of the whole compound is more perfect.

Description

A kind of high activity organic molybdenum and preparation and application thereof
Technical field
The present invention relates to a kind of new organic molybdenum and preparation and application thereof, especially it improves as friction Agent preparation and purposes comprise the lubricating composition of described compound.Belong to new material technology field.
Background technology:
Organic-molybdenum is dialkyl dithiophosphoric acid oxygen molybdenum, molybdenum dialkyldithiocarbamacompositions, molybdenum amine complex, molybdenum naphthenate, The general name of the oil-soluble organo-molybdenum compounds such as alkyl salicylate molybdenum.
Organic-molybdenum mainly has dialkyl dithiophosphoric acid oxygen molybdenum, nitrogenous dialkyl dithiophosphoric acid oxygen molybdenum, dialkyl group at present Molybdenum dithiocarbamate, molybdenum amine complex, molybdenum naphthenate, alkyl salicylate molybdenum.
The lubrication antifriction mechanism of organic-molybdenum is the most relevant with the polished surface of friction pair, and on the surface of friction pair, it is born at height The each point of lotus pressure, most advanced and sophisticated generation chemical reaction, promote organic-molybdenum to decompose, decomposite MOS2 and some phosphide, sulfide, nitrogen Compounds etc., these products are dispersed in oil solvent, adsorb and are deposited on rubbing surface, and MOS2 forms film and covers in wear-resistant friction layer On, thus reach antifriction, and wear-resistant, the effect of lubrication.
Now with the update of lubricating oil, the application of organic-molybdenum is gradually extensive, abroad for organic-molybdenum research and development relatively Early, and just have been widely used for I. C. engine oil in the nineties, in North America, West Europe and Japan attaching importance to environmental protection all especially, so Application comparison is extensive, and the application of domestic organic-molybdenum is after 2000, but is not the most used widely. The enterprise producing organic-molybdenum on the whole is fewer, mainly has Vanderbilt, Rhein chemistry, Japan's rising sun electrification, and state Interior mainly Pacific Ocean associating [Beijing] petrochemical industry.But existing organic-molybdenum lacks activity, causes being added into lubricating oil In, produced effect is not it is obvious that it is thus desirable to improved further.
Be not found to have the patent literature constructed with the present invention by patent retrieval, related to the present invention is main Have following:
1, Patent No. CN200880003804.X, entitled " organic molybdenum and the fluid composition containing this compound " Patent of invention, which discloses a kind of organic molybdenum and containing the fluid composition of this compound, for organic molybdenum, its Purposes as friction improver and the lubricating composition containing described compound.Described organic molybdenum can be by shown Formula (1) represent, wherein A1 and A2 is can be with the heterocycle of substituent group.
2, Patent No. CN201310491136.2, entitled " preparation method of a kind of oil-soluble organic molybdenum additive " Patent of invention, which disclose the preparation method of a kind of oil-soluble organic molybdenum additive first with sexavalence molybdenum source with and equimolar Alkali substance reaction is to being completely dissolved, and then with alkylated salicylamide acid reaction, sexavalence molybdenum source is 1 with the mol ratio of alkyl salicylate: 0.5～1.5；Sexavalence molybdenum source: acetone, benzene, toluene, water or N,N-dimethylformamide press 1:100～2000；Add catalyst C1 ～the single methanol of C20 or polyhydric alcohol, or C1～C10 glycidyl ether；React 3～10 hours at room temperature～200 DEG C.This invention will Have antifriction, the molybdenum element of antioxygenic property and have detergent-dispersant performance can alkyl salicylate organically combine, preparation organic Molybdenum additives had both had antifriction, antioxygenic property, was not easily formed deposit simultaneously.
3, Patent No. CN200880003729.7, entitled " organic molybdenum and the lubrication group containing described compound Compound " patent of invention, which disclose a kind of organic molybdenum and containing the lubricating composition of described compound, by as follows Cyclopentadienyl group molybdenum six-carbonyl complex that formula (1) represents, in this formula, R1-R10 represents independently of one another and is selected from The group of hydrogen, methyl and ethyl；It can be used as the lubricating additive without p and s, and it increases coefficient of friction and controls wet The friction of formula clutch, the most optimally provides the friction improver comprising described compound.
Though these patents above-mentioned have been directed to organic molybdenum, some organic molybdenums are wherein also related to Improvement, but these organic molybdenums the most effectively solve the activity problems of organic molybdenum, are therefore adding profit Time in lubricating oil as additive, its effect is the most undesirable, and the action-reaction forming protection is inconspicuous, takes long enough just effective Really, so it is still necessary to being improved.
Summary of the invention
The purpose of the present invention is exactly the problem not enough according to activity existing for current organic molybdenum, and proposing one can have Effect improves the activity of organic molybdenum, quickly improves the greasy property of lubricating oil, and the obvious high activity of using effect is organic Molybdenum compound and preparation method thereof and using method.
According to foregoing invention purpose, technical scheme proposed by the invention is: a kind of high activity organic molybdenum, described Organic molybdenum carries out being grafted interior structure by intramolecular " S=C mono-S-" group and molybdenum " Mo ", the chemistry of organic molybdenum Formula (1) is as follows:
In this formula, with molybdenum " Mo " as nucleophilic center, " Mo " has around been grafted two " S=C mono-S-" groups, makes invention product divide Minor structure has the feature (configuration of similar " molybdenum bisuphide " and feature) of "-S-Mo-S-"；By intramolecular " S=C One S-" group and molybdenum " Mo " be configured to polyamines Quito bamic acid molybdenum in being grafted, and polyamines Quito bamic acid molybdenum is grafted more Many " S=C mono-S-" polar groups, higher to the absorption affinity of metal, heat stability is more preferable.
Further, described formula (1) is the formula of product " polyamines Quito bamic acid molybdenum "；X place in formula Be connected together with the group at y place identical of group or two " polyamine group " differing；Including " being connected with fatty amine Group, with virtue amide and the group that is connected of aromatic amine, the group being connected with fragrant fat amine, the group being connected with quaternary amine "；X and y divides Do not represent the quantity of two " polyamine group linked together "；Including: alkyl polyamine and alkyl multiamide；Upstream materials are also Include following material: alkyl diamine, alkyl diamide complexes, alkyl triamine, alkyl tetramine, alkyl five amine；Diethylenetriamine, three second Alkene tetramine, TEPA, five hexamine and hexamethylenetetramine, phenylenediamine.
Further, in described invention product of formula (1), an amido is grafted with two " S=C mono-S-" groups；Separately " S=C mono-S-" group it is grafted with on one amido；Product molecule structure i.e. has three " S=C mono-S-" (SCS skeleton symbols) Group.
Further, two " the S=C mono-S-" groups being grafted on amido in described formula (1), the most independent one " S=C mono-S-" group is free active group, and metal or other polar group are had adsorption.
Further, in described formula (1), carbochain is connected to multiple amido, it may be assumed that can have many in product molecule structure Individual amido；
Further, in described formula (1), be connected with amido is organic group, including: alkyl, fats group, acyl Base, alkylene, linear alkene group, branched chain alkene groups, phenyl and benzene alkyl olefin group, cycloalkyl and Heterocyclylalkyl alkene Group；The olefin group of linear base, the olefin group of branched chain acyl, benzoyl group and the olefin group of benzene alkanoyl, cycloalkanes Base acyl group and the olefin group of Heterocyclylalkyl acyl group.
The preparation method of a kind of organic molybdenum, uses a kind of organic polyamine and Carbon bisulfide and ammonium molybdate reaction, adds Enter oxidant, alkali and chain-transferring agent to react again, prepare the organic molybdenum with chemical general formula (1):
Described organic polyamine uses----" alkyl polyamine and polyene Quito amido；Or alkyl multiamide and polyene Quito The organic polyamine of amide groups ", including: alkyl diamine, alkyl diamide complexes, alkyl triamine, alkyl tetramine, alkyl five amine；Ethylenediamine, Propane diamine, butanediamine, pentanediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, TEPA, five hexamine and six Asias Tetramine.
The weight of material proportioning of organic molybdenum is as follows:
Organic polyamine 0.5---2.5moL
Carbon bisulfide 0---2AmoL
Molybdenum source 0---AmoL
Alkali 0---2AmoL
Oxidant is chosen by product total amount 0.2-3 ‰；Chain-transferring agent is chosen by product total amount 0.2-2 ‰；
Wherein, institute's amino-contained quantity summation during " A " is formula (1) material.
Further, described oxidant is potassium permanganate, potassium chlorate, potassium hyperchlorate, sodium perchlorate, potassium chlorate or high chlorine Any one or two or more mixture in acid potassium；Described chain-transferring agent uses organic ruthenium or organic rhodium.
Further, described technological process is as follows:
1) in load weighted organic polyamine, add Carbon bisulfide to react 3 hours；After reaction terminates, then to react 2 little with aqueous slkali Time about；
2) load weighted molybdenum source is dissolved in ammonia, makes ammonium molybdate solution；
3) ammonium molybdate solution is joined together with organic ruthenium reaction about 3 hours in above-mentioned " reaction system "；Again to reactant System adds " oxidant ", temperature is increased to about 40--80 DEG C, adjusts pH value with acid, pH value is adjusted to PH=9.
4) product is carried out filter pressing post-drying；Or in suction vacuum hydroextractor, carry out vacuum dehydration and be dried (dehydration temperature Degree controls at about 80 DEG C).
A kind of using method of organic molybdenum, for Motor Protect, using method is as follows:
With " base oil " or " high boiling organic solvent ", organic molybdenum is dissolved in 80 DEG C, make that " organic-molybdenum is organic Liquid "；This " organic-molybdenum liquid " can be directly appended to " electromotor " the inside, and addition is: organic molybdenum is electromotor inner engine oil The 0.5--4 ‰ of consumption.Adding fashionable, the temperature of " base oil " system is less than 90 DEG C, utilizes metal to organic molybdenum pole Property group and polar molecule there is adsorption, make lubricating oil form the lubricating oil that thick layer is real in the metal surface of mechanical part Film, effectively plays lubrication and corrosion-resisting function.
The using method of a kind of organic molybdenum, is used for lubricating oil additive, and using method is as follows:
With " base oil " or " high boiling organic solvent ", organic molybdenum is dissolved in 80 DEG C, make that " organic-molybdenum is organic Liquid "；This " organic-molybdenum liquid " can be directly appended in " lubricating base oils ", and addition is: organic molybdenum is lubricating oil total amount 0.5--4 ‰.Adding fashionable, the temperature of " base oil " system is less than 90 DEG C, utilizes metal to organic molybdenum polar group Group and polar molecule have adsorption, make lubricating oil form the lubricating oil film that thick layer is real in the metal surface of mechanical part, Effectively play lubrication and corrosion-resisting function.
It is an advantage of the current invention that:
The invention has the advantages that in invention product molecule, be grafted " S=C mono-S-" group, and one of them is free " S=C One S-" polar group, thus, produce active organic molybdenum, utilize metal to containing polar group and polarity The organic molybdenum molecule of molecule has this feature of adsorption, and having invented can be quickly to electromotor (engine internal machinery Parts metals surface) form abundant lubricating film, the method quickly improving greasy property---utilize the method to can be designed that perhaps Many factory formulas, utilize these formula can produce many functional products；Utilize these functional products to be added on to start Inside machine or be added on inside the lubricating oil of electromotor, greasy property can be significantly improved, reduce mechanical wear, reduce electromotor and make an uproar Sound, improves electromotor and exerts oneself, reduce fuel oil consumption, increasing service life of engine.Product of the present invention is used to have following Feature:
(1) formula utilizing the method to design, the functional product produced, there is good intermiscibility with lubricating oil, can be complete Together with being entirely dissolved in lubricating oil.
(2) formula utilizing the method to design, the functional product produced, it is added to inside lubricating oil, can be in short-term In significantly improve greasy property, and effect is obvious.
(3) formula utilizing the method to design, the functional product produced, after being added to inside electromotor, at automobile Before not yet starting, just can form the comprehensive protection to engine.
(4) formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can improve Exerting oneself of electromotor, and effect substantially (obvious sense is but arrived car and driven effectively, light).
(5) formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can be substantially (being added to inside electromotor, after engine start a few minutes, engine sound immediately just lowers the noise of reduction electromotor , have obvious effect).
(6) formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can save Fuel oil 10--30%(measuring).
(7) formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can isolate Mechanical engine members and the corrosive medium in lubricating oil system, extend the service life of electromotor.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment one
A kind of high activity organic molybdenum, described organic molybdenum is by intramolecular " S=C mono-S-" group and molybdenum " Mo " Carrying out being grafted interior structure, the chemical general formula (1) of organic molybdenum is as follows:
In this formula, with molybdenum " Mo " as nucleophilic center, " Mo " has around been grafted two " S=C mono-S-" groups, makes invention product divide Minor structure has the feature (configuration of similar " molybdenum bisuphide " and feature) of "-S-Mo-S-"；By intramolecular " S=C One S-" group and molybdenum " Mo " be configured to polyamines Quito bamic acid molybdenum in being grafted, and polyamines Quito bamic acid molybdenum is grafted more Many " S=C mono-S-" polar groups, higher to the absorption affinity of metal, heat stability is more preferable.
Further, in described formula (1), an amido is grafted with two " S=C mono-S-" groups；Another amido On be grafted with " S=C mono-S-" group；Product molecule structure i.e. has the group of three " S=C mono-S-" (SCS skeleton symbols).
Further, two " the S=C mono-S-" groups being grafted on amido in described formula (1), the most independent one " S=C mono-S-" group is free active group, and metal or other polar group are had adsorption.
Further, described formula (1) is alkyl polyamine and polyenoid hydrocarbyl polyamine, including: diethylenetriamine, triethylene Tetramine, TEPA, five hexamine；That is: product molecule structure can there is multiple amido.
Further, described formula (1) is the formula of " polyamines Quito bamic acid molybdenum "；The group at x place in formula Be connected together with the group at y place identical or two " polyamine group " differing；Including " the base being connected with fatty amine Group, the group being connected with virtue amide and aromatic amine, the group being connected with virtue fat amine, the group being connected with quaternary amine "；X and y generation respectively The quantity of two, table " polyamine group linked together ", including: alkyl polyamine and alkyl multiamide；Including: straight chain alkanamine and Alkene amine groups, side chain alkanamine and alkene amine groups, phenyl amido and phenylalkylamine base olefin group, cycloalkyl amido and miscellaneous Cycloalkyl amido olefin group；The alkene amine groups of linear base, the alkene amine groups of side chain amide groups, Benzamido Olefin group, cyclic alkyl amides base and the olefin group of Heterocyclylalkyl amide groups with benzene alkyl amide.
The chemical equation of invention product is:
(～R-C=CNH2-) x+MoO3+CS2+NaOH+HAc →
The design of example one formula is as follows:
Described formula (1) is polyene Quito amido organic amine.
Described molybdenum (Mo) a total of 3 its versions around are reduced to the group of " SCS ", and multiple amido.
The preparation method of a kind of organic molybdenum, uses " polyene Quito amido organic amine " and Carbon bisulfide and molybdic acid Ammonium reacts, and adds oxidant, alkali and chain-transferring agent and reacts, prepares the organic molybdenum with chemical general formula (1).
Described " polyene Quito amido organic amine " uses diethylenetriamine.
The weight of material proportioning of organic molybdenum is as follows:
Diethylenetriamine: 1moL
Carbon bisulfide 3moL
Molybdenum oxide 1moL
Sodium hydroxide 3 moL
Acetic acid 2.8 moL；
Oxidant is potassium chlorate, chooses by product total amount 0.5 ‰；
Chain-transferring agent is organic ruthenium, chooses by product total amount 0.5 ‰.
Described technological process is as follows:
1) in load weighted " diethylenetriamine ", add " Carbon bisulfide " and react about 3 hours；After question response terminates, then with alkali Solution one reacts about 3 hours.
2) load weighted molybdenum source is dissolved in ammonia, makes ammonium molybdate solution；
3) ammonium molybdate solution is joined together with organic ruthenium reaction about 3 hours in above-mentioned " reaction system "；Again to reactant System adds " oxidant ", temperature is increased to about 40--80 DEG C, adjusts pH value with acid, pH value is adjusted to PH=9.
4) product is carried out filter pressing post-drying；Or in suction vacuum hydroextractor, carry out vacuum dehydration and be dried (dehydration temperature Degree controls at about 80 DEG C).
A kind of using method of organic molybdenum, for Motor Protect, using method is as follows:
With " base oil " or " high boiling organic solvent ", organic molybdenum is dissolved in 80 DEG C, make that " organic-molybdenum is organic Liquid "；This " organic-molybdenum liquid " can be directly appended to " electromotor " the inside, and addition is: organic molybdenum is electromotor inner engine oil The 0.5--4 ‰ of consumption.Adding fashionable, the temperature of " base oil " system is less than 90 DEG C, utilizes metal to organic molybdenum pole Property group and polar molecule there is adsorption, make lubricating oil form the lubricating oil that thick layer is real in the metal surface of mechanical part Film, effectively plays raising greasy property and corrosion-resisting function.
The using method of a kind of organic molybdenum, is used for lubricating oil additive, and using method is as follows:
With " base oil " or " high boiling organic solvent ", organic molybdenum is dissolved in 80 DEG C, make that " organic-molybdenum is organic Liquid "；This " organic-molybdenum liquid " can be directly appended in " lubricating base oils ", and addition is: organic molybdenum is lubricating oil total amount 0.5--4 ‰.Adding fashionable, the temperature of " base oil " system is less than 90 DEG C, utilizes metal to organic molybdenum polar group Group and polar molecule have adsorption, make lubricating oil form the lubricating oil film that thick layer is real in the metal surface of mechanical part, Effectively play raising greasy property and corrosion-resisting function.
Embodiment two
Embodiment two is essentially the same with the principle of embodiment one, and the raw material " organic polyamine " simply used is different, this example Two use " TEPA ", and it is also the most similar with example one function, feature for generating product, for a kind of high activity organic-molybdenum Compound.
The product that example two is generated, as invention product of formula (1) and example one, has a features:
Product: with molybdenum " Mo " as nucleophilic center, " Mo " has around been grafted two " S=C mono-S-" groups, has made in product molecule structure There is the feature (configuration of similar " molybdenum bisuphide " and feature) of "-S-Mo-S-".
Further, product molecule structure can be grafted three or more " S=C mono-S-" group, it may be assumed that product molecule is tied Structure can have the group of three or more " S=C mono-S-" (SCS skeleton symbol)；Wherein, product molecule structure is grafted with three with On the product of " S=C mono-S-" group, be invention product of formula (1) and the derivant of example product.
Further, in the product of example two and derivant, independent " S=C mono-S-" group is free active group, Metal or other polar group had adsorption.
Further, example two product and derivant are all connected to five amidos, it may be assumed that containing individual in product molecule structure Five amidos；
Further, described formula (1) is the formula of " polyamines Quito bamic acid molybdenum "；The group at x place and y institute in formula Be connected together identical of group or two " polyamine group " differing；Including " group being connected with fatty amine, with The group that virtue amide and aromatic amine connect, the group being connected with virtue fat amine, the group being connected with quaternary amine "；X and y represents two respectively The quantity of individual " polyamine group linked together ", including: alkyl polyamine and alkyl multiamide；Upstream materials also include down Row material: alkyl diamine, alkyl diamide complexes, alkyl triamine, alkyl tetramine, alkyl five amine；Diethylenetriamine, triethylene tetramine, TEPA, five hexamine and hexamethylenetetramine, phenylenediamine.
" organic polyamine " employing " TEPA " described in this example, with " TEPA " and Carbon bisulfide and molybdenum Acid ammonium reaction, adds oxidant, alkali and chain-transferring agent react again, prepares and has chemical general formula (1) structure and performance is the most similar As organic molybdenum and derivant, this compound and derivant have the similar performance of formula (1) and structure.
The weight of material proportioning of organic molybdenum is as follows:
TEPA: 1moL
Carbon bisulfide 4moL
Sodium molybdate (calculates with the molar equivalent of molybdenum): 1moL
Sodium hydroxide 4.moL
Acetic acid 3.8 moL；
Oxidant is potassium chlorate, chooses by product total amount 0.5 ‰；
Chain-transferring agent is organic ruthenium, chooses by product total amount 0.5 ‰.
Described technological process is as follows:
1) in load weighted " TEPA ", add CS2, react about 3 hours；React 3 hours left sides again with aqueous slkali one Right.
2) load weighted sodium molybdate is dissolved in water, makes sodium molybdate solution；
3) sodium molybdate solution is joined together with organic ruthenium reaction about 3 hours in above-mentioned " reaction system "；Again to reactant System adds " oxidant ", temperature is increased to about 40--80 DEG C, adjusts pH value with acid, pH value is adjusted to PH=9.
4) product is carried out filter pressing post-drying；Or in suction vacuum hydroextractor, carry out vacuum dehydration and be dried (dehydration temperature Degree controls at about 80 DEG C).
The using method of a kind of organic molybdenum, for Motor Protect, using method is as described in embodiment one.
Embodiment three
Embodiment three is essentially the same with the principle of embodiment one, and the raw material " organic polyamine " simply used is different, this example Two use " alkyl tetramine ", and it is also the most similar with example one function, feature for generating product, for a kind of high activity organic-molybdenum chemical combination Thing.Component prescription and the proportioning of high activity organic molybdenum are as follows:
Alkyl tetramine 0.5---2.5moL
Carbon bisulfide 0---2AmoL
Molybdenum source 0---AmoL
Alkali 0---2AmoL
Oxidant is chosen by product total amount 0.2-3 ‰；Chain-transferring agent is chosen by product total amount 0.2-2 ‰；
Wherein, institute's amino-contained quantity summation during " A " is formula (1) material.
Further, described oxidant is potassium permanganate, potassium chlorate, potassium hyperchlorate, sodium perchlorate, potassium chlorate or high chlorine Any one or two or more mixture in acid potassium；Described chain-transferring agent uses organic ruthenium or organic rhodium.
Further, described technological process is as follows:
1) in load weighted organic polyamine, add Carbon bisulfide to react 3 hours；After reaction terminates, then to react 2 little with aqueous slkali Time about；
2) load weighted molybdenum source is dissolved in ammonia, makes ammonium molybdate solution；
3) ammonium molybdate solution is joined together with organic ruthenium reaction about 3 hours in above-mentioned " reaction system "；Again to reactant System adds " oxidant ", temperature is increased to about 40--80 DEG C, adjusts pH value with acid, pH value is adjusted to PH=9.
4) product is carried out filter pressing post-drying；Or in suction vacuum hydroextractor, carry out vacuum dehydration and be dried (dehydration temperature Degree controls at about 80 DEG C).
Above example is simply to illustrate that the present invention, cited some more preferably detailed description of the invention, this area skill The usual variations and alternatives that art personnel are carried out in the range of the technical program should comprise within the scope of the present invention.
It is an advantage of the current invention that:
The invention has the advantages that in invention product molecule, be grafted " S=C mono-S-" group, and one of them is free " S=C One S-" polar group, thus, produce active organic molybdenum, utilize metal to containing polar group and polarity The organic molybdenum molecule of molecule has this feature of adsorption, and having invented can be quickly to electromotor (engine internal machinery Parts metals surface) form abundant lubricating film, the method quickly improving greasy property---utilize the method to can be designed that perhaps Many factory formulas, utilize these formula can produce many functional products；Utilize these functional products to be added on to start Inside machine or be added on inside the lubricating oil of electromotor, greasy property can be significantly improved, reduce mechanical wear, reduce electromotor and make an uproar Sound, improves electromotor and exerts oneself, reduce fuel oil consumption, increasing service life of engine.Product of the present invention is used to have following Feature:
(1) formula utilizing the method to design, the functional product produced, there is good intermiscibility with lubricating oil, can be complete Together with being entirely dissolved in lubricating oil.
(2) formula utilizing the method to design, the functional product produced, it is added to inside lubricating oil, can be in short-term In significantly improve greasy property, and effect is obvious.
(3) formula utilizing the method to design, the functional product produced, after being added to inside electromotor, at automobile Before not yet starting, just can form the comprehensive protection to engine.
(4) formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can improve Exerting oneself of electromotor, and effect substantially (obvious sense is but arrived car and driven effectively, light).
(5) formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can be substantially (being added to inside electromotor, after engine start a few minutes, engine sound immediately just lowers the noise of reduction electromotor , have obvious effect).
(6) formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can save Fuel oil 10--30%(measuring).
(7) formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can isolate Mechanical engine members and the corrosive medium in lubricating oil system, extend the service life of electromotor.
(8) to have raw material sources wide for the present invention, and can use the most general machine that common are amine and polyamines and Organic phenols, low price, make product cost reduce, it is simple to popularize application in an all-round way；
(9) it is easy in the molecular structure of product and derivant, design and be grafted more "-S-C=S-" polar group, makes invention Product is higher to the absorption affinity of metal surface, makes greasy property more preferable, and effect becomes apparent from；
(3), on the amido of same molecule, utilizing "-S-C=S-" group and " Mo " to carry out grafting and interior structure, invention product will Have more preferable heat stability.
Inventive method (principle)----feature:
(1), utilize the reaction of CS2 and amido, in the carbochain containing amido grafted polar group (-S-C=S group) (see: change Learn reaction equation and product structural formula)；Containing the invention product of this polarity (-S-C=S) group, joining in electromotor Behind face, immediately engine interior mechanical part metal surface can be formed absorption, the purpose of initial protection before reaching engine start.
(2), when after engine start, working temperature effect, directly (C=S) double bond is aoxidized, make (C=S) double bond break Key, becomes new polar group, and new polar group can form three-dimensional absorption in system, thus strengthens engine internal machinery The absorption on parts metals surface.
(3), by grafting, decomposing, double decomposition, Functional group interconversion waits sequence chemical reaction and means, makes functional product Containing part " organic-molybdenum (R-N--C-S-Mo-s-) " in product material molecule；This " organic-molybdenum " is that " unsaturated double-bond " occurs again Decomposition reaction and the good catalyst of double bond chain tra nsfer, it can promote the unsaturated double-bond in " lubricating oil system " occur transfer and Double decomposition, forms new double bond organic structure, then makes the double bond played pendulum occur under the working condition of electromotor Scission of link, becomes new free polar molecule and polar group, and this new polar group can form again three-dimensional suction in system Attached, thus strengthen the absorption to engine interior mechanical part metal surface；Improve greasy property.
And, these invention products (product) itself also have good greasy property, can be started after absorption film-forming Machine internal mechanical part provides good lubricant effect.
(4), in " functional product material " system, transition metal organic compound such as " organic rutheniums " is added, with " organic-molybdenum " formation " compound unsaturated double-bond chain transfer catalyst " in system, catalytic effect is greatly improved；Make body Double bond in system is quickly subjected to displacement and scission of link, produces new polar molecule and polar group；Form a large amount of free polarity to divide Son, strengthens the absorption to engine interior mechanical part metal surface, has just reached the greasy property of quick raising lubricating oil Purpose.
(5), "-S-C=S " polar group is to the tactile mill of mechanical movement and stimulates very sensitive, after engine start, sends out During motivation work, the mechanical movement such as touching and can stimulate it between piston and cylinder sleeve, makes "-S-C=S " polar group fast activating, Produce scission of link, form free polar molecule and polar group, strengthen the absorption of the mechanical part metal surface to electromotor, then Improve the greasy property of lubricating oil further.
"-S-C=S " polar group of grafting in product of the present invention, after the engine started, it is double that operating mode can aoxidize C=S Key, makes C=S double bond become "-C-S-" polar group, and adding " functional product " has good intermiscibility, with profit with lubricating oil Alkane in lubricating oil system, alkene, aromatic hydrocarbons, lipid etc. form three-dimensional absorption, make polar molecule alkyl molecule chain lengthen, cause pole Property molecule end group polarity strengthen further, the polarity making polar molecule is higher, make further lubricating oil three-dimensional absorption higher, This is a chain reaction, and final result is to cause the absorption lubricating film in mechanical part metal surface more abundant.

Claims (10)

1. a high activity organic molybdenum, it is characterised in that described organic molybdenum uses " S=C mono-S-" by intramolecular Group and molybdenum " Mo " carry out being grafted interior structure, and the chemical general formula (1) of organic molybdenum is as follows:
In this formula, with molybdenum " Mo " as nucleophilic center, " Mo " has around been grafted two " S=C mono-S-" groups, makes invention product divide Minor structure has the feature (configuration of similar " molybdenum bisuphide " and feature) of "-S-Mo-S-"；By intramolecular " S=C One S-" group and molybdenum " Mo " be configured to polyamines Quito bamic acid molybdenum in being grafted, and polyamines Quito bamic acid molybdenum is grafted more Many " S=C mono-S-" polar groups, higher to the absorption affinity of metal, heat stability is more preferable.
2. high activity organic molybdenum as claimed in claim 1, it is characterised in that described formula (1) is product " polyamines Quito bamic acid molybdenum " formula；Be connected together with the group at y place identical of the group at x place or not phase in formula Two same " polyamine group "；Including " group being connected with fatty amine, the group being connected with virtue amide and aromatic amine, with virtue fat The group that amine connects, the group being connected with quaternary amine "；X and y represents the quantity of two " polyamine group linked together " respectively； Including: alkyl polyamine and alkyl multiamide；Upstream materials also include following material: alkyl diamine, alkyl diamide complexes, alkyl Triamine, alkyl tetramine, alkyl five amine；Diethylenetriamine, triethylene tetramine, TEPA, five hexamine and hexa-methylene Tetramine, phenylenediamine.
3. high activity organic molybdenum as claimed in claim 1, it is characterised in that in described invention product of formula (1), Two " S=C mono-S-" groups it are grafted with on one amido；" S=C mono-S-" group it is grafted with on another amido；I.e. product Molecular structure has the group of three " S=C mono-S-" (SCS skeleton symbols).
4. high activity organic molybdenum as claimed in claim 1, it is characterised in that connect on amido in described formula (1) Branch two " S=C mono-S-" groups, the most independent " S=C mono-S-" group is free active group, to metal or its Its polar group has adsorption；In described formula (1), carbochain is connected to multiple amido, it may be assumed that can in product molecule structure There to be multiple amido.
5. high activity organic molybdenum as claimed in claim 1, it is characterised in that in described formula (1), with amido even Connect is organic group, including: alkyl, fats group, acyl group, alkylene, linear alkene group, branched chain alkene groups, benzene Base and benzene alkyl olefin group, cycloalkyl and Heterocyclylalkyl olefin group；The olefin group of linear base, the alkene of branched chain acyl Hydrocarbyl group, benzoyl group and the olefin group of benzene alkanoyl, cycloalkanoyl and the olefin group of Heterocyclylalkyl acyl group.
6. a preparation method for organic molybdenum, uses a kind of organic polyamine and Carbon bisulfide and ammonium molybdate reaction, adds Oxidant, alkali and chain-transferring agent react again, prepare the organic molybdenum with chemical general formula (1):
The chemical general formula (1) of organic molybdenum is as follows:
In this formula, with molybdenum " Mo " as nucleophilic center, " Mo " has around been grafted two " S=C mono-S-" groups, makes invention product divide Minor structure has the feature of "-S-Mo-S-", the configuration of similar " molybdenum bisuphide " and feature；By intramolecular " S=C One S-" group and molybdenum " Mo " be configured to polyamines Quito bamic acid molybdenum in being grafted, and polyamines Quito bamic acid molybdenum is grafted more Many " S=C mono-S-" polar groups, higher to the absorption affinity of metal, heat stability is more preferable.
7. the preparation method of organic molybdenum as claimed in claim 6, it is characterised in that described organic polyamine uses alkane Quito amine and polyene Quito amido；Or alkyl multiamide and the organic polyamine of polyene Quito amide groups, including: alkyl two Amine, alkyl diamide complexes, alkyl triamine, alkyl tetramine, alkyl five amine；Ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, Diethylenetriamine, triethylene tetramine, TEPA, five hexamine and hexamethylenetetramine.
8. the preparation method of organic molybdenum as claimed in claim 6, it is characterised in that the material weight of organic molybdenum Amount proportioning is as follows:
Organic polyamine 0.5---2.5moL
Carbon bisulfide 0---2AmoL
Molybdenum source 0---AmoL
Alkali 0---2AmoL
Oxidant is chosen by product total amount 0.2-3 ‰；Chain-transferring agent is chosen by product total amount 0.2-2 ‰；
Wherein, institute's amino-contained quantity summation during " A " is formula (1) material.
9. the preparation method of organic molybdenum as claimed in claim 8, it is characterised in that described oxidant is permanganic acid Any one or two or more mixture in potassium, potassium chlorate, potassium hyperchlorate, sodium perchlorate, potassium chlorate or potassium hyperchlorate； Described chain-transferring agent uses organic ruthenium or organic rhodium.
10. the preparation method of organic molybdenum as claimed in claim 6, it is characterised in that described technological process is as follows:
1) in load weighted organic polyamine, add Carbon bisulfide to react 3 hours；After reaction terminates, then to react 2 little with aqueous slkali Time about；
2) load weighted molybdenum source is dissolved in ammonia, makes ammonium molybdate solution；
3) ammonium molybdate solution is joined together with organic ruthenium reaction about 3 hours in above-mentioned " reaction system "；Again to reactant System adds " oxidant ", temperature is increased to about 40--80 DEG C, adjusts pH value with acid, pH value is adjusted to PH=9；
4) product is carried out filter pressing post-drying；Or in suction vacuum hydroextractor, carry out vacuum dehydration and be dried (dehydration temperaturre control System is at about 80 DEG C).
CN201610368013.3A 2016-05-30 2016-05-30 High-activity organic molybdenum compound and preparation and use method thereof Pending CN105968140A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419589A (en) * 1965-10-01 1968-12-31 American Metal Climax Inc Organic molybdenum compounds containing sulfur and method of preparation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419589A (en) * 1965-10-01 1968-12-31 American Metal Climax Inc Organic molybdenum compounds containing sulfur and method of preparation

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