CN105884667A - High-activity organic molybdenum compound and preparation method and use method thereof - Google Patents
High-activity organic molybdenum compound and preparation method and use method thereof Download PDFInfo
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- CN105884667A CN105884667A CN201610295578.3A CN201610295578A CN105884667A CN 105884667 A CN105884667 A CN 105884667A CN 201610295578 A CN201610295578 A CN 201610295578A CN 105884667 A CN105884667 A CN 105884667A
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- molybdenum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/16—Salts of dithiocarbamic acids
-
- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
-
- 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
Abstract
The invention relates to a high-activity organic molybdenum compound and a preparation method and a use method thereof. A general chemical formula of the organic molybdenum compound is as shown in a general formula (1). In the general formula, molybdenum Mo is used as a nucleophilic center, and Mo is grafted with two groups S=C-S-, so that the molecular structure of the product disclosed by the invention not only has the characteristics of -S-Mo-S, but also has the characteristics of -S=S-Mo-S=C-S-; Mo has a structural form and characteristics similar with molybdenum disulfide in the molecular structure of the product disclosed by the invention; the R1 end of Mo is grafted with an organic amine containing two pieces of ammonio; the R2 end of Mo is grafted with an amide containing two pieces of acylamino; the molecular structure of the product contains two pieces of ammonio and two pieces of acylamino; two groups S=C-S- are grafted in the molecular structure of the product in total, so that the molecular structure of the product contains two groups SCS (short form).
Description
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 MOS2With some phosphide, sulfide, nitrogen
Compounds etc., these products are dispersed in oil solvent, adsorb and are deposited on rubbing surface, MOS2Form film to cover 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, therefore in adding lubricating oil
During as additive, its effect is the most undesirable, and the action-reaction forming protection is inconspicuous, takes long enough the most effective, institute
With it is still necessary to 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
The chemical general formula (1) of organic molybdenum is as follows:
In this formula, with molybdenum " Mo " as nucleophilic center, " Mo " has been grafted two " S=C-S-" groups, makes invention product molecule tie
Feature existing "-S-Mo-S-" in structure, has again the feature of "-S=S-Mo-S=C-S-"；" Mo " is in invention product molecule structure
There is configuration and the feature of similar " molybdenum bisuphide "；Mo " R1 one end, two ends be grafted two amidos；R2 one end is grafting
Two amide groups；Make in product molecule structure containing 4 amidos (respectively: 2 amidos and 2 amide groups)；Product molecule
2 " S=C-S-" groups of total cograft in structure so that containing two SCS(skeleton symbols in product molecule structure) group.
Further, in described formula, R1 with R2 is the identical or group that differs connected with amido, including: straight
Alkyl group, branched alkyl, phenyl and benzene alkyl, cycloalkyl and Heterocyclylalkyl.
Further, the end amido of described R1 one end has been grafted " a CLO4" oxidizer radicals, this oxidation
Group is oxidation unsaturated double-bond, this "--CLO4" position of hydrogen on oxide group any one amide groups in the structure
Position mutually；Generate the derivant of formula (1).
Further, the end amide groups of one end of described R2 is grafted with " S=C-S-" polar group, makes whole
Molecular structure has 3 " S=C-S-" groups；Generate the derivant of formula (1).
Further, the end amide groups of one end of described R2 is grafted with " S=C-S-" polar group, makes whole
Molecular structure has 3 " S=C-S-" groups；" CLO4 " oxidizer radicals it has been grafted on the end amido of R1 one end, this
Individual oxide group is oxidation unsaturated double-bond；“--CLO4" and the position of " S=C-S-polar group " " H-" on amide groups
Carry out mutual position；Generate the derivant of formula (1).
Further, the end amide groups of one end of described R2 is grafted with " S=C-S-" polar group, makes whole
Molecular structure has 3 " S=C-S-" groups；" CLO it has been grafted on another amide groups of R2 one end4" oxidant base
Group, this oxide group is oxidation unsaturated double-bond；“--CLO4" and " S=C-S-group " can " H-" on amide groups
Position carries out mutual position；Generate the derivant of formula (1).
The preparation method of a kind of organic molybdenum, uses organic amine, organic amide, Carbon bisulfide and the mixing of molybdenum source, adds
Enter oxidant, alkali and chain-transferring agent and be mixed with out the organic molybdenum with chemical general formula (1)；Containing two in organic amine
Amido；Containing two amide groups in organic amide.
The weight of material proportioning of organic molybdenum is as follows:
Organic amine 0.5--1moL
Organic amide 0.5--1moL
Carbon bisulfide 1--2moL
Molybdenum source 0.5--1moL
Alkali 2--5moL；
Oxidant is chosen by product total amount 0.2-3 ‰；Chain-transferring agent is chosen by product total amount 0.2-1 ‰.
Further, described oxidant is in potassium permanganate, potassium chlorate, potassium hyperchlorate, potassium chlorate or potassium hyperchlorate
Any one or two or more mixture；Described chain-transferring agent is organic ruthenium, organic technetium or organic rhodium.
Further, described technological process is as follows:
1) load weighted organic amine and organic amide are added in the reaction system of Carbon bisulfide and aqueous slkali, anti-after stirring
Answer about 2 hours；
2) load weighted molybdenum source is dissolved in ammonia, makes ammonium molybdate solution；
3) ammonium molybdate solution is joined together with chain-transferring agent reaction about 1 hour in above-mentioned " reaction system "；Again to reaction
System adds " oxidant ", temperature is increased to about 80 DEG C, adjusts pH value with acid, pH value is adjusted to PH=9-10(necessary
It is alkalescence)；Again by reaction mass suction vacuum hydroextractor, carry out vacuum dehydration (dehydration temperaturre 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 protective action.
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 protective action.
It is an advantage of the current invention that:
The present invention takes active organic molybdenum so that metal is to the Organic substance containing polar group and polar molecule
Molecule has adsorption, electromotor (engine internal mechanical part metal surface) quickly can be formed abundant lubricating film and protect
Protect, and lubricating oil can be catalyzed by " functional product " of patent, the method quickly improving the greasy property of lubricating oil---profit
Can be designed that many factory formulas by the method, utilize these formula can produce many functional products；Utilize these
Functional product is added on inside electromotor or is added on inside the lubricating oil of electromotor, can improve greasy property, reduces machinery
Abrasion, reduces engine noise, improves electromotor and exerts oneself, reduces fuel oil consumption, increasing service life of engine.Use the present invention
There is the following advantage:
1, the formula utilizing the method to design, the functional product produced, there is good intermiscibility with lubricating oil, can be completely
Together with being dissolved in lubricating oil.
2, the 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, the 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, the 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, the 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, the formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can save
Fuel oil 10--30%(measuring).
7, the 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, the chemical general formula (1) of described organic molybdenum is as follows:
In this formula, with molybdenum " Mo " as nucleophilic center, " Mo " has been grafted two " S=C-S-" groups, makes invention product molecule tie
Feature existing "-S-Mo-S-" in structure, has again the feature of "-S=S-Mo-S=C-S-"；" Mo " is in invention product molecule structure
There is configuration and the feature of similar " molybdenum bisuphide "；Mo " R1 one end, two ends be grafted two amidos；R2 one end is grafting
Two amide groups；Make in product molecule structure containing 2 amidos and 2 amide groups；Total cograft 2 in product molecule structure
Individual " S=C-S-" group so that containing two SCS(skeleton symbols in product molecule structure) group.
The chemical equation of invention product is:
RC2O2(NH2)2+R(NH2)2+MoO3+CS2+NaOH+HClO4+HCl+W→RC2N2H3CS2MoO2S2CNOCHRCONH2
Described organic amine is cyclohexanediamine；Amide is succinamide:
The preparation method of a kind of organic molybdenum, uses cyclohexanediamine, succinamide, Carbon bisulfide and the mixing of molybdenum source, adds
Oxidant, alkali and chain-transferring agent are mixed with out the organic molybdenum with chemical general formula (1).
The weight of material proportioning of organic molybdenum is as follows:
Cyclohexanediamine 1moL
Succinamide 1moL
Carbon bisulfide 2.5moL
Molybdenum oxide 1moL
Alkali 3moL；
Use potassium permanganate as oxidant, choose by product total amount 0.2-3 ‰；Use rhodium oxide as chain-transferring agent, press
Product total amount 0.2-1 ‰ is chosen.
Described technological process is as follows:
1) load weighted cyclohexanediamine and succinamide are added in Carbon bisulfide and aqueous slkali reaction system, anti-after stirring
Answer about 2 hours；
2) load weighted molybdenum oxide is dissolved in ammonia, makes ammonium molybdate solution；
3) ammonium molybdate solution is joined together with technetium oxide reaction about 1 hour in above-mentioned " reaction system "；Again to reactant
System adds " oxidant ", temperature is increased to about 80 DEG C, adjusts pH value with acid, pH value is adjusted to PH=9-10；Again will be anti-
In answering material suction vacuum hydroextractor, carry out vacuum dehydration (dehydration temperaturre 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 protective action.
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 protective action.
Embodiment two
Embodiment two is essentially the same with the principle of embodiment, and the most described material is different, for a kind of high activity organic-molybdenum
Compound, the chemical general formula (2) of described organic molybdenum is as follows:
In this formula, with molybdenum " Mo " as nucleophilic center, " Mo " has been grafted two " S=C-S-" groups, makes invention product molecule tie
Feature existing "-S-Mo-S-" in structure, has again the feature of "-S=S-Mo-S=C-S-"；" Mo " is in invention product molecule structure
There is configuration and the feature of similar " molybdenum bisuphide "；Mo " R1 one end, two ends be grafted two amidos；R2 one end is grafting
Two amide groups；Make in product molecule structure containing 2 amidos and 2 amide groups；Total cograft 2 in product molecule structure
Individual " S=C-S-" group so that containing two SCS(skeleton symbols in product molecule structure) group.The end amine of described R1 one end
" CLO it has been grafted on base4" oxidizer radicals, this oxide group is oxidation unsaturated double-bond, this "--CLO4" oxidation
The mutual position, position of the hydrogen on group any one amide groups in the structure；Generate the derivant of formula (1).
In described formula, R1 is pentanediamine, and R2 is succinamide.
The preparation method of a kind of organic molybdenum, uses pentanediamine, succinamide, Carbon bisulfide and the mixing of molybdenum source, adds
Enter oxidant, alkali and chain-transferring agent and be mixed with out the organic molybdenum with chemical general formula (1).
The weight of material proportioning of organic molybdenum is as follows:
Pentanediamine 0.5moL
Succinamide 0.5moL
Carbon bisulfide 1moL
Ammonium molybdate 0.5moL
Sodium hydroxide 1.5 moL
Acetic acid 1.4 moL
Use potassium hyperchlorate as oxidant, choose by product total amount 0.2-3 ‰；Use the double (thricyclohexyl of phenylmethylene
Phosphorus) ruthenous chloride as chain-transferring agent, choose by product total amount 0.2-1 ‰.
Described technological process is as follows:
1) load weighted pentanediamine, succinamide are added to the mixture system that Carbon bisulfide and sodium hydroxide react, and to react 2 little
Time about.
2) load weighted ammonium molybdate is dissolved in ammonia, makes ammonium molybdate solution.
3) ammonium molybdate solution is joined together with organic rhodium above-mentioned steps 1) reactant reacts about 1 hour；Again to
Reaction system adds potassium permanganate, temperature is increased to about 80 DEG C, adjust with acetic acid (or sulphuric acid, hydrochloric acid, acetic acid, tartaric acid)
Whole pH value, adjusts pH value to PH=9-10；Again by reaction mass suction vacuum hydroextractor, carry out vacuum dehydration (dehydration temperaturre
Control at about 80 DEG C).
4) the product base oil after dehydrate or organic solvent are diluted.
The organic molybdenum prepared in this way may be used for Motor Protect, 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 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 protective action.
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 protective action.
Embodiment three
Embodiment three is essentially the same with the principle of embodiment, and the most described material is different, for a kind of high activity organic-molybdenum
Compound, the chemical general formula (3) of described organic molybdenum is as follows:
In this formula, with molybdenum " Mo " as nucleophilic center, " Mo " has been grafted two " S=C-S-" groups, makes invention product molecule tie
Feature existing "-S-Mo-S-" in structure, has again the feature of "-S=S-Mo-S=C-S-"；" Mo " is in invention product molecule structure
There is configuration and the feature of similar " molybdenum bisuphide "；Mo " R1 one end, two ends be grafted two amidos；R2 one end is grafting
Two amide groups；Make in product molecule structure containing 2 amidos and 2 amide groups；Total cograft 2 in product molecule structure
Individual " S=C-S-" group so that containing two SCS(skeleton symbols in product molecule structure) group.
In described formula, R1 is p-phenylenediamine, and R2 is Malondiamide.
The preparation method of a kind of organic molybdenum, uses p-phenylenediamine, Malondiamide, Carbon bisulfide and the mixing of molybdenum source,
Add oxidant, alkali and chain-transferring agent and be mixed with out the organic molybdenum with chemical general formula (1).
The weight of material proportioning of organic molybdenum is as follows:
P-phenylenediamine 0.8moL
Malondiamide 0.8moL
Ammonium molybdate 1moL
Carbon bisulfide: 2moL
Sodium hydroxide 1.5 moL
Acetic acid 1.4 moL
Use potassium hyperchlorate as oxidant, choose by product total amount 0.2-3 ‰；Use the double (thricyclohexyl of phenylmethylene
Phosphorus) ruthenous chloride as chain-transferring agent, choose by product total amount 0.2-1 ‰.
Described technological process is as follows:
2) mixture system that load weighted p-phenylenediamine and Malondiamide join Carbon bisulfide and sodium hydroxide reaction is anti-
Answer about 2 hours.
2) load weighted ammonium molybdate is dissolved in ammonia, makes ammonium molybdate solution.
3) ammonium molybdate solution is joined together with organic rhodium above-mentioned steps 1) reactant reacts about 1 hour；Again to
Reaction system adds potassium permanganate, temperature is increased to about 80 DEG C, adjust with acetic acid (or sulphuric acid, hydrochloric acid, acetic acid, tartaric acid)
Whole pH value, adjusts pH value to PH=9-10；Again by reaction mass suction vacuum hydroextractor, carry out vacuum dehydration (dehydration temperaturre
Control at about 80 DEG C).
4) the product base oil after dehydrate or organic solvent are diluted.
Using method is as embodiment one.
Embodiment four
Embodiment four is essentially the same with the principle of embodiment, and the most described material is different, for a kind of high activity organic-molybdenum
Compound, the chemical general formula (4) of described organic molybdenum is as follows:
In this formula, with molybdenum " Mo " as nucleophilic center, " Mo " has been grafted two " S=C-S-" groups, makes invention product molecule tie
Feature existing "-S-Mo-S-" in structure, has again the feature of "-S=S-Mo-S=C-S-"；" Mo " is in invention product molecule structure
There is configuration and the feature of similar " molybdenum bisuphide "；Mo " R1 one end, two ends be grafted two amidos；R2 one end is grafting
Two amide groups；Make in product molecule structure containing 2 amidos and 2 amide groups；Total cograft 2 in product molecule structure
Individual " S=C-S-" group so that containing two SCS(skeleton symbols in product molecule structure) group.The end of one end of described R2
It is grafted with " S=C-S-" group on amide groups, makes that whole molecular structure has three " S=C-S-" groups；R1 one end
It has been grafted " a CLO on end amido4" oxidizer radicals, this oxide group is oxidation unsaturated double-bond；“--CLO4" and " S
=C-S-polar group " position of " H-" on amide groups mutual position can be carried out.
In described formula, R1 is p-phenylenediamine, and R2 is Malondiamide.
The preparation method of a kind of organic molybdenum, uses alkyl butanediamine, benzene diamides, Carbon bisulfide and molybdenum source mixed
Close, add oxidant, alkali and chain-transferring agent and be mixed with out the organic molybdenum with chemical general formula (1).
The weight of material proportioning of organic molybdenum is as follows:
Methyl butanediamine 0.5moL
Face benzene diamides 0.5moL
Ammonium molybdate 0.7moL
Carbon bisulfide 2moL
Sodium hydroxide 2.1moL
Acetic acid 1.9moL
Use potassium hyperchlorate as oxidant, choose by product total amount 0.2-3 ‰；Use the double (thricyclohexyl of phenylmethylene
Phosphorus) ruthenous chloride as chain-transferring agent, choose by product total amount 0.2-1 ‰.
Described technological process is as follows:
3) by load weighted, methyl butanediamine is joined Carbon bisulfide and the mixture of sodium hydroxide reaction with facing benzene diamides
System is reacted about 2 hours.
2) load weighted ammonium molybdate is dissolved in ammonia, makes ammonium molybdate solution.
3) ammonium molybdate solution is joined together with organic rhodium above-mentioned steps 1) reactant reacts about 1 hour；Again to
Reaction system adds potassium permanganate, temperature is increased to about 80 DEG C, adjust with acetic acid (or sulphuric acid, hydrochloric acid, acetic acid, tartaric acid)
Whole pH value, it must be alkaline for being adjusted by pH value to PH=9-10()；Again by reaction mass suction vacuum hydroextractor, carry out vacuum
Dehydration (dehydration temperaturre controls at about 80 DEG C).
4) the product base oil after dehydrate or organic solvent are diluted.
Using method is as embodiment one.
Embodiment five
Embodiment five is essentially the same with the principle of embodiment, and the most described material is different, for a kind of high activity organic-molybdenum
Compound, the chemical general formula (5) of described organic molybdenum is as follows:
In this formula, with molybdenum " Mo " as nucleophilic center, " Mo " has been grafted two " S=C-S-" groups, makes invention product molecule tie
Feature existing "-S-Mo-S-" in structure, has again the feature of "-S=S-Mo-S=C-S-"；" Mo " is in invention product molecule structure
There is configuration and the feature of similar " molybdenum bisuphide "；Mo " R1 one end, two ends be grafted two amidos；R2 one end is grafting
Two amide groups；Make in product molecule structure containing 2 amidos and 2 amide groups；Total cograft 2 in product molecule structure
Individual " S=C-S-" group so that containing two SCS(skeleton symbols in product molecule structure) group.The end of one end of described R2
It is grafted with " S=C-S-" group on amide groups, makes that whole molecular structure has three " S=C-S-" groups；R2 one end
" CLO it has been grafted on another amide groups4" oxidizer radicals, this oxide group can aoxidize unsaturated double-bond；“--
CLO4" and " S=C-S-group " position of " H-" on amide groups mutual position can be carried out.
In described formula, R1 is pentanediamine, and R2 is adipamide.
The preparation method of a kind of organic molybdenum, uses pentanediamine, adipamide, Carbon bisulfide and the mixing of molybdenum source, adds
Enter oxidant, alkali and chain-transferring agent and be mixed with out the organic molybdenum with chemical general formula (1).
The weight of material proportioning of organic molybdenum is as follows:
Alkyl pentanediamine 1moL
Adipamide 1moL
Ammonium molybdate 1moL
Sodium hydroxide 2.3 moL
Acetic acid 2.0 moL
Use potassium hyperchlorate as oxidant, choose by product total amount 0.2-3 ‰；Use the double (thricyclohexyl of phenylmethylene
Phosphorus) ruthenous chloride as chain-transferring agent, choose by product total amount 0.2-1 ‰.
Described technological process is as follows:
1)-mixture system that load weighted pentanediamine and adipamide join Carbon bisulfide and sodium hydroxide reaction is anti-
Answer about 2 hours.
2) load weighted ammonium molybdate is dissolved in ammonia, makes ammonium molybdate solution.
3) ammonium molybdate solution is joined together with organic rhodium above-mentioned steps 1) reactant reacts about 1 hour；Again to
Reaction system adds potassium permanganate, temperature is increased to about 80 DEG C, adjust with acetic acid (or sulphuric acid, hydrochloric acid, acetic acid, tartaric acid)
Whole pH value, it must be alkaline for being adjusted by pH value to PH=9-10()；Again by reaction mass suction vacuum hydroextractor, carry out vacuum
Dehydration (dehydration temperaturre controls at about 80 DEG C).
4) the product base oil after dehydrate or organic solvent are diluted.
Using method is as embodiment one.
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 present invention takes active organic molybdenum so that metal is to containing polarized
The organic molecule of group and polar molecule has adsorption, can be quickly to electromotor (engine internal mechanical part metal watch
Face) form abundant lubricating film protection, and lubricating oil can be catalyzed by " functional product " of patent, quickly improves lubricating oil
The method of greasy property---utilize the method to can be designed that many factory formulas, utilize these formula can produce perhaps
Multi-functional product；Utilize these functional products to be added on inside electromotor or be added on inside the lubricating oil of electromotor, energy
Improving greasy property, reduce mechanical wear, reduce engine noise, improve electromotor and exert oneself, reduce fuel oil consumption, prolongation is started
Machine service life.The present invention is used to have a following advantage:
1, the formula utilizing the method to design, the functional product produced, there is good intermiscibility with lubricating oil, can be completely
Together with being dissolved in lubricating oil.
2, the formula utilizing the method to design, the functional product produced, it is added to inside lubricating oil, can be in the short time
Inside significantly improve greasy property, and effect is obvious.
3, the formula utilizing the method to design, the functional product produced, after being added to inside electromotor, at automobile still
Before not starting, just can form the comprehensive protection to engine.
4, the formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can improve and send out
Exerting oneself of motivation, and effect substantially (obvious sense is but arrived car and driven effectively, light).
5, the formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can substantially drop
The noise of low electromotor (being added to inside electromotor, after engine start a few minutes, engine sound immediately just lowers,
There is obvious effect).
6, the formula utilizing the method to design, the functional product produced, after being added to inside electromotor, combustion can be saved
Oil 10--30%(measuring).
7, the formula utilizing the method to design, the functional product produced, after being added to inside electromotor, can isolate and send out
Motivation mechanical part and the corrosive medium in lubricating oil system, extend the service life of electromotor.
In use, the reaction of CS2 and amido, grafted polar group in the carbochain containing amido are on the one hand utilized
(-S-C=S) group (see: chemical equation and product structural formula)；This polarity (-S-C=S) group, starts joining
After inside machine, the most immediately engine machinery parts metals surface can be formed absorption, the purpose of initial protection before reaching engine start.
On the other hand, by grafting, decomposing, double decomposition, Functional group interconversion waits sequence chemical reaction and means, functional
Containing partial oxidation agent group (-CLO in product material molecule4) and unsaturated (C=S) double bond；This oxygen being grafted on molecule
Agent (-CLO4) group, when, after engine start, decomposing under working temperature effect, directly to (C=S and C=C) double bond
Aoxidizing, make (C=S and C=C) double bond scission of link, become polar group, in formation system, Organic substance three-dimensional is adsorbed and to engine machine
The absorption on tool parts metals surface.
Simultaneously also by grafting, decomposing, double decomposition, Functional group interconversion waits sequence chemical reaction and means, makes functional
Containing part organic-molybdenum (R-N--C-S-Mo-s-) in product material molecule；This organic-molybdenum is " unsaturated double-bond generation subdivision
Solve reaction and the good catalyst of chain tra nsfer ", it can promote the unsaturated double-bond in " lubricating oil system " that transfer and subdivision occur
Solve, form new organic structure, then under the working condition of electromotor, make double bond generation scission of link, form new free polarity and divide
Sub and new polar group, strengthens the absorption to engine machinery parts metals surface；And, these products also have very itself
Good greasy property, can provide good lubricant effect to mechanical engine members after absorption film-forming.
And in " functional product material " system, adding the transition metal such as organic ruthenium or organic technetium, organic rhodium has
Machine compound, is formed " compound unsaturated chain transfer catalyst " with the organic-molybdenum in system, and catalytic effect obtains the biggest proposing
High；Make the double bond in system be subjected to displacement and scission of link, produce new polar molecule and polar group；Form a large amount of free polarity
Molecule, strengthens the absorption to engine components metal surface.
Also by chemical reaction and means such as grafting, decomposition, double decomposition, Functional group interconversion, at " the product thing of functional product
Matter molecule " middle the segment polarity (-S-C=S) group being grafted, machinery is touched mill and stimulates very sensitive, after engine start,
During electromotor work, the mechanical movement such as touching and can stimulate it between piston and cylinder sleeve, makes polarity (-S-C=S) group activation, and
Produce scission of link, form free polar molecule and polar group, strengthen the mechanical part metal surface that engine is moved
Absorption.
The oxidizer radicals (-CLO of grafting in the organic-molybdenum of the present invention4) after the engine started, working temperature can make it
Decompose, discharge active oxygen, direct oxidation C=S double bond, make C=S double bond become "-C-S-" polar group, add " merit
Can property product material " there are the good intermiscibility, so "-C-S-" polar group will be with the alkane in lubricating oil system with lubricating oil
Hydrocarbon, alkene, aromatic hydrocarbons, lipid etc. form three-dimensional absorption, after three-dimensional absorption, make polar molecule alkyl molecule chain lengthen, cause polarity
The end group polarity of molecule is strengthened further, and then, the polarity making polar molecule is higher, further makes the three-dimensional absorption of lubricating oil
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, the chemical general formula (1) of described organic molybdenum is as follows: a kind of high activity is organic
Molybdenum compound, the chemical general formula (1) of described organic molybdenum is as follows:
In this formula, with molybdenum " Mo " as nucleophilic center, " Mo " has been grafted two " S=C-S-" groups, makes invention product molecule tie
Feature existing "-S-Mo-S-" in structure, has again the feature of "-S=S-Mo-S=C-S-"；" Mo " is in invention product molecule structure
There is configuration and the feature of similar " molybdenum bisuphide "；Mo " R1 one end, two ends be grafted two amidos；R2 one end is grafting
Two amide groups；Make in product molecule structure containing 2 amidos and 2 amide groups；Total cograft 2 in product molecule structure
Individual " S=C-S-" group so that containing two SCS(skeleton symbols in product molecule structure) group.
2. high activity organic molybdenum as claimed in claim 1, it is characterised in that: in described formula R1 and R2 be with
Identical or the group that differs that amido connects, including: straight chained alkyl, branched alkyl, phenyl and benzene alkyl, cycloalkyl and heterocycle
Alkyl.
3. high activity organic molybdenum as claimed in claim 2, it is characterised in that: connect on the end amido of described R1 one end
One " CLO of branch4" oxidizer radicals, this oxide group is oxidation unsaturated double-bond, this "--CLO4" oxide group exists
The mutual position, position of the hydrogen on any one amide groups in structure；Generate the derivant of formula (1).
4. high activity organic molybdenum as claimed in claim 2, it is characterised in that: the end amide groups of one end of described R2
On be grafted with " S=C-S-" polar group, make that whole molecular structure has 3 " S=C-S-" groups；Generate formula (1)
Derivant.
5. high activity organic molybdenum as claimed in claim 2, it is characterised in that: the end amide groups of one end of described R2
On be grafted with " S=C-S-" polar group, make that whole molecular structure has 3 " S=C-S-" groups；The end amine of R1 one end
" CLO it has been grafted on base4" oxidizer radicals, this oxide group is oxidation unsaturated double-bond；“--CLO4" and " S=C-
S-polar group " position of " H-" on amide groups carries out mutual position；Generate the derivant of formula (1).
6. high activity organic molybdenum as claimed in claim 2, it is characterised in that: the end amide groups of one end of described R2
On be grafted with " S=C-S-" polar group, make that whole molecular structure has 3 " S=C-S-" groups；Another of R2 one end
" CLO it has been grafted on individual amide groups4" oxidizer radicals, this oxide group is oxidation unsaturated double-bond；“--CLO4" and
" S=C-S-group " position of " H-" on amide groups can carry out mutual position；Generate the derivant of formula (1).
7. the preparation method of organic molybdenum described in a claim 1, it is characterised in that: use organic amine, amide, two sulfur
Change carbon and the mixing of molybdenum source, add oxidant, alkali and chain-transferring agent and be mixed with out the organic-molybdenum chemical combination with chemical general formula (1)
Thing；Containing two diamides bases in organic amine；
The weight of material proportioning of organic molybdenum is as follows:
Organic amine 0.5--1moL
Organic amide 0.5--1moL
Carbon bisulfide 1--5moL
Molybdenum source 0.5--1moL
Alkali 1--5moL；
Oxidant is chosen by product total amount 0.2-3 ‰；Chain-transferring agent is chosen by product total amount 0.2-1 ‰.
8. the preparation method of organic molybdenum as claimed in claim 7, it is characterised in that: described oxidant is permanganic acid
Any one or two or more mixture in potassium, potassium chlorate, potassium hyperchlorate, potassium chlorate or potassium hyperchlorate；Described chain
Transfer agent is organic ruthenium, organic technetium or organic rhodium.
9. the preparation method of organic molybdenum as claimed in claim 8, it is characterised in that: described technological process is as follows:
1) load weighted organic amine and organic amide are joined in the system of Carbon bisulfide and aqueous slkali reaction, after stirring
React about 2 hours；
2) load weighted molybdenum source is dissolved in ammonia, makes ammonium molybdate solution；
3) ammonium molybdate solution is joined together with chain-transferring agent reaction about 1 hour in above-mentioned " reaction system "；Again to reaction
System adds " oxidant ", temperature is increased to about 80 DEG C, adjusts pH value with acid, pH value is adjusted to PH=9-10(necessary
It is alkalescence)；Again by reaction mass suction vacuum hydroextractor, carry out vacuum dehydration (dehydration temperaturre controls at about 80 DEG C).
10. the using method of organic molybdenum described in a claim 1, it is characterised in that: for Motor Protect, make
As follows by method:
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 protective action；
Or it is used for lubricating oil additive, 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 protective action.
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Application publication date: 20160824 |