CN105129755B - Prepare the phosphatic method and its application of single-layer metal - Google Patents
Prepare the phosphatic method and its application of single-layer metal Download PDFInfo
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- CN105129755B CN105129755B CN201510555574.XA CN201510555574A CN105129755B CN 105129755 B CN105129755 B CN 105129755B CN 201510555574 A CN201510555574 A CN 201510555574A CN 105129755 B CN105129755 B CN 105129755B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/24—Compounds containing phosphorus, arsenic or antimony
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
Abstract
The present invention proposes that one kind prepares the phosphatic method and its application of single-layer metal, and methods described includes：(1) intercalation processing is carried out to layered metal phosphates using hydramine, obtains intercalation material；(2) lift-off processing and then in ionic liquid to the intercalation material is carried out, single-layer metal phosphate is obtained.Single-layer metal phosphate can be effectively prepared using this method, this method is simple, convenient quick, and the single-layer metal phosphate mixt prepared can be used for preparing high perofmrnace lubricating oils or high-performance composite materials.
Description
Technical field
The present invention relates to field of material technology, in particular it relates to prepare the phosphatic method and its application of single-layer metal, more
In particular it relates to the phosphatic method of single-layer metal is prepared, and purposes of the single-layer metal phosphate in lubricating oil is prepared.
Background technology
Salt of the fusing point less than 100 degrees Celsius is generally called ionic liquid, in general, and it is (special by organic cation
It is the organic cation containing nitrogen, phosphorus or sulphur) and Weakly coordinating anions composition.
Substantially, ionic liquid is mainly quaternary ammonium salt, quaternary alkylphosphonium salts or sulfonium salt., Ube Industries Ltd.'s strain formula meeting in 1992
A kind of method (US5102948 (A)) being scattered in the clay of quaternary ammonium salts in polyamide material has been invented first by society, obtains
Composite be applied to bumper when show extraordinary performance.Inspired by this, United States Patent (USP) US2014/
0005415 (A1) utilizes quaternary ammonium salt chlorination 1- butyl -3- methylimidazoles insertion laminar alpha zirconium phosphate (α-ZrP, Zr (HPO4)2·
H2O), corresponding intercalation material has been obtained.
However, above-mentioned intercalation method limits further application of the lamellar compound in high performance material, thus, it is desirable to
The method that can peel off sheet metal phosphate.For relevant knowledge and experience, in existing research, the only tetrabutyl
Ammonium hydroxide (TBA) can make in water-soluble medium stratiform α-ZrP peel off, however, due to TBA be a kind of unstable alkali and its
Alkalescence is too strong, and it is not suitable for being used for stripped laminar α-ZrP in commercialization composite.Polyetheramine monoamine (PEA-M) can be
Stripped laminar α-ZrP in acetone, but in the product of stripping, PEA-M mass ratio is too big, can significantly reduce composite
Intensity, so that obtained most products almost can not in polymer composites (such as epoxy resin composite material)
Using.
Thus, the method and its application on stripped laminar metal phosphate still have much room for improvement at present.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.Therefore, the present invention
One purpose be propose it is a kind of can in ionic liquid stripped laminar metal phosphate method, peel off product in ionic liquid
The mixture formed in body may be directly applied to lubricating oil or polymer composites.
In one aspect of the invention, the phosphatic method of single-layer metal is prepared the invention provides one kind.According to this hair
Bright embodiment, this method includes：(1) intercalation processing is carried out to layered metal phosphates using hydramine, to obtain intercalation material
Material；And (2) carry out lift-off processing in ionic liquid to the intercalation material, to obtain single-layer metal phosphate.Invention
People has found, fast and effectively layered metal phosphates can be peeled off using the method for the present invention, so as to prepare list
Layer metal phosphate, and this method step is simple, it is easy, with low cost to operate, be easily achieved industrialized production, is obtained while preparing
The single-layer metal phosphate obtained can show good performance effective for preparing lubricating oil, high-performance composite materials etc., expand
Single-layer metal phosphate further applying in high performance material is opened up.
Embodiments in accordance with the present invention, hydramine is preferably mono amino alcohol or polyetheramine monoamine.
The topological structure of embodiments in accordance with the present invention, mono amino alcohol or polyetheramine monoamine be linear, star, annular or its
Combination.
Embodiments in accordance with the present invention, the molecular weight of hydramine is 50~5000, preferably 500~5000,
Embodiments in accordance with the present invention, hydramine is selected from monoethanolamine, aminopropanol, amino butanol, diglycolamine, three (hydroxyls
Methyl) aminomethane, polyethylene glycol monoamine, at least one of polypropylene glycol monoamine and PolyTHF monoamine.
Embodiments in accordance with the present invention, layered metal phosphates preferably are selected from alpha zirconium phosphate, θ-basic zirconium phosphate and γ-basic zirconium phosphate
At least one.
Embodiments in accordance with the present invention, step (1) includes：Hydramine and layered metal phosphates are mixed, will be resulting
Mixture carries out ultrasonication, obtains ultrasonically treated product；Ultrasonically treated product is centrifuged, precipitated；Utilize second
Alcohol carries out centrifuge washing to precipitation, obtains washed product；In under normal temperature condition, washed product is dried under reduced pressure, inserted
Layer material.
In embodiments in accordance with the present invention, step (2), lift-off processing through the following steps that carry out：By inserting for obtaining
Layer material and ionic liquid mixing, then carry out ultrasonication by resulting mixture.
Embodiments in accordance with the present invention, ionic liquid be small molecule organic ion liquid or polymer ions liquid, wherein,
Ionic liquid contains anion and organic cation.Embodiments in accordance with the present invention, anion is preferably halide ion, further
Preferably chlorion or bromide ion.Embodiments in accordance with the present invention, organic cation contains nitrogen, phosphorus or sulphur.
Embodiments in accordance with the present invention, ionic liquid be small molecule organic ion liquid, and organic cation be selected from
It is at least one of following：Imidazole salts, pyrazoles salt, thiazole salt, pyridiniujm, pyrrolidinium, pyrimidine salt, pyridazine
Salt, piperidinium salt, quinolinium, isoquinolin salt, pyrazoline salt, thiazoline Yan, oxazolines salt, triazoline salt,
Phosphonium salt and sulfonium salt.It is preferred that organic cation has selected from one of following structural formula：
Wherein, R, R1, R2, R3, R4And R5It is each independently alkyl or alkoxy.Embodiments in accordance with the present invention, on
Alkyl is stated for C1-C22Alkyl, above-mentioned alkoxy is C1-C22Alkoxy.
Embodiments in accordance with the present invention, ionic liquid is polymer ions liquid, and the polymer ions liquid is to use
Prepared selected from least one following monomer：It is vinylpyridine salt, vinylpiperidine salt, vinylquinoline salt, double
Pi-allyl ammonium salt, N- vinyl imidazoles salt, vinyl pyrazoles salt and vinylthiazole salt.Specifically, polymer ions
Liquid is preferably to be prepared using the monomer for possessing one of the following chemical structure：
Wherein, R, R1And R2It is each independently alkyl or alkoxy.Embodiments in accordance with the present invention, above-mentioned alkyl is
C1-C22Alkyl, above-mentioned alkoxy is C1-C22Alkoxy.
In another aspect of this invention, the invention provides a kind of single-layer metal phosphate.Embodiments in accordance with the present invention,
The single-layer metal phosphate is prepared by foregoing method.Inventor has found that the single-layer metal phosphate can have
Effect is used to prepare lubricating oil or high-performance composite materials, when being especially applicable to lubricating oil, with relatively low coefficient of friction and
Relatively low wear extent, shows excellent friction resistant performance.
In another aspect of the invention, the invention provides foregoing single-layer metal phosphate in lubricating oil is prepared
Purposes.Inventor is had found, above-mentioned single-layer metal phosphate is used to prepare lubricating oil, friction coefficient of lubricating oil is obtained smaller
It is smaller with wear extent, good anti-wear performance is shown, the using effect of lubricating oil can be significantly improved.
In still another aspect of the invention, the invention provides a kind of lubricating oil.Embodiments in accordance with the present invention, the lubricating oil
Contain foregoing single-layer metal phosphate.The lubricating oil according to embodiments of the present invention, with relatively low coefficient of friction and
Relatively low wear extent, possesses preferable friction resistant performance, shows the performance better than existing goods lubricating oil.
Brief description of the drawings
Fig. 1 shows the α-ZrP-3M prepared in the embodiment of the present invention XRD spectrum；
Fig. 2 shows the α-ZrP-3M prepared in the embodiment of the present invention TEM photos；
Fig. 3 shows the intercalation DGA- α-ZrP-3M-12h prepared in the embodiment of the present invention and the paste DGA- of stripping
α-ZrP-3M-12h high-resolution XRD spectrum；
Fig. 4 shows the structure schematic diagram that four-ball tribotester is used in the embodiment of the present invention；
Fig. 5 show the α-ZrP ionic liquid mixtures peeled off in the embodiment of the present invention, commercial lubricating oil when m- rub
Wipe index contrast curve；
Fig. 6 shows the α-ZrP ionic liquid mixtures peeled off in the embodiment of the present invention, the when m- mill of commercial lubricating oil
Trace depth correlation curve；
Fig. 7 is shown to be carried out after four-ball wear test to the α-ZrP ionic liquid mixtures peeled off in the embodiment of the present invention,
The polishing scratch size of wear test ball；
Fig. 8 is shown to be carried out after wear test to a kind of commercial lubricating oil, the polishing scratch size of wear test ball.
Embodiment
Embodiments of the invention are described below in detail.The embodiments described below is exemplary, is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Unreceipted particular technique or condition in embodiment, according to text in the art
Offer described technology or condition or carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument,
For can be by the conventional products of acquisition purchased in market.
In one aspect of the invention, the phosphatic method of single-layer metal is prepared the invention provides one kind.According to this hair
Bright embodiment, this method comprises the following steps：
(1) intercalation processing is carried out to layered metal phosphates using hydramine, to obtain intercalation material.
Embodiments in accordance with the present invention, hydramine can be mono amino alcohol or polyetheramine monoamine.Thus, hydramine can be effectively
Overcome the intermolecular interaction of layered metal phosphates interlayer, insert the interlayer of layered metal phosphates, obtain intercalation material
Material, while the efficiency and intercalation effect for obtaining intercalation material can be improved.
The topological structure of embodiments in accordance with the present invention, mono amino alcohol or polyetheramine monoamine can be linear, star, annular
Or its combination.Many experimental results show that mono amino alcohol or polyetheramine monoamine with above topology structure can be inserted effectively
Enter the interlayer of layered metal phosphates, insertion effect is preferable, and insertion efficiency is higher.
Embodiments in accordance with the present invention, the molecular weight of the hydramine used can be 50~5000.Thus, hydramine is conducive to insert
Enter the interlayer of layered metal phosphates, and then improve insertion efficiency and insertion effect.If the molecular weight of hydramine is too high or too low,
Insert efficiency and insertion effect is not very good.Under preferable case, the molecular weight of the hydramine used can be 500~5000.
Thereby, it is possible to further improve insertion effect and insertion efficiency, and the intercalation material performance obtained is preferable, is conducive to subsequent step
Progress.
According to a preferred embodiment of the invention, hydramine can be selected from monoethanolamine, aminopropanol, amino butanol, diethylene glycol (DEG)
Amine, three (methylol) aminomethanes, polyethylene glycol monoamine, at least one of polypropylene glycol monoamine and PolyTHF monoamine.
Thus, be conducive to improving the efficiency for obtaining intercalation material, the intercalation material performance of acquisition is preferable, is conducive to entering for subsequent step
OK.
Embodiments in accordance with the present invention, layered metal phosphates preferably are selected from alpha zirconium phosphate, θ-basic zirconium phosphate and γ-basic zirconium phosphate
At least one.Thus, be conducive to improving the efficiency for obtaining intercalation material, the intercalation material performance of acquisition is preferable, after being conducive to
The progress of continuous step.In addition, using above-mentioned layered metal phosphates, the end-product of acquisition can be further used for preparing lubricating oil
And high-performance composite materials, it is with a wide range of applications.Embodiments in accordance with the present invention, the preferred diameter of layered metal phosphates
Flake nano particle less than 4000 nanometers, thus, it is possible to further improve the performance of intercalation material and end-product.
Embodiments in accordance with the present invention, step (1) may further include：Layered metal phosphates and hydramine are mixed,
Resulting mixture is subjected to ultrasonication and obtains ultrasonically treated product；Then, ultrasonically treated product is centrifuged, obtained
To precipitation；Centrifuge washing is carried out to precipitation using ethanol, washed product is obtained；In under normal temperature condition, washed product is subtracted
Press dry dry, obtain intercalation material.Thereby, it is possible to which hydramine to be fast and effeciently inserted into the interlayer of layered metal phosphates, obtain
The intercalation material of better performances, and it is simple to operate, it is convenient and swift, it is easy to accomplish.In this step, by ultrasonication, energy
Enough interlayers for effectively causing hydramine to insert layered metal phosphates, obtain intercalation material, wherein, ultrasonically treated power and time
It is not particularly limited, those skilled in the art can flexibly select according to actual needs, in some embodiments of the invention, surpasses
The frequency of sonication can be 40~80KHz, and power can be 100~300W, and the time can be 2~15 hours.Pass through centrifugation
Washing, can effectively remove the hydramine and other impurities of residual, and it will be understood by those skilled in the art that centrifuge washing can enter
Row is one or many, until excessive hydramine and other impurities are cleaned up, you can carry out next step.By being dried under reduced pressure,
The volatilization of cleaning solvent ethanol can effectively be caused, intercalation material free from foreign meter is obtained, and then be conducive to the progress of subsequent step.
Embodiments in accordance with the present invention, in step (1), the addition of hydramine is excessive, under preferable case, according to rubbing
That ratio meter, hydramine is excessively 10%.Thus, be conducive to improving the yield of intercalation efficiency and intercalation material.
(2) lift-off processing is carried out to intercalation material in ionic liquid, to obtain single-layer metal phosphate.
In embodiments in accordance with the present invention, step (2), lift-off processing is by by the mixing of intercalation material and ionic liquid
Thing carries out ultrasonication progress.Wherein, ultrasonically treated power is not particularly limited with the time, and those skilled in the art can
With flexibly selection according to actual needs, in some embodiments of the invention, ultrasonically treated frequency can be 40~80KHz,
Power can be 100~300W, and the time can be 2~15 hours.Thereby, it is possible to carry out lift-off processing under the suitable conditions,
Obtain the preferable single-layer metal phosphate of performance.
Embodiments in accordance with the present invention, ionic liquid can be small molecule organic ion liquid or polymer ions liquid,
Wherein, ionic liquid contains anion and organic cation.Embodiments in accordance with the present invention, anion is preferably halide ion,
In the case of further preferably, anion can be chlorion or bromide ion.Embodiments in accordance with the present invention, organic cation contains
Nitrogen, phosphorus or sulphur.Thus, be conducive to carrying out lift-off processing to layered metal phosphates, obtain single-layer metal phosphate.
Embodiments in accordance with the present invention, ionic liquid be small molecule organic ion liquid, and organic cation be selected from
It is at least one of following：Imidazole salts, pyrazoles salt, thiazole salt, pyridiniujm, pyrrolidinium, pyrimidine salt, pyridazine
Salt, piperidinium salt, quinolinium, isoquinolin salt, pyrazoline salt, thiazoline Yan, oxazolines salt, triazoline salt,
Phosphonium salt and sulfonium salt.Under preferable case, organic cation has selected from least one following structural formula：
Wherein, R, R1, R2, R3, R4And R5It is each independently alkyl or alkoxy.Embodiments in accordance with the present invention, on
Alkyl is stated for C1-C22Alkyl, above-mentioned alkoxy is C1-C22Alkoxy, wherein, C1-C22Alkyl is including but not limited to optionally substituted
Methyl, ethyl, propyl group, butyl (normal-butyl, isobutyl group, the tert-butyl group), amyl group, hexyl, octyl group, vinyl, acrylic etc.,
C1-C22Alkoxy includes but is not limited to optionally substituted methoxyl group, ethyoxyl, propoxyl group, butoxy etc..Those skilled in the art
It is appreciated that above-mentioned only list C1-C22Alkyl and C1-C22Some specific examples of alkoxy, protection scope of the present invention is simultaneously
Not limited to this, the alkyl and alkoxy that carbon number is 1-22 are within protection scope of the present invention.Thereby, it is possible to effectively will
It is single-layer metal phosphate that layered metal phosphates, which are peeled off, and simple to operate, convenient, while list of this method without limitation on acquisition
The further application of layer metal phosphate, it can apply in lubricating oil, high-performance composite materials.
Embodiments in accordance with the present invention, ionic liquid is polymer ions liquid, and the polymer ions liquid is to use
Prepared selected from least one following monomer：It is vinylpyridine salt, vinylpiperidine salt, vinylquinoline salt, double
Pi-allyl ammonium salt, N- vinyl imidazoles salt, vinyl pyrazoles salt and vinylthiazole salt.Specifically, polymer ions
Liquid is preferably to be prepared using the monomer for possessing one of the following chemical structure：
Wherein, R, R1And R2It is each independently alkyl or alkoxy.Embodiments in accordance with the present invention, above-mentioned alkyl is
C1-C22Alkyl, above-mentioned alkoxy is C1-C22Alkoxy, wherein, C1-C22Alkyl includes but is not limited to optionally substituted methyl, second
Base, propyl group, butyl (normal-butyl, isobutyl group, the tert-butyl group), amyl group, hexyl, octyl group, vinyl, acrylic etc., C1-C22Alkoxy
Including but not limited to optionally substituted methoxyl group, ethyoxyl, propoxyl group, butoxy etc..It will be understood by those skilled in the art that on
State and only list C1-C22Alkyl and C1-C22Some specific examples of alkoxy, protection scope of the present invention is not limited to this, carbon
The alkyl and alkoxy that atomicity is 1-22 are within protection scope of the present invention.Thereby, it is possible to effectively by laminated metal phosphorus
It is single-layer metal phosphate that hydrochlorate, which is peeled off, and simple to operate, convenient, while single-layer metal phosphoric acid of this method without limitation on acquisition
The further application of salt, it can apply in lubricating oil, high-performance composite materials.
Inventor is had found, single-layer metal phosphate can be fast and effectively prepared using the method for the present invention, and should
Method and step is simple, and operation is easy, with low cost, it is easy to accomplish industrialized production, while the single-layer metal phosphoric acid prepared
Salt can show good performance, extend single-layer metal phosphorus effective for preparing lubricating oil, high-performance composite materials etc.
Hydrochlorate further applying in high performance material.
It should be noted that the single-layer metal phosphate prepared using this method according to embodiments of the present invention is in single
The form of mixtures of layer metal phosphate and ionic liquid, is also with single layer of gold when being applied to lubricating oil, composite etc.
The form of mixtures of category phosphate and ionic liquid is directly used.In addition, being prepared using this method according to embodiments of the present invention
The single-layer metal phosphate of acquisition is single-layer metal phosphate nano piece.
In another aspect of this invention, the invention provides a kind of single-layer metal phosphate.Embodiments in accordance with the present invention,
The single-layer metal phosphate is prepared by foregoing method.Inventor has found that the single-layer metal phosphate can have
Effect is used to prepare lubricating oil or high-performance composite materials, when being especially applicable to lubricating oil, with relatively low coefficient of friction and
Relatively low wear extent, shows preferable friction resistant performance.
In another aspect of the invention, the invention provides foregoing single-layer metal phosphate in lubricating oil is prepared
Purposes.Inventor is had found, above-mentioned single-layer metal phosphate is used to prepare lubricating oil, friction coefficient of lubricating oil is obtained smaller
It is smaller with wear extent, good anti-wear performance is shown, the using effect of lubricating oil can be significantly improved.
In still another aspect of the invention, the invention provides a kind of lubricating oil.Embodiments in accordance with the present invention, the lubricating oil
Contain foregoing single-layer metal phosphate.The lubricating oil according to embodiments of the present invention, with relatively low coefficient of friction and
Less wear extent, preferable friction resistant performance shows the performance better than existing goods lubricating oil.
Embodiments of the invention are described below in detail.
Embodiment 1：The preparation of alpha zirconium phosphate
By 8.0g ZrOCl2.8H2O is 3.0mol/L H with 80.0ml concentration3PO4(85%wt) is mixed, mixed by what is obtained
Compound is sealed in the pressure vessel of teflon lined, and be heated to 200 degrees Celsius keep 24 hours, obtain reaction product
α-ZrP, are designated as α-ZrP-3M.Reaction terminate after, by obtained reaction product wash after and be collected by centrifugation 5 times, then, will obtain
α-ZrP-3M at 65 DEG C dry 24h.Using mortar by dried α-ZrP-3M grind into powders.α-the ZrP-3M of acquisition
XRD (X-ray diffraction) spectrogram of powder is shown in Fig. 1, and TEM photos are shown in Fig. 2.
Embodiment 2：The preparation of small molecular ion liquid：Bromination 1- methyl -3- octylimidazole salt
In three-neck flask, by 74.574g 1- methylimidazoles (CAS No.：100ml anhydrous propanones 616-47-7) are dissolved in,
Then, under nitrogen atmosphere, lasting stirring condition, the three-neck flask for filling mixed solution is placed in 85 DEG C of oil baths, then will
192.969g n-octane bromides (with molar amount, excessive about 10%, CAS No.：111-83-1) add in three-neck flask, then
By resulting mixed solution is in 85 DEG C of constant temperature and continues to keep reaction 12~24 hours under stirring condition.As reaction is carried out,
Reaction solution gradually becomes faint yellow, after reaction terminates, and rotary evaporation in vacuo removes solvent, obtains sticky weak yellow liquid shape or slurry
Body shape product, then adds resulting sticky product in 1000ml ethyl acetate, after being well mixed, obtains water white transparency
Sticky product, produces bromination 1- methyl -3- octylimidazole salt.
Embodiment 3：The preparation of small molecular ion liquid：Bromination 1- methyl -3- hexyl pyridiniujms
In three-neck flask, by 79.10g pyridines (CAS No.：100ml anhydrous propanones 110-86-1) are dissolved in, then,
Under nitrogen atmosphere, lasting stirring condition, the three-neck flask for filling mixed solution is placed in 85 DEG C of oil baths, then by 181.588g
Bromo n-hexane (with molar amount, excessive about 10%, CAS No.：111-25-1) add in three-neck flask, then will be resulting
Mixed solution in 85 DEG C of constant temperature and continue stirring condition under keep reaction 12~24 hours.With reaction carry out, reaction solution by
Fade to it is faint yellow, reaction terminate after, rotary evaporation in vacuo remove solvent, obtain sticky weak yellow liquid shape or slurry shape production
Thing, then adds resulting sticky product in 1000ml ethyl acetate, after being well mixed, and obtains the viscosity production of water white transparency
Thing, produces bromination 1- methyl -3- hexyl pyridiniujms.
Embodiment 4：The preparation of small molecular ion liquid：Bromination 1- butyl quinoliniums
In three-neck flask, by 129.16g quinoline (CAS No.：200ml anhydrous propanones 91-22-5) are dissolved in, then,
Under nitrogen atmosphere, lasting stirring condition, the three-neck flask for filling mixed solution is placed in 85 DEG C of oil baths, then by 150.733g
Bromination of n-butane (with molar amount, excessive about 10%, CAS No.：109-65-9) add in three-neck flask, then will be resulting
Mixed solution in 85 DEG C of constant temperature and continue stirring condition under keep reaction 12~24 hours.With reaction carry out, reaction solution by
Fade to it is faint yellow, reaction terminate after, rotary evaporation in vacuo remove solvent, obtain sticky weak yellow liquid shape or slurry shape production
Thing, then adds resulting sticky product in 1000ml ethyl acetate, after being well mixed, and obtains the viscosity production of water white transparency
Thing, produces bromination 1- butyl quinoliniums.
Embodiment 5：The preparation of small molecular ion liquid：Bromination 1- vinyl -3- octylimidazole salt
In three-neck flask, by 94.11g N- vinyl imidazoles (CAS No.：1072-63-5) it is dissolved in 200ml anhydrous third
Ketone, then, in nitrogen atmosphere, continues under stirring condition, the three-neck flask for filling mixed solution is placed in 85 DEG C of oil baths, then
By 212.443g n-octane bromides (with molar amount, excess about 10%, CAS No.：111-83-1) add in three-neck flask, connect
And keep reacting 12~24 hours under 85 DEG C of constant temperature and lasting stirring condition by resulting mixed solution.With react into
OK, reaction solution gradually becomes faint yellow, after reaction terminates, and rotary evaporation in vacuo removes solvent, obtains sticky weak yellow liquid shape
Or slurry shape product, then resulting sticky product is added in 1000ml ethyl acetate, after being well mixed, obtains colourless
Bright sticky product, produces the octylimidazole salt of bromination 1- vinyl -3.
Embodiment 6：The preparation of small molecular ion liquid：Bromination 1- vinyl -3- hexyl imidazolium salt
In three-neck flask, by 94.11g 1- vinyl imidazoles (CAS No.：1072-63-5) it is dissolved in 100ml anhydrous third
Ketone, then, in nitrogen atmosphere, continues under stirring condition, the three-neck flask for filling mixed solution is placed in 85 DEG C of oil baths, then
By 181.588g bromos n-hexane (with molar amount, excess about 10%, CAS No.：111-25-1) add in three-neck flask, connect
And keep reacting 12~24 hours under 85 DEG C of constant temperature and lasting stirring condition by resulting mixed solution.With react into
OK, reaction solution gradually becomes faint yellow, after reaction terminates, and rotary evaporation in vacuo removes solvent, obtains sticky weak yellow liquid shape
Or slurry shape product, then resulting sticky product is added in 1000ml ethyl acetate, after being well mixed, obtains colourless
Bright sticky product, produces bromination 1- vinyl -3- hexyl imidazolium salt.
Embodiment 7：The preparation of small molecular ion liquid：Bromination 4- vinyl -3- butyl-pyridinium salt
In three-neck flask, by 105.14g 4-vinylpridines (CAS No.：100-43-6) it is dissolved in 100ml anhydrous third
Ketone, then, in nitrogen atmosphere, continues under stirring condition, the three-neck flask for filling mixed solution is placed in 85 DEG C of oil baths, then
By 150.733g bromination of n-butane (with molar amount, excess about 10%, CAS No.：109-65-9) add in three-neck flask, connect
And keep reacting 12~24 hours under 85 DEG C of constant temperature and lasting stirring condition by resulting mixed solution.With react into
OK, reaction solution gradually becomes faint yellow, after reaction terminates, and rotary evaporation in vacuo removes solvent, obtains sticky weak yellow liquid shape
Or slurry shape product, then resulting sticky product is added in 1000ml ethyl acetate, after being well mixed, obtains colourless
Bright sticky product, produces bromination 4- vinyl -3- butyl-pyridinium salt.
Embodiment 8：It is prepared by low-molecular weight polymer homopolymer ionic liquid：Poly- (bromination 1- vinyl -3- octylimidazoles
Salt)
In three-neck flask, the octylimidazole salt of bromination 1- vinyl -3 prepared in 57.5g embodiments 5 is dissolved in
250ml dry toluenes, then, under nitrogen atmosphere, continued mechanical stirring condition, the three-neck flask for filling mixed solution is placed in
In 70 DEG C of oil baths.Then 5.75g azodiisobutyronitriles (AIBN) are dissolved in 100ml toluene, are then added dropwise in three-neck flask,
Then by resulting mixed solution is in 70 DEG C of constant temperature and continues to keep reaction 10 hours under stirring condition.As reaction is carried out,
Solution viscosity gradually increases.After reaction terminates, most of solvent is removed under reduced pressure first, viscous product is obtained, then will be resulting
Viscous product add in 300ml isopropanols, after being well mixed, obtain the viscous product of water white transparency, point liquid produces low molecule
Weight polymers homopolymer ionic liquid：Poly- (bromination 1- vinyl -3- octylimidazoles salt).
Embodiment 9：It is prepared by low-molecular weight polymer terpolymer ionomer liquid：Poly- (bromination 1- vinyl -3- hexyl imidazoliums
Salt-co- bromination 4- vinyl -3- butyl-pyridiniums salt)
In three-neck flask, the bromination 1- vinyl -3- hexyl imidazoliums salt and 20g that are prepared in 40g embodiments 6 are implemented
The bromination 4- vinyl -3- butyl-pyridinium salt prepared in example 7 is dissolved in 250ml dry toluenes, then, in nitrogen atmosphere, continues
Under mechanical agitation, the three-neck flask for filling mixed solution is placed in 70 DEG C of oil baths.Then by 6.0g azodiisobutyronitriles
(AIBN) be dissolved in 100ml toluene, be then added dropwise in three-neck flask, then by resulting mixed solution in 70 DEG C of constant temperature,
And continue to keep reaction 10 hours under stirring condition.As reaction is carried out, solution viscosity gradually increases.After reaction terminates, first
Most of solvent is removed under reduced pressure, viscous product is obtained, then adds resulting viscous product in 300ml isopropanols, mixing
After uniform, the viscous product of water white transparency is obtained, point liquid produces low-molecular weight polymer terpolymer ionomer liquid：Poly- (bromination 1-
Vinyl -3- hexyl imidazolium salt-co- bromination 4- vinyl -3- butyl-pyridiniums salt).
Embodiment 10：Diglycolamine (DGA) intercalation α-ZrP
In two vials, 0.2g α-ZrP-3M and 25g diglycolamine (CAS No. are separately added into：929-06-6) simultaneously
It is well mixed, obtained mixture is carried out to ultrasonication (frequency 40KHz, power 150W) respectively 8 hours and 12 hours, obtained
To product be designated as DGA- α-ZrP-3M-8h and DGA- α-ZrP-3M-12h respectively.
After ultrasonication, obtain two blend samples are subjected to centrifuge washing at least three times using ethanol, then,
In under normal temperature condition, the product that washing is obtained is dried under reduced pressure, and obtains the α-ZrP-3M powder of DGA intercalations.Obtained DGA
The high-resolution XRD spectrum of the α-ZrP-3M powder of intercalation is shown in Fig. 3.
Embodiment 11：α-ZrP the powder of DGA intercalations is in the liquid brominated 1- methyl -3- octylimidazole salt of small molecular ion
Middle carry out lift-off processing
In 25ml vials, it will be obtained in DGA- α-ZrP-3M-8h and the 20g embodiment 2 obtained in 0.1g embodiments 10
The liquid brominated 1- methyl -3- octylimidazoles salt mixing of small molecular ion obtained, by obtained mixture ultrasonication (frequency
40KHz, power 150W) 3 hours, the paste mixture peeled off then is obtained by ultracentrifugation, the end-product is designated as DGA-
Ionic-α-ZrP-3M.Obtained DGA-Ionic- α-ZrP-3M high-resolution XRD spectrum is shown in Fig. 3.
Embodiment 12：Prepare the α-ZrP- small molecular ion liquid 1- methyl -3- octylimidazole salt mixtures peeled off
Step (1)：
In 100ml vial, α-ZrP-3M and 50g diglycolamines (CAS No. prepared by 0.4g embodiments 1：
929-06-6) mix, then by obtained mixture ultrasonication (frequency 40KHz, power 150W) 8 hours.Then, utilize
Ethanol then under normal temperature condition, obtained product is subtracted the mixture centrifuge washing after ultrasonication at least 3 times
Press dry dry, obtain the α-ZrP-3M powder of DGA intercalations.
Step (2)：
In 15ml vials, the α-ZrP-3M and 12g of DGA intercalations prepared by 0.04g the present embodiment above-mentioned steps (1)
The liquid brominated 1- methyl -3- octylimidazoles salt mixing of small molecular ion obtained in embodiment 2, and obtained mixture is surpassed
Sonicated (frequency 40KHz, power 150W) 3 hours, produces the α-ZrP ionic liquid mixtures of stripping.
Embodiment 13：Prepare peel off α-ZrP- low-molecular weight polymer terpolymer ionomer liquid it is poly- (bromination 1- vinyl-
3- hexyl imidazolium salt-co- bromination 4- vinyl -3- butyl-pyridiniums salt) mixture
Step (1)：Monoethanolamine (MEA) intercalation α-ZrP
In two vials, 0.2g α-ZrP-3M and 20g monoethanolamine (CAS No. are separately added into：141-43-5) and mix
Close uniform, obtained mixture is carried out to ultrasonication (frequency 40KHz, power 150W) respectively 8 hours and 12 hours, obtained
Product be designated as MEA- α-ZrP-3M-8h and MEA- α-ZrP-3M-12h respectively.
After ultrasonication, obtain two blend samples are subjected to centrifuge washing at least three times using ethanol, then,
In under normal temperature condition, the product that washing is obtained is dried under reduced pressure, and obtains the α-ZrP-3M powder of MEA intercalations.
Step (2)：α-ZrP the powder of MEA intercalations is in poly- (the bromination 1- ethene of low-molecular weight polymer terpolymer ionomer liquid
Base -3- hexyl imidazolium salt-co- bromination 4- vinyl -3- butyl-pyridiniums salt) lift-off processing is carried out in mixture
In 25ml vials, the MEA- α-ZrP-3M-8h and 30g that will be obtained in 0.1g the present embodiment above-mentioned steps (1)
Poly- (the bromination 1- vinyl -3- hexyl imidazolium salt-co- of low-molecular weight polymer terpolymer ionomer liquid obtained in embodiment 9
Bromination 4- vinyl -3- butyl-pyridiniums salt) mixing, by obtained mixture ultrasonication (frequency 40KHz, power 150W)
4.5 hours, the paste mixture of stripping then can be obtained by ultracentrifugation, the end-product be designated as MEA-Ionic- α-
ZrP-3M。
Embodiment 14：Tribology tester
According to ASTM D4172 testing standards, by the α-ZrP- small molecular ion liquid of the stripping prepared in embodiment 12
Body 1- methyl -3- octylimidazoles salt mixture and commodity full formula lubricating oil purchased in market carry out four-ball wear test, four ball millings
Damage test principle sketch and see Fig. 4.In four-ball wear test, the surface of lubricant grease immersion ball and disk sample, experiment parameter
It is shown in Table 1.
Table 1：Four-ball wear test parameter
| Parameter | Pattern/value |
| Testing standard | Four balls are tested |
| Temperature | 75±2℃ |
| Speed | 600rpm |
| Duration | 240min |
| Load | 147±0.05N |
| Sample ball material | Stainless steel |
In four-ball wear test, the α-ZrP ionic liquid mixtures of the stripping prepared in embodiment 12 are have detected
With the friction coefficient μ, Wear track depth Z, polishing scratch size of commercially available commodity full formula lubricating oil, testing result is shown in Fig. 5-Fig. 8.Experiment
As a result show, the friction coefficient μs of the α-ZrP ionic liquid mixtures of the stripping prepared in embodiment 12, Wear track depth Z,
Polishing scratch size is significantly less than commercial lubricating oil, and this shows the α-ZrP ionic liquid mixtures of stripping according to embodiments of the present invention
Can be effective for preparing lubricating oil.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or the spy that the embodiment or example are described
Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the not be the same as Example or the feature of example and non-be the same as Example or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
1. one kind prepares the phosphatic method of single-layer metal, it is characterised in that including：
Hydramine and layered metal phosphates are mixed, resulting mixture is subjected to ultrasonication, ultrasonically treated production is obtained
Thing；
The ultrasonically treated product is centrifuged, precipitated；
Centrifuge washing is carried out to the precipitation using ethanol, washed product is obtained；
In under normal temperature condition, the washed product is dried under reduced pressure, intercalation material is obtained；
The intercalation material and ionic liquid are mixed, ultrasonication is carried out to resulting mixture, with to the intercalation
Material carries out lift-off processing, obtains single-layer metal phosphate.
2. according to the method described in claim 1, it is characterised in that the hydramine is mono amino alcohol or polyetheramine monoamine,
Optionally, the topological structure of the mono amino alcohol or polyetheramine monoamine be linear, star, annular or its combine,
Optionally, the molecular weight of the hydramine is 50~5000.
3. method according to claim 2, it is characterised in that the molecular weight of the hydramine is 500~5000.
4. according to the method in claim 2 or 3, it is characterised in that the hydramine is selected from monoethanolamine, aminopropanol, ammonia
Base butanol, diglycolamine, three (methylol) aminomethanes, polyethylene glycol monoamine, polypropylene glycol monoamine and PolyTHF monoamine
At least one of.
5. according to the method described in claim 1, it is characterised in that layered metal phosphate be selected from alpha zirconium phosphate, θ-
At least one of basic zirconium phosphate and γ-basic zirconium phosphate.
6. according to the method described in claim 1, it is characterised in that the ionic liquid is small molecule organic ion liquid or poly-
Compound ionic liquid,
Wherein, the ionic liquid contains anion and organic cation；
Optionally, the anion is halide ion；
Optionally, the organic cation contains nitrogen, phosphorus or sulphur.
7. method according to claim 6, it is characterised in that the anion is chlorion or bromide ion.
8. method according to claim 6, it is characterised in that the ionic liquid is small molecule organic ion liquid, and
And the organic cation is selected from least one of following：Imidazole salts, pyrazoles salt, thiazole salt, pyridiniujm, pyrroles
Alkane salt, pyrimidine salt, pyridazine salt, piperidinium salt, quinolinium, isoquinolin salt, pyrazoline salt, thiazoline salt,
At least one of oxazoline salt, triazoline Yan, phosphonium salts and sulfonium salt,
Or,
The ionic liquid is polymer ions liquid, and the polymer ions liquid is used selected from least one following
Monomer prepare：Vinylpyridine salt, vinylpiperidine salt, vinylquinoline salt, diallyl ammonium salt, N- ethene
Base imidazole salts, vinyl pyrazoles salt and vinylthiazole salt.
9. method according to claim 8, it is characterised in that the organic cation have the following chemical structure formula it
One:
Wherein, R, R1, R2, R3, R4And R5Alkyl or alkoxy are each independently, the alkyl is C1-C22Alkyl, the alkane
Epoxide is C1-C22Alkoxy.
10. method according to claim 8, it is characterised in that the polymer ions liquid is to use to possess followingization
Learn the monomer preparation of one of structure：
Wherein, R, R1And R2Alkyl or alkoxy are each independently,
Optionally, the alkyl is C1-C22Alkyl, the alkoxy is C1-C22Alkoxy.
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| WO2017088188A1 (en) * | 2015-11-27 | 2017-06-01 | 深圳纳伟力科技有限公司 | Lubricating oil antiwear agent, lubricating oil composite agent, lubricating oil and use |
| WO2017152347A1 (en) * | 2016-03-07 | 2017-09-14 | 南方科技大学 | Laminated nano-particle, peeling method and application |
| CN105800579B (en) * | 2016-03-07 | 2019-01-18 | 南方科技大学 | A kind of layered nanoparticulate, stripping means and application |
| CN109336076B (en) * | 2018-11-13 | 2020-07-28 | 华南理工大学 | Green and efficient method for stripping layered zirconium phosphate |
| JP7231153B2 (en) * | 2019-05-08 | 2023-03-01 | 学校法人常翔学園 | Latent curing catalyst and resin composition containing the same |
| CN110484020B (en) * | 2019-09-17 | 2021-06-18 | 南方科技大学 | Slurry and preparation method and application thereof |
| CN110499205B (en) * | 2019-09-17 | 2022-03-25 | 南方科技大学 | Oil-soluble slurry dispersed with graphene oxide, and preparation method and application thereof |
| CN110591294B (en) * | 2019-09-30 | 2021-09-21 | 华南理工大学 | Modified zirconium phosphate-epoxy nanocomposite and preparation method thereof |
| CN111204728B (en) * | 2020-03-10 | 2021-09-24 | 辽宁盛泽精细化工科技有限公司 | Preparation method of ultrathin two-dimensional vanadium phosphorus oxygen composite metal oxide nanosheet |
| CN114426898B (en) * | 2021-12-29 | 2023-03-31 | 太原理工大学 | Lubricating grease compound additive and lubricating grease composition prepared from same |
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