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CN106699806A - Low-impurity content zinc dialkyl dithiophosphate and preparation method and application thereof - Google Patents

Low-impurity content zinc dialkyl dithiophosphate and preparation method and application thereof Download PDF

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Publication number
CN106699806A
CN106699806A CN201510783549.7A CN201510783549A CN106699806A CN 106699806 A CN106699806 A CN 106699806A CN 201510783549 A CN201510783549 A CN 201510783549A CN 106699806 A CN106699806 A CN 106699806A
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zinc
impurity content
low impurity
dialkyl dithiophosphate
acid
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CN106699806B (en
Inventor
冯建湘
王志刚
刘升高
夏骏远
贺军令
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Jiangxi Fuel & Lubraicant Additive Co ltd
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/06—Metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Lubricants (AREA)

Abstract

The invention discloses low-impurity content zinc dialkyl dithiophosphate (ZDDP). In the zinc dialkyl dithiophosphate, phosphorus is volatile impurity phosphorus and available phosphorus; the molar percentage content of the volatile impurity phosphorus measured through a 31P-NMR spectrum does not exceed 7.2% of the total phosphorus content of the zinc dialkyl dithiophosphate. The invention further provides a preparation method of the low-impurity content zinc dialkyl dithiophosphate. The zinc dialkyl dithiophosphate provided by the invention has low impurity content and high available phosphorus content, has excellent volatility resistance and better oxidation resistance, wear resistance, corrosion resistance and other properties, and can effectively reduce the using mount in engine and transmission lubricating oil and reduce the risk of poisoning failure of an exhaust gas treatment catalyst.

Description

The zinc dialkyl dithiophosphate of low impurity content, its preparation method and application
Technical field
The present invention be more particularly directed to a kind of zinc dialkyl dithiophosphate of low impurity content, its preparation method and application, category In engine and transmission lubricant field.
Background technology
Zinc dialkyl dithiophosphate (ZDDP) as the wear-resistant anti-rotten multifunction additive of antioxygen, in lubricating oil More than 60 years, be function admirable and most comprehensive multifunction additive, in the prior art still without a kind of additive energy Replace ZDDP completely.Research in recent years find, the p and ses in zinc dialkyl dithiophosphate can cause Particulate Emission and Other pollutant emissions increase.Additionally, the easily accumulation of phosphorous volatile matter is in the active metal catalyst position of exhaust catalytic converter On point, cause catalyst poisoning, cause catalytic efficiency to reduce, exhaust emissions is unqualified.With the hair of GF-4 standards Cloth, phosphorus content requirement is less than 0.08%, while also requiring to improve oxidation stability, wear resistance etc..In order to meet Anti-oxidant, wear-resistant and control deposit requirement, it is necessary to more additives are added in formula, or improves addition The performance of agent single dose.
Known references, such as US4263150, US4289635, US4308154, US4417990, EP0666264, The disclosure such as US3328335, US3843530, US4957649, production and commercialized ZDDP, the skill of common concern Art index is the content and zinc-phosphorus ratio of zinc and phosphorus, and its phosphorus content refers to total phosphorus content in ZDDP products, comprising waving The content of hair property foreign matter of phosphor and available phosphorus.The common structure containing phosphorus impurities includes (RO)2P(S)SR、(RS)3P(S)、 [(RO)2P(S)]2S、(RO)2P(S)H、(RO)3P(S)、(RO)2P(S)OH、[(RO)2P(O)]2S etc.【Lin Yichao, ripple Spectroscopy magazine, 13 (4) in 1996:365-370】, these are not only mistakened as being available phosphorus content containing phosphorus impurities, also significantly Reduce the quality of ZDDP.Meanwhile, research shows, the impurity containing P in ZDDP is volatile because without metal, Easily cause catalyst poisoning.Then, there is no document report to cross at present can effectively control phosphorous impurity content in ZDDP Method.
The content of the invention
In view of deficiency of the prior art, the dialkyl group two it is a primary object of the present invention to provide a kind of low impurity content D2EHDTPA zinc, with the impurity content far below commercial product, ZDDP active ingredients high, can reduce its Consumption in engine and transmission lubricant.
The present invention also aims to provide a kind of side of the zinc dialkyl dithiophosphate for synthesizing the low impurity content Method, to reduce the impurity content of ZDDP single doses, volatile component particularly therein improves available phosphorus content, together The performances such as Shi Youhua its antioxygen, wear-resistant and anti-corruption.
Application the present invention also aims to provide the zinc dialkyl dithiophosphate of the low impurity content.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of zinc dialkyl dithiophosphate of low impurity content, the dialkyl disulfides are provided in certain embodiments It is volatile impurity phosphorus and available phosphorus for the phosphorus in trbasic zinc phosphate, wherein the mole percent level of the volatile impurity phosphorus No more than 7.2% of total phosphorus content in the zinc dialkyl dithiophosphate.
Further, in the zinc dialkyl dithiophosphate of the low impurity content, Mole percent of the non-salt containing phosphorus impurities Than content no more than 7.2%, preferably more than 7.0% of total phosphorus content in the zinc dialkyl dithiophosphate, especially Preferably shorter than 6.5%.
Further, in the zinc dialkyl dithiophosphate of the low impurity content, zinc dialkyl dithiophosphate Mass content is 10-99%.
A kind of method of the zinc dialkyl dithiophosphate for synthesizing the low impurity content is provided in certain embodiments, Including：
Reacted to comprising sulphur phosphoric acid is introduced in diluent, zinc compound, the mixture of organic metal salt, and The reaction is kept in first temperature range, zinc compound and the first catalyst is added and is formed slurry；
In the range of second temperature, reacted to addition sulphur phosphoric acid in the slurry, and in the second temperature scope The reaction is kept, the second catalyst is added and is proceeded reaction, reactant mixture is post-treated, obtains described low miscellaneous The zinc dialkyl dithiophosphate of matter content.
The zinc dialkyl dithiophosphate of any one foregoing low impurity content is provided in certain embodiments or by foregoing The zinc dialkyl dithiophosphate of low impurity content obtained in any one method is used as the wear-resistant anti-rotten multifunction additive of antioxygen Purposes.
A kind of compositions of additives, the dioxane comprising any one foregoing low impurity content are provided in certain embodiments Base zinc dithiophosphate or as obtained in foregoing any one method low impurity content zinc dialkyl dithiophosphate.
Further, the zinc dialkyl dithiophosphate of the low impurity content is effective in the compositions of additives Addition is 0.001%-5%.
A kind of lubricating composition, the dioxane comprising any one foregoing low impurity content are provided in certain embodiments Base zinc dithiophosphate or as obtained in foregoing any one method low impurity content zinc dialkyl dithiophosphate.
In certain embodiments there is provided the zinc dialkyl dithiophosphate comprising foregoing low impurity content, by foregoing Any one in the zinc dialkyl dithiophosphate of low impurity content, foregoing lubricating composition obtained in a kind of method Device.
Further, described device includes engine or transmission device, but not limited to this.
Compared with prior art, the present invention at least has following good effect：
(1) zinc dialkyl dithiophosphate that the present invention is provided has a low impurity content, available phosphorus content high, together When also there is excellent anti-volatile, the more preferably performance such as antioxygen, wear-resistant and anti-corruption, and be effectively reduced in engine and The risk of usage amount and reduction catalyst poisoning in transmission lubricant；
(2) method provided using the present invention can synthesize the zinc dialkyl dithiophosphate of described low impurity.
Specific embodiment
The above quite roughly outlines the features of the present invention and technological merit, to more fully understand subsequent this hair Bright detailed description.Other feature of the present invention and advantage is described below, they constitute claims of the present invention Theme.It should be appreciated that disclosed principle and specific embodiment can be easily used as to change or designing reality Apply the basis of other systems of identical purpose of the invention.It should also be appreciated that such equivalents are without departing from appended The present invention proposed in claim.With reference to result, it is considered as the present invention to be better understood from following description Feature assembled about it and operating method novel feature, and other objects and advantages.
One aspect of the present invention provides a kind of zinc dialkyl dithiophosphate of low impurity content, in particular low to wave Zinc dialkyl dithiophosphate of the hair property containing phosphorus impurities.
More specifically, among the zinc dialkyl dithiophosphate of the low impurity content that the present invention is provided, volatile impurity The mole percent level of phosphorus particularly, is led to no more than 7.2% of total phosphorus content in the zinc dialkyl dithiophosphate Cross31The phosphorous impurity content of non-salt that P-NMR spectrums are measured is more preferably small no more than 7.2%, preferably more than 7.0% In 6.5%.
The zinc dialkyl dithiophosphate of low impurity content of the invention, in particular improving antioxygen, wear-resistant and anti-corruption has Imitate the zinc dialkyl dithiophosphate of the relative amount of composition.
The non-salt of the ZDDP of low impurity content of the invention has containing phosphorus impurities well below commercially produced product, and ZDDP Effect composition is high, can reduce its consumption in engine and transmission lubricant.
Another aspect provides a kind of synthesis low zinc dialkyl dithiophosphate method containing phosphorus impurities, It can include：
Reacted by sulphur phosphoric acid is introduced at least one diluent, zinc compound and organic metal salt mixture, Under suitable temperature conditionss, such as at 0-100 DEG C, to introducing additional amount of ZnO in batches in above-mentioned reactant mixture, And add the first catalyst to form slurry at the appropriate time；Then in suitable temperature, such as 50-150 DEG C, upwards State and add additional amount of sulphur phosphoric acid in slurry, while after the reaction certain hour is kept in the temperature range, then add Enter the second catalyst to react, the post-treated dialkyl dithio phosphorus for obtaining the low impurity content of reactant mixture Sour zinc product.
In synthetic method of the invention, at least one organic metal salt is used to suppress impurity generation and closed as zinc impregnation The auxiliary dispersants of thing, its species may include carboxylic metallic salt, organic phosphate, alkyl-thio-phosphate, dialkyl group One kind of metal dithiophosphate or its mixture.Zinc compound is comprising in zinc oxide, zinc hydroxide or zinc carbonate Any one or its mixture, it is preferable to zinc oxide.In preferred embodiment more, the organic gold for using Category salt can be organic phosphate/alkyl-thio-phosphate/dialkyl dithiophosphate, such as ZDDP.Other one In a little more preferred embodiments, the organic metal salt for using can selected from organic phosphate, alkyl-thio-phosphate, The ZDDP of dialkyl dithiophosphate mixing.In other more preferred embodiment, used is organic Slaine also can be by (instant) the reaction generation in original position.
In synthetic method of the invention, temperature is preferably controlled in 0-100 DEG C when adding zinc compound, especially preferably 40-80 DEG C, more preferably 42-65 DEG C, impurity generation can be reduced and prevent from generating the aggregate of zinc compound.
It is to add the second catalyst, second catalysis in suitable temperature and time in synthetic method of the invention Agent may be selected from but be not limited to water, metal salt of organic carboxylic acid, organic carboxyl acid ammonium salt a kind of or its mixture, for example, can be excellent Selected from salts of carboxylic acids, acetic acid ammonium salt and its mixture or the aqueous solution, more preferably from zinc acetate and zinc acetate aqueous solution. In some embodiments of the invention, the aqueous solution of zinc acetate can be added, the wherein consumption of zinc acetate about zinc total moles are used The 0.1-50% of amount.Wherein, the addition of the second catalyst, the generation and/or decomposition that can substantially reduce impurity has been generated Impurity.
It is that reactant mixture is post-processed in suitable temperature in synthetic method of the invention, temperature can be with excellent Elect 50-120 DEG C, especially preferably 80-95 DEG C, the impurity that generation can be avoided unnecessary as.
In some embodiments of the present invention, synthesized ZDDP is used as lubricant oil concentrate and lubricating oil Additive.These lubricant oil concentrates and lubricating oil can be added in engine and transmission device.
In of the invention one more specific case study on implementation, aforementioned synthetic methods may include steps of：
Reacted by sulphur phosphoric acid is introduced in diluent, zinc compound and organic metal salt mixture；
The reaction is kept in the first temperature range, while to above-mentioned mixed comprising diluent, zinc compound and slaine Other quantity zinc compound and catalyst are introduced in compound to form slurry；
In second temperature scope, to additional amount of sulphur phosphoric acid is added in above-mentioned slurry, while in the temperature range Keep the reaction；
The second catalyst is added to form zinc dialkyl dithiophosphate in the second temperature scope.
Post processing above reactant obtains zinc dialkyl dithiophosphate product.
In synthetic method of the invention, foregoing diluent may be selected from but be not limited to base oil, alkane, aromatic hydrocarbons, halo One kind in hydrocarbon, alcohol, ether, ketones solvent or both and more than.Wherein base oil can be natural oil, artificial oil Or their mixture.
Wherein, natural oil may be selected from but be not limited to animal oil and vegetable oil (such as castor oil, lard), liquid petroleum and The mineral oil of alkane, the hydrofinishing of cycloalkanes and mixing alkane-naphthene types, solvent treatment or acid treatment, from coal The oil of the lubricant viscosity of charcoal or shale also serves as useful base oil.
Wherein, artificial oil may be selected from but be not limited to hydrocarbon ils and the hydrocarbon ils of halogen substitution, such as polymerization and the mutually alkene (example of polymerization Such as, polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylenes, poly- (1- hexenes), poly- (1- octenes), Poly- (1- decene))；Alkylbenzene is (for example, detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2- ethyl hexyls Base) benzene)；Polyphenyl (for example, biphenyl, terphenyl, polyphenol of alkylation)；Diphenyl ether and alkylation with alkylation Diphenyl sulfide and its derivative, analog and homologue.Gas from Fiscber-Tropscb synthesis hydrocarbon to liquid technique artificial oil also It is useful, they are commonly referred to gas to liquid, or " GTL " base oils.
Wherein oneself warp of terminal hydroxyl passes through the modified oxyalkylene polymer such as esterification, etherificate and interpretation and their derivative Thing constitutes another kind of known artificial oil.Their example includes being prepared by the polymerization of ethylene oxide or propylene oxide Polyoxyalkylene polymers, and polyoxyalkylene polymers alkyl and aryl ether (for example, molecular weight be 1000 methyl- Poly- Isopropanediol ether or molecular weight are the diphenyl ether of the polyethylene glycol of 1000-1500)；With their list and polybasic carboxylic acid Ester, such as acetic acid esters, the oxygen-containing acid diesters of the C13 of C3-C8 fatty acid esters and TEG of mixing.
Another kind of suitable synthetic lubricant fluid includes dicarboxylic acids (such as phthalic acid, butanedioic acid, alkyl succinic acid With alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimer, Malonic acid, alkyl malonic acid, alkenyl malonic etc.) with various alcohol (such as butanol, hexanol, lauryl alcohol, 2- ethyls Hexanol, ethylene glycol, diethylene glycol monoether, propane diols etc.) ester.
Can be used as the ester of artificial oil also include by C5-C12 monocarboxylic acids and polyalcohol and polyol ester such as neopentyl glycol, Trimethylolpropane, pentaerythrite, dipentaerythritol, tripentaerythritol be made those.
Oil based on silicon such as poly- alkyl, poly- aryl, poly-alkoxyl or poly- aryloxy group silicone oil and silicic acid ester oil constitute another The useful syntholube of class；This oil includes tetraethyl orthosilicate, the isopropyl ester of silicic acid four, silicic acid four (2- ethylhexyls) Ester, silicic acid four (4- methyl -2- ethylhexyls) ester, silicic acid four (to tert-butyl-phenyl) ester, six (4- methyl -2- second Base hexyl) disiloxane, poly- (methyl) siloxanes and poly- (aminomethyl phenyl) siloxanes.Other synthetic lubricant fluid bags Include phosphorous sour liquid ester (such as diethyl ester of tricresyl phosphate, trioctyl phosphate, decylphosphonic acid) and poly- Tetrahydrofuran.
In synthetic method of the invention, foregoing organic metal salt can be carboxylic metallic salt, organic phosphate, alkyl Thiophosphate, one kind of dialkyl dithiophosphoric acid slaine or its mixture, the carboxylic acid group include C1-C18 The hydroxy-acid group of alkyl, aryl and halogen, sulphur, phosphorus heteroatoms substituted hydrocarbon radical etc.；The dialkyl dithiophosphoric acid base Any commercialized sulphur phosphoric acid and its mixture are may be selected from, is generated also selected from by any C3-C18 alcohol, alkyl phenol Single or mix sulphur phosphoric acid；The metal is including sodium, potassium, magnesium, calcium, barium, iron, cobalt, nickel, copper, zinc etc..
Foregoing sulphur phosphoric acid may be selected from any commercialized sulphur phosphoric acid and its mixture, also selected from by any alkyl, cycloalkanes It is single or mixed that the alcohol and phosphorus pentasulfide of base, aralkyl or alkaryl and the basic alkyl with similar structures are generated Close sulphur phosphoric acid；The alcohol includes straight chain and side chain and the primary, secondary, tertiary and quaternary alcohol and its mixture of isomerization.It is so-called Basic hydrocarbon refers to the base containing substitution, and such as ether, ester group, nitro and halogen, these groups do not influence this alkyl substantially That hydrocarbon of hydrocarbon characteristic.
Described alkyl may be selected from but be not limited to isopropyl, isobutyl group, normal-butyl, sec-butyl, various amyl groups, heptyl, 2- ethylhexyls, double isobutyl groups, iso-octyl, nonyl, docosyl, decyl, dodecyl, three decyls etc..Institute The alkane phenyl for enumerating is etc. butylbenzene base, penta phenyl, dodecylphenyl, heptan phenyl.Cycloalkyl is also similarly have , and they mainly include cyclohexyl and relatively low alkyl-cyclohexyl group.Most substituted hydrocarbon radicals can also be used, Such as chloro amyl group, dichloro- phenyl and dichloro- decyl.
The preparation method of foregoing sulphur phosphoric acid can be all known commercialized production methods, or The synthetic method being widely known by the people in the patents such as US4263150, US4289635, US4308154, US4417990. Above-mentioned patent is incorporated into present specification by being cited these disclosures herein.I.e. by phosphorus pentasulfide with The mixture phase reaction of a kind of alcohol, a kind of phenol, the mixture of alcohol or alcohol and phenol prepares this sulphur phosphoric acid.Every mole five vulcanization Alcohol of two phosphorus with 4-5 moles or phenol participate in reaction, and the temperature of this reaction can be in about 50 DEG C~about 200 DEG C of scope Inside carry out.
Foregoing first catalyst includes acid, ammonium carboxylate salt and carboxylic metallic salt；Sour preferred aliphatic series acid or alicyclic carboxylic acid, Can be monocarboxylic acid and polybasic carboxylic acid, generally contain from 1 to about 3 carboxyl, preferably containing only 1 carboxyl.Carboxylic acid can With containing from about 2 to about 40 carbon atoms, preferably containing from about 2 to about 20 carbon atoms, preferably containing about 2 to about 8 carbon atoms.Preferred carboxylic acid is the carboxylic acid with general formula R COOH, and R is aliphatic series or cycloaliphatic hydroxyl group in formula. Suitable acid includes ethanol, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, n-nonanoic acid, capric acid, lauric acid/dodecanoic acid, stearic acid With 20 acid, and olefinic acid, such as oleic acid, linoleic acid, linolenic and linoleic dimer.Preferred polynary carboxylic Acid can be butanedioic acid, alkane tomb and alkenyl succinic, hexanedioic acid, decanedioic acid and citric acid etc..The ammonium carboxylate salt And carboxylic metallic salt, including aforementioned carboxylic acid ammonium salt and carboxylic metallic salt.The preferred acetic acid of catalyst, ammonium acetate and Zinc acetate.
Foregoing first temperature range at 0-100 DEG C, preferably 40-80 DEG C, more preferably 42-65 DEG C.
Foregoing second temperature scope at 50-150 DEG C, preferably 60-125 DEG C, more preferably 70-90 DEG C.
Foregoing second catalyst may be selected from water, carboxylic metallic salt, ammonium carboxylate salt one kind or its mixture.Carboxylic metallic salt, Carboxylic acid in ammonium carboxylate salt may be selected from aliphatic acid or alicyclic carboxylic acid, can be monocarboxylic acid and polybasic carboxylic acid, generally contain From 1 to about 3 carboxyl, preferably containing only 1 carboxyl.Carboxylic acid can contain from about 2 to about 40 carbon atoms, preferably contain From about 2 to about 20 carbon atoms, preferably containing about 2 to about 8 carbon atoms.Preferred carboxylic acid is with formula The carboxylic acid of RCOOH, R is aliphatic series or cycloaliphatic hydroxyl group in formula.Suitable acid includes ethanol, propionic acid, butyric acid, penta Acid, caproic acid, octanoic acid, n-nonanoic acid, capric acid, lauric acid/dodecanoic acid, stearic acid and 20 acid, and olefinic acid, such as oleic acid, Linoleic acid, linolenic and linoleic dimer.Preferred polybasic carboxylic acid can be butanedioic acid, alkane tomb and alkenyl amber Acid, hexanedioic acid, decanedioic acid and citric acid etc..Wherein preferred scheme is salts of carboxylic acids and acetic acid ammonium salt and its mixture Or the aqueous solution, preferred scheme is zinc acetate and zinc acetate aqueous solution.The water of the preferred zinc acetate of the catalyst of the above second Solution, zinc acetate consumption is the 0.1-50% molar concentrations of the total consumption of zinc.
Foregoing post-processing approach can have various, for example：
Post-processing approach optionally vacuum can strip the reactant mixture, and temperature is 50-120 DEG C, preferably 80-95 DEG C；
Post-processing approach optionally can filter the reactant mixture to remove solid particle；
Post-processing approach can dilute the reactant mixture optionally with base oil, thus produce the low impurity content Zinc dialkyl dithiophosphate.
ZDDP of the invention or its mixture can be applied in the formula of lubricating oil, lubricating grease, the ZDDP compounds With low impurity content, available phosphorus content high, except with wear-resistant, antioxygen and anti-corrosion property, also resists with excellent Volatility etc..
Technical scheme is described in more detail below by way of some embodiments, but the embodiment is not constituted Limitation of the present invention.
Explanation：All percentage compositions are molar content below, are bases31P-NMR is calculated.
Embodiment 1 and embodiment 2 (comparative example)
Two classes obtained by commercially available approach mix the commercialization sample ZDDP1 that secondary alkyl ZDDP, multiple commercial vendors are produced And ZDDP2, any change is not added with, directly test.Test to obtain impurity phosphorus content average out to 7.38% and 7.65%, alkali Formula ZDDP contents average out to 23% and 27%.
Embodiment 3
The present embodiment refers to EP0866113 using the homemade secondary alkyl sulfide phosphoric acid of mixing, its preparation method, its alcohol knot Structure and ratio are identical with embodiment 1 and embodiment 2.
By 10g base oils (150N), 0.5gZnO and 5g mix secondary alkyl sulfide phosphoric acid be added to be equipped with puddler, In four neck round-bottom flasks of thermometer, condenser pipe and dropping funel, in dispersed with stirring at 45 DEG C.Then keep temperature At 40-60 DEG C, 7.0g ZnO are dividedly in some parts, add 0.07g glacial acetic acid.75 DEG C are warmed up to, 45g sulphur phosphoric acid is added dropwise. Completion of dropwise addition, after reaction 2h, adds the 3g saturated acetic acid zinc aqueous solution.After reacting 2h again, 95 DEG C are warming up to, subtracted Pressure distillation 30min, the impurity such as water removal and alcohol.Subsequent diatomite drainage, removes solid impurity, obtains ZDDP products. Test foreign matter of phosphor be 4.1%, alkali formula ZDDP contents be 24%.
Embodiment 4
The present embodiment refers to EP0866113 using the homemade secondary alkyl sulfide phosphoric acid of mixing, preparation method, average each alcohol Containing about 4.5 carbon atoms, its alcohol structure and ratio are identical with sulphur phosphoric acid used in embodiment 1.
By 10g base oils (150N), 0.5g ZnO and 5g mix secondary alkyl sulfide phosphoric acid be added to be equipped with puddler, In four neck round-bottom flasks of thermometer, condenser pipe and dropping funel, in dispersed with stirring at 45 DEG C.Then keep temperature At 40-60 DEG C, 6.35g ZnO are dividedly in some parts, add 0.07g glacial acetic acid.75 degree are warmed up to, 45g sulphur phosphoric acid is added dropwise. Completion of dropwise addition, after isothermal reaction 4h, is warming up to 95 DEG C, vacuum distillation 30min, the impurity such as water removal and alcohol.Subsequent silicon Diatomaceous earth drainage, removes solid impurity, obtains ZDDP products.Test foreign matter of phosphor be 6.2%, alkali formula ZDDP contents 2%.
Embodiment 5
The present embodiment contains about 4.5 carbon atoms, preparation side using the homemade secondary alkyl sulfide phosphoric acid of mixing, average each alcohol Method refers to EP0866113, and its alcohol structure and ratio are identical with sulphur phosphoric acid used in embodiment 1.
By 10g base oils (150N), 0.5gZnO and 5g mix secondary alkyl sulfide phosphoric acid be added to be equipped with puddler, In four neck round-bottom flasks of thermometer, condenser pipe and dropping funel, in dispersed with stirring at 45 DEG C.Then keep temperature At 40-60 DEG C, 6.35gZnO is dividedly in some parts, adds 0.07g glacial acetic acid.75 DEG C are warmed up to, 45g sulphur phosphoric acid is added dropwise. Completion of dropwise addition, after reaction 2h, adds the 3g saturated acetic acid zinc aqueous solution.After reacting 2h again, 95 DEG C are warming up to, subtracted Pressure distillation 30min, the impurity such as water removal and alcohol.Subsequent diatomite drainage, removes solid impurity, obtains ZDDP products. Test foreign matter of phosphor be 5.9%, alkali formula ZDDP contents 13.4%.
Embodiment 6 (comparative example)
The present embodiment uses homemade pair of Xin Baiji sulphur phosphoric acid, its preparation method to refer to EP0866113.
21g base oils (150N), 0.5gZnO and 25g sulphur phosphoric acid are added to and are equipped with puddler, thermometer, cold In four neck round-bottom flasks of solidifying pipe and dropping funel, in dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at, 7.51g ZnO are dividedly in some parts, 0.07g glacial acetic acid is added.75 DEG C are warmed up to, 45g sulphur phosphoric acid is added dropwise.Completion of dropwise addition, After reaction 4h, 95 DEG C, vacuum distillation 30min, the impurity such as water removal and alcohol are warming up to.Subsequent diatomite drainage, removes Solid impurity, obtains ZDDP products.Test foreign matter of phosphor be 6.4%, alkali formula ZDDP contents be 16.5%.
Embodiment 7
The present embodiment uses homemade pair of Xin Baiji sulphur phosphoric acid identical with embodiment 6.
21g base oils (150N), 0.5gZnO and 25g sulphur phosphoric acid are added to and are equipped with puddler, thermometer, cold In four neck round-bottom flasks of solidifying pipe and dropping funel, in dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at, 7.51g ZnO are dividedly in some parts, 0.07g glacial acetic acid is added.75 DEG C are warmed up to, 45g sulphur phosphoric acid is added dropwise.Completion of dropwise addition, After reaction 2h, 1.36g deionized waters are added.After reacting 2h again, 95 DEG C are warming up to, vacuum distillation 30min is removed The impurity such as water and alcohol.Subsequent diatomite drainage, removes solid impurity, obtains ZDDP products.Test foreign matter of phosphor be 5.1%, Alkali formula ZDDP contents are 36.3%.
Embodiment 8 (comparative example)
The present embodiment refers to EP0866113 using homemade mixing primary alkyl sulphur phosphoric acid, its preparation method.
21g base oils (150N), 0.5gZnO and 23g sulphur phosphoric acid are added to and are equipped with puddler, thermometer, cold In four neck round-bottom flasks of solidifying pipe and dropping funel, in dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at, 6.93g ZnO are dividedly in some parts, 0.08g glacial acetic acid is added.75 DEG C are warmed up to, 47g sulphur phosphoric acid is added dropwise.Completion of dropwise addition, After reaction 4h, 95 DEG C, vacuum distillation 30min, the impurity such as water removal and alcohol are warming up to.Subsequent diatomite drainage, removes Solid impurity, obtains ZDDP products.Test foreign matter of phosphor be 8.1%, alkali formula ZDDP contents be 25.5%.
Embodiment 9
The present embodiment homemade mixes primary alkyl sulphur phosphoric acid using identical with embodiment 8.
21g base oils (150N), 0.5gZnO and 23g sulphur phosphoric acid are added to and are equipped with puddler, thermometer, cold In four neck round-bottom flasks of solidifying pipe and dropping funel, in dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at, 7.8g ZnO are dividedly in some parts, 0.12g glacial acetic acid is added.75 DEG C are warmed up to, 47g sulphur phosphoric acid is added dropwise.Completion of dropwise addition, After reaction 2h, the 2.6g saturated acetic acid zinc aqueous solution is added.After reacting 2h at 80 DEG C again, 95 DEG C, decompression are warming up to Distillation 30min, the impurity such as water removal and alcohol.Subsequent diatomite drainage, removes solid impurity, obtains ZDDP products.Survey Try foreign matter of phosphor be 6.7%, alkali formula ZDDP contents be 39.3%.
Embodiment 10-18
As seen from the above embodiment, the ZDDP impurity contents synthesized by the method for the present invention are much smaller than commercial product, greatly The big quality that improve ZDDP.
Embodiment described above has been described in detail to technical scheme, it should be understood that the above is only Be specific embodiment of the invention, be not intended to limit the invention, it is all done in spirit of the invention it is any Modification, supplement or similar fashion replacement etc., should be included within the scope of the present invention.

Claims (10)

1.一种低杂质含量的二烷基二硫代磷酸锌，所述二烷基二硫代磷酸锌中的磷为挥发性杂质磷和有效磷，其特征在于：所述挥发性杂质磷的摩尔百分比含量不超过所述二烷基二硫代磷酸锌中总磷含量的7.2％；1. a zinc dialkyl dithiophosphate with low impurity content, the phosphorus in the zinc dialkyl dithiophosphate is volatile impurity phosphorus and available phosphorus, it is characterized in that: the volatile impurity phosphorus The molar percentage content is no more than 7.2% of the total phosphorus content in the zinc dialkyldithiophosphate; 优选的，所述的低杂质含量的二烷基二硫代磷酸锌中，非盐含磷杂质的摩尔百分比含量不超过7.2％，优选低于6.5％；Preferably, in the zinc dialkyldithiophosphate with low impurity content, the molar percentage of non-salt phosphorus-containing impurities is no more than 7.2%, preferably less than 6.5%; 进一步优选的，所述的低杂质含量的二烷基二硫代磷酸锌中，二烷基二硫代磷酸锌盐的质量百分比含量为10-99％。Further preferably, in the zinc dialkyldithiophosphate with low impurity content, the content of the zinc dialkyldithiophosphate salt is 10-99% by mass. 2.如权利要求1所述低杂质含量的二烷基二硫代磷酸锌的制备方法，其特征在于包括：2. the preparation method of the zinc dialkyl dithiophosphate of low impurity content as claimed in claim 1, is characterized in that comprising: 向包含稀释剂、锌化合物、有机金属盐的混合物中引入硫磷酸而发生反应，并在第一温度范围内保持该反应，再加入锌化合物和第一催化剂而形成浆料；introducing sulfuric acid into a mixture comprising a diluent, a zinc compound, and an organic metal salt to react, and maintaining the reaction within a first temperature range, and then adding a zinc compound and a first catalyst to form a slurry; 在第二温度范围内，向所述浆料内加入硫磷酸进行反应，并在该第二温度范围中保持该反应，再加入第二催化剂继续进行反应，反应混合物经后处理，获得所述低杂质含量的二烷基二硫代磷酸锌；In the second temperature range, add sulfuric acid to the slurry for reaction, and maintain the reaction in the second temperature range, then add the second catalyst to continue the reaction, and the reaction mixture is post-treated to obtain the low Impurity content of zinc dialkyldithiophosphate; 优选的，所述第一温度范围为0-100℃，尤其优选为40-80℃，更优选的是42-65℃；Preferably, the first temperature range is 0-100°C, especially preferably 40-80°C, more preferably 42-65°C; 和/或，优选的，所述第二温度范围为50-150℃，尤其优选为60-125℃，更优选的是70-90℃。And/or, preferably, the second temperature range is 50-150°C, especially preferably 60-125°C, more preferably 70-90°C. 3.根据权利要求2所述低杂质含量的二烷基二硫代磷酸锌的制备方法，其特征在于：3. according to the preparation method of the zinc dialkyl dithiophosphate of low impurity content described in claim 2, it is characterized in that: 所述稀释剂包含基础油、烷烃、芳烃、卤代烃、醇、醚、酮类溶剂中的任一种或者两者以上的组合；The diluent contains any one of base oil, alkanes, aromatics, halogenated hydrocarbons, alcohols, ethers, ketone solvents or a combination of two or more; 和/或，所述锌化合物包含氧化锌、氢氧化锌或碳酸锌中的任一种或两种以上的组合；And/or, the zinc compound comprises any one or a combination of two or more of zinc oxide, zinc hydroxide or zinc carbonate; 和/或，所述有机金属盐包含羧酸金属盐、有机磷酸盐、烷基硫代磷酸盐、二烷基二硫代磷酸金属盐中的任一种或两种以上的组合；And/or, the organometallic salt comprises any one or a combination of two or more of carboxylate metal salts, organophosphates, alkylthiophosphates, and dialkyldithiophosphate metal salts; 优选的，在所述有机金属盐中所采用的羧酸基包含有C1-C18烃基，芳基、卤素、硫、磷杂原子取代烃基中的任一种或两种以上；Preferably, the carboxylic acid group used in the organometallic salt contains a C1-C18 hydrocarbon group, and any one or two or more of the hydrocarbon groups are substituted by aryl, halogen, sulfur, and phosphorus heteroatoms; 优选的，在所述有机金属盐中所含的金属元素包括钠、钾、镁、钙、钡、铁、钴、镍、铜、锌中的任一种或两种以上。Preferably, the metal elements contained in the organometallic salt include any one or two or more of sodium, potassium, magnesium, calcium, barium, iron, cobalt, nickel, copper, and zinc. 4.根据权利要求2-3中任一项所述低杂质含量的二烷基二硫代磷酸锌的制备方法，其特征在于所述硫磷酸包括任意商业化的硫磷酸，由任意C3-C18醇、烷基酚生成的单一或者混合硫磷酸中的任一种或两种以上的组合；4. according to the preparation method of the zinc dialkyl dithiophosphate of low impurity content described in any one in claim 2-3, it is characterized in that described sulfuric acid comprises any commercialized sulfuric acid, by any C3-C18 Any one or a combination of two or more of the single or mixed sulfuric acid generated from alcohols and alkylphenols; 所述醇包括直链、支链及异构化的伯、仲、叔和季醇中的任一种或两种以上的组合。The alcohol includes any one or a combination of two or more of linear, branched and isomerized primary, secondary, tertiary and quaternary alcohols. 5.根据权利要求2所述低杂质含量的二烷基二硫代磷酸锌的制备方法，其特征在于所述第一催化剂包含酸、羧酸铵盐、羧酸金属盐中的任一种或两种以上的组合，优选自选自脂族酸或脂环族羧酸，或者，优选自醋酸、醋酸铵或醋酸锌；5. according to the preparation method of the described zinc dialkyl dithiophosphate of low impurity content of claim 2, it is characterized in that described first catalyst comprises any one in acid, carboxylate ammonium salt, carboxylate metal salt or A combination of two or more, preferably selected from aliphatic acids or alicyclic carboxylic acids, or, preferably from acetic acid, ammonium acetate or zinc acetate; 和/或，所述第二催化剂包括水、羧酸金属盐、羧酸铵盐中的任一种或两种以上的组合，优选自羧酸锌盐、醋酸铵盐中的任一种或两种以上的组合或其水溶液，更优选自醋酸锌和/或醋酸锌水溶液，进一步优选为醋酸锌的水溶液，更为优选的，所述第二催化剂的用量为锌总摩尔用量的0.1-50％。And/or, the second catalyst includes any one or a combination of two or more of water, metal carboxylate, ammonium carboxylate, preferably any one or both of zinc carboxylate and ammonium acetate More than one combination or an aqueous solution thereof, more preferably from zinc acetate and/or an aqueous solution of zinc acetate, more preferably an aqueous solution of zinc acetate, more preferably, the amount of the second catalyst is 0.1-50% of the total molar amount of zinc . 6.根据权利要求2所述低杂质含量的二烷基二硫代磷酸锌的制备方法，其特征在于该方法采用的后处理方法至少选自真空气提法、过滤法、稀释法；6. according to the preparation method of the zinc dialkyl dithiophosphate of low impurity content described in claim 2, it is characterized in that the aftertreatment method that this method adopts is at least selected from vacuum air extraction method, filtration method, dilution method; 其中，所述真空气提法中采用的温度条件为50-120℃，优选为80-95℃；Wherein, the temperature condition adopted in the vacuum extraction method is 50-120°C, preferably 80-95°C; 其中，所述过滤法包括：过滤该反应混合物以除去固体颗粒；Wherein, the filtration method comprises: filtering the reaction mixture to remove solid particles; 其中，所述稀释法包括：采用基础油稀释该反应混合物。Wherein, the dilution method includes: diluting the reaction mixture with base oil. 7.如权利要求1所述低杂质含量的二烷基二硫代磷酸锌或由权利要求2-6中任一项所述方法制得的低杂质含量的二烷基二硫代磷酸锌作为抗氧抗磨抗腐多功能添加剂的用途。7. the zinc dialkyl dithiophosphate of low impurity content as claimed in claim 1 or the zinc dialkyl dithiophosphate of the low impurity content that is made by the method described in any one in claim 2-6 as Use of anti-oxidation, anti-wear and anti-corrosion multifunctional additives. 8.一种添加剂组合物，其特征在于包含权利要求1所述低杂质含量的二烷基二硫代磷酸锌或由权利要求2-6中任一项所述方法制得的低杂质含量的二烷基二硫代磷酸锌；8. An additive composition, characterized in that comprising zinc dialkyldithiophosphate with low impurity content as claimed in claim 1 or zinc dithiophosphate with low impurity content obtained by the method according to any one of claims 2-6. Zinc dialkyldithiophosphate; 优选的，所述低杂质含量的二烷基二硫代磷酸锌在所述添加剂组合物中的有效添加量为0.001％-50％。Preferably, the effective addition amount of the zinc dialkyldithiophosphate with low impurity content in the additive composition is 0.001%-50%. 9.一种润滑用组合物，其特征在于包含权利要求1中所述低杂质含量的二烷基二硫代磷酸锌或由权利要求2-6中任一项所述方法制得的低杂质含量的二烷基二硫代磷酸锌；9. A lubricating composition, characterized in that it comprises zinc dialkyldithiophosphate with low impurity content described in claim 1 or the low impurity zinc dithiophosphate made by the method described in any one of claims 2-6. content of zinc dialkyldithiophosphate; 优选的，所述低杂质含量的二烷基二硫代磷酸锌在所述润滑用组合物中的有效添加量为0.001％-5％，尤其优选为0.005％-4％。Preferably, the effective addition amount of the zinc dialkyldithiophosphate with low impurity content in the lubricating composition is 0.001%-5%, especially preferably 0.005%-4%. 10.包含权利要求1中所述低杂质含量的二烷基二硫代磷酸锌、由权利要求2-6中任一项所述方法制得的低杂质含量的二烷基二硫代磷酸锌、权利要求8所述的添加剂组合物、权利要求9所述的润滑用组合物中任一种的装置；10. Zinc dialkyl dithiophosphate comprising low impurity content described in claim 1, the zinc dialkyl dithiophosphate of low impurity content prepared by the method described in any one of claims 2-6 , the additive composition described in claim 8, the device of any one in the lubricating composition described in claim 9; 优选的，所述装置包括发动机或传动装置。Preferably, said means comprises an engine or a transmission.
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