CN110484020B

CN110484020B - Slurry and preparation method and application thereof

Info

Publication number: CN110484020B
Application number: CN201910874780.5A
Authority: CN
Inventors: 孙大陟; 李丹丹
Original assignee: Southwest University of Science and Technology
Current assignee: Southwest University of Science and Technology
Priority date: 2019-09-17
Filing date: 2019-09-17
Publication date: 2021-06-18
Anticipated expiration: 2039-09-17
Also published as: CN110484020A

Abstract

The invention provides a slurry and a preparation method and application thereof, wherein the slurry comprises oil-soluble hydroxylamine, and modified zirconium phosphate, graphene and poly (isobutylene-b-propylene alcohol-b-isobutylene) block copolymer dispersed in oil-soluble amine; the slurry can stably disperse the modified zirconium phosphate and the graphene at the same time, has better dispersion stability and lower friction resistance coefficient, and can keep the phenomena of sedimentation and dispersion and the like for a longer time; the preparation method of the slurry is simple, the raw materials are easy to obtain, the price is low, the implementation is easy, and the slurry is convenient to be industrially applied to lubricating oil or lubricating grease, so that the friction resistance of the lubricating oil or the lubricating grease is improved.

Description

Slurry and preparation method and application thereof

Technical Field

The invention belongs to the field of materials, relates to a slurry, a preparation method and an application thereof, and particularly relates to an oil-soluble slurry with modified zirconium phosphate and graphene stably dispersed, and a preparation method and an application thereof.

Background

The lubricating oil is a liquid or semisolid lubricating agent used on automobiles and mechanical equipment to reduce friction and protect machines and workpieces, and mainly plays roles in lubrication, cooling, rust prevention, cleaning, sealing, buffering and the like. The chemical properties of common lubricating oil in the current market are unstable, so that a product which has a good lubricating effect, is environment-friendly and has a long service life is lacking in the current market. Graphene is the thinnest material and the toughest material, and the breaking strength is 200 times higher than that of the best steel. Meanwhile, the plastic has good elasticity, the stretching amplitude can reach 20% of the size of the plastic, and the plastic can have good conductivity by doping one percent of graphene into the plastic; one thousandth of graphene is added, so that the heat resistance of the plastic can be improved by 30 ℃, and the graphene has stable chemical properties.

CN109486548A discloses a lubricating oil, which comprises the following raw materials in parts by weight: 75-95 parts of neutral base oil, 2-5 parts of dispersant, 3-8 parts of viscosity index improver, 2-5 parts of silane coupling agent, 5-10 parts of phosphite ester, 2-5 parts of tackifier, 4-9 parts of talcum powder, 2-5 parts of sorbitol and 0.2-0.8 part of antioxidant and corrosion inhibitor. The lubricating oil can solve the problem that the viscosity index of the existing lubricating oil is low, has good cooling and lubricating effects, has small friction force during use, but has poor stability.

CN107254345A discloses a lubricating oil, provides a graphene lubricating oil, solves the problems that the lubricating oil in the prior art is poor in wear resistance and oxidation resistance and has certain pollution to the environment due to the adoption of fluoride modified lubricating oil, comprises base oil, a modified graphene additive and an auxiliary agent, wherein the dosage ratio of the base oil to the modified graphene additive to the auxiliary agent is 1: 0.05-0.2: 0.05-0.15 in parts by weight, and the preparation method of the modified graphene additive comprises the following steps: dispersing graphene: mixing graphene with dimethylformamide, sodium alkyl benzene sulfonate and Arabic gum, and performing ultrasonic dispersion treatment for 30-50 min at the ultrasonic power of 800-1000W to obtain a dispersed graphene solution; and mixing the dispersed graphene solution with aminobenzoic acid, and uniformly stirring for 45-60 min at a stirring speed of 300-500 r/min, wherein the friction resistance of the graphene solution is still to be improved.

CN106147295A discloses a graphene slurry, which comprises the following components in parts by weight: 80-90 wt% of solvent, 5-15 wt% of alkylated modified graphene and 2-7 wt% of oily dispersant; according to the graphene oil-soluble slurry provided by the invention, the alkyl chain is connected to the surface of the graphene sheet layer by using the alkylation modifier, the graphene after alkylation modification is more oleophilic, and then is dispersed in an organic solvent under the action of an oily dispersant, so that the high dispersibility and stability of the graphene in the oily solvent are realized, but the technical problem of stably dispersing the modified zirconium phosphate in the oil-soluble slurry cannot be solved.

Therefore, it is necessary to develop an oil-soluble slurry having good dispersion stability and a low friction resistance coefficient.

Disclosure of Invention

The invention aims to provide slurry and a preparation method and application thereof, wherein the slurry can simultaneously and stably disperse modified zirconium phosphate and graphene, has better dispersion stability and lower friction resistance coefficient, and can be kept for a long time without sedimentation and dispersion; the preparation method of the slurry is simple, the raw materials are easy to obtain, the price is low, the implementation is easy, and the slurry is convenient to be industrially applied to lubricating oil or lubricating grease, so that the friction resistance of the lubricating oil or the lubricating grease is improved.

In order to achieve the purpose, the invention adopts the following technical scheme:

it is an object of the present invention to provide a slurry comprising an oil soluble hydroxylamine and a modified zirconium phosphate, graphene and poly (isobutylene-b-propylene alcohol-b-isobutylene) block copolymer dispersed in an oil soluble amine.

The slurry disclosed by the invention can be used for stably dispersing the modified zirconium phosphate and the graphene at the same time, has better dispersion stability and lower friction resistance coefficient, and can be kept for a longer time without sedimentation and dispersion.

In the invention, the modified zirconium phosphate and the graphene are not easily dispersed in the oil-soluble organic solvent, and the graphene and the modified zirconium phosphate are cooperatively used, so that the dispersion of the graphene and the modified zirconium phosphate in an oil phase can be mutually promoted, and in addition, the graphene is thin and easily enters a friction contact surface, and the graphene and the modified zirconium phosphate are mutually exclusive, so that the problem that the graphene or the modified zirconium phosphate is easily agglomerated can be avoided, and the oil-soluble slurry in which the modified zirconium phosphate and the graphene are stably dispersed can be obtained; the poly (isobutylene-b-ethylenepropyleneoxy-b-isobutylene) block copolymer can effectively disperse the modified zirconium phosphate in the oil-soluble hydrocarbon amine, and the formed dispersion system has high stability and can be stored for a long time without sedimentation.

In the invention, the modified zirconium phosphate is modified by an intercalation agent.

In the present invention, the intercalating agent comprises an organic amine.

In the present invention, the organic amine includes any one of diglycolamine, hexylamine or oleylamine or a combination of at least two thereof.

In the invention, the surface charge density of the modified zirconium phosphate is 5-15mC/m²E.g. 5mC/m²、6mC/m²、7mC/m²、8mC/m²、9mC/m²、10mC/m²、11mC/m²、12mC/m²、13mC/m²、14mC/m²、15mC/m²And the like. When the charge density of the surface of the modified zirconium phosphate is too high, the dispersibility is not good; when the charge density of the surface of the modified zirconium phosphate is too low, the binding force is too weak, and the lubricating effect is affected.

In the present invention, the molar ratio of the zirconium phosphate to the intercalating agent in the modified zirconium phosphate is 1 (1-5), such as 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, etc.

In the present invention, the average particle size of the modified zirconium phosphate is 100-1200nm, for example, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1100nm, 1200nm, etc. When the average particle size of the modified zirconium phosphate is less than 100nm, the lamella is smaller, and the lubricating effect is weakened; when the average particle diameter of the modified zirconium phosphate is more than 1200nm, the dispersibility is not good and the lubricating effect is also affected.

In the invention, the microscopic morphology of the modified zirconium phosphate is a layered structure.

In the present invention, the interlayer spacing of the layered structure is

For example

And the like.

In the invention, when the microstructure of the modified zirconium phosphate is a layered structure, the modified zirconium phosphate can play a role in buffering, reducing friction and improving lubricating performance.

In the present invention, the total thickness of the layered structure is 80 to 200nm, such as 80nm, 100nm, 120nm, 150nm, 180nm, 200nm, and the like.

The modified zirconium phosphate obtained by modifying zirconium phosphate by the intercalation agent has high surface charge density and super-hydrophilicity, and is convenient to better disperse in oil-soluble slurry.

In the invention, the preparation method of the modified zirconium phosphate comprises the following steps: adding an intercalation agent into the zirconium phosphate solution and mixing to obtain the modified zirconium phosphate.

In the invention, the solvent of the zirconium phosphate solution is ethanol.

In the present invention, the mass fraction of zirconium phosphate in the zirconium phosphate solution is 0.1 to 2 wt%, for example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, etc.

In the present invention, the mixing manner is rotational mixing.

In the present invention, the mixing time is 300-500min, such as 300min, 320min, 350min, 370min, 400min, 420min, 450min, 470min, 500min, etc.

In the present invention, the average particle size of the graphene is 100-1000nm, such as 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, etc. When the average particle size of the graphene is too high, dispersion is not facilitated; when the average particle size of the graphene is too small, the supporting surface is too small, which may reduce the lubricating effect.

In the invention, the electron mobility of the graphene is 10000-14000cm²/(V^.S), for example 10000cm²/(V^.S)、10500cm²/(V^.S)、11000cm²/(V^.S)、11500cm²/(V^.S)、12000cm²/(V^.S)、12500cm²/(V^.S)、13000cm²/(V^.S)、13500cm²/(V^.S)、14000cm²/(V^.S), and the like. When the electron mobility of the graphene is too high or too low, the dispersion of the graphene is not facilitated.

In the present invention, the poly (isobutylene-b-propanol-b-isobutylene) block copolymer comprises a first block, a second block and a third block, wherein the first block is polyisobutylene, the second block is polypropyleneethanol and the third block is polyisobutylene.

In the present invention, the number average molecular weight of the first block is 100-300, such as 100, 120, 150, 170, 200, 220, 250, 270, 300, etc., preferably 200.

In the present invention, the number average molecular weight of the second block is 200-400, such as 200, 220, 250, 270, 300, 320, 350, 370, 400, etc., preferably 300.

In the present invention, the number average molecular weight of the third block is 100-300, such as 100, 120, 150, 170, 200, 220, 250, 270, 300, etc., preferably 200.

In the present invention, the oil-soluble amine includes any one of primary amine, secondary amine, tertiary amine, or cyclic amine or a combination of at least two thereof.

In the present invention, the oil-soluble hydrocarbon amine includes any one of or a combination of at least two of primary guerbet amines, fatty amines, or polymerized fatty amines.

In the present invention, the primary guerbet amine has the following structure:

wherein R is₁Is a straight or branched chain hydrocarbon group of 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20).

In the present invention, the fatty amine has the following structure:

wherein R is₂Is a straight or branched chain hydrocarbon radical containing from 4 to 20 carbon atoms (e.g. 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20), R₃And R₄Each independently selected from any one of a hydrogen atom, a methyl group or an ethyl group.

In the invention, the aliphatic amine is unsaturated aliphatic primary amine containing carbon-carbon double bond.

In the present invention, the fatty amines include oleyl amine, parsley amine, erucic amine, linoleyl amine, linolenyl amine, ricinoleic amine, 10-undecenoic amine, octadecatrienoic amine, vernonic amine, santalenic amine, eicosenoic amine, alpha-tungstic amine, punicic amine, the aliphatic amine can be any one of or a combination of at least two of oleic acid amide Hofmann degraded amine, parsley acid amide Hofmann degraded amine, erucic acid amide Hofmann degraded amine, linoleic acid amide Hofmann degraded amine, linolenic acid amide Hofmann degraded amine, ricinoleic acid amide Hofmann degraded amine, 10-undecylenic acid Hofmann degraded amine, octadecatrienoic acid amide Hofmann degraded amine, veronicic acid amide Hofmann degraded amine, santalenic acid amide Hofmann degraded amine, 5-eicosenoic acid amide Hofmann degraded amine, alpha-eleostearic acid amide Hofmann degraded amine or punicic acid amide Hofmann degraded amine.

In the invention, the poly-aliphatic amine is a homopolymer or a copolymer of unsaturated aliphatic primary amine containing carbon-carbon double bonds.

In the present invention, the mass ratio of the modified zirconium phosphate to the graphene is (1-10):1, for example, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, and the like, preferably 5: 1.

In the present invention, the mass ratio of the modified zirconium phosphate to the poly (isobutylene-b-propylene-ethanol-b-isobutylene) block copolymer is 1 (2-20), for example, 1:2, 1:5, 1:8, 1:10, 1:12, 1:15, 1:17, 1:20, etc., preferably 1: 10.

In the present invention, the mass ratio of the graphene to the oil-soluble hydrocarbon amine is 1 (5-50), for example, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, etc., preferably 1: 20.

a second object of the present invention is to provide a method for preparing an oil-soluble slurry according to the first object, comprising the steps of:

(1) mixing the modified zirconium phosphate and the poly (isobutylene-b-ethyl/propoxy-b-isobutylene) block copolymer to obtain a mixture A;

(2) mixing the graphene dispersion liquid with oil-soluble hydrocarbon amine to obtain a mixture B;

(3) and (3) mixing the mixture A obtained in the step (1) and the mixture B obtained in the step (2) to obtain the oil-soluble slurry in which the modified zirconium phosphate and the graphene are stably dispersed.

In the invention, the mixing mode of the step (1) is ultrasonic dispersion.

In the present invention, the mixing time in step (1) is 10-300min, such as 10min, 50min, 80min, 100min, 120min, 150min, 170min, 200min, 220min, 250min, 270min, 300min, etc., preferably 120 min.

In the invention, the graphene dispersion liquid in the step (2) is a dispersion liquid of graphene in dimethylformamide.

In the present invention, the concentration of the graphene dispersion liquid in the step (2) is 0.1 to 1%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc., preferably 0.5%.

In the present invention, the mixing time in step (2) is 30-100min, such as 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, etc.

In the present invention, the mixing in step (2) is carried out under ultrasonic conditions.

In the present invention, the mixing time in step (3) is 30-100min, such as 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, etc.

In the present invention, the mixing in step (3) is carried out under mechanical stirring conditions.

As a preferred technical scheme of the invention, the preparation method comprises the following steps:

s1, adding the modified zirconium phosphate into the poly (isobutylene-b-ethyl/propoxy-b-isobutylene) block copolymer for ultrasonic dispersion for 10-300min to obtain a mixture containing modified zirconium phosphate nanoparticles;

s2, mixing the dimethylformamide dispersion liquid of 0.1-1% graphene with oil-soluble hydrocarbon amine under stirring for 30-100min to obtain the graphene dispersion liquid;

and S3, mixing the mixture containing the modified zirconium phosphate nanoparticles obtained in the step (1) and the dispersion liquid of the graphene obtained in the step (2) under the condition of mechanical stirring for 30-100min to obtain the oil-soluble slurry in which the modified zirconium phosphate nanoparticles and the graphene are stably dispersed.

The invention also aims to provide the application of the slurry in lubricating oil or lubricating grease.

Compared with the prior art, the invention has the following beneficial effects:

the slurry can stably disperse the modified zirconium phosphate and the graphene at the same time, has better dispersion stability and lower friction resistance coefficient, can keep the phenomena of sedimentation and dispersion and the like for a longer time, wherein the friction coefficient is as low as 0.06, and can not generate sedimentation after being placed for two months; the preparation method of the slurry is simple, the raw materials are easy to obtain, the price is low, the implementation is easy, and the slurry is convenient to be industrially applied to lubricating oil or lubricating grease, so that the friction resistance of the lubricating oil or the lubricating grease is improved.

Drawings

FIG. 1(A) is a graph showing the effect of dispersing an oil-soluble slurry in example 1;

FIG. 1(B) is a graph showing the effect of the inverted dispersion of the oil-soluble slurry in example 1;

FIG. 2(A) is a graph showing the effect of dispersion of graphene in oleylamine in example 1;

FIG. 2(B) is a graph of the dispersion of graphene in amine oleate after addition of the poly (isobutylene-B-ethyl/propoxy-B-isobutylene) block copolymer in example 1;

fig. 2(C) is a dispersion diagram of graphene in oleylamine oleate after addition of modified zirconium phosphate in example 1.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The raw materials used in the examples are purchased from regular sources, such as alatin, sigma, TCI, shanghai taitan and the like, and if the raw materials are prepared by self, the corresponding preparation methods are provided in the examples.

Example 1

This example provides a slurry comprising an oil soluble hydroxylamine and a modified zirconium phosphate, graphene and poly (isobutylene-b-propanol-b-isobutylene) block copolymer dispersed in an oil soluble amine; wherein the surface charge density of the modified zirconium phosphate is 10mC/m²The modified zirconium phosphate has a layered structure in the microscopic morphology, and the average interlayer spacing of the layered structure is

The total thickness of the layered structure is 150nm, and the average particle size is 500 nm; the preparation method of the modified zirconium phosphate comprises the following steps: dissolving 1mol of zirconium phosphate in ethanol to obtain a zirconium phosphate solution with the mass fraction of 1 wt%, adding 3mol of diglycolamine into the zirconium phosphate solution, and carrying out rotary mixing for 400min to obtain modified zirconium phosphate; the average particle size of the graphene is 500nm, and the electron mobility is 12000cm²/(V^.S); the number average molecular weight of the first block polyisobutylene in the poly (isobutylene-b-propoxy-b-isobutylene) block copolymer is 200, the number average molecular weight of the second block polypropoxy group is 300, and the number average molecular weight of the third block polyisobutylene is 200; the oil-soluble hydroxylamine is oleic amine; the mass ratio of the modified zirconium phosphate to the graphene is 5:1, the mass ratio of the modified zirconium phosphate to the poly (isobutylene-b-ethylenepropyleneoxy-b-isobutylene) block copolymer is 1:10, and the mass ratio of the graphene to the oleylamine is 1: 20.

The embodiment also provides a preparation method of the slurry, which comprises the following steps:

s1, adding the modified zirconium phosphate into the poly (isobutylene-b-ethyl/propoxy-b-isobutylene) block copolymer for ultrasonic dispersion for 150min to obtain a mixture containing modified zirconium phosphate nanoparticles;

s2, mixing the dimethylformamide dispersion liquid of 0.5% graphene with oil-soluble hydrocarbon amine under stirring for 60min to obtain the graphene dispersion liquid;

and S3, mixing the mixture containing the modified zirconium phosphate nanoparticles obtained in the step (1) and the dispersion liquid of the graphene obtained in the step (2) under the condition of mechanical stirring for 60min to obtain the oil-soluble slurry in which the modified zirconium phosphate nanoparticles and the graphene are stably dispersed.

Fig. 1(a) is a graph showing the dispersion effect of the oil-soluble slurry in this example, and fig. 1(B) is a graph showing the dispersion effect of the oil-soluble slurry in this example inverted, and as can be seen from fig. 1(a) and fig. 1(B), the modified zirconium phosphate nanoparticles and the graphene in the oil-soluble slurry have very good dispersion properties, and when the oil-soluble slurry is left for 2 months, neither the modified zirconium phosphate nanoparticles nor the graphene are found to be settled.

Fig. 2(a) is a graph showing the dispersion effect of graphene in oleylamine, and as can be seen from fig. 2(a), oil-soluble slurry adheres to the bottle wall, which shows that the dispersion is poor, and a black substance adheres to the bottom of the bottle when the bottle is inverted; fig. 2(B) is a graph showing the dispersion effect of graphene in oleylamine oleate by adding a poly (isobutylene-B-ethyl/propoxy-B-isobutylene) block copolymer, and when the graphene is inverted, a black substance is also observed to adhere to the bottom of the bottle, and from fig. 2(B), an oil-soluble slurry adheres to the wall of the bottle, which indicates that the dispersion is poor, and fig. 2(C) is a graph showing the dispersion effect of graphene in oleylamine oleate by adding modified zirconium phosphate, and from fig. 2(C), the upper layer of the slurry is lighter in color, and the lower layer of the slurry is darker in color, which indicates that the dispersion is not uniform; as can be seen from a comparison of fig. 2(a), 2(B), 2(C) and 1(a), the dispersion of graphene in oil-soluble hydroxylamine can be promoted by adding the modified zirconium phosphate and the poly (isobutylene-B-ethyl/propoxy-B-isobutylene) block copolymer to the oil-soluble slurry.

And preparing the oil-soluble slurry into lubricating oil, and testing the friction coefficient of the lubricating oil by a four-ball method by adopting a Bruker UMT Tribo-lab friction wear tester, wherein the reference standard of the four-ball method experiment is SH/T0762-2005. By this test method, the friction coefficient was measured to be 0.06 at a pressure of 196.2N.

Example 2

This example provides a slurry comprising an oil soluble hydroxylamine and a modified zirconium phosphate, graphene and poly (isobutylene-b-propanol-b-isobutylene) block copolymer dispersed in an oil soluble amine; wherein the surface charge density of the modified zirconium phosphate is 5mC/m²The modified zirconium phosphate has a layered structure in the microscopic morphology, and the average interlayer spacing of the layered structure is

The total thickness of the layered structure is 100nm, and the average particle size is 100 nm; the preparation method of the modified zirconium phosphate comprises the following steps: dissolving 0.1mol of zirconium phosphate in ethanol to obtain a zirconium phosphate solution with the mass fraction of 0.1 wt%, adding 0.3mol of diglycolamine into the zirconium phosphate solution, and rotationally mixing for 300min to obtain modified zirconium phosphate; the average particle size of the graphene is 1000nm, and the electron mobility is 14000cm²/(V^.S); the number average molecular weight of the first block polyisobutylene in the poly (isobutylene-b-propoxy-b-isobutylene) block copolymer is 100, the number average molecular weight of the second block polypropoxy group is 400, and the number average molecular weight of the third block polyisobutylene is 100; the oil-soluble hydroxylamine is vernonic acid amide Hofmann degradation amine; the mass ratio of the modified zirconium phosphate to the graphene is 1:1, the mass ratio of the modified zirconium phosphate to the poly (isobutylene-b-ethylenepropyleneoxy-b-isobutylene) block copolymer is 1:20, and the mass ratio of the graphene to the vernonic acid amide Hofmann degraded amine is 1: 5.

s1, adding the modified zirconium phosphate into the poly (isobutylene-b-ethyl/propoxy-b-isobutylene) block copolymer for ultrasonic dispersion for 10min to obtain a mixture containing modified zirconium phosphate nanoparticles;

s2, mixing the 1% graphene dimethylformamide dispersion liquid and the oil-soluble hydrocarbon amine under the stirring condition for 30min to obtain the graphene dispersion liquid;

and S3, mixing the mixture containing the modified zirconium phosphate nanoparticles obtained in the step (1) and the dispersion liquid of the graphene obtained in the step (2) under the condition of mechanical stirring, wherein the mixing time is 100min, and obtaining the oil-soluble slurry in which the modified zirconium phosphate nanoparticles and the graphene are stably dispersed.

The modified zirconium phosphate and the graphene in the oil-soluble slurry prepared in the embodiment have very good dispersibility, and when the oil-soluble slurry is left standing for 2 months, the modified zirconium phosphate and the graphene are not settled.

The oil-soluble slurry was prepared into lubricating oil, and a four-ball test was performed in the same manner as in example 1, and the friction coefficient was measured to be 0.11.

Example 3

This example provides a slurry comprising an oil soluble hydroxylamine and a modified zirconium phosphate, graphene and poly (isobutylene-b-propanol-b-isobutylene) block copolymer dispersed in an oil soluble amine; wherein the surface charge density of the modified zirconium phosphate is 15mC/m²The modified zirconium phosphate has a layered structure in the microscopic morphology, and the average interlayer spacing of the layered structure is

The total thickness of the layered structure is 1200nm, and the average particle size is 1200 nm; the preparation method of the modified zirconium phosphate comprises the following steps: dissolving 2mol of zirconium phosphate in ethanol to obtain a zirconium phosphate solution with the mass fraction of 2 wt%, adding 10mol of diglycolamine into the zirconium phosphate solution, and rotationally mixing for 500min to obtain modified zirconium phosphate; the average particle diameter of the graphene is 100nm, and the electron mobility is 10000cm²/(V^.S); the number average molecular weight of the first block polyisobutylene in the poly (isobutylene-b-propoxy-b-isobutylene) block copolymer is 300, the number average molecular weight of the second block polypropoxy group is 200, and the number average molecular weight of the third block polyisobutyleneThe number average molecular weight of (2) is 300; the oil-soluble hydroxylamine is alpha-aleurone; the mass ratio of the modified zirconium phosphate to the graphene is 10:1, the mass ratio of the modified zirconium phosphate to the poly (isobutylene-b-ethylenepropyleneoxy-b-isobutylene) block copolymer is 1:2, and the mass ratio of the graphene to the vernonic acid amide Hofmann degraded amine is 1: 50.

s1, adding the modified zirconium phosphate into the poly (isobutylene-b-ethyl/propoxy-b-isobutylene) block copolymer for ultrasonic dispersion for 300min to obtain a mixture containing modified zirconium phosphate nanoparticles;

s2, mixing the dimethylformamide dispersion liquid of 0.1% graphene with oil-soluble hydrocarbon amine under stirring for 100min to obtain the graphene dispersion liquid;

and S3, mixing the mixture containing the modified zirconium phosphate nanoparticles obtained in the step (1) and the dispersion liquid of the graphene obtained in the step (2) under the condition of mechanical stirring for 30min to obtain the oil-soluble slurry in which the modified zirconium phosphate nanoparticles and the graphene are stably dispersed.

The oil-soluble slurry was prepared into lubricating oil, and a four-ball test was performed in the same manner as in example 1, and the friction coefficient was measured to be 0.12.

Example 4

The difference from example 1 is only that the mass ratio of the modified zirconium phosphate nanoparticles to the graphene in the slurry is 0.5:1, and the rest of the composition and the preparation method are the same as those in example 1.

The oil-soluble slurry was prepared into lubricating oil, and a four-ball test was performed in the same manner as in example 1, and the friction coefficient was measured to be 0.16.

Example 5

The difference from example 1 is only that the mass ratio of the modified zirconium phosphate nanoparticles to the graphene in the slurry is 15:1, and the rest of the composition and the preparation method are the same as those in example 1.

The oil-soluble slurry was prepared into lubricating oil, and a four-ball test was performed in the same manner as in example 1, and the friction coefficient was measured to be 0.18.

Example 6

The only difference from example 1 is that the mass ratio of the modified zirconium phosphate nanoparticles to the poly (isobutylene-b-ethylenepropyleneoxy-b-isobutylene) block copolymer in the slurry is 1:1, and the rest of the composition and the preparation method are the same as those of example 1.

The oil-soluble slurry prepared in this example had slightly poor dispersibility of the modified zirconium phosphate and graphene, and when the oil-soluble slurry was left to stand for 2 months, it was found that the modified zirconium phosphate and graphene were slightly sedimented.

The oil-soluble slurry was prepared into a lubricating oil, and a four-ball test was carried out in the same manner as in example 1, whereby the friction coefficient was 0.14.

Example 7

The only difference from example 1 is that the mass ratio of the modified zirconium phosphate nanoparticles to the poly (isobutylene-b-ethylenepropyleneoxy-b-isobutylene) block copolymer in the slurry is 1:30, and the rest of the composition and the preparation method are the same as those of example 1.

The oil-soluble slurry was prepared into lubricating oil, and a four-ball test was performed in the same manner as in example 1 to determine a friction coefficient of 0.17.

Example 8

The difference from example 1 is only that the mass ratio of graphene to oil-soluble hydrocarbon amine is 1:1, and the rest of the composition and the preparation method are the same as those of example 1.

The oil-soluble slurry was prepared into lubricating oil, and a four-ball test was performed in the same manner as in example 1, and the friction coefficient was measured to be 0.15.

Example 9

The difference from example 1 is only that the mass ratio of graphene to oil-soluble hydrocarbon amine is 1:150, and the rest of the composition and the preparation method are the same as those of example 1.

Example 10

The only difference from example 1 is that the surface charge density of the modified zirconium phosphate nanoparticles is 1mC/m²The rest of the composition and the preparation method are the same as those of example 1.

The modified zirconium phosphate and the graphene in the oil-soluble slurry prepared in the embodiment both have very good dispersibility, and when the oil-soluble slurry is left standing for 2 months, the modified zirconium phosphate and the graphene are found to be partially settled.

Example 11

The only difference from example 1 is that the surface charge density of the modified zirconium phosphate nanoparticles is 20mC/m²The rest components and the preparation method are all implementedExample 1 is the same.

The oil-soluble slurry was prepared into lubricating oil, and a four-ball test was performed in the same manner as in example 1, and the friction coefficient was measured to be 0.10.

Example 12

The difference from example 1 is only that the average particle size of graphene is 50nm, and the remaining composition and preparation method are the same as those of example 1.

The modified zirconium phosphate and the graphene in the oil-soluble slurry prepared in the embodiment both have very good dispersibility, and when the oil-soluble slurry is left standing for 2 months, the modified zirconium phosphate and the graphene are not settled.

Example 13

The difference from example 1 is only that the average particle size of graphene is 2000nm, and the remaining composition and preparation method are the same as those of example 1.

The oil-soluble slurry prepared in this example has very good dispersibility of both the modified zirconium phosphate and the graphene, and when the oil-soluble slurry is left standing for 2 months, the modified zirconium phosphate and the graphene are found to be partially settled.

Example 14

The only difference from example 1 is that the electron mobility of graphene is 8000cm²/(V^.S), the remaining composition and preparation method were the same as in example 1.

Example 15

The difference from example 1 is only that the electron mobility of graphene is 16000cm²/(V^.S), the remaining composition and preparation method were the same as in example 1.

Example 16

The only difference from example 1 is that the average particle size of the modified zirconium phosphate is 50nm, and the remaining composition and preparation method are the same as those of example 1.

The oil-soluble slurry was prepared into lubricating oil, and a four-ball test was performed in the same manner as in example 1, and the friction coefficient was measured to be 0.19.

Example 17

The only difference from example 1 is that the average particle size of the modified zirconium phosphate was 2000nm, and the remaining composition and preparation method were the same as those of example 1.

Comparative example 1

The difference from example 1 is only that the modified zirconium phosphate nanoparticles were replaced with zirconium phosphate nanoparticles of the same mass, and the remaining composition and preparation method were the same as those of example 1.

The oil-soluble slurry obtained in the comparative example was prepared into lubricating oil in the same manner as in example 1, black matter adhered to the wall of the bottle, and partial precipitates were found at the bottom when the bottle was inverted, indicating that the dispersibility of the oil-soluble slurry was poor and that a larger amount of precipitates were found at the bottom when the bottle was left to stand for 2 months, by replacing the modified zirconium phosphate with zirconium phosphate.

Comparative example 2

The only difference from example 1 is that the same mass of polyamide is used instead of the poly (isobutylene-b-ethylenepropyleneoxy-b-isobutylene) block copolymer, and the composition and preparation method are the same as those of example 1.

The oil-soluble slurry obtained in the comparative example was prepared into a lubricating oil in the same manner as in example 1, black matter adhered to the wall of the bottle, and the bottom of the bottle was turned upside down to find that a partial precipitate appeared, indicating that graphene and modified zirconium phosphate had poor dispersibility in oleylamine when the poly (isobutylene-b-propylene-ethanol-b-isobutylene) block copolymer was replaced with another polymer.

Comparative example 3

The difference from example 1 is only that graphene is replaced by the same mass of α -zirconium hypophosphite, and the rest of the composition and the preparation method are the same as those of example 1.

The oil-soluble slurry obtained in this comparative example was prepared into a lubricating oil in the same manner as in example 1, black matter adhered to the wall of the bottle, and the bottom of the bottle was turned upside down to find that a partial precipitate appeared, indicating that the graphene was replaced with a-zirconium hypophosphite, which also failed to disperse well in the oleylamine under the action of the modified zirconium phosphate and the poly (isobutylene-b-propoxy-b-isobutylene) block copolymer.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. A slurry comprising an oil soluble hydrocarbon amine and a modified zirconium phosphate, graphene, and poly (isobutylene-b-propylene alcohol-b-isobutylene) block copolymer dispersed in the oil soluble hydrocarbon amine;

the surface charge density of the modified zirconium phosphate is 5-15mC/m²；

The average particle size of the modified zirconium phosphate is 100-1200 nm;

the average particle size of the graphene is 100-1000 nm;

the electron mobility of the graphene is 10000-14000cm²/(V.S)；

The modified zirconium phosphate is obtained by modifying zirconium phosphate through an intercalation agent;

the intercalating agent comprises an organic amine;

the organic amine comprises any one or the combination of at least two of diglycolamine, hexylamine or oleylamine;

the mass ratio of the modified zirconium phosphate to the graphene is (1-10) to 1;

the mass ratio of the modified zirconium phosphate to the poly (isobutylene-b-propylene alcohol-b-isobutylene) block copolymer is 1 (2-20);

the mass ratio of the graphene to the oil-soluble hydrocarbon amine is 1 (5-50).

2. The slurry of claim 1, wherein the molar ratio of the zirconium phosphate to the intercalant in the modified zirconium phosphate is 1 (1-5).

3. The slurry of claim 1, wherein the modified zirconium phosphate has a layered microstructure in its micro-morphology.

4. The slurry according to claim 3, characterized in that the average interlayer spacing of the layered structure is

5. The paste according to claim 3, characterized in that the total thickness of the layered structure is 80-200 nm.

6. The slurry according to claim 1, wherein the preparation method of the modified zirconium phosphate comprises: adding an intercalation agent into the zirconium phosphate solution and mixing to obtain the modified zirconium phosphate.

7. The slurry according to claim 6, characterized in that the solvent of the zirconium phosphate solution is ethanol.

8. The slurry according to claim 6, wherein the mass fraction of zirconium phosphate in the zirconium phosphate solution is 0.1 to 2 wt%.

9. The slurry of claim 6, wherein the mixing is by rotational mixing.

10. The slurry of claim 6, wherein the mixing time is 300-500 min.

11. The slurry of claim 1, wherein the poly (isobutylene-b-propylene-ethanol-b-isobutylene) block copolymer comprises a first block, a second block, and a third block, wherein the first block is polyisobutylene, the second block is polypropylene ethanol, and the third block is polyisobutylene.

12. The slurry of claim 11, wherein the number average molecular weight of the first block is 100-300.

13. The slurry of claim 11, wherein the first block has a number average molecular weight of 200.

14. The slurry of claim 11, wherein the number average molecular weight of the second block is 200-400.

15. The slurry of claim 11, wherein the second block has a number average molecular weight of 300.

16. The slurry of claim 11, wherein the number average molecular weight of the third block is 100-300.

17. The slurry of claim 11, wherein the number average molecular weight of the third block is 200.

18. The slurry of claim 1, wherein the oil-soluble hydrocarbon amine comprises any one of a primary amine, a secondary amine, a tertiary amine, or a cyclic amine, or a combination of at least two thereof.

19. The slurry according to claim 1, wherein the oil-soluble hydrocarbon amine comprises any one of or a combination of at least two of primary guerbet amines, fatty amines, or polymerized fatty amines.

20. The slurry of claim 19, wherein the primary guerbet amine has the structure:

wherein R is₁Is straight chain or branched chain alkyl containing 1-20 carbon atoms.

21. The slurry of claim 19, wherein the fatty amine has the structure:

wherein R is₂Is a straight-chain or branched-chain hydrocarbon radical containing from 4 to 20 carbon atoms, R₃And R₄Each independently selected from any one of a hydrogen atom, a methyl group or an ethyl group.

22. The slurry of claim 19, wherein the fatty amine is an unsaturated primary fatty amine containing a carbon-carbon double bond.

23. The slurry according to claim 19, wherein the fatty amine comprises any one or at least two of oleic, erucic, linoleic, linolenic, ricinoleic, 10-undecenoic, octadecenoic, vernonic, santalenic, eicosenoic, alpha-elaeostearic, punicic, oleamide huffman-degrading, parsley amide huffman-degrading, erucamide huffman-degrading, linoleate amide huffman-degrading, linolenate amide huffman-degrading, ricinoleic amide huffman-degrading, 10-undecenic acid huffman-degrading, octadecatrienoic amide huffman-degrading, vernonic amide huffman-degrading, santaloenoic acid amide huffman-degrading, 5-eicosenoic amide huffman-degrading, alpha-elaeostearic acid amide huffman-degrading or punicic amide huffman-degrading Combinations of (a) and (b).

24. The slurry of claim 19, wherein the poly-aliphatic amine is a homopolymer or copolymer of an unsaturated primary aliphatic amine containing a carbon-carbon double bond.

25. The slurry according to claim 1, wherein the mass ratio of the modified zirconium phosphate to the graphene is 5: 1.

26. The slurry according to claim 1, wherein the mass ratio of the modified zirconium phosphate to the poly (isobutylene-b-propylene-ethanol-b-isobutylene) block copolymer is 1: 10.

27. The slurry according to claim 1, wherein the mass ratio of the graphene to the oil-soluble hydrocarbon amine is 1: 20.

28. A method for preparing a slurry according to any one of claims 1 to 27, characterized in that it comprises the steps of:

29. The method for preparing a slurry according to claim 28, wherein the mixing in step (1) is carried out by ultrasonic dispersion.

30. The method for preparing a slurry according to claim 28, wherein the mixing time of step (1) is 10-300 min.

31. The method for preparing a slurry according to claim 28, wherein the mixing time of step (1) is 120 min.

32. The method for preparing slurry according to claim 28, wherein the graphene dispersion liquid in the step (2) is a dispersion liquid of graphene in dimethylformamide.

33. The method for preparing slurry according to claim 28, wherein the concentration of the graphene dispersion liquid in the step (2) is 0.1-1%.

34. The method for preparing slurry according to claim 28, wherein the concentration of the graphene dispersion liquid in the step (2) is 0.5%.

35. The method for preparing slurry according to claim 28, wherein the mixing time of the step (2) is 30-100 min.

36. The method of preparing a slurry according to claim 28, wherein the mixing of step (2) is performed under ultrasonic conditions.

37. The method for preparing a slurry according to claim 28, wherein the mixing time of the step (3) is 30-100 min.

38. The method for preparing a slurry according to claim 28, wherein the mixing in the step (3) is performed under mechanical stirring.

39. A method for preparing a slurry according to claim 28, characterized in that it comprises the steps of:

s2, mixing the dimethylformamide dispersion liquid of graphene with the concentration of 0.1-1% and oil-soluble hydrocarbon amine under the ultrasonic condition for 30-100min to obtain the graphene dispersion liquid;

40. Use of a paste according to any of claims 1 to 27 in a lubricating oil or grease.