CN105129755A - Method for preparing single-layer metal phosphate and application thereof - Google Patents
Method for preparing single-layer metal phosphate and application thereof Download PDFInfo
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- CN105129755A CN105129755A CN201510555574.XA CN201510555574A CN105129755A CN 105129755 A CN105129755 A CN 105129755A CN 201510555574 A CN201510555574 A CN 201510555574A CN 105129755 A CN105129755 A CN 105129755A
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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
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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
- 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
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- 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
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- 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 invention provides a method for preparing single-layer metal phosphate and application thereof. The method comprises the steps that 1, intercalation treatment is performed on layered metal phosphate through alkylol amine to obtain an intercalation material; 2, stripping treatment is performed on the intercalation material in ionic liquid to obtain the single-layer metal phosphate. Through the method, the single-layer metal phosphate can be effectively prepared, the method is easy to operate, convenient and rapid, and the prepared single-layer metal phosphate mixture can be used for preparing high-performance lubricating oil or high-performance composite materials.
Description
Technical field
The present invention relates to field of material technology, particularly, relate to and prepare the phosphatic method of single-layer metal and application thereof, more specifically, relate to and prepare the phosphatic method of single-layer metal, and single-layer metal phosphoric acid salt is preparing the purposes in lubricating oil.
Background technology
Fusing point is called ionic liquid usually lower than the salt of 100 degrees Celsius, and in general, it is made up of organic cation (organic cation particularly containing nitrogen, phosphorus or sulphur) and weakly coordinating anion.
In fact, ionic liquid mainly quaternary ammonium salt, quaternary alkylphosphonium salt or sulfonium salt.1992, first UBE Industries Ltd. invents a kind of by the method for the clay dispersion of quaternary ammonium salts in polyamide material (US5102948 (A)), shows extraordinary performance when the matrix material obtained is applied to bumper.Inspire by this, US Patent No. 2014/0005415 (A1) utilizes quaternary ammonium salt chlorination 1-butyl-3-Methylimidazole to insert laminar alpha zirconium phosphate (α-ZrP, Zr (HPO
4)
2h
2o), corresponding intercalation material is obtained.
But above-mentioned intercalation method limits the further application of lamellar compound in high performance material, thus, the method that sheet metal phosphoric acid salt can be made to peel off is needed.With regard to relevant knowledge and experience, in existing research, only have TBAH (TBA) that stratiform α-ZrP can be made in water-soluble medium to peel off, but, because TBA is a kind of alkali of instability and its alkalescence is too strong, it is not suitable in commercialization matrix material for stripped laminar α-ZrP.Polyetheramine monoamine (PEA-M) can stripped laminar α-ZrP in acetone, but in the product peeled off, the mass ratio of PEA-M is too large, significantly can reduce the intensity of matrix material, make the most products obtained almost cannot apply in polymer composites (such as epoxy resin composite material) thus.
Thus, at present about stripped laminar metal phosphate method and application still have much room for improvement.
Summary of the invention
The present invention is intended to solve one of technical problem in correlation technique at least to a certain extent.For this reason, one object of the present invention be to propose a kind of can in ionic liquid the method for stripped laminar metal phosphate, peel off the mixture that product formed in ionic liquid and can directly apply to lubricating oil or polymer composites.
In one aspect of the invention, the invention provides one and prepare the phosphatic method of single-layer metal.According to embodiments of the invention, the method comprises: (1) utilizes hydramine to carry out intercalation processing to layered metal phosphates, to obtain intercalation material; And (2) carry out lift-off processing to described intercalation material in ionic liquid, to obtain single-layer metal phosphoric acid salt.Contriver finds, method of the present invention is utilized to peel off layered metal phosphates fast and effectively, thus prepare single-layer metal phosphoric acid salt, and the method step is simple, processing ease, with low cost, be easy to realize suitability for industrialized production, the single-layer metal phosphoric acid salt simultaneously prepared can be effective to prepare lubricating oil, high performance composite etc., show good performance, extend the further application of single-layer metal phosphoric acid salt in high performance material.
According to embodiments of the invention, hydramine is preferably mono amino alcohol or polyetheramine monoamine.
According to embodiments of the invention, the topological framework of mono amino alcohol or polyetheramine monoamine is linear, star, annular or its combination.
According to embodiments of the invention, the molecular weight of hydramine is 50 ~ 5000, is preferably 500 ~ 5000,
According to embodiments of the invention, hydramine for being selected from thanomin, aminopropanol, amino butanol, diglycolamine, three (methylol) aminomethane, polyoxyethylene glycol monoamine, at least one in polypropylene glycol monoamine and polytetrahydrofuran monoamine.
According to embodiments of the invention, at least one of layered metal phosphates preferably in alpha zirconium phosphate, θ-zirconium phosphate and γ-zirconium phosphate.
According to embodiments of the invention, step (1) comprising: by hydramine and layered metal phosphates mixing, obtained mixture is carried out ultrasonication, obtains supersound process product; Supersound process product is carried out centrifugal, is precipitated; Utilize ethanol to carry out centrifuge washing to precipitation, obtain washed product; Under normal temperature condition, washed product is carried out drying under reduced pressure, obtains intercalation material.
According to embodiments of the invention, in step (2), lift-off processing is undertaken by following steps: the intercalation material obtained and ionic liquid are mixed, then obtained mixture is carried out ultrasonication.
According to embodiments of the invention, ionic liquid is small molecules organic ion liquid or polymer ions liquid, and wherein, ionic liquid contains negatively charged ion and organic cation.According to embodiments of the invention, negatively charged ion is preferably halide-ions, more preferably chlorion or bromide anion.According to embodiments of the invention, organic cation contains nitrogen, phosphorus or sulphur.
According to embodiments of the invention, ionic liquid is small molecules organic ion liquid, and organic cation be selected from following one of at least: imidazole salts, pyrazoles salt, thiazole salt, pyridinium salt, pyrrolidinium, pyrimidine salt, pyridazine salt, piperidinium salt, quinolinium, isoquinoline 99.9 salt, pyrazoline salt, thiazoline Yan, oxazoline salt, triazoline Yan, phosphonium salt and sulfonium salt.Preferred organic cation has and is selected from one of following structural formula:
Wherein, R, R
1, R
2, R
3, R
4and R
5be alkyl or alkoxyl group independently of one another.According to embodiments of the invention, above-mentioned alkyl is C
1-C
22alkyl, above-mentioned alkoxyl group is C
1-C
22alkoxyl group.
According to embodiments of the invention, ionic liquid is polymer ions liquid, and described polymer ions liquid adopts to be selected from following monomer one of at least and to prepare: vinyl pyridine salt, vinylpiperidine salt, vinylquinoline salt, diallyl ammonium salt, N-vinyl imidazole salt, vinyl pyrazoles salt and vinylthiazole salt.Concrete, polymer ions liquid is preferably and adopts the monomer possessing one of the following chemical structure to prepare:
Wherein, R, R
1and R
2be alkyl or alkoxyl group independently of one another.According to embodiments of the invention, above-mentioned alkyl is C
1-C
22alkyl, above-mentioned alkoxyl group is C
1-C
22alkoxyl group.
In another aspect of this invention, the invention provides a kind of single-layer metal phosphoric acid salt.According to embodiments of the invention, this single-layer metal phosphoric acid salt is prepared by foregoing method.Contriver finds, this single-layer metal phosphoric acid salt can effectively be applied to prepares lubricating oil or high performance composite, when being particularly applied to lubricating oil, has lower frictional coefficient and lower abrasion loss, shows excellent friction resistant performance.
In another aspect of the invention, the invention provides foregoing single-layer metal phosphoric acid salt and preparing the purposes in lubricating oil.Contriver finds, by above-mentioned single-layer metal phosphoric acid salt for the preparation of lubricating oil, obtains friction coefficient of lubricating oil less less with abrasion loss, shows good wear resisting property, can significantly improve the result of use of lubricating oil.
In still another aspect of the invention, the invention provides a kind of lubricating oil.According to embodiments of the invention, this lubricating oil contains foregoing single-layer metal phosphoric acid salt.According to this lubricating oil of the embodiment of the present invention, there is lower frictional coefficient and lower abrasion loss, possess good friction resistant performance, show the performance being better than existing goods lubricating oil.
Accompanying drawing explanation
Fig. 1 shows the XRD figure spectrum of the α-ZrP-3M prepared in the embodiment of the present invention;
Fig. 2 shows the TEM photo of the α-ZrP-3M prepared in the embodiment of the present invention;
Fig. 3 shows the high resolving power XRD figure spectrum of the paste DGA-α-ZrP-3M-12h of intercalation DGA-α-ZrP-3M-12h and the stripping prepared in the embodiment of the present invention;
Fig. 4 shows in the embodiment of the present invention structural representation sketch using four-ball tribotester;
Fig. 5 show peel off in the embodiment of the present invention α-ZrP ionic liquid mixture, commercial lubricating oil time m-frictional coefficient correlation curve;
Fig. 6 show peel off in the embodiment of the present invention α-ZrP ionic liquid mixture, commercial lubricating oil time m-Wear track depth correlation curve;
After Fig. 7 shows and carries out four-ball wear test to the α-ZrP ionic liquid mixture peeled off in the embodiment of the present invention, the polishing scratch size of wearing test ball;
After Fig. 8 shows and carries out wearing test to a kind of commercial lubricating oil, the polishing scratch size of wearing test ball.
Embodiment
Embodiments of the invention are described below in detail.Embodiment described below is exemplary, only for explaining the present invention, and can not be interpreted as limitation of the present invention.Unreceipted concrete technology or condition in embodiment, according to the technology described by the document in this area or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercial acquisition.
In one aspect of the invention, the invention provides one and prepare the phosphatic method of single-layer metal.According to embodiments of the invention, the method comprises the following steps:
(1) hydramine is utilized to carry out intercalation processing to layered metal phosphates, to obtain intercalation material.
According to embodiments of the invention, hydramine can be mono amino alcohol or polyetheramine monoamine.Thus, hydramine can overcome the intermolecular interaction of layered metal phosphates interlayer effectively, inserts the interlayer of layered metal phosphates, obtains intercalation material, can improve the efficiency obtaining intercalation material and intercalation effect simultaneously.
According to embodiments of the invention, the topological framework of mono amino alcohol or polyetheramine monoamine can be linear, star, annular or its combination.Many experimental results shows, has the interlayer that the mono amino alcohol of above topology structure or polyetheramine monoamine all effectively can insert layered metal phosphates, insert effect better, and it is higher to insert efficiency.
According to embodiments of the invention, the molecular weight of the hydramine of employing can be 50 ~ 5000.Thus, be conducive to the interlayer that hydramine inserts layered metal phosphates, and then improve insertion efficiency and insert effect.If the molecular weight of hydramine is too high or too low, insert efficiency and insert effect all not very good.Under preferable case, the molecular weight of the hydramine of employing can be 500 ~ 5000.Insert effect thereby, it is possible to improve further and insert efficiency, and the intercalation material performance obtained is desirable, is conducive to the carrying out of subsequent step.
According to a preferred embodiment of the invention, hydramine can for being selected from thanomin, aminopropanol, amino butanol, diglycolamine, three (methylol) aminomethane, polyoxyethylene glycol monoamine, at least one in polypropylene glycol monoamine and polytetrahydrofuran monoamine.Thus, be conducive to improving the efficiency obtaining intercalation material, the intercalation material performance of acquisition is desirable, is conducive to the carrying out of subsequent step.
According to embodiments of the invention, at least one of layered metal phosphates preferably in alpha zirconium phosphate, θ-zirconium phosphate and γ-zirconium phosphate.Thus, be conducive to improving the efficiency obtaining intercalation material, the intercalation material performance of acquisition is desirable, is conducive to the carrying out of subsequent step.In addition, adopt above-mentioned layered metal phosphates, the end product of acquisition can be further used for preparing lubricating oil and high performance composite, is with a wide range of applications.According to embodiments of the invention, the preferred diameter of layered metal phosphates is less than the flake nano particle of 4000 nanometers, thus, can improve the performance of intercalation material and end product further.
According to embodiments of the invention, step (1) may further include: by layered metal phosphates and hydramine mixing, obtained mixture is carried out ultrasonication and obtains supersound process product; Then, supersound process product is carried out centrifugal, is precipitated; Utilize ethanol to carry out centrifuge washing to precipitation, obtain washed product; Under normal temperature condition, washed product is carried out drying under reduced pressure, obtains intercalation material.Thereby, it is possible to fast and effeciently hydramine to be inserted into the interlayer of layered metal phosphates, obtain the good intercalation material of performance, and simple to operate, convenient and swift, be easy to realize.In this step, pass through ultrasonication, hydramine effectively can be made to insert the interlayer of layered metal phosphates, obtain intercalation material, wherein, power and the time of supersound process are not particularly limited, those skilled in the art can select according to actual needs flexibly, and in some embodiments of the invention, the frequency of supersound process can be 40 ~ 80KHz, power can be 100 ~ 300W, and the time can be 2 ~ 15 hours.By centrifuge washing, effectively can remove residual hydramine and other impurity, and it will be understood by those skilled in the art that centrifuge washing can carry out one or many, until excessive hydramine and other impurity clean up, can next step be carried out.By drying under reduced pressure, cleaning solvent ethanol effectively can be made to volatilize, obtain intercalation material free from foreign meter, and then be conducive to the carrying out of subsequent step.
According to embodiments of the invention, in step (1), the add-on of hydramine is excessive, and under preferable case, according to molar ratio meter, hydramine is excessive is 10%.Thus, the productive rate improving intercalation efficiency and intercalation material is conducive to.
(2) in ionic liquid, lift-off processing is carried out to intercalation material, to obtain single-layer metal phosphoric acid salt.
According to embodiments of the invention, in step (2), lift-off processing is undertaken by the mixture of intercalation material and ionic liquid is carried out ultrasonication.Wherein, power and the time of supersound process are not particularly limited, and those skilled in the art can select according to actual needs flexibly, in some embodiments of the invention, the frequency of supersound process can be 40 ~ 80KHz, and 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 single-layer metal phosphoric acid salt that performance is desirable.
According to embodiments of the invention, ionic liquid can be small molecules organic ion liquid or polymer ions liquid, and wherein, ionic liquid contains negatively charged ion and organic cation.According to embodiments of the invention, negatively charged ion is preferably halide-ions, and under further preferable case, negatively charged ion can be chlorion or bromide anion.According to embodiments of the 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 phosphoric acid salt.
According to embodiments of the invention, ionic liquid is small molecules organic ion liquid, and organic cation be selected from following one of at least: imidazole salts, pyrazoles salt, thiazole salt, pyridinium salt, pyrrolidinium, pyrimidine salt, pyridazine salt, piperidinium salt, quinolinium, isoquinoline 99.9 salt, pyrazoline salt, thiazoline Yan, oxazoline salt, triazoline Yan, phosphonium salt and sulfonium salt.Under preferable case, organic cation has and is selected from following structural formula one of at least:
Wherein, R, R
1, R
2, R
3, R
4and R
5be alkyl or alkoxyl group independently of one another.According to embodiments of the invention, above-mentioned alkyl is C
1-C
22alkyl, above-mentioned alkoxyl group is C
1-C
22alkoxyl group, wherein, C
1-C
22alkyl include but not limited to optional replace methyl, ethyl, propyl group, butyl (normal-butyl, isobutyl-, the tertiary butyl), amyl group, hexyl, octyl group, vinyl, propenyl etc., C
1-C
22alkoxyl group includes but not limited to the optional methoxyl group, oxyethyl group, propoxy-, butoxy etc. that replace.It will be understood by those skilled in the art that and above-mentionedly only list C
1-C
22alkyl and C
1-C
22some concrete examples of alkoxyl group, protection scope of the present invention is not limited to this, and carbonatoms is that the alkyl of 1-22 and alkoxyl group are all within protection scope of the present invention.Thereby, it is possible to effectively layered metal phosphates is peeled off as single-layer metal phosphoric acid salt, and simple to operate, convenient, the method can not limit the phosphatic further application of single-layer metal of acquisition simultaneously, and it can be applied in lubricating oil, high performance composite.
According to embodiments of the invention, ionic liquid is polymer ions liquid, and described polymer ions liquid adopts to be selected from following monomer one of at least and to prepare: vinyl pyridine salt, vinylpiperidine salt, vinylquinoline salt, diallyl ammonium salt, N-vinyl imidazole salt, vinyl pyrazoles salt and vinylthiazole salt.Concrete, polymer ions liquid is preferably and adopts the monomer possessing one of the following chemical structure to prepare:
Wherein, R, R
1and R
2be alkyl or alkoxyl group independently of one another.According to embodiments of the invention, above-mentioned alkyl is C
1-C
22alkyl, above-mentioned alkoxyl group is C
1-C
22alkoxyl group, wherein, C
1-C
22alkyl include but not limited to optional replace methyl, ethyl, propyl group, butyl (normal-butyl, isobutyl-, the tertiary butyl), amyl group, hexyl, octyl group, vinyl, propenyl etc., C
1-C
22alkoxyl group includes but not limited to the optional methoxyl group, oxyethyl group, propoxy-, butoxy etc. that replace.It will be understood by those skilled in the art that and above-mentionedly only list C
1-C
22alkyl and C
1-C
22some concrete examples of alkoxyl group, protection scope of the present invention is not limited to this, and carbonatoms is that the alkyl of 1-22 and alkoxyl group are all within protection scope of the present invention.Thereby, it is possible to effectively layered metal phosphates is peeled off as single-layer metal phosphoric acid salt, and simple to operate, convenient, the method can not limit the phosphatic further application of single-layer metal of acquisition simultaneously, and it can be applied in lubricating oil, high performance composite.
Contriver finds, utilize method of the present invention can prepare single-layer metal phosphoric acid salt fast and effectively, and the method step is simple, processing ease, with low cost, be easy to realize suitability for industrialized production, the single-layer metal phosphoric acid salt simultaneously prepared can be effective to prepare lubricating oil, high performance composite etc., all show good performance, extend the further application of single-layer metal phosphoric acid salt in high performance material.
It should be noted that, utilization is the form of mixtures of single-layer metal phosphoric acid salt and ionic liquid according to the single-layer metal phosphoric acid salt that the method for the embodiment of the present invention prepares, when being applied to lubricating oil, matrix material etc., be also directly use with the form of mixtures of single-layer metal phosphoric acid salt and ionic liquid.In addition, the single-layer metal phosphoric acid salt prepared according to the method for the embodiment of the present invention is utilized to be single-layer metal phosphate nano sheet.
In another aspect of this invention, the invention provides a kind of single-layer metal phosphoric acid salt.According to embodiments of the invention, this single-layer metal phosphoric acid salt is prepared by foregoing method.Contriver finds, this single-layer metal phosphoric acid salt can effectively be applied to prepares lubricating oil or high performance composite, when being particularly applied to lubricating oil, has lower frictional coefficient and lower abrasion loss, shows good friction resistant performance.
In another aspect of the invention, the invention provides foregoing single-layer metal phosphoric acid salt and preparing the purposes in lubricating oil.Contriver finds, by above-mentioned single-layer metal phosphoric acid salt for the preparation of lubricating oil, obtains friction coefficient of lubricating oil less less with abrasion loss, shows good wear resisting property, can significantly improve the result of use of lubricating oil.
In still another aspect of the invention, the invention provides a kind of lubricating oil.According to embodiments of the invention, this lubricating oil contains foregoing single-layer metal phosphoric acid salt.According to this lubricating oil of the embodiment of the present invention, have lower frictional coefficient and less abrasion loss, good friction resistant performance, shows the performance being better than existing goods lubricating oil.
Embodiments of the invention are described below in detail.
Embodiment 1: the preparation of alpha zirconium phosphate
By 8.0gZrOCl
2.8H
2o and 80.0ml concentration is 3.0mol/LH
3pO
4(85%wt) mix, the mixture obtained is sealed in the pressurized vessel of teflon lined, and be heated to 200 degrees Celsius of maintenances 24 hours, obtain reaction product α-ZrP, be designated as α-ZrP-3M.After reaction terminates, the reaction product obtained is washed rear also collected by centrifugation 5 times, then, by the α-ZrP-3M dry 24h at 65 DEG C obtained.Utilize mortar by dried α-ZrP-3M grind into powder.XRD (X-ray diffraction) spectrogram of the α-ZrP-3M powder obtained is shown in Fig. 1, and Fig. 2 is shown in by TEM photo.
Embodiment 2: the preparation of small molecular ion liquid: bromination 1-methyl-3-octylimidazole salt
In three-necked flask, 74.574g1-Methylimidazole (CASNo.:616-47-7) is dissolved in 100ml anhydrous propanone, then, under nitrogen atmosphere, Keep agitation condition, the three-necked flask filling mixing solutions is placed in 85 DEG C of oil baths, then by 192.969g n-octane bromide (with molar amount, excessive about 10%, CASNo.:111-83-1) add in three-necked flask, then obtained mixing solutions is kept reaction 12 ~ 24 hours under 85 DEG C of constant temperature and Keep agitation condition.Along with reaction is carried out, reaction solution gradually becomes faint yellow, after reaction terminates, rotary evaporation in vacuo is except desolventizing, obtain viscosity weak yellow liquid shape or slurry shape product, then obtained sticky product is added in 1000ml ethyl acetate, after mixing, obtain water white sticky product, obtain bromination 1-methyl-3-octylimidazole salt.
Embodiment 3: the preparation of small molecular ion liquid: bromination 1-methyl-3-hexyl pyridinium salt
In three-necked flask, 79.10g pyridine (CASNo.:110-86-1) is dissolved in 100ml anhydrous propanone, then, under nitrogen atmosphere, Keep agitation condition, the three-necked flask filling mixing solutions is placed in 85 DEG C of oil baths, then by 181.588g bromo normal hexane (with molar amount, excessive about 10%, CASNo.:111-25-1) add in three-necked flask, then obtained mixing solutions is kept reaction 12 ~ 24 hours under 85 DEG C of constant temperature and Keep agitation condition.Along with reaction is carried out, reaction solution gradually becomes faint yellow, after reaction terminates, rotary evaporation in vacuo is except desolventizing, obtain viscosity weak yellow liquid shape or slurry shape product, then obtained sticky product is added in 1000ml ethyl acetate, after mixing, obtain water white sticky product, obtain bromination 1-methyl-3-hexyl pyridinium salt.
Embodiment 4: the preparation of small molecular ion liquid: bromination 1-butyl quinolinium
In three-necked flask, 129.16g quinoline (CASNo.:91-22-5) is dissolved in 200ml anhydrous propanone, then, under nitrogen atmosphere, Keep agitation condition, the three-necked flask filling mixing solutions is placed in 85 DEG C of oil baths, then by 150.733g bromination of n-butane (with molar amount, excessive about 10%, CASNo.:109-65-9) add in three-necked flask, then obtained mixing solutions is kept reaction 12 ~ 24 hours under 85 DEG C of constant temperature and Keep agitation condition.Along with reaction is carried out, reaction solution gradually becomes faint yellow, after reaction terminates, rotary evaporation in vacuo is except desolventizing, obtain viscosity weak yellow liquid shape or slurry shape product, then obtained sticky product is added in 1000ml ethyl acetate, after mixing, obtain water white sticky product, obtain bromination 1-butyl quinolinium.
Embodiment 5: the preparation of small molecular ion liquid: bromination 1-vinyl-3-octylimidazole salt
In three-necked flask, 94.11gN-vinyl imidazole (CASNo.:1072-63-5) is dissolved in 200ml anhydrous propanone, then, under nitrogen atmosphere, Keep agitation condition, the three-necked flask filling mixing solutions is placed in 85 DEG C of oil baths, then by 212.443g n-octane bromide (with molar amount, excessive about 10%, CASNo.:111-83-1) add in three-necked flask, then obtained mixing solutions is kept reaction 12 ~ 24 hours under 85 DEG C of constant temperature and Keep agitation condition.Along with reaction is carried out, reaction solution gradually becomes faint yellow, after reaction terminates, rotary evaporation in vacuo is except desolventizing, obtain viscosity weak yellow liquid shape or slurry shape product, then obtained sticky product is added in 1000ml ethyl acetate, after mixing, obtain water white sticky product, obtain bromination 1-vinyl-3 octylimidazole salt.
Embodiment 6: the preparation of small molecular ion liquid: bromination 1-vinyl-3-hexyl imidazolium salt
In three-necked flask, 94.11g1-vinyl imidazole (CASNo.:1072-63-5) is dissolved in 100ml anhydrous propanone, then, under nitrogen atmosphere, Keep agitation condition, the three-necked flask filling mixing solutions is placed in 85 DEG C of oil baths, then by 181.588g bromo normal hexane (with molar amount, excessive about 10%, CASNo.:111-25-1) add in three-necked flask, then obtained mixing solutions is kept reaction 12 ~ 24 hours under 85 DEG C of constant temperature and Keep agitation condition.Along with reaction is carried out, reaction solution gradually becomes faint yellow, after reaction terminates, rotary evaporation in vacuo is except desolventizing, obtain viscosity weak yellow liquid shape or slurry shape product, then obtained sticky product is added in 1000ml ethyl acetate, after mixing, obtain water white sticky product, obtain 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-necked flask, 105.14g4-vinyl pyridine (CASNo.:100-43-6) is dissolved in 100ml anhydrous propanone, then, under nitrogen atmosphere, Keep agitation condition, the three-necked flask filling mixing solutions is placed in 85 DEG C of oil baths, then by 150.733g bromination of n-butane (with molar amount, excessive about 10%, CASNo.:109-65-9) add in three-necked flask, then obtained mixing solutions is kept reaction 12 ~ 24 hours under 85 DEG C of constant temperature and Keep agitation condition.Along with reaction is carried out, reaction solution gradually becomes faint yellow, after reaction terminates, rotary evaporation in vacuo is except desolventizing, obtain viscosity weak yellow liquid shape or slurry shape product, then obtained sticky product is added in 1000ml ethyl acetate, after mixing, obtain water white sticky product, obtain bromination 4-vinyl-3-butyl-pyridinium salt.
Embodiment 8: prepared by low-molecular weight polymer homopolymer ionic liquid: poly-(bromination 1-vinyl-3-octylimidazole salt)
In three-necked flask, bromination 1-vinyl-3 octylimidazole salt of preparation in 57.5g embodiment 5 is dissolved in 250ml dry toluene, then, under nitrogen atmosphere, continued mechanical agitation condition, the three-necked flask filling mixing solutions is placed in 70 DEG C of oil baths.Then 5.75g Diisopropyl azodicarboxylate (AIBN) is dissolved in 100ml toluene, is then added dropwise in three-necked flask, then obtained mixing solutions is kept reaction 10 hours under 70 DEG C of constant temperature and Keep agitation condition.Along with reaction is carried out, soltion viscosity increases gradually.After reaction terminates, first the most of solvent of decompression removing, obtain viscous product, then obtained viscous product is added in 300ml Virahol, after mixing, obtain water white viscous product, namely separatory obtains low-molecular weight polymer homopolymer ionic liquid: poly-(bromination 1-vinyl-3-octylimidazole salt).
Embodiment 9: prepared by low-molecular weight polymer terpolymer ionomer liquid: poly-(bromination 1-vinyl-3-hexyl imidazolium salt-co-bromination 4-vinyl-3-butyl-pyridinium salt)
In three-necked flask, the bromination 4-vinyl-3-butyl-pyridinium salt of preparation in the bromination 1-vinyl-3-hexyl imidazolium salt of preparation in 40g embodiment 6 and 20g embodiment 7 is dissolved in 250ml dry toluene, then, under nitrogen atmosphere, continued mechanical agitation condition, the three-necked flask filling mixing solutions is placed in 70 DEG C of oil baths.Then 6.0g Diisopropyl azodicarboxylate (AIBN) is dissolved in 100ml toluene, is then added dropwise in three-necked flask, then obtained mixing solutions is kept reaction 10 hours under 70 DEG C of constant temperature and Keep agitation condition.Along with reaction is carried out, soltion viscosity increases gradually.After reaction terminates, first the most of solvent of decompression removing, obtain viscous product, then obtained viscous product is added in 300ml Virahol, after mixing, obtain water white viscous product, namely separatory obtains low-molecular weight polymer terpolymer ionomer liquid: poly-(bromination 1-vinyl-3-hexyl imidazolium salt-co-bromination 4-vinyl-3-butyl-pyridinium salt).
Embodiment 10: diglycolamine (DGA) intercalation α-ZrP
In two vials, add 0.2g α-ZrP-3M and 25g diglycolamine (CASNo.:929-06-6) respectively and mix, the mixture obtained is carried out ultrasonication (frequency 40KHz respectively, power 150W) 8 hours and 12 hours, the product obtained is designated as DGA-α-ZrP-3M-8h and DGA-α-ZrP-3M-12h respectively.
After ultrasonication, utilize ethanol that two blend sample obtained are carried out centrifuge washing at least three times, then, under normal temperature condition, carrying out drying under reduced pressure by washing the product obtained, obtaining the α-ZrP-3M powder of DGA intercalation.The high resolving power XRD figure spectrum of the α-ZrP-3M powder of the DGA intercalation obtained is shown in Fig. 3.
α-ZrP the powder of embodiment 11:DGA intercalation carries out lift-off processing in the liquid brominated 1-methyl of small molecular ion-3-octylimidazole salt
In 25ml vial, by the liquid brominated 1-methyl of the small molecular ion-3-octylimidazole salt mixing obtained in the DGA-α-ZrP-3M-8h obtained in 0.1g embodiment 10 and 20g embodiment 2, by mixture ultrasonication (the frequency 40KHz obtained, power 150W) 3 hours, then obtained the paste mixture peeled off by ultracentrifugation, this end product is designated as DGA-Ionic-α-ZrP-3M.The high resolving power XRD figure spectrum of the DGA-Ionic-α-ZrP-3M obtained is shown in Fig. 3.
Embodiment 12: the α-ZrP-small molecular ion liquid 1-methyl-3-octylimidazole salt mixture that preparation is peeled off
Step (1):
In the vial of 100ml, the α-ZrP-3M prepare 0.4g embodiment 1 and 50g diglycolamine (CASNo.:929-06-6) mixing, then by the mixture ultrasonication (frequency 40KHz, power 150W) that obtains 8 hours.Then, utilize ethanol by the mixture centrifuge washing after ultrasonication at least 3 times, then under normal temperature condition, the product obtained is carried out drying under reduced pressure, obtain the α-ZrP-3M powder of DGA intercalation.
Step (2):
In 15ml vial, the liquid brominated 1-methyl of the small molecular ion-3-octylimidazole salt mixing obtained in the α-ZrP-3M of DGA intercalation prepared by 0.04g the present embodiment above-mentioned steps (1) and 12g embodiment 2, and mixture ultrasonication (the frequency 40KHz that will obtain, power 150W) 3 hours, obtain the α-ZrP ionic liquid mixture of stripping.
Embodiment 13: poly-(bromination 1-vinyl-3-hexyl imidazolium salt-co-bromination 4-vinyl-3-butyl-pyridinium salt) mixture of α-ZrP-low-molecular weight polymer terpolymer ionomer liquid that preparation is peeled off
Step (1): thanomin (MEA) intercalation α-ZrP
In two vials, add 0.2g α-ZrP-3M and 20g thanomin (CASNo.:141-43-5) respectively and mix, the mixture obtained is carried out ultrasonication (frequency 40KHz respectively, power 150W) 8 hours and 12 hours, the product obtained is designated as MEA-α-ZrP-3M-8h and MEA-α-ZrP-3M-12h respectively.
After ultrasonication, utilize ethanol that two blend sample obtained are carried out centrifuge washing at least three times, then, under normal temperature condition, carrying out drying under reduced pressure by washing the product obtained, obtaining the α-ZrP-3M powder of MEA intercalation.
Step (2): the α-ZrP powder of MEA intercalation carries out lift-off processing in poly-(the bromination 1-vinyl-3-hexyl imidazolium salt-co-bromination 4-vinyl-3-butyl-pyridinium salt) mixture of low-molecular weight polymer terpolymer ionomer liquid
In 25ml vial, by low-molecular weight polymer terpolymer ionomer liquid poly-(the bromination 1-vinyl-3-hexyl imidazolium salt-co-bromination 4-vinyl-3-butyl-pyridinium salt) mixing obtained in the MEA-α-ZrP-3M-8h obtained in 0.1g the present embodiment above-mentioned steps (1) and 30g embodiment 9, by mixture ultrasonication (the frequency 40KHz obtained, power 150W) 4.5 hours, then can be obtained the paste mixture of stripping by ultracentrifugation, this end product is designated as MEA-Ionic-α-ZrP-3M.
Embodiment 14: tribology tester
According to ASTMD4172 testing standard, α-ZrP-small molecular ion liquid 1-methyl-3-octylimidazole the salt mixture of the stripping prepared in embodiment 12 and commercial commodity full formula lubricating oil are carried out four-ball wear test, and Fig. 4 is shown in by four-ball wear test principle sketch.In four-ball wear test, lubricating grease immerses the surface of ball and disk sample, and experiment parameter is in table 1.
Table 1: four-ball wear test parameter
| Parameter | Pattern/value |
| Testing standard | Four ball tests |
| Temperature | 75±2℃ |
| Speed | 600rpm |
| Time length | 240min |
| Load | 147±0.05N |
| Sample ball material | Stainless steel |
In four-ball wear test, have detected the α-ZrP ionic liquid mixture of the stripping prepared in embodiment 12 and coefficientoffrictionμ, Wear track depth Z, the polishing scratch size of commercially available commodity full formula lubricating oil, detected result is shown in Fig. 5-Fig. 8.Test-results shows, the coefficientoffrictionμ of the α-ZrP ionic liquid mixture of the stripping prepared in embodiment 12, Wear track depth Z, polishing scratch size are significantly less than commercial lubricating oil, and this shows can be effective to prepare lubricating oil according to the α-ZrP ionic liquid mixture of the stripping of the embodiment of the present invention.
In the description of this specification sheets, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not must for be identical embodiment or example.And the specific features of description, structure, material or feature can combine in one or more embodiment in office or example in an appropriate manner.In addition, when not conflicting, the feature of the different embodiment described in this specification sheets or example and different embodiment or example can carry out combining and combining by those skilled in the art.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, and those of ordinary skill in the art can change above-described embodiment within the scope of the invention, revises, replace and modification.
Claims (10)
1. prepare the phosphatic method of single-layer metal, it is characterized in that, comprising:
(1) utilize hydramine to carry out intercalation processing to layered metal phosphates, obtain intercalation material;
(2) then in ionic liquid, lift-off processing is carried out to described intercalation material, obtain single-layer metal phosphoric acid salt.
2. method according to claim 1, is characterized in that, described hydramine is mono amino alcohol or polyetheramine monoamine,
Optionally, the topological framework of described mono amino alcohol or polyetheramine monoamine is linear, star, annular or its combination,
Optionally, the molecular weight of described hydramine is 50 ~ 5000, is preferably 500 ~ 5000,
Preferably, described hydramine for being selected from thanomin, aminopropanol, amino butanol, diglycolamine, three (methylol) aminomethane, polyoxyethylene glycol monoamine, at least one in polypropylene glycol monoamine and polytetrahydrofuran monoamine.
3. method according to claim 1, is characterized in that, layered metal phosphate is be selected from least one in alpha zirconium phosphate, θ-zirconium phosphate and γ-zirconium phosphate.
4. method according to claim 1, is characterized in that, step (1) comprising:
By described hydramine and the mixing of layered metal phosphate, obtained mixture is carried out ultrasonication, obtains supersound process product;
Described supersound process product is carried out centrifugal, is precipitated;
Utilize ethanol to carry out centrifuge washing to described precipitation, obtain washed product;
Under normal temperature condition, described washed product is carried out drying under reduced pressure, obtain described intercalation material.
5. method according to claim 1, is characterized in that, in step (2), described lift-off processing is undertaken by following steps: by described intercalation material and the mixing of described ionic liquid, carry out ultrasonication to obtained mixture.
6. method according to claim 1, is characterized in that, described ionic liquid is small molecules organic ion liquid or polymer ions liquid,
Wherein, described ionic liquid contains negatively charged ion and organic cation;
Optionally, described negatively charged ion is halide-ions, is preferably chlorion or bromide anion;
Optionally, described organic cation contains nitrogen, phosphorus or sulphur.
7. method according to claim 6, it is characterized in that, described ionic liquid is small molecules organic ion liquid, and described organic cation be selected from following one of at least: at least one in imidazole salts, pyrazoles salt, thiazole salt, pyridinium salt, pyrrolidinium, pyrimidine salt, pyridazine salt, piperidinium salt, quinolinium, isoquinoline 99.9 salt, pyrazoline salt, thiazoline Yan, oxazoline salt, triazoline Yan, phosphonium salt and sulfonium salt, described organic cation preferably has one of the following chemical structure formula:
Wherein, R, R
1, R
2, R
3, R
4and R
5be alkyl or alkoxyl group independently of one another;
Or,
Described ionic liquid is polymer ions liquid, and described polymer ions liquid adopts to be selected from following monomer one of at least and to prepare: vinyl pyridine salt, vinylpiperidine salt, vinylquinoline salt, diallyl ammonium salt, N-vinyl imidazole salt, vinyl pyrazoles salt and vinylthiazole salt
Preferred described polymer ions liquid adopts the monomer possessing one of the following chemical structure to prepare:
Wherein, R, R
1and R
2be alkyl or alkoxyl group independently of one another,
Optionally, described alkyl is C
1-C
22alkyl, described alkoxyl group is C
1-C
22alkoxyl group.
8. a single-layer metal phosphoric acid salt, is characterized in that, is to be prepared by the method according to any one of claim 1-7.
9. single-layer metal phosphoric acid salt according to claim 8 is preparing the purposes in lubricating oil.
10. a lubricating oil, is characterized in that, containing single-layer metal phosphoric acid salt according to claim 8.
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