WO2018072252A1

WO2018072252A1 - Oil-soluble polyamine, method of dispersing carbon halide material, and mixture containing carbon halide material

Info

Publication number: WO2018072252A1
Application number: PCT/CN2016/106142
Authority: WO
Inventors: 雍怀松; 孙大陟; 张至
Original assignee: 南方科技大学
Priority date: 2016-10-20
Filing date: 2016-11-16
Publication date: 2018-04-26
Also published as: CN106519248A

Abstract

Provided are an oil-soluble polyamine, a method of dispersing a carbon halide material, and a mixture containing the carbon halide material. The oil-soluble polyamine is a graft polymer, and comprises a polyamine backbone and an oil-soluble graft chain segment connected to the polyamine backbone. The chemical structure of the polyamine backbone comprises at least one of a polyethyleneimine, a polyethylene polyamine, a polyallylamine, a polyvinyl amine, a poly-lysine, a poly(4-aminostyrene), a poly(N-(3-amino propyl)alkyl imine), a poly(2-aminoethyl alkyl acrylate), a polyamide-amine type dendritic macromolecule, and a polyalkyl imine dendritic polymer. The oil-soluble graft chain segment comprises at least one of an alkyl chain segment and an alkoxy chain segment.

Description

Oil-soluble polyamine, method for dispersing halogenated carbon material, and mixture containing carbon halide material

Technical field

The present invention relates to the field of materials, and in particular, to oil-soluble polyamines, methods of dispersing halogenated carbon materials, and mixtures containing carbon halide materials.

Background technique

In the preparation of many products, such as oil painting, coatings, pastes, lubricants, etc., the stability of fluorinated graphite materials in liquid media is a very important factor, and fluorinated graphite materials are difficult to disperse by conventional means. The material, and thus the dispersion of fluorinated graphite, is challenging. Amines have been used to disperse fluorinated graphite in water or organic media, by electrophilic nucleophilic forces of similar bonding forces present between the fluorinated graphite material and the amine. This reaction allows the fluorinated graphite material to be partially dispersed in the amine. However, conventional amines for dispersing graphite fluoride, such as polyetheramines or alkylamines, have a lower amino number density, while lower amino number densities limit the dispersibility of their dispersed fluorinated graphite materials.

Therefore, the current research on the dispersion of fluorocarbon materials still needs to be improved.

Summary of the invention

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 an oil-soluble polyamine which can effectively disperse a halocarbon material.

In one aspect of the invention, the invention provides an oil soluble polyamine. According to an embodiment of the present invention, the oil-soluble polyamine is a graft polymer, and comprises a polyamine skeleton and an oil-soluble graft segment attached to the polyamine skeleton, wherein the chemical structure of the polyamine skeleton Including polyethyleneimine, polyethene polyamine, polyallylamine, polyvinylamine, polylysine, poly(4-aminostyrene), poly(N-(3-aminopropyl)alkylimine) At least one of poly(2-aminoethyl acrylate), polyamide-amine dendrimer and polyalkylenimine dendrimer, the oil-soluble graft segment comprising a hydrocarbyl chain At least one of a segment and an alkoxy segment. The inventors have found that the oil-soluble polyamine can quickly and effectively disperse the halogenated carbon material uniformly and stably in the organic medium. Under the condition of room temperature, the dispersed halocarbon material can be stably existed for at least one month without occurrence. Layer, sedimentation and other phenomena. It is particularly pointed out that the oil-soluble polyamine can be used to easily and conveniently disperse a halogenated carbon material, such as a graphite fluoride material, in a lubricating oil or a grease, and the obtained lubricating oil or grease has a remarkable improvement in friction resistance. Moreover, the method is simple and convenient to operate, has no special requirements for equipment and technicians, is easy to implement, and has low cost.

According to an embodiment of the invention, the chemical structure of the polyamine skeleton comprises at least one of the following:

Wherein x is an integer greater than 1, and R is a hydrogen atom or an alkyl group.

According to an embodiment of the invention, the polyamine backbone has a molecular weight of from 100 to 20,000,000 Daltons, preferably from 200 to 100,000 Daltons.

According to an embodiment of the invention, the hydrocarbyl segment and the alkoxy segment are each independently a small molecular segment or a single blocked polymer segment.

According to an embodiment of the invention, the small molecular segment comprises at least one of a fatty acid derivative and an unsaturated alpha olefin derivative.

According to an embodiment of the invention, the fatty acid derivative comprises at least one of a fatty acid and a fatty isocyanate, the unsaturated alpha olefin derivative comprising a succinic anhydride-terminated alpha olefin. According to an embodiment of the invention, the fatty acid is a C ₆ -C ₂₂ fatty acid, the fatty isocyanate is a C ₆ -C ₂₂ fatty isocyanate, and the succinic anhydride-terminated alpha olefin is a C ₆ -C ₂₂ alkylalkenyl amber Anhydride.

According to an embodiment of the invention, the single-end polymer segment comprises a mono-capped functional polyolefin, wherein the terminal functional group comprises at least one of an acid anhydride, an isocyanate group, and a carboxyl group.

According to an embodiment of the invention, the monocapped functional polyolefin comprises at least one of a monocapped functional polyisobutylene, a monocapped functional polybutene, and a monocapped functional polybutadiene.

According to an embodiment of the invention, the monocapped functional polyolefin comprises at least one of the following:

Wherein m1, m2, n and n1 are each independently an integer greater than 1, i+j+k=1.

According to an embodiment of the present invention, the molar ratio of the oil-soluble graft segment to the polyamine skeleton is (500-1):1, preferably (200-2):1.

In another aspect of the invention, the invention provides a method of dispersing a halocarbon material. According to an embodiment of the present invention, the method comprises: mixing the oil-soluble polyamine described above and the halogenated carbon material to obtain a first mixture; and adding the first mixture to an organic medium, and obtaining the obtained The mixture was sonicated to give a second mixture. The inventors have found that the halogenated carbon material can be uniformly and stably dispersed in an organic medium quickly and efficiently by using the method, and the dispersed halocarbon material can be stably existed for at least one month at room temperature without delamination. , settlement and other phenomena. It should be particularly pointed out that the method can be used to easily and conveniently disperse a halogenated carbon material, such as a graphite fluoride material, in a lubricating oil or a grease, and the obtained lubricating oil or grease has a significant improvement in friction resistance. Moreover, the method is simple and convenient to operate, has no special requirements for equipment and technicians, is easy to implement, and has low cost.

According to an embodiment of the present invention, the halogenated carbon material comprises oxidized fluorinated graphite, organic graft modified fluorinated graphite, fluorinated graphite, fluorinated graphene, fluorinated graphene alkyne, fluorinated carbon nanorod, fluorinated carbon At least one of a nanowire, a fluorinated carbon nanotube, a fluorinated carbon nanosphere, a fluorinated amorphous carbon, a fluorinated carbon fiber, and a fluorinated carbon black.

According to an embodiment of the invention, the organic medium is a lubricating base oil.

In still another aspect of the invention, the invention provides a mixture comprising a halocarbon material. According to an embodiment of the invention, the mixture containing the halocarbon material is prepared by the method described above. The inventors have unexpectedly discovered that the mixture containing a halogenated carbon material can be effectively used in lubricating oils, grease memory nanocomposites, especially when used in lubricating oils or greases, the lubricating oil or grease containing the mixture has Ideal for friction resistance.

DRAWINGS

1 shows a schematic diagram of a dispersion mechanism of dispersed fluorinated graphite according to an embodiment of the present invention;

Figure 2 shows a schematic representation of the synthesis of an oil soluble polyamine surfactant in accordance with an embodiment of the present invention;

Figure 3 shows a photograph of different concentrations of fluorinated graphite material dispersed in a base oil in accordance with an embodiment of the present invention;

4 shows an XRD spectrum of a fluorinated graphite material and fluorinated graphite dispersed using a polyamine surfactant, in accordance with an embodiment of the present invention;

Figure 5 shows a schematic view of a ball disk experiment in accordance with an embodiment of the present invention;

Figure 6 shows the average coefficient of friction <μ> as a function of the mass fraction of fluorinated graphite (CF) _n in the base oil, in accordance with an embodiment of the present invention;

Figure 7 shows the coefficient of friction as a function of the mass fraction of the graphite fluoride (CF) _n in the base oil, in accordance with an embodiment of the present invention.

Figure 8 shows a scanning electron micrograph of graphite fluoride (CF) _n in accordance with an embodiment of the present invention.

detailed description

The present invention has been completed based on the following findings of the inventors:

The inventors have found through research that the fluorinated graphite can be effectively dispersed in an organic medium by an electrophilic nucleophilic force similar to the bonding force existing between the fluorinated graphite material and the amine. And this reaction can partially disperse the fluorinated graphite material in the amine. However, conventional amines for dispersing graphite fluoride, such as polyetheramines or alkylamines, have a lower amino number density, while lower amino number densities limit the dispersibility of their dispersed fluorinated graphite materials. At the same time, there is a gravitational force such as Van der Waals force between the dispersant and the unbonded atoms in the surface group of the particles. The above-mentioned gravitational force between the low molecular weight dispersant and the particles is not obvious, but the case of using the polymer dispersant is completely different. The number of structural units in the polymer chain is very large, and the size of each structural unit is comparable to that of a small molecule. The above-mentioned gravitational force has no directivity and does not saturate, and therefore, the gravitational force between the polymer chain and the particles is sufficiently large to allow the polymer to cover a part of the surface of the particle. Based on the electrophilic-nucleophilic and gravitational effects of similar bonding forces described above, the inventors have devised a series of new oil-soluble polyamine surfactants comprising a polyamine structure which can be used for the halogenated carbon material. (including but not limited to graphite fluoride materials) are dispersed in an organic medium. The dispersed halocarbon material can be stably present for at least one month at room temperature.

In view of this, in one aspect of the invention, the invention provides an oil soluble polyamine. According to an embodiment of the present invention, the oil-soluble polyamine is a graft polymer, and comprises a polyamine skeleton and an oil-soluble graft segment attached to the polyamine skeleton, wherein the chemical structure of the polyamine skeleton Including polyethyleneimine, polyethene polyamine, polyallylamine, polyvinylamine, polylysine, poly(4-aminostyrene), poly(N-(3-aminopropyl)alkylimine) At least one of poly(2-aminoethyl acrylate), polyamide-amine dendrimer and polyalkylenimine dendrimer, the oil-soluble graft segment comprising a hydrocarbyl chain At least one of a segment and an alkoxy segment. The inventors have found that the oil-soluble polyamine can quickly and effectively disperse the halogenated carbon material uniformly and stably in the organic medium. Under the condition of room temperature, the dispersed halocarbon material can be stably existed for at least one month without occurrence. Layer, sedimentation and other phenomena. It is particularly pointed out that the oil-soluble polyamine can be used to easily and conveniently disperse a halogenated carbon material, such as a graphite fluoride material, in a lubricating oil or a grease, and the obtained lubricating oil or grease has a remarkable improvement in friction resistance. Moreover, the method is simple and convenient to operate, has no special requirements for equipment and technicians, is easy to implement, and has low cost.

According to an embodiment of the present invention, a specific method for synthesizing an oil-soluble polyamine surfactant is not particularly limited and may be employed. The type of the polymer reaction used may be an addition reaction between an amino group and an isocyanate group, a substitution reaction between an amino group and an acid anhydride, and an amidation reaction. The molar ratio between the grafted hydrophobic segment and the hydrophilic backbone is between 500 and 1, preferably between 200 and 2. A schematic of a synthetic oil soluble polyamine surfactant is shown in Figure 2. Specific examples of some synthetic oil-soluble polyamine surfactants are as follows:

Dendritic polyethyleneimine (PEI) and polyisobutylene succinic anhydride (PIBSA) reaction

Dendritic polyethyleneimine (PEI) r and dodecenyl succinic anhydride (DDSA) reaction

Polyvinylamine (PVAm) and dodecenyl succinic anhydride (DDSA) reaction

Polyvinylamine (PVAm) polyisobutylene succinic anhydride (PIBSA) reaction

According to an embodiment of the present invention, the chemical structure of the polyamine skeleton which may be employed includes polyethyleneimine, polyethene polyamine, polyallylamine, polyvinylamine, polylysine, poly(4-aminostyrene), Poly(N-(3-aminopropyl)alkylenimine), poly(2-aminoethyl acrylate), polyamide-amine dendrimer and polyalkylenimine dendrimer At least one of them. That is, the polyamine skeleton may be composed of one or two or more of the above structures, and the inventors have found that with the above structure, the amino group has a high density, which can effectively improve the ability to disperse the halogenated carbon material and obtain a better dispersion. product. When used in lubricating oils, its anti-friction properties are significantly improved.

According to an embodiment of the present invention, the chemical structure of the polyamine skeleton that can be employed includes at least one of the following:

It should be noted that "*" in the chemical structure herein indicates a position to be connected to other chemical structures.

In some embodiments of the invention, the chemical structure of the polyamine backbone that may be employed includes, but is not limited to, the following structures:

Where n is an integer greater than one.

According to an embodiment of the present invention, the molecular weight of the above polyamine skeleton is not particularly limited. In some embodiments of the invention, the polyamine backbone has a molecular weight of from 100 to 20,000,000 Daltons. In some preferred embodiments, the polyamine backbone has a molecular weight of from 200 to 100,000 Daltons. Therefore, the electrophilic-nucleophilic action and the gravitational force are strong, and the dispersion effect and stability of the halogenated carbon material are good.

According to an embodiment of the invention, the oil-soluble graft segment comprises at least one of a hydrocarbyl segment and an alkoxy segment. In particular, monocapped hydrocarbyl chains and alkoxy chains are the most commonly used raw materials for graft/comb structures. In one aspect, these hydrocarbyl chains and alkoxy chains can be small molecular segments such as fatty acid derivatives, unsaturated alpha olefin derivatives. Specifically may be fatty acids, fatty isocyanates and succinic anhydride-terminated alpha olefins. Wherein, the fatty acid is preferably a C ₆ -C ₂₂ fatty acid, the fatty isocyanate is preferably a C ₆ -C ₂₂ fatty isocyanate, and the succinic anhydride-terminated alpha olefin is preferably a C ₆ -C ₂₂ alkylalkenyl succinic anhydride, for example but not limited to ten Dienyl succinic anhydride, n-octenyl succinic anhydride, nonenyl succinic anhydride, tetrasuccinic anhydride. Thereby, the dispersion effect of the halocarbon material can be further improved. Alternatively, these hydrocarbyl and alkoxy chains may be mono-terminated polymers, such as mono-terminated functional polyolefins, wherein the terminal functional groups may be anhydrides, isocyanate groups, and carboxyl groups.

For mono-terminated functional polyolefins, these terminal functional groups can be grafted onto the polymer chain by different synthetic methods, such as an ene-anhydride addition reaction, a functional initiator used in conventional radical polymerization, and anionic polymerization. Functional termination reaction, controllable/living free radical polymerization, and the like. Among them, a preferred grafting method which is excellent in versatility and stability is a functional initiator used in conventional radical polymerization. Peroxide initiators and azide initiators are the most commonly used initiators for the synthesis of oil soluble polyolefins. During the synthesis, 4,4'-azobis(4-cyano-1-pentanol) and 4,4'-azobis(4-cyanovaleric acid) are the most commonly used initiators in the initiation reaction. Agent. The chemical structures of the two are as follows:

In conventional free radical polymerization, there are two kinds of chain terminations, coupling termination and disproportionation termination. Unlike most free radical polymerizations which tend to be terminated by coupling to obtain products with narrow molecular weight distribution and high molecular weight, in order to obtain single-end functionalized polyolefins and relatively low molecular weight products, appropriate high temperatures are required to cause disproportionation termination reactions. . In addition, in order to make the disproportionation termination reaction proceed smoothly, it is necessary to select an appropriate monomer, such as a body-substituted hydrophobic vinyl monomer 2,4,4-trimethylpentene, a long-chain alkyl-1-ene, an α-olefin. , vinyl acetate and its derivatives, long-chain alkyl methacrylate and long-chain alkyl acrylate.

As a typical example, the synthesis route of a poly-α-olefin, such as a single-ended hydroxy poly(1-octene), is as follows:

Raised:

Extend,

End cap (mainly disproportionation termination)

Wherein m1, m2, n and n1 are each independently an integer greater than 1, i+j+k=1, and n1 is preferably an integer of 20-100. The above-mentioned single-end functional polyolefin can be effectively used as the oil-soluble graft segment to effectively improve the dispersion effect and stability of the halogenated carbon material.

According to an embodiment of the present invention, the molar ratio of the oil-soluble graft segment to the polyamine skeleton is at (200-1):1, preferably (50-2):1. Within the above range, the dispersion effect of the polyamine surfactant is ideal, and the obtained mixture has good stability, and is stable for at least one month at room temperature, and delamination and sedimentation do not occur. When used in lubricating oils or greases, it can effectively improve its anti-friction properties.

In another aspect of the invention, the invention provides a method of dispersing a halocarbon material. According to an embodiment of the present invention, the method comprises: mixing the oil-soluble polyamine described above and the halogenated carbon material to obtain a first mixture; and adding the first mixture to an organic medium, and obtaining the obtained The mixture was sonicated to give a second mixture. The inventors have found that the method can quickly and effectively disperse the halogenated carbon material uniformly and stably in the organic medium. In the middle and room temperature conditions, the dispersed halocarbon material can be stably existed for at least one month without delamination and sedimentation. It should be particularly pointed out that the method can be used to easily and conveniently disperse a halogenated carbon material, such as a graphite fluoride material, in a lubricating oil or a grease, and the obtained lubricating oil or grease has a significant improvement in friction resistance. Moreover, the method is simple and convenient to operate, has no special requirements for equipment and technicians, is easy to implement, and has low cost.

Specifically, taking fluorinated graphite as an example, the dispersion mechanism is shown in FIG. 1 . In particular, the crystal structure of fluorinated graphite is not always ideal, and there may be some defects such as the presence of ≡CF, ≥CF, -CF ₂ - and -CF ₃ groups at the edges of the crystal structure. These defects are the breakthrough point of dispersing fluorinated graphite materials. Oil-soluble polyamine based on the electrophilic-affinity interaction between the amino group in the oil-soluble polyamine surfactant and the carbon atom in the graphite fluoride and the gravitational interaction between the oil-soluble polyamine surfactant and the graphite fluoride The surfactant covers a part of the surface of the fluorinated graphite, and further has good fat solubility by the oil-soluble graft segment, so that the fluorinated graphite is stably and uniformly dispersed in the organic medium.

According to an embodiment of the present invention, the specific kind of the halogenated carbon material is not particularly limited. In some embodiments of the present invention, the halocarbon material may include oxidized fluorinated graphite, organic graft modified fluorinated graphite, fluorinated graphite, fluorinated graphene, fluorinated graphene alkyne, fluorinated carbon nanorods, fluorinated At least one of carbon nanowires, fluorinated carbon nanotubes, fluorinated carbon nanospheres, fluorinated amorphous carbon, fluorinated carbon fibers, and fluorinated carbon black. Therefore, the dispersion effect is satisfactory, and the stability is preferable. Particularly, when the dispersed carbon halide material is used for preparing a lubricating oil or a grease, the obtained lubricating oil or grease has excellent anti-friction properties.

According to an embodiment of the invention, the organic medium is a lubricating base oil. Thus, there is a lubricant which is effective in obtaining an anti-friction property.

In another aspect of the invention, the invention provides a mixture comprising a halocarbon material. According to an embodiment of the invention, the mixture containing the halocarbon material is prepared by the method described above. The inventors have unexpectedly discovered that the mixture containing a halogenated carbon material can be effectively used in lubricating oils, greases and nano-polymer composites, especially when used in lubricating oils or greases, lubricating oil or lubricating containing the mixture. The grease has the ideal anti-friction properties. In addition, all of the features and abbreviations of the foregoing method of dispersing a halocarbon material are applicable to the mixture containing the halocarbon material, and will not be further described herein.

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.

Example 1: Synthesis of PIBSA-grafted PEI

10 g of ethylenediamine-terminated dendritic poly(ethyleneimine) (PEI, BASF product, molecular weight of about 800 g/mol) And 30 ml of anhydrous acetone was dissolved in a 250 ml three-necked flask. The three-necked bottle containing the PEI solution was placed in a 58 ° C oil bath under stirring conditions under a nitrogen atmosphere. 47.6 g of polyisobutylene succinic anhydride (PIBSA) (molecular weight about 1100 g/mol) was dissolved in 100 ml of n-hexane using a 150 ml constant pressure dropping funnel. When the temperature of the solution was equilibrated at 58 ° C, the PIBSA solution was added dropwise to a three-necked flask, and the dropping rate of the solution was 1 drop to 3 drops per second. The resulting mixed solution was kept at a constant temperature of 58 ° C and stirred for 12 to 24 hours. The mixed solution first became creamy white, and as the reaction time progressed, the reaction solution gradually turned orange-red or red-brown. After the reaction, the solvent in the solution was removed by vacuum rotary evaporation. Then, a viscous reddish brown liquid or slurry product is obtained.

Example 2: Synthesis of PIBSA-grafted HPA-X

Dissolve 5.5 g of heavy polyamine X (hpa-x, Dow Chemical, molecular weight approximately 275 g/mol, a mixture of polyethyleneimine and small molecular amine) and 30 ml of anhydrous acetone in a 250 ml three-neck bottle The three-necked flask containing the hpa-x solution was placed in a 57 ° C oil bath under stirring and under nitrogen atmosphere. 44 g of polyisobutylene succinic anhydride (PIBSA) (molecular weight of about 1100 g/mol) was dissolved in 100 ml of hexane using a 150 ml constant pressure dropping funnel. When the temperature of the solution was equilibrated at 57 ° C, the PIBSA solution was added dropwise to a three-necked flask, and the dropping rate of the solution was 1 drop to 3 drops per second. The resulting mixed solution was kept at a constant temperature of 57 ° C and stirred for 12 to 24 hours. The mixed solution first became creamy white, and as the reaction time progressed, the reaction solution gradually turned orange-red or red-brown. After the reaction, the solvent in the solution was removed by vacuum rotary evaporation. Then, a viscous reddish brown liquid or slurry product is obtained.

Example 3: Synthesis of DDSA-grafted PEI

10 g of ethylenediamine-terminated dendritic poly(ethyleneimine) ((PEI, BASF product, molecular weight about 800 g/mol) and 30 ml of anhydrous acetone were dissolved in a 250 ml three-necked flask, and stirred under a nitrogen atmosphere to contain PEI. A three-necked solution of the solution was placed in an oil bath at 58 C. 33.55 g of dodecenyl succinic anhydride (DDSA, molecular weight of about 268.39 g/mol) was dissolved in 100 ml of anhydrous acetone using a 150 ml constant pressure dropping funnel. When the temperature of the solution was equilibrated at 58 ° C, the DDSA solution was added dropwise to a three-necked flask, and the dropping rate of the solution was 1 drop to 3 drops per second. The obtained mixed solution was kept at a constant temperature of 58 ° C and stirred for 12 to 24 hours. As time progresses, the reaction solution gradually becomes viscous. After the reaction, the solvent in the solution is removed by vacuum rotary evaporation, and then a viscous reddish brown liquid or slurry product is obtained.

Example 4: Mixing fluorinated graphite with prepared oil-soluble graft/comb polyamine surfactant

First, 2 × 8 × 10 ^-4 g, 4 × 8 × 10 ^-4 g, 6 × 8 × 10 ^-4 g, 8 × 8 × 10 ^-4 g, 10 × 8 × 10 ^-4 g, respectively ×8×10 ^-4 g, 20×8×10 ^-4 g, 25×8×10 ⁻⁴ g, 30×8×10 ⁻⁴ g, 40×8×10 ⁻⁴ g, 50×8×10 ^{− 4} g, 75 × 8 × 10 ^-4 g, 100 × 8 × 10 ^-4 g of fluorinated graphite (see Figure 8 for scanning electron micrographs) and 500 × 8 × 10 ^-4 g of oil-soluble graft/comb polyamine surface Activity (25 x 8 x 10 ^-4 g PIBSA-grafted PEI, 25 x 8 x 10 ^-4 g DDSA-grafted PEI and 450 x 8 x 10 ^-4 g PIBSA-grafted HPA-X) in 10 ml glass vials The mixture was mixed, and then the base oil was added to a different glass bottle to a weight of the mixture in the glass bottle of 8.0 g. The mixture in the glass bottle was evenly dispersed by ultrasonication.

It can be seen that from a lower solid concentration to a higher solid concentration, the well-dispersed fluorinated graphite mixture in the base oil is a stable pale yellow transparent solution or microemulsion, and is stable for at least one month at room temperature, different A photograph of the concentration of the fluorinated graphite material dispersed in the base oil is shown in Figure 3, where the left panel is a mixture of high fluorinated graphite and the right is a mixture of low fluorinated graphite. The XRD spectrum of the graphite fluoride material and the graphite fluoride dispersed by the polyamine surfactant is shown in Fig. 4.

Example 5: Ball plate experiment

The experimental object is the mixture obtained in Example 4. The experimental standard of the ball disk experiment is ASTM G99, and the schematic diagram of the ball disk experiment is shown in Fig. 5. In the ball plate experiment, the lubricating oil was immersed on the surface of the ball and disk samples, and the test parameters are shown in Table 1.

Table 1: Ball test test parameters

Figure 6 is a graph showing the average friction coefficient <μ> of the oil-soluble graft/comb polyamine surfactant at a mass fraction concentration of 500 × 10 ^-4 and the mass fraction of fluorinated graphite (CF) _n in the base oil. Functional relationship. Obviously, as the mass fraction of fluorinated graphite (CF) _n in the base oil increases, <μ> gradually decreases. As can be seen from Fig. 6, the lowest value of <μ> is about 0.05. In Fig. 6, the average friction coefficient <μ> is the time average of the friction coefficient (for the calculation method, see the following formula), and the optimum test time is 900 s.

Δμ is calculated by the minimum absolute deviation method:

Figure 7 shows the friction coefficient μ as a function of time for the two base oil dispersions of the fluorinated graphite (CF) _n base oil dispersion and the base oil. The mass fraction of fluorinated graphite in the base oil dispersion containing fluorine-containing graphite is 50×10 ^-4 , and the mass fraction concentration of the oil-soluble graft/comb polyamine surfactant is 500×10 ^-4 . Based on the test results in Figures 6 and 7, it is apparent that well-dispersed fluorinated graphite can be effectively used for lubricating oils or grease additives.

In the description of the present invention, it is to be understood that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, features defining "first" and "second" may include one or more of the features either explicitly or implicitly. In the description of the present invention, the meaning of "a plurality" is two or more unless specifically and specifically defined otherwise.

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.

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

An oil-soluble polyamine, characterized in that the oil-soluble polyamine is a graft polymer, and comprises a polyamine skeleton and an oil-soluble graft segment attached to the polyamine skeleton,

Wherein, the chemical structure of the polyamine skeleton comprises polyethyleneimine, polyethene polyamine, polyallylamine, polyvinylamine, polylysine, poly(4-aminostyrene), poly(N-(3) -aminopropyl)alkylimine), poly(2-aminoethyl acrylate), at least one of a polyamide-amine dendrimer and a polyalkylenimine dendrimer,

The oil-soluble graft segment includes at least one of a hydrocarbyl segment and an alkoxy segment.
The oil-soluble polyamine according to claim 1, wherein the chemical structure of the polyamine skeleton comprises at least one of the following:

Wherein x is an integer greater than 1, and R is a hydrogen atom or an alkyl group.
The oil-soluble polyamine according to claim 1 or 2, wherein the polyamine skeleton has a molecular weight of from 100 to 20,000,000 Daltons.
The oil-soluble polyamine according to claim 3, wherein the polyamine skeleton has a molecular weight of 200 -100,000 Daltons.
The oil-soluble polyamine according to any one of claims 1 to 4, wherein the hydrocarbyl segment and the hydrocarbyloxy group are each independently a small molecular segment or a single-end polymer segment.
The oil-soluble polyamine according to claim 5, wherein the small molecular segment comprises at least one of a fatty acid derivative and an unsaturated alpha olefin derivative.
The oil-soluble polyamine according to claim 6, wherein the fatty acid derivative comprises at least one of a fatty acid and a fatty isocyanate, and the unsaturated alpha olefin derivative comprises a succinic anhydride-terminated alpha olefin.
The oil-soluble polyamine according to claim 7, wherein the fatty acid is a C 6 -C 22 fatty acid, the fatty isocyanate is a C 6 -C 22 fatty isocyanate, and the succinic anhydride-terminated alpha olefin is C. 6- C 22 alkylalkenyl succinic anhydride.
The oil-soluble polyamine according to claim 5, wherein the single-end polymer segment comprises a mono-capped functional polyolefin, wherein the terminal functional group comprises at least one of an acid anhydride, an isocyanate group, and a carboxyl group. .
The oil-soluble polyamine according to claim 9, wherein the mono-capped functional polyolefin comprises monocapped functional polyisobutylene, monocapped functional polybutene, and monocapped functional polybutadiene. At least one.
The oil-soluble polyamine according to claim 10, wherein the mono-capped functional polyolefin comprises at least one of the following:

Wherein m1, m2, n and n1 are each independently an integer greater than 1, i+j+k=1.
The oil-soluble polyamine according to any one of claims 1 to 11, wherein a molar ratio of the oil-soluble graft segment to the polyamine skeleton is (500-1):1.
The oil-soluble polyamine according to claim 12, wherein the molar ratio of the oil-soluble graft segment to the polyamine skeleton is (200-2):1.
A method of dispersing a halogenated carbon material, comprising:

Mixing the oil-soluble polyamine according to any one of claims 1 to 13 and the halogenated carbon material to obtain a first mixture;

The first mixture is added to an organic medium, and the resulting mixture is sonicated to obtain a second mixture.
The method according to claim 14, wherein said halogenated carbon material comprises oxidized fluorinated graphite, organic graft modified fluorinated graphite, fluorinated graphite, fluorinated graphene, fluorinated graphene alkyne, fluorinated At least one of carbon nanorods, fluorinated carbon nanowires, fluorinated carbon nanotubes, fluorinated carbon nanospheres, fluorinated amorphous carbon, fluorinated carbon fibers, and fluorinated carbon black.
The method according to claim 14 or 15, wherein the organic medium is a lubricating base oil.
A mixture comprising a halocarbon material, which is prepared by the method of any one of claims 14-16.