WO2017035879A1 - Method for preparing single-layer metal phosphate and applications thereof - Google Patents

Method for preparing single-layer metal phosphate and applications thereof Download PDF

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WO2017035879A1
WO2017035879A1 PCT/CN2015/090253 CN2015090253W WO2017035879A1 WO 2017035879 A1 WO2017035879 A1 WO 2017035879A1 CN 2015090253 W CN2015090253 W CN 2015090253W WO 2017035879 A1 WO2017035879 A1 WO 2017035879A1
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salt
ionic liquid
metal phosphate
group
vinyl
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PCT/CN2015/090253
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French (fr)
Chinese (zh)
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雍怀松
孙大陟
夏方青
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南方科技大学
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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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to the field of materials, and in particular to a method for preparing a single layer of metal phosphate and its use, and more particularly to a method for preparing a single layer of metal phosphate, and a use of a single layer of metal phosphate in the preparation of a lubricating oil. .
  • Salts having a melting point below 100 degrees Celsius are often referred to as ionic liquids and, in general, are composed of organic cations (especially organic cations containing nitrogen, phosphorus or sulfur) and weakly coordinating anions.
  • the ionic liquid is primarily a quaternary ammonium salt, a quaternary phosphonium salt or a phosphonium salt.
  • Japan Ube Industries Co., Ltd. first invented a method of dispersing quaternary ammonium intercalated clay in a polyamide material (US Pat. No. 5,102,948 (A)). The obtained composite material was very useful when applied to automobile bumpers. Good performance.
  • US Patent US 2014/0005415 uses a quaternary ammonium salt of 1-butyl-3-methylimidazolium chloride to insert a layered ⁇ -zirconium phosphate ( ⁇ -ZrP, Zr(HPO 4 ) 2 ⁇ H 2 O), the corresponding intercalation material is obtained.
  • the present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, it is an object of the present invention to provide a process for stripping a layered metal phosphate in an ionic liquid, the mixture of which is formed in an ionic liquid, which can be directly applied to a lubricating oil or a polymer composite.
  • the invention provides a method of making a single layer of metal phosphate.
  • the method comprises: (1) intercalating a layered metal phosphate with an alcohol amine to obtain an intercalation material; and (2) stripping the intercalation material in an ionic liquid Treatment to obtain a single layer of metal phosphate.
  • the method of the invention can quickly and effectively strip the layered metal phosphate to prepare a single layer of metal phosphate, and the method has the advantages of simple steps, easy operation, low cost, easy industrialized production, and preparation.
  • Single-layer metal phosphates can be effectively used in the preparation of lubricating oils, high-performance composites, etc., exhibiting good performance and extending the further application of single-layer metal phosphates in high-performance materials.
  • the alkanolamine is preferably a monoamino alcohol or a polyetheramine monoamine.
  • the topology of the monoamino alcohol or polyetheramine monoamine is linear, star, ring or a combination thereof.
  • the alcoholamine has a molecular weight of 50 to 5,000, preferably 500 to 5,000.
  • the alkanolamine is selected from the group consisting of ethanolamine, aminopropanol, aminobutanol, diglycolamine, tris(hydroxymethyl)aminomethane, polyethylene glycol monoamine, polypropylene glycol monoamine and polytetrahydrofuran. At least one of the monoamines.
  • the layered metal phosphate is preferably at least one selected from the group consisting of ⁇ -zirconium phosphate, ⁇ -zirconium phosphate, and ⁇ -zirconium phosphate.
  • the step (1) comprises: mixing an alcohol amine and a layered metal phosphate, subjecting the obtained mixture to ultrasonic treatment to obtain a sonicated product; centrifuging the sonicated product to obtain a precipitate; using ethanol The precipitate was subjected to centrifugal washing to obtain a washed product; under normal temperature conditions, the washed product was dried under reduced pressure to obtain an intercalation material.
  • the peeling treatment is carried out by mixing the obtained intercalation material and the ionic liquid, and then subjecting the resulting mixture to ultrasonic treatment.
  • the ionic liquid is a small molecule organic ionic liquid or a polymeric ionic liquid, wherein the ionic liquid contains an anion and an organic cation.
  • the anion is preferably a halide ion, further preferably a chloride ion or a bromide ion.
  • the organic cation contains nitrogen, phosphorus or sulfur.
  • the ionic liquid is a small molecule organic ionic liquid
  • the organic cation is at least one selected from the group consisting of an imidazolium salt, a pyrazolium salt, a thiazolium salt, a pyridinium salt, a pyrrolidinium salt, Pyrimidinium salt, pyridazinium salt, piperidinium salt, quinolinium salt, isoquinolinium salt, pyrazolinium salt, thiazolinium salt, oxazolinium salt, triazoline salt, barium Salt and barium salts.
  • the organic cation has a structural formula selected from one of the following:
  • R, R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrocarbon group or an alkoxy group.
  • the above hydrocarbon group is a C 1 - C 22 hydrocarbon group
  • the above alkoxy group is a C 1 - C 22 alkoxy group.
  • the ionic liquid is a polymer ionic liquid prepared by using a monomer selected from at least one of the group consisting of vinyl pyridinium salt, vinyl piperidinium salt, and vinyl group.
  • a monomer selected from at least one of the group consisting of vinyl pyridinium salt, vinyl piperidinium salt, and vinyl group.
  • the polymer ionic liquid is preferably prepared using a monomer having one of the following chemical structures:
  • R, R 1 and R 2 are each independently a hydrocarbon group or an alkoxy group.
  • the above hydrocarbon group is a C 1 - C 22 hydrocarbon group
  • the above alkoxy group is a C 1 - C 22 alkoxy group.
  • the invention provides a single layer metal phosphate.
  • the monolayer of metal phosphate is prepared by the method described above. The inventors have found that the single-layer metal phosphate can be effectively applied to the preparation of lubricating oil or high-performance composite materials, especially when applied to lubricating oils, having a low coefficient of friction and a low amount of wear, exhibiting excellent anti-friction. performance.
  • the invention provides the use of a single layer of metal phosphate as described above for the preparation of a lubricating oil.
  • the inventors have found that the above-mentioned single-layer metal phosphate is used for preparing lubricating oil, and the lubricating oil has a small friction coefficient and a small amount of wear, exhibits good wear resistance, and can significantly improve the use effect of the lubricating oil.
  • the invention provides a lubricating oil.
  • the lubricating oil contains the single layer metal phosphate described above.
  • the lubricating oil according to the embodiment of the present invention has a lower friction coefficient and a lower wear amount, has better anti-friction performance, and exhibits performance superior to that of the existing commercial lubricating oil.
  • Figure 1 shows an XRD pattern of ⁇ -ZrP-3M prepared in the examples of the present invention
  • Figure 2 shows a TEM photograph of ⁇ -ZrP-3M prepared in the examples of the present invention
  • Figure 3 shows a high resolution XRD pattern of intercalated DGA- ⁇ -ZrP-3M-12h and exfoliated creamy DGA- ⁇ -ZrP-3M-12h prepared in the examples of the present invention
  • Figure 4 is a schematic view showing the structure of a four-ball abrasion tester used in an embodiment of the present invention
  • Figure 5 shows the time-friction of the peeled ⁇ -ZrP ionic liquid mixture and commercial lubricating oil in the embodiment of the present invention. Coefficient comparison curve;
  • Figure 6 is a graph showing the time-wear depth comparison curve of the peeled ⁇ -ZrP ionic liquid mixture and the commercial lubricating oil in the embodiment of the present invention
  • Figure 7 is a graph showing the wear scar size of the abrasion test ball after the four-ball abrasion test of the peeled ⁇ -ZrP ionic liquid mixture in the embodiment of the present invention.
  • Figure 8 shows the wear scar size of the wear test ball after a wear test of a commercial lubricating oil.
  • the invention provides a method of making a single layer of metal phosphate. According to an embodiment of the invention, the method comprises the steps of:
  • the layered metal phosphate is intercalated with an alcoholamine to obtain an intercalation material.
  • the alkanolamine may be a monoamino alcohol or a polyether amine monoamine.
  • the alkanolamine can effectively overcome the intermolecular interaction between the layered metal phosphate layers, intercalate between the layers of the layered metal phosphate to obtain the intercalation material, and at the same time improve the efficiency and intercalation of the intercalation material. effect.
  • the topology of the monoamino alcohol or polyetheramine monoamine may be linear, star, ring or a combination thereof.
  • the alcoholamine used may have a molecular weight of 50 to 5,000. Thereby, it is advantageous to insert the alcohol amine into the interlayer of the layered metal phosphate, thereby improving the insertion efficiency and the insertion effect. If the molecular weight of the alcoholamine is too high or too low, the insertion efficiency and the insertion effect are not very satisfactory.
  • the alcoholamine used may have a molecular weight of from 500 to 5,000. Thereby, the insertion effect and the insertion efficiency can be further improved, and the obtained intercalation material is ideal in performance, which is advantageous for the subsequent steps.
  • the alkanolamine may be selected from the group consisting of ethanolamine, aminopropanol, aminobutanol, diglycolamine, tris(hydroxymethyl)aminomethane, polyethylene glycol monoamine, polypropylene glycol monoamine and At least one of polytetrahydrofuran monoamines. Therefore, the efficiency of obtaining the intercalation material is improved, and the obtained intercalation material has an ideal performance, which is favorable for the subsequent steps.
  • the layered metal phosphate is preferably selected from the group consisting of ⁇ -zirconium phosphate, ⁇ -zirconium phosphate, and ⁇ -zirconium phosphate.
  • the efficiency of obtaining the intercalation material is improved, and the obtained intercalation material has an ideal performance, which is favorable for the subsequent steps.
  • the obtained final product can be further used for preparing lubricating oil and high-performance composite materials, and has broad application prospects.
  • the layered metal phosphate is preferably a sheet-like nanoparticle having a diameter of less than 4000 nm, whereby the properties of the intercalation material and the final product can be further improved.
  • the step (1) may further comprise: mixing the layered metal phosphate and the alcohol amine, subjecting the obtained mixture to ultrasonic treatment to obtain a sonicated product; and then, centrifuging the sonicated product to obtain a precipitate
  • the precipitate was subjected to centrifugal washing with ethanol to obtain a washed product; under normal temperature conditions, the washed product was dried under reduced pressure to obtain an intercalation material.
  • the alcohol amine can be quickly and efficiently inserted between the layers of the layered metal phosphate to obtain a better intercalation material, and the operation is simple, convenient, and easy to implement.
  • the alcohol amine can be effectively inserted between the layers of the layered metal phosphate to obtain an intercalation material
  • the power and time of the ultrasonic treatment are not particularly limited, and those skilled in the art can according to actual needs.
  • the frequency of the ultrasonic treatment may be 40 to 80 KHz
  • the power may be 100 to 300 W
  • the time may be 2 to 15 hours.
  • the residual alcoholamine and other impurities can be effectively removed by centrifugation, and it will be understood by those skilled in the art that the centrifugal washing can be carried out one or more times until the excess alcoholamine and other impurities are cleaned, and the next step can be carried out.
  • the washing solvent can be effectively volatilized to obtain an intercalation material containing no impurities, which is advantageous for the subsequent steps.
  • the amount of the alkanolamine added is an excess, and preferably, the molar excess of the alcoholamine is 10% in terms of a molar ratio.
  • the intercalation material is subjected to a release treatment in an ionic liquid to obtain a single layer of metal phosphate.
  • the peeling treatment is performed by ultrasonically treating a mixture of the intercalation material and the ionic liquid.
  • the power and time of the ultrasonic processing are not particularly limited, and those skilled in the art can flexibly select according to actual needs.
  • the frequency of the ultrasonic processing may be 40-80 KHz, and the power may be 100-300 W.
  • the time can be 2 to 15 hours.
  • the ionic liquid may be a small molecule organic ionic liquid or a polymer ionic liquid, wherein the ionic liquid contains an anion and an organic cation.
  • the anion is preferably a halide ion, and further preferably, the anion may be a chloride ion or a bromide ion.
  • the organic cation contains nitrogen, phosphorus or sulfur.
  • the ionic liquid is a small molecule organic ionic liquid
  • the organic cation is selected from the group consisting of At least one of the columns: imidazolium salt, pyrazolium salt, thiazolium salt, pyridinium salt, pyrrolidinium salt, pyrimidine salt, pyridazinium salt, piperidinium salt, quinolinium salt, isoquinoline Anthracene salts, pyrazolinium salts, thiazolinium salts, oxazolinium salts, triazolinium salts, phosphonium salts and phosphonium salts.
  • the organic cation has a structural formula selected from at least one of the following:
  • R, R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrocarbon group or an alkoxy group.
  • the above hydrocarbon group is a C 1 -C 22 hydrocarbon group
  • the above alkoxy group is a C 1 -C 22 alkoxy group
  • the C 1 -C 22 hydrocarbon group includes, but is not limited to, an optionally substituted methyl group, Ethyl, propyl, butyl (n-butyl, isobutyl, tert-butyl), pentyl, hexyl, octyl, vinyl, propenyl, etc.
  • C 1 -C 22 alkoxy including but not limited to A substituted methoxy, ethoxy, propoxy, butoxy group or the like is selected.
  • the ionic liquid is a polymer ionic liquid prepared by using a monomer selected from at least one of the group consisting of vinyl pyridinium salt, vinyl piperidinium salt, and vinyl group.
  • a monomer selected from at least one of the group consisting of vinyl pyridinium salt, vinyl piperidinium salt, and vinyl group.
  • the polymer ionic liquid is preferably prepared using a monomer having one of the following chemical structures:
  • R, R 1 and R 2 are each independently a hydrocarbon group or an alkoxy group.
  • the above hydrocarbon group is a C 1 -C 22 hydrocarbon group
  • the above alkoxy group is a C 1 -C 22 alkoxy group
  • the C 1 -C 22 hydrocarbon group includes, but is not limited to, an optionally substituted methyl group, Ethyl, propyl, butyl (n-butyl, isobutyl, tert-butyl), pentyl, hexyl, octyl, vinyl, propenyl, etc.
  • C 1 -C 22 alkoxy including but not limited to A substituted methoxy, ethoxy, propoxy, butoxy group or the like is selected.
  • the inventors have found that the single-layer metal phosphate can be obtained quickly and efficiently by the method of the invention, and the method has the advantages of simple steps, easy operation, low cost and easy industrialized production, and the single-layer metal phosphate obtained can be effectively used. It has shown good performance in the preparation of lubricating oils, high-performance composite materials, etc., and has expanded the further application of single-layer metal phosphates in high-performance materials.
  • the single-layer metal phosphate prepared by the method according to the embodiment of the present invention is in the form of a mixture of a single-layer metal phosphate and an ionic liquid, and is applied to a lubricating oil, a composite material, etc.
  • the mixture of the layer metal phosphate and the ionic liquid is used as it is.
  • the single-layer metal phosphate obtained by the method according to the embodiment of the present invention is a single-layer metal phosphate nanosheet.
  • the invention provides a single layer metal phosphate.
  • the monolayer of metal phosphate is prepared by the method described above. The inventors have found that the single-layer metal phosphate can be effectively applied to the preparation of lubricating oil or high-performance composite materials, especially when applied to lubricating oils, having a low coefficient of friction and a low amount of wear, showing good resistance. Friction performance.
  • the invention provides the use of a single layer of metal phosphate as described above for the preparation of a lubricating oil.
  • the inventors have found that the above-mentioned single-layer metal phosphate is used for preparing lubricating oil, and the lubricating oil has a small friction coefficient and a small amount of wear, exhibits good wear resistance, and can significantly improve the use effect of the lubricating oil.
  • the invention provides a lubricating oil.
  • the lubricating oil contains the single layer metal phosphate described above.
  • the lubricating oil according to the embodiment of the present invention has a lower friction coefficient and a smaller amount of wear, better anti-friction performance, and exhibits superior performance to existing commercial lubricating oils.
  • Example 2 Preparation of a small molecule ionic liquid: 1-methyl-3-octyl imidazolium bromide salt
  • Example 3 Preparation of a small molecule ionic liquid: 1-methyl-3-hexylpyridinium bromide salt
  • Example 5 Preparation of a small molecule ionic liquid: 1-vinyl-3-octyl imidazolium bromide salt
  • the solvent is removed by evaporation in vacuo to give a viscous pale yellow liquid or slurry product, and then the obtained viscous product is added to 1000 ml of ethyl acetate and mixed. After homogenization, a colorless, transparent, viscous product is obtained, that is, a 1-vinyl-3-octyl imidazolium bromide salt is obtained.
  • Example 6 Preparation of a small molecule ionic liquid: 1-vinyl-3-hexyl imidazolium bromide salt
  • the solvent is removed by evaporation in vacuo to give a viscous pale yellow liquid or slurry product, and then the obtained viscous product is added to 1000 ml of ethyl acetate and mixed. After homogenization, a colorless, transparent, viscous product is obtained, that is, a 1-vinyl-3-hexylimidazolium bromide salt is obtained.
  • Example 7 Preparation of a small molecule ionic liquid: 4-vinyl-3-butylpyridinium bromide salt
  • Example 8 Preparation of a low molecular weight polymer homopolymer ionic liquid: poly(1-vinyl-3-octyl imidazolium bromide)
  • Example 9 Preparation of a low molecular weight polymer copolymer ionic liquid: poly(1-vinyl-3-hexylimidazolium bromide-co-bromo-4-vinyl-3-butylpyridinium salt)
  • Example 6 40 g of the 1-vinyl-3-hexylimidazolium bromide salt prepared in Example 6 and 20 g of the 4-vinyl-3-butylpyridinium bromide salt prepared in Example 7 were dissolved in a three-necked flask.
  • the three-necked flask containing the mixed solution was placed in a 70 ° C oil bath under 250 ml of anhydrous toluene, and then under a nitrogen atmosphere under continuous mechanical stirring.
  • the obtained two mixture samples were subjected to centrifugal washing at least three times with ethanol, and then, the washed product was dried under reduced pressure at normal temperature to obtain a DGA intercalated ⁇ -ZrP-3M powder.
  • the high resolution XRD pattern of the obtained DGA intercalated ⁇ -ZrP-3M powder is shown in Fig. 3.
  • Example 11 DGA intercalated ⁇ -ZrP powder was stripped in a small molecular ionic liquid brominated 1-methyl-3-octyl imidazolium salt
  • Example 10 0.1 g of DGA- ⁇ -ZrP-3M-8h obtained in Example 10 and 20 g of the small molecule ionic liquid 1-methyl-3-octyl imidazolium bromide obtained in Example 2 in a 25 ml glass vial After mixing, the resulting mixture was ultrasonicated (frequency 40 KHz, power 150 W) for 3 hours, and then a peeled paste mixture was obtained by ultracentrifugation, and the final product was designated as DGA-Ionic- ⁇ -ZrP-3M.
  • the high resolution XRD pattern of the obtained DGA-Ionic- ⁇ -ZrP-3M is shown in Fig. 3.
  • Example 12 Preparation of exfoliated ⁇ -ZrP-small molecule ionic liquid 1-methyl-3-octyl imidazolium salt mixture
  • ⁇ -ZrP-3M prepared in Example 1 0.4 g of ⁇ -ZrP-3M prepared in Example 1 and 50 g of diglycolamine (CAS No.: 929-06-6) were mixed in a 100 ml glass vial, and the resulting mixture was ultrasonicated (frequency 40 KHz, Power 150W) 8 hours. Next, the ultrasonically treated mixture was centrifuged at least 3 times with ethanol, and then the obtained product was dried under reduced pressure at room temperature to obtain a DGA intercalated ⁇ -ZrP-3M powder.
  • Example 13 Preparation of exfoliated ⁇ -ZrP-low molecular weight polymer copolymer ionic liquid poly(1-vinyl-3-hexylimidazolium bromide-co-4-vinyl-3-butylpyridinium bromide) Salt) mixture
  • Step (1) ethanolamine (MEA) intercalation ⁇ -ZrP
  • ⁇ -ZrP-3M and 20 g of ethanolamine were separately added to the two glass vials and uniformly mixed, and the obtained mixture was separately subjected to ultrasonic treatment (frequency 40 KHz, power 150 W) for 8 hours. And 12 hours, the obtained products were recorded as MEA- ⁇ -ZrP-3M-8h and MEA- ⁇ -ZrP-3M-12h, respectively.
  • the obtained two mixture samples were subjected to centrifugal washing at least three times with ethanol, and then, the washed product was dried under reduced pressure at room temperature to obtain MEA intercalated ⁇ -ZrP-3M powder.
  • Step (2) MEA intercalated ⁇ -ZrP powder in low molecular weight polymer copolymer ionic liquid poly(1-vinyl-3-hexyl imidazolium bromide-co-bromo-4-vinyl-3-butyl Stripping treatment in a mixture of pyridinium salts
  • Example 9 In a 25 ml glass vial, 0.1 g of the MEA- ⁇ -ZrP-3M-8h obtained in the above step (1) of the present example and 30 g of the low molecular weight polymer copolymer ionic liquid obtained in Example 9 were poly(brominated 1). -vinyl-3-hexylimidazolium salt-co-bromo 4-vinyl-3-butylpyridinium salt), the resulting mixture was sonicated (frequency 40 KHz, power 150 W) for 4.5 hours, then passed ultra-high speed A stripped paste mixture was obtained by centrifugation and the final product was designated MEA-Ionic- ⁇ -ZrP-3M.

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Abstract

The present invention provides a method for preparing single-layer metal phosphate and applications thereof. The method comprises: (1) carrying out intercalation treatment on layered metal phosphate by means of alkylol amine, so as to obtain an intercalation material; and (2) carrying out stripping treatment on the intercalation material in an ionic liquid, so as to obtain single-layer metal phosphate.

Description

制备单层金属磷酸盐的方法及其应用Method for preparing single layer metal phosphate and application thereof 技术领域Technical field
本发明涉及材料技术领域，具体地，涉及制备单层金属磷酸盐的方法及其应用，更具体地，涉及制备单层金属磷酸盐的方法，以及单层金属磷酸盐在制备润滑油中的用途。The present invention relates to the field of materials, and in particular to a method for preparing a single layer of metal phosphate and its use, and more particularly to a method for preparing a single layer of metal phosphate, and a use of a single layer of metal phosphate in the preparation of a lubricating oil. .
背景技术Background technique
熔点低于100摄氏度的盐通常被叫做离子液体，一般来讲，其由有机阳离子(特别是含有氮、磷或硫的有机阳离子)和弱配位阴离子构成。Salts having a melting point below 100 degrees Celsius are often referred to as ionic liquids and, in general, are composed of organic cations (especially organic cations containing nitrogen, phosphorus or sulfur) and weakly coordinating anions.
实质上，离子液体主要是季铵盐、季鏻盐或锍鎓盐。1992年，日本宇部兴产株式会社首先发明了一种将季铵盐插层的粘土分散于聚酰胺材料中的方法(US5102948(A))，得到的复合材料应用于汽车保险杠时表现出非常好的性能。受此启发，美国专利US2014/0005415(A1)利用季铵盐氯化1-丁基-3-甲基咪唑鎓插入层状α-磷酸锆(α-ZrP,Zr(HPO4)2·H2O)，得到了相应的插层材料。Essentially, the ionic liquid is primarily a quaternary ammonium salt, a quaternary phosphonium salt or a phosphonium salt. In 1992, Japan Ube Industries Co., Ltd. first invented a method of dispersing quaternary ammonium intercalated clay in a polyamide material (US Pat. No. 5,102,948 (A)). The obtained composite material was very useful when applied to automobile bumpers. Good performance. Inspired by this, US Patent US 2014/0005415 (A1) uses a quaternary ammonium salt of 1-butyl-3-methylimidazolium chloride to insert a layered α-zirconium phosphate (α-ZrP, Zr(HPO 4 ) 2 ·H 2 O), the corresponding intercalation material is obtained.
然而，上述插层方法限制了层状化合物在高性能材料中的进一步应用，由此，需要可以使片状金属磷酸盐剥离的方法。就相关知识和经验来说，在已有的研究中，只有四丁基氢氧化铵(TBA)可在水溶性介质中使层状α-ZrP剥离，然而，由于TBA是一种不稳定的碱且其碱性太强，其不适合在商业化复合材料中用于剥离层状α-ZrP。聚醚胺单胺(PEA-M)可以在丙酮中剥离层状α-ZrP，然而在剥离的产品中，PEA-M的质量比太大，会显著降低复合材料的强度，由此使得得到的大多数产品在聚合物复合材料(例如环氧树脂复合材料)中几乎无法应用。However, the above intercalation method limits the further application of the layered compound in a high performance material, and thus, a method which can peel the sheet metal phosphate is required. In terms of knowledge and experience, only tetrabutylammonium hydroxide (TBA) can strip layered α-ZrP in water-soluble media in existing studies, however, since TBA is an unstable base and its Alkaline is too strong, it is not suitable for stripping layered α-ZrP in commercial composites. Polyetheramine monoamine (PEA-M) can strip layered α-ZrP in acetone. However, in the peeled product, the mass ratio of PEA-M is too large, which will significantly reduce the strength of the composite, thereby making the obtained Most products are almost impossible to apply in polymer composites such as epoxy composites.
因而，目前关于剥离层状金属磷酸盐的方法及其应用仍有待改进。Thus, current methods for stripping layered metal phosphates and their applications remain to be improved.
发明内容Summary of the invention
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本发明的一个目的在于提出一种可以在离子液体中剥离层状金属磷酸盐的方法，剥离产物在离子液体中形成的混合物可以直接应用于润滑油或聚合物复合材料。The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, it is an object of the present invention to provide a process for stripping a layered metal phosphate in an ionic liquid, the mixture of which is formed in an ionic liquid, which can be directly applied to a lubricating oil or a polymer composite.
在本发明的一个方面，本发明提供了一种制备单层金属磷酸盐的方法。根据本发明的实施例，该方法包括：(1)利用醇胺对层状金属磷酸盐进行插层处理，以便获得插层材料；以及(2)在离子液体中对所述插层材料进行剥离处理，以便获得单层金属磷酸盐。发明人 发现，利用本发明的方法能够快速有效的对层状金属磷酸盐进行剥离，从而制备获得单层金属磷酸盐，且该方法步骤简单、操作容易、成本低廉、易于实现工业化生产，同时制备获得的单层金属磷酸盐能够有效用于制备润滑油、高性能复合材料等，表现出良好的性能，扩展了单层金属磷酸盐在高性能材料中的进一步应用。In one aspect of the invention, the invention provides a method of making a single layer of metal phosphate. According to an embodiment of the invention, the method comprises: (1) intercalating a layered metal phosphate with an alcohol amine to obtain an intercalation material; and (2) stripping the intercalation material in an ionic liquid Treatment to obtain a single layer of metal phosphate. inventor It has been found that the method of the invention can quickly and effectively strip the layered metal phosphate to prepare a single layer of metal phosphate, and the method has the advantages of simple steps, easy operation, low cost, easy industrialized production, and preparation. Single-layer metal phosphates can be effectively used in the preparation of lubricating oils, high-performance composites, etc., exhibiting good performance and extending the further application of single-layer metal phosphates in high-performance materials.
根据本发明的实施例，醇胺优选为单氨基醇或聚醚胺单胺。According to an embodiment of the invention, the alkanolamine is preferably a monoamino alcohol or a polyetheramine monoamine.
根据本发明的实施例，单氨基醇或聚醚胺单胺的拓扑结构为线形、星形、环形或其组合。According to an embodiment of the invention, the topology of the monoamino alcohol or polyetheramine monoamine is linear, star, ring or a combination thereof.
根据本发明的实施例，醇胺的分子量为50～5000，优选为500～5000，According to an embodiment of the present invention, the alcoholamine has a molecular weight of 50 to 5,000, preferably 500 to 5,000.
根据本发明的实施例，醇胺为选自乙醇胺，氨基丙醇，氨基丁醇，二甘醇胺，三(羟甲基)氨基甲烷，聚乙二醇单胺，聚丙二醇单胺和聚四氢呋喃单胺中的至少一种。According to an embodiment of the invention, the alkanolamine is selected from the group consisting of ethanolamine, aminopropanol, aminobutanol, diglycolamine, tris(hydroxymethyl)aminomethane, polyethylene glycol monoamine, polypropylene glycol monoamine and polytetrahydrofuran. At least one of the monoamines.
根据本发明的实施例，层状金属磷酸盐优选自α-磷酸锆、θ-磷酸锆和γ-磷酸锆中的至少一种。According to an embodiment of the present invention, the layered metal phosphate is preferably at least one selected from the group consisting of α-zirconium phosphate, θ-zirconium phosphate, and γ-zirconium phosphate.
根据本发明的实施例，步骤(1)包括：将醇胺和层状金属磷酸盐混合，将所得到的混合物进行超声波处理，得到超声处理产物；将超声处理产物进行离心，得到沉淀；利用乙醇对沉淀进行离心洗涤，得到洗涤产物；于常温条件下，将洗涤产物进行减压干燥，得到插层材料。According to an embodiment of the present invention, the step (1) comprises: mixing an alcohol amine and a layered metal phosphate, subjecting the obtained mixture to ultrasonic treatment to obtain a sonicated product; centrifuging the sonicated product to obtain a precipitate; using ethanol The precipitate was subjected to centrifugal washing to obtain a washed product; under normal temperature conditions, the washed product was dried under reduced pressure to obtain an intercalation material.
根据本发明的实施例，步骤(2)中，剥离处理是通过以下步骤进行的：将得到的插层材料和离子液体混合，然后将所得到的混合物进行超声波处理。According to an embodiment of the present invention, in the step (2), the peeling treatment is carried out by mixing the obtained intercalation material and the ionic liquid, and then subjecting the resulting mixture to ultrasonic treatment.
根据本发明的实施例，离子液体为小分子有机离子液体或聚合物离子液体，其中，离子液体含有阴离子和有机阳离子。根据本发明的实施例，阴离子优选为卤素离子，进一步优选为氯离子或溴离子。根据本发明的实施例，有机阳离子含有氮、磷或硫。According to an embodiment of the invention, the ionic liquid is a small molecule organic ionic liquid or a polymeric ionic liquid, wherein the ionic liquid contains an anion and an organic cation. According to an embodiment of the invention, the anion is preferably a halide ion, further preferably a chloride ion or a bromide ion. According to an embodiment of the invention, the organic cation contains nitrogen, phosphorus or sulfur.
根据本发明的实施例，离子液体为小分子有机离子液体，并且有机阳离子为选自下列的至少之一：咪唑鎓盐、吡唑鎓盐、噻唑鎓盐、吡啶鎓盐、吡咯烷鎓盐、嘧啶鎓盐、哒嗪鎓盐、哌啶鎓盐、喹啉鎓盐、异喹啉鎓盐、吡唑啉鎓盐、噻唑啉鎓盐、噁唑啉鎓盐、三唑啉鎓盐、鏻鎓盐和锍鎓盐。优选有机阳离子具有选自下列之一的结构式：According to an embodiment of the present invention, the ionic liquid is a small molecule organic ionic liquid, and the organic cation is at least one selected from the group consisting of an imidazolium salt, a pyrazolium salt, a thiazolium salt, a pyridinium salt, a pyrrolidinium salt, Pyrimidinium salt, pyridazinium salt, piperidinium salt, quinolinium salt, isoquinolinium salt, pyrazolinium salt, thiazolinium salt, oxazolinium salt, triazoline salt, barium Salt and barium salts. Preferably, the organic cation has a structural formula selected from one of the following:
Figure PCTCN2015090253-appb-000001
Figure PCTCN2015090253-appb-000001
Figure PCTCN2015090253-appb-000002
Figure PCTCN2015090253-appb-000002
其中，R，R1，R2，R3，R4和R5各自独立地为烃基或者烷氧基。根据本发明的实施例，上述烃基为C1-C22烃基，上述烷氧基为C1-C22烷氧基。Wherein R, R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrocarbon group or an alkoxy group. According to an embodiment of the present invention, the above hydrocarbon group is a C 1 - C 22 hydrocarbon group, and the above alkoxy group is a C 1 - C 22 alkoxy group.
根据本发明的实施例，离子液体为聚合物离子液体，所述聚合物离子液体是采用选自下列至少之一的单体制备的：乙烯基吡啶鎓盐、乙烯基哌啶鎓盐、乙烯基喹啉鎓盐、双烯丙基铵盐、N-乙烯基咪唑鎓盐、乙烯基吡唑鎓盐和乙烯基噻唑鎓盐。具体的，聚合物离子液体优选为采用具备下列化学结构之一的单体制备的：According to an embodiment of the present invention, the ionic liquid is a polymer ionic liquid prepared by using a monomer selected from at least one of the group consisting of vinyl pyridinium salt, vinyl piperidinium salt, and vinyl group. Quinolinium salt, bisallyl ammonium salt, N-vinylimidazolium salt, vinyl pyrazolium salt and vinyl thiazolium salt. Specifically, the polymer ionic liquid is preferably prepared using a monomer having one of the following chemical structures:
Figure PCTCN2015090253-appb-000003
Figure PCTCN2015090253-appb-000003
Figure PCTCN2015090253-appb-000004
Figure PCTCN2015090253-appb-000004
其中，R，R1和R2各自独立地为烃基或者烷氧基。根据本发明的实施例，上述烃基为C1-C22烃基，上述烷氧基为C1-C22烷氧基。Wherein R, R 1 and R 2 are each independently a hydrocarbon group or an alkoxy group. According to an embodiment of the present invention, the above hydrocarbon group is a C 1 - C 22 hydrocarbon group, and the above alkoxy group is a C 1 - C 22 alkoxy group.
在本发明的另一方面，本发明提供了一种单层金属磷酸盐。根据本发明的实施例，该单层金属磷酸盐是通过前面所述的方法制备的。发明人发现，该单层金属磷酸盐能够有效应用于制备润滑油或高性能复合材料，特别是应用于润滑油时，具有较低的摩擦系数和较低的磨损量，表现出优异的抗摩擦性能。In another aspect of the invention, the invention provides a single layer metal phosphate. According to an embodiment of the invention, the monolayer of metal phosphate is prepared by the method described above. The inventors have found that the single-layer metal phosphate can be effectively applied to the preparation of lubricating oil or high-performance composite materials, especially when applied to lubricating oils, having a low coefficient of friction and a low amount of wear, exhibiting excellent anti-friction. performance.
在本发明的再一方面，本发明提供了前面所述的单层金属磷酸盐在制备润滑油中的用途。发明人发现，将上述的单层金属磷酸盐用于制备润滑油，获得润滑油摩擦系数较小和磨损量较小，表现出良好的耐磨性能，能够显著提高润滑油的使用效果。In yet another aspect of the invention, the invention provides the use of a single layer of metal phosphate as described above for the preparation of a lubricating oil. The inventors have found that the above-mentioned single-layer metal phosphate is used for preparing lubricating oil, and the lubricating oil has a small friction coefficient and a small amount of wear, exhibits good wear resistance, and can significantly improve the use effect of the lubricating oil.
在本发明的又一方面，本发明提供了一种润滑油。根据本发明的实施例，该润滑油含有前面所述的单层金属磷酸盐。根据本发明实施例的该润滑油，具有较低的摩擦系数和较低的磨损量，具备较好的抗摩擦性能，表现出优于现有商品润滑油的性能。In yet another aspect of the invention, the invention provides a lubricating oil. According to an embodiment of the invention, the lubricating oil contains the single layer metal phosphate described above. The lubricating oil according to the embodiment of the present invention has a lower friction coefficient and a lower wear amount, has better anti-friction performance, and exhibits performance superior to that of the existing commercial lubricating oil.
附图说明DRAWINGS
图1显示了本发明实施例中制备获得的α-ZrP-3M的XRD图谱；Figure 1 shows an XRD pattern of α-ZrP-3M prepared in the examples of the present invention;
图2显示了本发明实施例中制备获得的α-ZrP-3M的TEM照片；Figure 2 shows a TEM photograph of α-ZrP-3M prepared in the examples of the present invention;
图3显示了本发明实施例中制备获得的插层DGA-α-ZrP-3M-12h和剥离的膏状DGA-α-ZrP-3M-12h的高分辨率XRD图谱；Figure 3 shows a high resolution XRD pattern of intercalated DGA-α-ZrP-3M-12h and exfoliated creamy DGA-α-ZrP-3M-12h prepared in the examples of the present invention;
图4显示了本发明实施例中使用四球磨损试验机的结构示意简图；Figure 4 is a schematic view showing the structure of a four-ball abrasion tester used in an embodiment of the present invention;
图5显示了本发明实施例中剥离的α-ZrP离子液体混合物、商品润滑油的时间-摩擦 系数对比曲线；Figure 5 shows the time-friction of the peeled α-ZrP ionic liquid mixture and commercial lubricating oil in the embodiment of the present invention. Coefficient comparison curve;
图6显示了本发明实施例中剥离的α-ZrP离子液体混合物、商品润滑油的时间-磨痕深度对比曲线；Figure 6 is a graph showing the time-wear depth comparison curve of the peeled α-ZrP ionic liquid mixture and the commercial lubricating oil in the embodiment of the present invention;
图7显示了对本发明实施例中剥离的α-ZrP离子液体混合物进行四球磨损试验后，磨损试验球的磨痕尺寸；Figure 7 is a graph showing the wear scar size of the abrasion test ball after the four-ball abrasion test of the peeled α-ZrP ionic liquid mixture in the embodiment of the present invention;
图8显示了对一种商品润滑油进行磨损试验后，磨损试验球的磨痕尺寸。Figure 8 shows the wear scar size of the wear test ball after a wear test of a commercial lubricating oil.
具体实施方式detailed description
下面详细描述本发明的实施例。下面描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。Embodiments of the present invention are described in detail below. The embodiments described below are illustrative only and are not to be construed as limiting the invention. Where specific techniques or conditions are not indicated in the examples, they are carried out according to the techniques or conditions described in the literature in the art or in accordance with the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are conventional products that can be obtained commercially.
在本发明的一个方面，本发明提供了一种制备单层金属磷酸盐的方法。根据本发明的实施例，该方法包括以下步骤：In one aspect of the invention, the invention provides a method of making a single layer of metal phosphate. According to an embodiment of the invention, the method comprises the steps of:
(1)利用醇胺对层状金属磷酸盐进行插层处理，以便获得插层材料。(1) The layered metal phosphate is intercalated with an alcoholamine to obtain an intercalation material.
根据本发明的实施例，醇胺可以为单氨基醇或聚醚胺单胺。由此，醇胺可以有效地克服层状金属磷酸盐层间的分子间相互作用力，插入层状金属磷酸盐的层间，获得插层材料，同时可以提高获得插层材料的效率和插层效果。According to an embodiment of the invention, the alkanolamine may be a monoamino alcohol or a polyether amine monoamine. Thus, the alkanolamine can effectively overcome the intermolecular interaction between the layered metal phosphate layers, intercalate between the layers of the layered metal phosphate to obtain the intercalation material, and at the same time improve the efficiency and intercalation of the intercalation material. effect.
根据本发明的实施例，单氨基醇或聚醚胺单胺的拓扑结构可以为线形、星形、环形或其组合。大量试验结果表明，具有上述拓扑结构的单氨基醇或聚醚胺单胺均能够有效插入层状金属磷酸盐的层间，插入效果较好，且插入效率较高。According to an embodiment of the invention, the topology of the monoamino alcohol or polyetheramine monoamine may be linear, star, ring or a combination thereof. A large number of experimental results show that the monoamino alcohol or polyetheramine monoamine having the above topology can be effectively inserted into the layers of the layered metal phosphate, and the insertion effect is good, and the insertion efficiency is high.
根据本发明的实施例，采用的醇胺的分子量可以为50～5000。由此，有利于醇胺插入层状金属磷酸盐的层间，进而提高插入效率和插入效果。如果醇胺的分子量过高或过低，插入效率和插入效果均不十分理想。优选情况下，采用的醇胺的分子量可以为500～5000。由此，能够进一步提高插入效果和插入效率，且获得的插层材料性能理想，有利于后续步骤的进行。According to an embodiment of the present invention, the alcoholamine used may have a molecular weight of 50 to 5,000. Thereby, it is advantageous to insert the alcohol amine into the interlayer of the layered metal phosphate, thereby improving the insertion efficiency and the insertion effect. If the molecular weight of the alcoholamine is too high or too low, the insertion efficiency and the insertion effect are not very satisfactory. Preferably, the alcoholamine used may have a molecular weight of from 500 to 5,000. Thereby, the insertion effect and the insertion efficiency can be further improved, and the obtained intercalation material is ideal in performance, which is advantageous for the subsequent steps.
根据本发明的优选实施例，醇胺可以为选自乙醇胺，氨基丙醇，氨基丁醇，二甘醇胺，三(羟甲基)氨基甲烷，聚乙二醇单胺，聚丙二醇单胺和聚四氢呋喃单胺中的至少一种。由此，有利于提高获得插层材料的效率，获得的插层材料性能理想，有利于后续步骤的进行。According to a preferred embodiment of the invention, the alkanolamine may be selected from the group consisting of ethanolamine, aminopropanol, aminobutanol, diglycolamine, tris(hydroxymethyl)aminomethane, polyethylene glycol monoamine, polypropylene glycol monoamine and At least one of polytetrahydrofuran monoamines. Therefore, the efficiency of obtaining the intercalation material is improved, and the obtained intercalation material has an ideal performance, which is favorable for the subsequent steps.
根据本发明的实施例，层状金属磷酸盐优选自α-磷酸锆、θ-磷酸锆和γ-磷酸锆中的至 少一种。由此，有利于提高获得插层材料的效率，获得的插层材料性能理想，有利于后续步骤的进行。此外，采用上述层状金属磷酸盐，获得的终产物可以进一步用于制备润滑油和高性能复合材料，具有广泛的应用前景。根据本发明的实施例，层状金属磷酸盐优选直径小于4000纳米的片状纳米粒子，由此，可以进一步提高插层材料及终产物的性能。According to an embodiment of the present invention, the layered metal phosphate is preferably selected from the group consisting of α-zirconium phosphate, θ-zirconium phosphate, and γ-zirconium phosphate. One less. Therefore, the efficiency of obtaining the intercalation material is improved, and the obtained intercalation material has an ideal performance, which is favorable for the subsequent steps. In addition, with the above-mentioned layered metal phosphate, the obtained final product can be further used for preparing lubricating oil and high-performance composite materials, and has broad application prospects. According to an embodiment of the present invention, the layered metal phosphate is preferably a sheet-like nanoparticle having a diameter of less than 4000 nm, whereby the properties of the intercalation material and the final product can be further improved.
根据本发明的实施例，步骤(1)可以进一步包括：将层状金属磷酸盐和醇胺混合，将所得到的混合物进行超声波处理得到超声处理产物；接着，将超声处理产物进行离心，得到沉淀；利用乙醇对沉淀进行离心洗涤，得到洗涤产物；于常温条件下，将洗涤产物进行减压干燥，得到插层材料。由此，能够快速有效地将醇胺插入到层状金属磷酸盐的层间，获得性能较好的插层材料，且操作简单，方便快捷，易于实现。在该步骤中，通过超声波处理，能够有效使得醇胺插入层状金属磷酸盐的层间，获得插层材料，其中，超声处理的功率与时间不受特别限制，本领域技术人员可以根据实际需要灵活选择，在本发明的一些实施例中，超声处理的频率可以为40～80KHz，功率可以为100～300W，时间可以为2～15小时。通过离心洗涤，能够有效清除残留的醇胺和其他杂质，且本领域技术人员可以理解，离心洗涤可以进行一次或多次，直到过量的醇胺和其他杂质清洗干净，即可进行下一步骤。通过减压干燥，可以有效使得洗涤溶剂乙醇挥发，获得不含杂质的插层材料，进而有利于后续步骤的进行。According to an embodiment of the present invention, the step (1) may further comprise: mixing the layered metal phosphate and the alcohol amine, subjecting the obtained mixture to ultrasonic treatment to obtain a sonicated product; and then, centrifuging the sonicated product to obtain a precipitate The precipitate was subjected to centrifugal washing with ethanol to obtain a washed product; under normal temperature conditions, the washed product was dried under reduced pressure to obtain an intercalation material. Thereby, the alcohol amine can be quickly and efficiently inserted between the layers of the layered metal phosphate to obtain a better intercalation material, and the operation is simple, convenient, and easy to implement. In this step, by ultrasonic treatment, the alcohol amine can be effectively inserted between the layers of the layered metal phosphate to obtain an intercalation material, wherein the power and time of the ultrasonic treatment are not particularly limited, and those skilled in the art can according to actual needs. For flexible selection, in some embodiments of the present invention, the frequency of the ultrasonic treatment may be 40 to 80 KHz, the power may be 100 to 300 W, and the time may be 2 to 15 hours. The residual alcoholamine and other impurities can be effectively removed by centrifugation, and it will be understood by those skilled in the art that the centrifugal washing can be carried out one or more times until the excess alcoholamine and other impurities are cleaned, and the next step can be carried out. By drying under reduced pressure, the washing solvent can be effectively volatilized to obtain an intercalation material containing no impurities, which is advantageous for the subsequent steps.
根据本发明的实施例，在步骤(1)中，醇胺的加入量是过量的，优选情况下，按照摩尔比例计，醇胺过量为10％。由此，有利于提高插层效率和插层材料的产率。According to an embodiment of the present invention, in the step (1), the amount of the alkanolamine added is an excess, and preferably, the molar excess of the alcoholamine is 10% in terms of a molar ratio. Thereby, it is advantageous to increase the intercalation efficiency and the yield of the intercalation material.
(2)在离子液体中对插层材料进行剥离处理，以便获得单层金属磷酸盐。(2) The intercalation material is subjected to a release treatment in an ionic liquid to obtain a single layer of metal phosphate.
根据本发明的实施例，步骤(2)中，剥离处理是通过将插层材料和离子液体的混合物进行超声波处理进行的。其中，超声处理的功率与时间不受特别限制，本领域技术人员可以根据实际需要灵活选择，在本发明的一些实施例中，超声处理的频率可以为40～80KHz，功率可以为100～300W，时间可以为2～15小时。由此，能够在适合的条件下进行剥离处理，获得性能理想的单层金属磷酸盐。According to an embodiment of the present invention, in the step (2), the peeling treatment is performed by ultrasonically treating a mixture of the intercalation material and the ionic liquid. The power and time of the ultrasonic processing are not particularly limited, and those skilled in the art can flexibly select according to actual needs. In some embodiments of the present invention, the frequency of the ultrasonic processing may be 40-80 KHz, and the power may be 100-300 W. The time can be 2 to 15 hours. Thereby, the peeling treatment can be performed under suitable conditions, and a single-layer metal phosphate having excellent properties can be obtained.
根据本发明的实施例，离子液体可以为小分子有机离子液体或聚合物离子液体，其中，离子液体含有阴离子和有机阳离子。根据本发明的实施例，阴离子优选为卤素离子，进一步优选情况下，阴离子可以为氯离子或溴离子。根据本发明的实施例，有机阳离子含有氮、磷或硫。由此，有利于对层状金属磷酸盐进行剥离处理，获得单层金属磷酸盐。According to an embodiment of the present invention, the ionic liquid may be a small molecule organic ionic liquid or a polymer ionic liquid, wherein the ionic liquid contains an anion and an organic cation. According to an embodiment of the invention, the anion is preferably a halide ion, and further preferably, the anion may be a chloride ion or a bromide ion. According to an embodiment of the invention, the organic cation contains nitrogen, phosphorus or sulfur. Thereby, it is advantageous to carry out the release treatment of the layered metal phosphate to obtain a single layer of metal phosphate.
根据本发明的实施例，离子液体为小分子有机离子液体，并且有机阳离子为选自下 列的至少之一：咪唑鎓盐、吡唑鎓盐、噻唑鎓盐、吡啶鎓盐、吡咯烷鎓盐、嘧啶鎓盐、哒嗪鎓盐、哌啶鎓盐、喹啉鎓盐、异喹啉鎓盐、吡唑啉鎓盐、噻唑啉鎓盐、噁唑啉鎓盐、三唑啉鎓盐、鏻鎓盐和锍鎓盐。优选情况下，有机阳离子具有选自下列至少之一的结构式：According to an embodiment of the invention, the ionic liquid is a small molecule organic ionic liquid, and the organic cation is selected from the group consisting of At least one of the columns: imidazolium salt, pyrazolium salt, thiazolium salt, pyridinium salt, pyrrolidinium salt, pyrimidine salt, pyridazinium salt, piperidinium salt, quinolinium salt, isoquinoline Anthracene salts, pyrazolinium salts, thiazolinium salts, oxazolinium salts, triazolinium salts, phosphonium salts and phosphonium salts. Preferably, the organic cation has a structural formula selected from at least one of the following:
Figure PCTCN2015090253-appb-000005
Figure PCTCN2015090253-appb-000005
其中，R，R1，R2，R3，R4和R5各自独立地为烃基或者烷氧基。根据本发明的实施例，上述烃基为C1-C22烃基，上述烷氧基为C1-C22烷氧基，其中，C1-C22烃基包括但不限于任选取代的甲基、乙基、丙基、丁基(正丁基、异丁基、叔丁基)、戊基、己基、辛基、乙烯基、丙烯基等，C1-C22烷氧基包括但不限于任选取代的甲氧基、乙氧基、丙氧基、丁氧基等。本领域技术人员可以理解，上述仅列出了C1-C22烃基和C1-C22烷氧基的一些具体示例，本发明的保护范围并不限于此，碳原子数为1-22的烃基和烷 氧基均在本发明的保护范围之内。由此，能够有效将层状金属磷酸盐剥离为单层金属磷酸盐，且操作简单，方便，同时该方法不会限制获得的单层金属磷酸盐的进一步应用，其可以应用于润滑油、高性能复合材料中。Wherein R, R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrocarbon group or an alkoxy group. According to an embodiment of the present invention, the above hydrocarbon group is a C 1 -C 22 hydrocarbon group, and the above alkoxy group is a C 1 -C 22 alkoxy group, wherein the C 1 -C 22 hydrocarbon group includes, but is not limited to, an optionally substituted methyl group, Ethyl, propyl, butyl (n-butyl, isobutyl, tert-butyl), pentyl, hexyl, octyl, vinyl, propenyl, etc., C 1 -C 22 alkoxy including but not limited to A substituted methoxy, ethoxy, propoxy, butoxy group or the like is selected. It will be understood by those skilled in the art that only the specific examples of the C 1 -C 22 hydrocarbyl group and the C 1 -C 22 alkoxy group are listed above, and the scope of protection of the present invention is not limited thereto, and the number of carbon atoms is 1-22. Both hydrocarbyl and alkoxy groups are within the scope of the present invention. Thereby, the layered metal phosphate can be effectively stripped into a single layer of metal phosphate, and the operation is simple and convenient, and the method does not limit the further application of the obtained single layer metal phosphate, which can be applied to lubricating oil and high. Performance in composite materials.
根据本发明的实施例，离子液体为聚合物离子液体，所述聚合物离子液体是采用选自下列至少之一的单体制备的：乙烯基吡啶鎓盐、乙烯基哌啶鎓盐、乙烯基喹啉鎓盐、双烯丙基铵盐、N-乙烯基咪唑鎓盐、乙烯基吡唑鎓盐和乙烯基噻唑鎓盐。具体的，聚合物离子液体优选为采用具备下列化学结构之一的单体制备的：According to an embodiment of the present invention, the ionic liquid is a polymer ionic liquid prepared by using a monomer selected from at least one of the group consisting of vinyl pyridinium salt, vinyl piperidinium salt, and vinyl group. Quinolinium salt, bisallyl ammonium salt, N-vinylimidazolium salt, vinyl pyrazolium salt and vinyl thiazolium salt. Specifically, the polymer ionic liquid is preferably prepared using a monomer having one of the following chemical structures:
Figure PCTCN2015090253-appb-000006
Figure PCTCN2015090253-appb-000006
其中，R，R1和R2各自独立地为烃基或者烷氧基。根据本发明的实施例，上述烃基为C1-C22烃基，上述烷氧基为C1-C22烷氧基，其中，C1-C22烃基包括但不限于任选取代的甲基、乙基、丙基、丁基(正丁基、异丁基、叔丁基)、戊基、己基、辛基、乙烯基、丙烯基等，C1-C22烷氧基包括但不限于任选取代的甲氧基、乙氧基、丙氧基、丁氧基等。本领域技术人员可以理解，上述仅列出了C1-C22烃基和C1-C22烷氧基的一些具体示例，本发明的保护范围并不限于此，碳原子数为1-22的烃基和烷氧基均在本 发明的保护范围之内。由此，能够有效将层状金属磷酸盐剥离为单层金属磷酸盐，且操作简单，方便，同时该方法不会限制获得的单层金属磷酸盐的进一步应用，其可以应用于润滑油、高性能复合材料中。Wherein R, R 1 and R 2 are each independently a hydrocarbon group or an alkoxy group. According to an embodiment of the present invention, the above hydrocarbon group is a C 1 -C 22 hydrocarbon group, and the above alkoxy group is a C 1 -C 22 alkoxy group, wherein the C 1 -C 22 hydrocarbon group includes, but is not limited to, an optionally substituted methyl group, Ethyl, propyl, butyl (n-butyl, isobutyl, tert-butyl), pentyl, hexyl, octyl, vinyl, propenyl, etc., C 1 -C 22 alkoxy including but not limited to A substituted methoxy, ethoxy, propoxy, butoxy group or the like is selected. It will be understood by those skilled in the art that only the specific examples of the C 1 -C 22 hydrocarbyl group and the C 1 -C 22 alkoxy group are listed above, and the scope of protection of the present invention is not limited thereto, and the number of carbon atoms is 1-22. Both hydrocarbyl and alkoxy groups are within the scope of the present invention. Thereby, the layered metal phosphate can be effectively stripped into a single layer of metal phosphate, and the operation is simple and convenient, and the method does not limit the further application of the obtained single layer metal phosphate, which can be applied to lubricating oil and high. Performance in composite materials.
发明人发现，利用本发明的方法能够快速有效的制备获得单层金属磷酸盐，且该方法步骤简单，操作容易，成本低廉，易于实现工业化生产，同时制备获得的单层金属磷酸盐能够有效用于制备润滑油、高性能复合材料等，均表现出良好的性能，扩展了单层金属磷酸盐在高性能材料中的进一步应用。The inventors have found that the single-layer metal phosphate can be obtained quickly and efficiently by the method of the invention, and the method has the advantages of simple steps, easy operation, low cost and easy industrialized production, and the single-layer metal phosphate obtained can be effectively used. It has shown good performance in the preparation of lubricating oils, high-performance composite materials, etc., and has expanded the further application of single-layer metal phosphates in high-performance materials.
需要说明的是，利用根据本发明实施例的该方法制备获得的单层金属磷酸盐呈单层金属磷酸盐和离子液体的混合物形式，将其应用于润滑油、复合材料等时，也是以单层金属磷酸盐和离子液体的混合物形式直接使用。另外，利用根据本发明实施例的该方法制备获得的单层金属磷酸盐为单层金属磷酸盐纳米片。It should be noted that the single-layer metal phosphate prepared by the method according to the embodiment of the present invention is in the form of a mixture of a single-layer metal phosphate and an ionic liquid, and is applied to a lubricating oil, a composite material, etc. The mixture of the layer metal phosphate and the ionic liquid is used as it is. Further, the single-layer metal phosphate obtained by the method according to the embodiment of the present invention is a single-layer metal phosphate nanosheet.
在本发明的另一方面，本发明提供了一种单层金属磷酸盐。根据本发明的实施例，该单层金属磷酸盐是通过前面所述的方法制备的。发明人发现，该单层金属磷酸盐能够有效应用于制备润滑油或高性能复合材料，特别是应用于润滑油时，具有较低的摩擦系数和较低的磨损量，表现出较好的抗摩擦性能。In another aspect of the invention, the invention provides a single layer metal phosphate. According to an embodiment of the invention, the monolayer of metal phosphate is prepared by the method described above. The inventors have found that the single-layer metal phosphate can be effectively applied to the preparation of lubricating oil or high-performance composite materials, especially when applied to lubricating oils, having a low coefficient of friction and a low amount of wear, showing good resistance. Friction performance.
在本发明的再一方面，本发明提供了前面所述的单层金属磷酸盐在制备润滑油中的用途。发明人发现，将上述的单层金属磷酸盐用于制备润滑油，获得润滑油摩擦系数较小和磨损量较小，表现出良好的耐磨性能，能够显著提高润滑油的使用效果。In yet another aspect of the invention, the invention provides the use of a single layer of metal phosphate as described above for the preparation of a lubricating oil. The inventors have found that the above-mentioned single-layer metal phosphate is used for preparing lubricating oil, and the lubricating oil has a small friction coefficient and a small amount of wear, exhibits good wear resistance, and can significantly improve the use effect of the lubricating oil.
在本发明的又一方面，本发明提供了一种润滑油。根据本发明的实施例，该润滑油含有前面所述的单层金属磷酸盐。根据本发明实施例的该润滑油，具有较低的摩擦系数和较小的磨损量，较好的抗摩擦性能，表现出优于现有商品润滑油的性能。In yet another aspect of the invention, the invention provides a lubricating oil. According to an embodiment of the invention, the lubricating oil contains the single layer metal phosphate described above. The lubricating oil according to the embodiment of the present invention has a lower friction coefficient and a smaller amount of wear, better anti-friction performance, and exhibits superior performance to existing commercial lubricating oils.
下面详细描述本发明的实施例。Embodiments of the present invention are described in detail below.
实施例1：α-磷酸锆的制备Example 1: Preparation of α-zirconium phosphate
将8.0g ZrOCl2.8H2O与80.0ml浓度为3.0mol/L H3PO4(85％wt)混合，将得到的混合物密封于聚四氟乙烯衬里的压力容器中，并加热至200摄氏度保持24小时，获得反应产物α-ZrP，记为α-ZrP-3M。反应结束后，将得到的反应产物洗涤后并离心收集5次，然后，将得到的α-ZrP-3M于65℃下干燥24h。利用研钵将干燥后的α-ZrP-3M研磨成粉末。获得的α-ZrP-3M粉末的XRD(X射线衍射)谱图见图1，TEM照片见图2。8.0 g of ZrOCl 2 .8H 2 O was mixed with 80.0 ml of a concentration of 3.0 mol/L H 3 PO 4 (85% by weight), and the resulting mixture was sealed in a polytetrafluoroethylene-lined pressure vessel and heated to 200 ° C to maintain After 24 hours, the reaction product α-ZrP was obtained, which was designated as α-ZrP-3M. After completion of the reaction, the obtained reaction product was washed and collected by centrifugation 5 times, and then the obtained α-ZrP-3M was dried at 65 ° C for 24 hours. The dried α-ZrP-3M was ground into a powder using a mortar. The XRD (X-ray diffraction) spectrum of the obtained α-ZrP-3M powder is shown in Fig. 1, and the TEM photograph is shown in Fig. 2.
实施例2：小分子离子液体的制备：溴化1-甲基-3-辛基咪唑鎓盐Example 2: Preparation of a small molecule ionic liquid: 1-methyl-3-octyl imidazolium bromide salt
于三颈烧瓶中，将74.574g 1-甲基咪唑(CAS No.：616-47-7)溶于100ml无水丙酮， 然后，在氮气氛围、持续搅拌条件下，将盛有混合溶液的三颈烧瓶置于85℃油浴中，接着将192.969g溴代正辛烷(以摩尔量计，过量约10％,CAS No.：111-83-1)加入三颈烧瓶中，接着将所得到的混合溶液于85℃恒温、及持续搅拌条件下保持反应12～24小时。随着反应进行，反应液逐渐变为淡黄色，反应结束后，真空旋转蒸发除去溶剂，得到粘性淡黄色液体状或浆体状产物，接着将所得到的粘性产物加入1000ml乙酸乙酯中，混合均匀后，得到无色透明的粘性产物，即得溴化1-甲基-3-辛基咪唑鎓盐。In a three-necked flask, 74.574 g of 1-methylimidazole (CAS No.: 616-47-7) was dissolved in 100 ml of anhydrous acetone. Then, the three-necked flask containing the mixed solution was placed in an 85 ° C oil bath under a nitrogen atmosphere under continuous stirring, followed by 192.969 g of bromo n-octane (in terms of molar amount, an excess of about 10%, CAS No) .: 111-83-1) was added to a three-necked flask, and then the resulting mixed solution was kept at a constant temperature of 85 ° C and kept under stirring for 12 to 24 hours. As the reaction progresses, the reaction liquid gradually turns pale yellow. After the reaction is completed, the solvent is removed by evaporation in vacuo to give a viscous pale yellow liquid or slurry product, and then the obtained viscous product is added to 1000 ml of ethyl acetate and mixed. After homogenization, a colorless, transparent, viscous product is obtained which gives the 1-methyl-3-octyl imidazolium bromide salt.
实施例3：小分子离子液体的制备：溴化1-甲基-3-己基吡啶鎓盐Example 3: Preparation of a small molecule ionic liquid: 1-methyl-3-hexylpyridinium bromide salt
于三颈烧瓶中，将79.10g吡啶(CAS No.：110-86-1)溶于100ml无水丙酮，然后，在氮气氛围、持续搅拌条件下，将盛有混合溶液的三颈烧瓶置于85℃油浴中，接着将181.588g溴代正己烷(以摩尔量计，过量约10％,CAS No.：111-25-1)加入三颈烧瓶中，接着将所得到的混合溶液于85℃恒温、及持续搅拌条件下保持反应12～24小时。随着反应进行，反应液逐渐变为淡黄色，反应结束后，真空旋转蒸发除去溶剂，得到粘性淡黄色液体状或浆体状产物，接着将所得到的粘性产物加入1000ml乙酸乙酯中，混合均匀后，得到无色透明的粘性产物，即得溴化1-甲基-3-己基吡啶鎓盐。In a three-necked flask, 79.10 g of pyridine (CAS No.: 110-86-1) was dissolved in 100 ml of anhydrous acetone, and then a three-necked flask containing the mixed solution was placed under a nitrogen atmosphere under continuous stirring. In an 85 ° C oil bath, 181.888 g of bromo-n-hexane (about 10% by mole, CAS No.: 111-25-1) was added to a three-necked flask, followed by the resulting mixed solution at 85 ° The reaction was kept at a constant temperature of ° C for 12 to 24 hours under continuous stirring. As the reaction progresses, the reaction liquid gradually turns pale yellow. After the reaction is completed, the solvent is removed by evaporation in vacuo to give a viscous pale yellow liquid or slurry product, and then the obtained viscous product is added to 1000 ml of ethyl acetate and mixed. After homogenization, a colorless and transparent viscous product is obtained, that is, 1-methyl-3-hexylpyridinium bromide salt is obtained.
实施例4：小分子离子液体的制备：溴化1-丁基喹啉鎓盐Example 4: Preparation of a small molecule ionic liquid: 1-butylquinolinium bromide salt
于三颈烧瓶中，将129.16g喹啉(CAS No.：91-22-5)溶于200ml无水丙酮，然后，在氮气氛围、持续搅拌条件下，将盛有混合溶液的三颈烧瓶置于85℃油浴中，接着将150.733g溴代正丁烷(以摩尔量计，过量约10％,CAS No.：109-65-9)加入三颈烧瓶中，接着将所得到的混合溶液于85℃恒温、及持续搅拌条件下保持反应12～24小时。随着反应进行，反应液逐渐变为淡黄色，反应结束后，真空旋转蒸发除去溶剂，得到粘性淡黄色液体状或浆体状产物，接着将所得到的粘性产物加入1000ml乙酸乙酯中，混合均匀后，得到无色透明的粘性产物，即得溴化1-丁基喹啉鎓盐。In a three-necked flask, 129.16 g of quinoline (CAS No.: 91-22-5) was dissolved in 200 ml of anhydrous acetone, and then a three-necked flask containing the mixed solution was placed under a nitrogen atmosphere under continuous stirring. In a 85 ° C oil bath, 150.733 g of bromo n-butane (about 10% by mole, CAS No.: 109-65-9 in molar excess) was added to the three-necked flask, followed by the resulting mixed solution. The reaction was maintained at a constant temperature of 85 ° C under continuous stirring for 12 to 24 hours. As the reaction progresses, the reaction liquid gradually turns pale yellow. After the reaction is completed, the solvent is removed by evaporation in vacuo to give a viscous pale yellow liquid or slurry product, and then the obtained viscous product is added to 1000 ml of ethyl acetate and mixed. After homogenization, a colorless and transparent viscous product is obtained, that is, 1-butylquinolinium bromide salt is obtained.
实施例5：小分子离子液体的制备：溴化1-乙烯基-3-辛基咪唑鎓盐Example 5: Preparation of a small molecule ionic liquid: 1-vinyl-3-octyl imidazolium bromide salt
于三颈烧瓶中，将94.11g N-乙烯基咪唑(CAS No.：1072-63-5)溶于200ml无水丙酮，然后，在氮气氛围、持续搅拌条件下，将盛有混合溶液的三颈烧瓶置于85℃油浴中，接着将212.443g溴代正辛烷(以摩尔量计，过量约10％,CAS No.：111-83-1)加入三颈烧瓶中，接着将所得到的混合溶液于85℃恒温、及持续搅拌条件下保持反应12～24小时。随着反应进行，反应液逐渐变为淡黄色，反应结束后，真空旋转蒸发除去溶剂，得到粘性淡黄色液体状或浆体状产物，接着将所得到的粘性产物加入1000ml乙酸乙酯中，混合均匀后，得到无色透明的粘性产物，即得溴化1-乙烯基-3辛基咪唑鎓盐。 In a three-necked flask, 94.11 g of N-vinylimidazole (CAS No.: 1072-63-5) was dissolved in 200 ml of anhydrous acetone, and then, under a nitrogen atmosphere with continuous stirring, three mixed solutions were placed. The neck flask was placed in an oil bath at 85 ° C, and then 212.443 g of bromo n-octane (about 10% by mole, CAS No.: 111-83-1 in molar excess) was added to the three-necked flask, followed by The mixed solution was kept at a constant temperature of 85 ° C and kept under stirring for 12 to 24 hours. As the reaction progresses, the reaction liquid gradually turns pale yellow. After the reaction is completed, the solvent is removed by evaporation in vacuo to give a viscous pale yellow liquid or slurry product, and then the obtained viscous product is added to 1000 ml of ethyl acetate and mixed. After homogenization, a colorless, transparent, viscous product is obtained, that is, a 1-vinyl-3-octyl imidazolium bromide salt is obtained.
实施例6：小分子离子液体的制备：溴化1-乙烯基-3-己基咪唑鎓盐Example 6: Preparation of a small molecule ionic liquid: 1-vinyl-3-hexyl imidazolium bromide salt
于三颈烧瓶中，将94.11g 1-乙烯基咪唑(CAS No.：1072-63-5)溶于100ml无水丙酮，然后，在氮气氛围、持续搅拌条件下，将盛有混合溶液的三颈烧瓶置于85℃油浴中，接着将181.588g溴代正己烷(以摩尔量计，过量约10％,CAS No.：111-25-1)加入三颈烧瓶中，接着将所得到的混合溶液于85℃恒温、及持续搅拌条件下保持反应12～24小时。随着反应进行，反应液逐渐变为淡黄色，反应结束后，真空旋转蒸发除去溶剂，得到粘性淡黄色液体状或浆体状产物，接着将所得到的粘性产物加入1000ml乙酸乙酯中，混合均匀后，得到无色透明的粘性产物，即得溴化1-乙烯基-3-己基咪唑鎓盐。In a three-necked flask, 94.11 g of 1-vinylimidazole (CAS No.: 1072-63-5) was dissolved in 100 ml of anhydrous acetone, and then, under a nitrogen atmosphere with continuous stirring, three mixed solutions were placed. The neck flask was placed in an oil bath at 85 ° C, and then 18,588 g of bromo-n-hexane (about 10% by mole, CAS No.: 111-25-1 in molar excess) was added to the three-necked flask, and the resulting The mixed solution was kept at a constant temperature of 85 ° C and kept under stirring for 12 to 24 hours. As the reaction progresses, the reaction liquid gradually turns pale yellow. After the reaction is completed, the solvent is removed by evaporation in vacuo to give a viscous pale yellow liquid or slurry product, and then the obtained viscous product is added to 1000 ml of ethyl acetate and mixed. After homogenization, a colorless, transparent, viscous product is obtained, that is, a 1-vinyl-3-hexylimidazolium bromide salt is obtained.
实施例7：小分子离子液体的制备：溴化4-乙烯基-3-丁基吡啶鎓盐Example 7: Preparation of a small molecule ionic liquid: 4-vinyl-3-butylpyridinium bromide salt
于三颈烧瓶中，将105.14g 4-乙烯基吡啶(CAS No.：100-43-6)溶于100ml无水丙酮，然后，在氮气氛围、持续搅拌条件下，将盛有混合溶液的三颈烧瓶置于85℃油浴中，接着将150.733g溴代正丁烷(以摩尔量计，过量约10％,CAS No.：109-65-9)加入三颈烧瓶中，接着将所得到的混合溶液于85℃恒温、及持续搅拌条件下保持反应12～24小时。随着反应进行，反应液逐渐变为淡黄色，反应结束后，真空旋转蒸发除去溶剂，得到粘性淡黄色液体状或浆体状产物，接着将所得到的粘性产物加入1000ml乙酸乙酯中，混合均匀后，得到无色透明的粘性产物，即得溴化4-乙烯基-3-丁基吡啶鎓盐。In a three-necked flask, 105.14 g of 4-vinylpyridine (CAS No.: 100-43-6) was dissolved in 100 ml of anhydrous acetone, and then, under a nitrogen atmosphere with continuous stirring, the mixed solution was filled. The neck flask was placed in an oil bath at 85 ° C, and then 150.733 g of bromo n-butane (about 10% by mole, CAS No.: 109-65-9 in molar excess) was added to the three-necked flask, followed by The mixed solution was kept at a constant temperature of 85 ° C and kept under stirring for 12 to 24 hours. As the reaction progresses, the reaction liquid gradually turns pale yellow. After the reaction is completed, the solvent is removed by evaporation in vacuo to give a viscous pale yellow liquid or slurry product, and then the obtained viscous product is added to 1000 ml of ethyl acetate and mixed. After homogenization, a colorless, transparent, viscous product is obtained which gives the 4-vinyl-3-butylpyridinium bromide salt.
实施例8：低分子量聚合物均聚物离子液体制备：聚(溴化1-乙烯基-3-辛基咪唑鎓盐)Example 8: Preparation of a low molecular weight polymer homopolymer ionic liquid: poly(1-vinyl-3-octyl imidazolium bromide)
于三颈烧瓶中，将57.5g实施例5中制备的溴化1-乙烯基-3辛基咪唑鎓盐溶于250ml无水甲苯，然后，在氮气氛围、持续机械搅拌条件下，将盛有混合溶液的三颈烧瓶置于70℃油浴中。接着将5.75g偶氮二异丁腈(AIBN)溶于100ml甲苯中，然后滴加入三颈烧瓶中，接着将所得到的混合溶液于70℃恒温、及持续搅拌条件下保持反应10小时。随着反应进行，溶液粘度逐渐增大。反应结束后，首先减压除去大部分溶剂，得到粘稠产物，接着将所得到的粘稠产物加入300ml异丙醇中，混合均匀后，得到无色透明的粘稠产物，分液即得低分子量聚合物均聚物离子液体：聚(溴化1-乙烯基-3-辛基咪唑鎓盐)。In a three-necked flask, 57.5 g of the 1-vinyl-3-octyl imidazolium bromide salt prepared in Example 5 was dissolved in 250 ml of anhydrous toluene, and then, under a nitrogen atmosphere, under continuous mechanical stirring, The three-necked flask of the mixed solution was placed in a 70 ° C oil bath. Next, 5.75 g of azobisisobutyronitrile (AIBN) was dissolved in 100 ml of toluene, and then dropwise added to a three-necked flask, and then the resulting mixed solution was kept at a constant temperature of 70 ° C and kept under stirring for 10 hours. As the reaction proceeds, the viscosity of the solution gradually increases. After the reaction is completed, most of the solvent is first removed under reduced pressure to obtain a viscous product, and then the obtained viscous product is added to 300 ml of isopropyl alcohol, and after mixing uniformly, a colorless transparent viscous product is obtained, and the liquid separation is low. Molecular weight polymer homopolymer ionic liquid: poly(1-vinyl-3-octyl imidazolium bromide).
实施例9：低分子量聚合物共聚物离子液体制备：聚(溴化1-乙烯基-3-己基咪唑鎓盐-co-溴化4-乙烯基-3-丁基吡啶鎓盐) Example 9: Preparation of a low molecular weight polymer copolymer ionic liquid: poly(1-vinyl-3-hexylimidazolium bromide-co-bromo-4-vinyl-3-butylpyridinium salt)
于三颈烧瓶中，将40g实施例6中制备的溴化1-乙烯基-3-己基咪唑鎓盐和20g实施例7中制备的溴化4-乙烯基-3-丁基吡啶鎓盐溶于250ml无水甲苯，然后，在氮气氛围、持续机械搅拌条件下，将盛有混合溶液的三颈烧瓶置于70℃油浴中。接着将6.0g偶氮二异丁腈(AIBN)溶于100ml甲苯中，然后滴加入三颈烧瓶中，接着将所得到的混合溶液于70℃恒温、及持续搅拌条件下保持反应10小时。随着反应进行，溶液粘度逐渐增大。反应结束后，首先减压除去大部分溶剂，得到粘稠产物，接着将所得到的粘稠产物加入300ml异丙醇中，混合均匀后，得到无色透明的粘稠产物，分液即得低分子量聚合物共聚物离子液体：聚(溴化1-乙烯基-3-己基咪唑鎓盐-co-溴化4-乙烯基-3-丁基吡啶鎓盐)。40 g of the 1-vinyl-3-hexylimidazolium bromide salt prepared in Example 6 and 20 g of the 4-vinyl-3-butylpyridinium bromide salt prepared in Example 7 were dissolved in a three-necked flask. The three-necked flask containing the mixed solution was placed in a 70 ° C oil bath under 250 ml of anhydrous toluene, and then under a nitrogen atmosphere under continuous mechanical stirring. Next, 6.0 g of azobisisobutyronitrile (AIBN) was dissolved in 100 ml of toluene, and then dropwise added to a three-necked flask, and then the resulting mixed solution was kept at a constant temperature of 70 ° C and kept under stirring for 10 hours. As the reaction proceeds, the viscosity of the solution gradually increases. After the reaction is completed, most of the solvent is first removed under reduced pressure to obtain a viscous product, and then the obtained viscous product is added to 300 ml of isopropyl alcohol, and after mixing uniformly, a colorless transparent viscous product is obtained, and the liquid separation is low. Molecular Weight Polymer Copolymer Ionic Liquid: Poly(1-vinyl-3-hexylimidazolium bromide-co-4-vinyl-3-butylpyridinium bromide).
实施例10：二甘醇胺(DGA)插层α-ZrPExample 10: Diethylene glycol amine (DGA) intercalation α-ZrP
于两个玻璃瓶中，分别加入0.2gα-ZrP-3M和25g二甘醇胺(CAS No.：929-06-6)并混合均匀，将得到的混合物分别进行超声波处理(频率40KHz,功率150W)8小时和12小时，得到的产物分别记为DGA-α-ZrP-3M-8h和DGA-α-ZrP-3M-12h。In two glass bottles, 0.2 g of α-ZrP-3M and 25 g of diglycolamine (CAS No.: 929-06-6) were added and mixed uniformly, and the obtained mixture was separately subjected to ultrasonic treatment (frequency 40 KHz, power 150 W). At 8 hours and 12 hours, the obtained products were designated as DGA-α-ZrP-3M-8h and DGA-α-ZrP-3M-12h, respectively.
超声波处理后，利用乙醇将得到的两个混合物样品进行离心洗涤至少三次，接着，于常温条件下，将洗涤得到的产物进行减压干燥，得到DGA插层的α-ZrP-3M粉末。得到的DGA插层的α-ZrP-3M粉末的高分辨率XRD图谱见图3。After the ultrasonic treatment, the obtained two mixture samples were subjected to centrifugal washing at least three times with ethanol, and then, the washed product was dried under reduced pressure at normal temperature to obtain a DGA intercalated α-ZrP-3M powder. The high resolution XRD pattern of the obtained DGA intercalated α-ZrP-3M powder is shown in Fig. 3.
实施例11：DGA插层的α-ZrP粉末在小分子离子液体溴化1-甲基-3-辛基咪唑鎓盐中进行剥离处理Example 11: DGA intercalated α-ZrP powder was stripped in a small molecular ionic liquid brominated 1-methyl-3-octyl imidazolium salt
在25ml玻璃瓶中，将0.1g实施例10中获得的DGA-α-ZrP-3M-8h和20g实施例2中获得的小分子离子液体溴化1-甲基-3-辛基咪唑鎓盐混合，将得到的混合物超声波处理(频率40KHz,功率150W)3小时，然后通过超高速离心获得剥离的膏状混合物，该终产物记为DGA-Ionic-α-ZrP-3M。得到的DGA-Ionic-α-ZrP-3M的高分辨率XRD图谱见图3。0.1 g of DGA-α-ZrP-3M-8h obtained in Example 10 and 20 g of the small molecule ionic liquid 1-methyl-3-octyl imidazolium bromide obtained in Example 2 in a 25 ml glass vial After mixing, the resulting mixture was ultrasonicated (frequency 40 KHz, power 150 W) for 3 hours, and then a peeled paste mixture was obtained by ultracentrifugation, and the final product was designated as DGA-Ionic-α-ZrP-3M. The high resolution XRD pattern of the obtained DGA-Ionic-α-ZrP-3M is shown in Fig. 3.
实施例12：制备剥离的α-ZrP-小分子离子液体1-甲基-3-辛基咪唑鎓盐混合物Example 12: Preparation of exfoliated α-ZrP-small molecule ionic liquid 1-methyl-3-octyl imidazolium salt mixture
步骤(1)：step 1):
在100ml的玻璃瓶中，将0.4g实施例1制备的α-ZrP-3M和50g二甘醇胺(CAS No.：929-06-6)混合，然后将得到的混合物超声波处理(频率40KHz,功率150W)8小时。接着，利用乙醇将超声波处理后的混合物离心洗涤至少3次，然后于常温条件下，将得到的产物进行减压干燥，得到DGA插层的α-ZrP-3M粉末。0.4 g of α-ZrP-3M prepared in Example 1 and 50 g of diglycolamine (CAS No.: 929-06-6) were mixed in a 100 ml glass vial, and the resulting mixture was ultrasonicated (frequency 40 KHz, Power 150W) 8 hours. Next, the ultrasonically treated mixture was centrifuged at least 3 times with ethanol, and then the obtained product was dried under reduced pressure at room temperature to obtain a DGA intercalated α-ZrP-3M powder.
步骤(2)： Step (2):
在15ml玻璃瓶中，将0.04g本实施例上述步骤(1)制备的DGA插层的α-ZrP-3M和12g实施例2中获得的小分子离子液体溴化1-甲基-3-辛基咪唑鎓盐混合，并将得到的混合物超声波处理(频率40KHz,功率150W)3小时，即得剥离的α-ZrP离子液体混合物。In a 15 ml glass vial, 0.04 g of the DGA intercalated α-ZrP-3M prepared in the above step (1) of the present example and 12 g of the small molecule ionic liquid obtained in Example 2 were 1-methyl-3-octyl bromide. The imidazolium salt was mixed, and the resulting mixture was ultrasonicated (frequency 40 KHz, power 150 W) for 3 hours to obtain a peeled α-ZrP ionic liquid mixture.
实施例13：制备剥离的α-ZrP-低分子量聚合物共聚物离子液体聚(溴化1-乙烯基-3-己基咪唑鎓盐-co-溴化4-乙烯基-3-丁基吡啶鎓盐)混合物Example 13: Preparation of exfoliated α-ZrP-low molecular weight polymer copolymer ionic liquid poly(1-vinyl-3-hexylimidazolium bromide-co-4-vinyl-3-butylpyridinium bromide) Salt) mixture
步骤(1)：乙醇胺(MEA)插层α-ZrPStep (1): ethanolamine (MEA) intercalation α-ZrP
于两个玻璃瓶中，分别加入0.2gα-ZrP-3M和20g乙醇胺(CAS No.：141-43-5)并混合均匀，将得到的混合物分别进行超声波处理(频率40KHz,功率150W)8小时和12小时，得到的产物分别记为MEA-α-ZrP-3M-8h和MEA-α-ZrP-3M-12h。0.2 g of α-ZrP-3M and 20 g of ethanolamine (CAS No.: 141-43-5) were separately added to the two glass vials and uniformly mixed, and the obtained mixture was separately subjected to ultrasonic treatment (frequency 40 KHz, power 150 W) for 8 hours. And 12 hours, the obtained products were recorded as MEA-α-ZrP-3M-8h and MEA-α-ZrP-3M-12h, respectively.
超声波处理后，利用乙醇将得到的两个混合物样品进行离心洗涤至少三次，接着，于常温条件下，将洗涤得到的产物进行减压干燥，得到MEA插层的α-ZrP-3M粉末。After the ultrasonic treatment, the obtained two mixture samples were subjected to centrifugal washing at least three times with ethanol, and then, the washed product was dried under reduced pressure at room temperature to obtain MEA intercalated α-ZrP-3M powder.
步骤(2)：MEA插层的α-ZrP粉末在低分子量聚合物共聚物离子液体聚(溴化1-乙烯基-3-己基咪唑鎓盐-co-溴化4-乙烯基-3-丁基吡啶鎓盐)混合物中进行剥离处理Step (2): MEA intercalated α-ZrP powder in low molecular weight polymer copolymer ionic liquid poly(1-vinyl-3-hexyl imidazolium bromide-co-bromo-4-vinyl-3-butyl Stripping treatment in a mixture of pyridinium salts
在25ml玻璃瓶中，将0.1g本实施例上述步骤(1)中获得的MEA-α-ZrP-3M-8h和30g实施例9中获得的低分子量聚合物共聚物离子液体聚(溴化1-乙烯基-3-己基咪唑鎓盐-co-溴化4-乙烯基-3-丁基吡啶鎓盐)混合，将得到的混合物超声波处理(频率40KHz,功率150W)4.5小时，然后通过超高速离心可以获得剥离的膏状混合物，该终产物记为MEA-Ionic-α-ZrP-3M。In a 25 ml glass vial, 0.1 g of the MEA-α-ZrP-3M-8h obtained in the above step (1) of the present example and 30 g of the low molecular weight polymer copolymer ionic liquid obtained in Example 9 were poly(brominated 1). -vinyl-3-hexylimidazolium salt-co-bromo 4-vinyl-3-butylpyridinium salt), the resulting mixture was sonicated (frequency 40 KHz, power 150 W) for 4.5 hours, then passed ultra-high speed A stripped paste mixture was obtained by centrifugation and the final product was designated MEA-Ionic-α-ZrP-3M.
实施例14：摩擦学测试Example 14: Tribology test
按照ASTM D4172测试标准，将实施例12中制备获得的剥离的α-ZrP-小分子离子液体1-甲基-3-辛基咪唑鎓盐混合物和市购的商品全配方润滑油进行四球磨损试验，四球磨损试验原理简图见图4。在四球磨损试验中，润滑油脂浸入球和圆盘试样的表面，实验参数见表1。The stripped α-ZrP-small molecular ionic liquid 1-methyl-3-octyl imidazolium salt mixture prepared in Example 12 and a commercially available full-form lubricant were subjected to a four-ball abrasion test in accordance with the ASTM D4172 test standard. The schematic diagram of the four-ball wear test principle is shown in Figure 4. In the four-ball wear test, the grease was immersed in the surface of the ball and disc samples. The experimental parameters are shown in Table 1.
表1：四球磨损试验参数Table 1: Four-ball wear test parameters
参数parameter 模式/值Mode/value
测试标准standard test 四球测试Four ball test
温度temperature 75±2℃75±2°C
速度speed 600rpm600rpm
持续时间duration 240min240min
载荷Load 147±0.05N147±0.05N
样品球材质Sample ball material 不锈钢stainless steel
在四球磨损试验中，检测了实施例12中制备获得的剥离的α-ZrP离子液体混合物和市售的商品全配方润滑油的摩擦系数μ、磨痕深度Z、磨痕尺寸，检测结果见图5-图8。试验结果表明，实施例12中制备获得的剥离的α-ZrP离子液体混合物的摩擦系数μ、磨痕深度Z、磨痕尺寸明显小于商品润滑油，这表明根据本发明实施例的剥离的α-ZrP离子液体混合物能够有效用于制备润滑油。In the four-ball abrasion test, the friction coefficient μ, the wear scar depth Z, and the wear scar size of the peeled α-ZrP ionic liquid mixture prepared in Example 12 and the commercially available full-form lubricating oil were examined. 5-Figure 8. The test results showed that the friction coefficient μ, the wear scar depth Z, and the wear scar size of the peeled α-ZrP ionic liquid mixture prepared in Example 12 were significantly smaller than that of the commercial lubricating oil, indicating that the peeled α- according to the embodiment of the present invention. The ZrP ionic liquid mixture can be effectively used to prepare lubricating oils.
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。In the description of the present specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" and the like means a specific feature described in connection with the embodiment or example. A structure, material or feature is included in at least one embodiment or example of the invention. In the present specification, the schematic representation of the above terms is not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples. In addition, various embodiments or examples described in the specification, as well as features of various embodiments or examples, may be combined and combined.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。 Although the embodiments of the present invention have been shown and described, it is understood that the above-described embodiments are illustrative and are not to be construed as limiting the scope of the invention. The embodiments are subject to variations, modifications, substitutions and variations.

Claims (20)

  1. 一种制备单层金属磷酸盐的方法，其特征在于，包括：A method for preparing a single layer of metal phosphate, comprising:
    (1)利用醇胺对层状金属磷酸盐进行插层处理，获得插层材料；(1) intercalating the layered metal phosphate with an alcoholamine to obtain an intercalation material;
    (2)然后在离子液体中对所述插层材料进行剥离处理，获得单层金属磷酸盐。(2) The intercalation material is then subjected to a release treatment in an ionic liquid to obtain a monolayer of metal phosphate.
  2. 根据权利要求1所述的方法，其特征在于，所述醇胺为单氨基醇或聚醚胺单胺。The method of claim 1 wherein the alkanolamine is a monoamino alcohol or a polyetheramine monoamine.
  3. 根据权利要求2所述的方法，其特征在于，所述单氨基醇或聚醚胺单胺的拓扑结构为线形、星形、环形或其组合。The method according to claim 2, wherein the monoamino alcohol or polyetheramine monoamine has a topology of a linear shape, a star shape, a ring shape or a combination thereof.
  4. 根据权利要求2所述的方法，其特征在于，所述醇胺的分子量为50～5000。The method according to claim 2, wherein the alcoholamine has a molecular weight of from 50 to 5,000.
  5. 根据权利要求4所述的方法，其特征在于，所述醇胺的分子量为500～5000。The method according to claim 4, wherein the alcoholamine has a molecular weight of from 500 to 5,000.
  6. 根据权利要求2所述的方法，其特征在于，所述醇胺为选自乙醇胺，氨基丙醇，氨基丁醇，二甘醇胺，三(羟甲基)氨基甲烷，聚乙二醇单胺，聚丙二醇单胺和聚四氢呋喃单胺中的至少一种。The method according to claim 2, wherein the alcohol amine is selected from the group consisting of ethanolamine, aminopropanol, aminobutanol, diglycolamine, tris(hydroxymethyl)aminomethane, polyethylene glycol monoamine At least one of a polypropylene glycol monoamine and a polytetrahydrofuran monoamine.
  7. 根据权利要求1所述的方法，其特征在于，所述层状金属磷酸盐为选自α-磷酸锆、θ-磷酸锆和γ-磷酸锆中的至少一种。The method according to claim 1, wherein the layered metal phosphate is at least one selected from the group consisting of α-zirconium phosphate, θ-zirconium phosphate, and γ-zirconium phosphate.
  8. 根据权利要求1所述的方法，其特征在于，步骤(1)包括：The method of claim 1 wherein step (1) comprises:
    将所述醇胺和所述层状金属磷酸盐混合，将所得到的混合物进行超声波处理，得到超声处理产物；Mixing the alkanolamine and the layered metal phosphate, and subjecting the obtained mixture to ultrasonic treatment to obtain a sonicated product;
    将所述超声处理产物进行离心，得到沉淀；The sonicated product is centrifuged to obtain a precipitate;
    利用乙醇对所述沉淀进行离心洗涤，得到洗涤产物；The precipitate is subjected to centrifugal washing with ethanol to obtain a washed product;
    于常温条件下，将所述洗涤产物进行减压干燥，得到所述插层材料。The washed product is dried under reduced pressure at normal temperature to obtain the intercalation material.
  9. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述剥离处理是通过以下步骤进行的：将所述插层材料和所述离子液体混合，对所得到的混合物进行超声波处理。The method according to claim 1, wherein in the step (2), the peeling treatment is performed by mixing the intercalation material and the ionic liquid, and ultrasonically irradiating the obtained mixture. deal with.
  10. 根据权利要求1所述的方法，其特征在于，所述离子液体为小分子有机离子液体或聚合物离子液体，The method according to claim 1, wherein said ionic liquid is a small molecule organic ionic liquid or a polymer ionic liquid,
    其中，所述离子液体含有阴离子和有机阳离子。Wherein the ionic liquid contains an anion and an organic cation.
  11. 根据权利要求10所述的方法，其特征在于，所述阴离子为卤素离子，优选为氯离子或溴离子。Process according to claim 10, characterized in that the anion is a halide ion, preferably a chloride ion or a bromide ion.
  12. 根据权利要求10所述的方法，其特征在于，所述有机阳离子含有氮、磷或硫。The method of claim 10 wherein said organic cation comprises nitrogen, phosphorus or sulfur.
  13. 根据权利要求10所述的方法，其特征在于，所述离子液体为小分子有机离子液体，并且所述有机阳离子为选自下列的至少之一：咪唑鎓盐、吡唑鎓盐、噻唑鎓盐、吡啶鎓盐、吡咯烷鎓盐、嘧啶鎓盐、哒嗪鎓盐、哌啶鎓盐、喹啉鎓盐、异喹啉鎓盐、 吡唑啉鎓盐、噻唑啉鎓盐、噁唑啉鎓盐、三唑啉鎓盐、鏻鎓盐和锍鎓盐中的至少一种。The method according to claim 10, wherein the ionic liquid is a small molecule organic ionic liquid, and the organic cation is at least one selected from the group consisting of an imidazolium salt, a pyrazolium salt, and a thiazolium salt. , pyridinium salt, pyrrolidinium salt, pyrimidine salt, pyridazine salt, piperidinium salt, quinolinium salt, isoquinolinium salt, At least one of a pyrazolinium salt, a thiazolinium salt, an oxazolinium salt, a triazolinium salt, a phosphonium salt, and a phosphonium salt.
  14. 根据权利要求13所述的方法，其特征在于，所述有机阳离子具有下列化学结构式之一：The method of claim 13 wherein said organic cation has one of the following chemical structural formulas:
    Figure PCTCN2015090253-appb-100001
    Figure PCTCN2015090253-appb-100001
    其中，R，R1，R2，R3，R4和R5各自独立地为烃基或者烷氧基。Wherein R, R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrocarbon group or an alkoxy group.
  15. 根据权利要求14所述的方法，其特征在于，所述烃基为C1-C22烃基，所述烷氧基为C1-C22烷氧基。The method of claim 14 wherein said hydrocarbyl group is a C 1 -C 22 hydrocarbyl group and said alkoxy group is a C 1 -C 22 alkoxy group.
  16. 根据权利要求10所述的方法，其特征在于，所述离子液体为聚合物离子液体，并且所述聚合物离子液体是采用选自下列至少之一的单体制备的：乙烯基吡啶鎓盐、乙烯基哌啶鎓盐、乙烯基喹啉鎓盐、双烯丙基铵盐、N-乙烯基咪唑鎓盐、乙烯基吡唑鎓盐和乙烯基噻唑鎓盐。The method according to claim 10, wherein said ionic liquid is a polymer ionic liquid, and said polymer ionic liquid is prepared using a monomer selected from at least one of the group consisting of vinyl pyridinium salts, Vinyl piperidinium salt, vinyl quinolinium salt, bisallyl ammonium salt, N-vinylimidazolium salt, vinyl pyrazolium salt and vinyl thiazolium salt.
  17. 根据权利要求16所述的方法，其特征在于，所述聚合物离子液体是采用具备下列化学结构之一的单体制备的： The method of claim 16 wherein said polymeric ionic liquid is prepared using a monomer having one of the following chemical structures:
    Figure PCTCN2015090253-appb-100002
    Figure PCTCN2015090253-appb-100002
    其中，R，R1和R2各自独立地为烃基或者烷氧基，Wherein R, R 1 and R 2 are each independently a hydrocarbyl group or an alkoxy group,
    所述烃基为C1-C22烃基，所述烷氧基为C1-C22烷氧基。The hydrocarbon group is a C 1 -C 22 hydrocarbon group, and the alkoxy group is a C 1 -C 22 alkoxy group.
  18. 一种单层金属磷酸盐，其特征在于，是通过权利要求1-17中任一项所述的方法制备的。A single layer metal phosphate prepared by the method of any one of claims 1-17.
  19. 权利要求18所述的单层金属磷酸盐在制备润滑油中的用途。Use of the single layer metal phosphate of claim 18 for the preparation of a lubricating oil.
  20. 一种润滑油，其特征在于，含有权利要求18所述的单层金属磷酸盐。 A lubricating oil comprising the single layer metal phosphate of claim 18.
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