CN106519248A - Oil-soluble polyamine, dispersion method of halocarbon material and mixture containing halocarbon material - Google Patents
Oil-soluble polyamine, dispersion method of halocarbon material and mixture containing halocarbon material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/0206—Polyalkylene(poly)amines
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C08G83/004—After treatment of dendrimers
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- 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
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
- C10M2201/042—Carbon; Graphite; Carbon black halogenated, i.e. graphite fluoride
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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Abstract
The invention discloses oil-soluble polyamine, a dispersion method of a halocarbon material and a mixture containing a halocarbon material. The oil-soluble polyamine is a graft polymer, and includes a polyamine skeleton and an oil-soluble graft chain segment connected to the polyamine skeleton, wherein the chemical structure of the polyamine skeleton comprises at least one of polyethyleneimine, polyethylene polyamine, poly(allylamine), polyvinylamine, polylysine, poly(4-aminostyrene), poly(N-(3-aminopropyl)alkylimine) and poly(2-aminoethyl alkyl acrylate), polyamidoamine dendrimer and poly(alkylimine) dendritic polymer, and the oil-soluble graft chain segment comprises at least one of alkyl chain segment and alkoxy chain segment. The inventor finds that the oil-soluble polyamine can rapidly and effectively disperse the halocarbon material in an organic medium evenly and stably, and under a room temperature condition, the dispersed halocarbon material can exist stably for at least one month.
Description
Technical field
The present invention relates to field of material technology, in particular it relates to oil-soluble polyamine, the method for dispersion halogenation material with carbon element and contain
There is the mixture of halogenation material with carbon element.
Background technology
Many products are being prepared, such as in the technique such as oil painting, coating, mastic, lubricating oil, fluorinated graphite material is in liquid medium
In stability be very important factor, and fluorinated graphite material be one kind be difficult scattered material using conventional meanses, because
And dispersed fluorinated graphite is challenging.Amine has been used for the dispersed fluorinated graphite in water or organic media, by fluorine
The electrophilic nucleation power of the similar bonding force existed between fossil ink material and amine.This reaction can cause fluorographite material
Material is partially dispersed in amine.However, the amine of dispersed fluorinated graphite, such as polyetheramine or alkylamine is traditionally used for, with relatively low
Amino number density, and relatively low amino number density limits the dispersibility of its dispersed fluorinated graphite material.
Thus, still have much room for improvement with regard to the correlational study of fluorocarbon material dispersibility at present.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.For this purpose, the present invention
One purpose is to propose a kind of oil-soluble polyamine that can effectively disperse halogenation material with carbon element.
In one aspect of the invention, the invention provides a kind of oil-soluble polyamine.Embodiments in accordance with the present invention, the oil
Dissolubility polyamine is graft polymers, and including polyamine backbone and the oil-soluble being connected in polyamine backbone grafting segment, its
In, the chemical constitution of the polyamine backbone includes polyethyleneimine, polyethylene polyamine, polyallylamine, and polyvinylamine, poly rely ammonia
Acid, poly- (4- aminostyryls), poly- (N- (3- aminopropyls) alkyl imino), poly- (2- amino-ethyl alkyl acrylates) gather
At least one in amide-amine type dendrimer and poly- alkyl imino dendritic, the oil-soluble are grafted segment
Including at least one in alkyl segment and oxyl segment.Inventor's discovery, can be quickly effective using the oil-soluble polyamine
Halogenation material with carbon element uniform, stable is scattered in organic media, under room temperature condition, the halogenation material with carbon element after dispersion can be steady
Surely exist at least one month, the phenomenon such as will not be layered, settle.Specifically, it is poly- using the oil-soluble
Amine can simply and easily by halogenation material with carbon element, and such as fluorinated graphite material is scattered in lubricating oil or grease, the profit for obtaining
Lubricating oil or Lubricating Greases frictional property are significantly improved.It is and the method is simple to operate, convenient, it is not special to equipment and technical staff
Require, it is easy to accomplish, cost is relatively low.
Embodiments in accordance with the present invention, the chemical constitution of the polyamine backbone include following at least one:
Wherein, x is the integer more than 1, and R is hydrogen atom or alkyl.
Embodiments in accordance with the present invention, the molecular weight of the polyamine backbone is 100-20,000,000 dalton, preferably
200-100,000 dalton.
Embodiments in accordance with the present invention, the alkyl segment and oxyl segment are each independently small molecule segment or list
Terminated polymer segment.
Embodiments in accordance with the present invention, the small molecule segment include derivative of fatty acid and unsaturated alhpa olefin derivant
In at least one.
Embodiments in accordance with the present invention, the derivative of fatty acid include in fatty acid and aliphatic isocyanate at least one
Kind, the unsaturated alhpa olefin derivant includes the alhpa olefin of succinic anhydrides end-blocking.Embodiments in accordance with the present invention, the fatty acid
For C6-C22Fatty acid, the aliphatic isocyanate are C6-C22Aliphatic isocyanate, the alhpa olefin of succinic anhydrides end-blocking is
C6-C22Alkylalkenyl succinic anhydrides.
Embodiments in accordance with the present invention, single terminated polymer segment include single end-blocking functional polyolefins, wherein, end official
Energy group includes at least one in anhydride, isocyanate groups and carboxyl.
Embodiments in accordance with the present invention, single end-blocking functional polyolefins include that single end-blocking functional polyisobutylenes, list are blocked
At least one in sense polybutene and single end-blocking sense polybutadiene.
Embodiments in accordance with the present invention, single end-blocking functional polyolefins include following at least one:
Wherein, m1, m2, n and n1 are each independently the integer more than 1, i+j+k=1.
The mol ratio of embodiments in accordance with the present invention, the oil-soluble grafting segment and the polyamine backbone is (500-1):
1, preferably (200-2):1.
In another aspect of this invention, the present invention provided a kind of method of dispersion halogenation material with carbon element.According to the present invention
Embodiment, the method includes:By foregoing oil-soluble polyamine and the halocarbon material mixing, the first mixing is obtained
Thing;And add first mixture in organic media, and by resulting mixture supersound process, obtain the second mixing
Thing.Halogenation material with carbon element uniform, stable, using the method, fast and effectively can be scattered in organic media by inventor's discovery
In, under room temperature condition, the halogenation material with carbon element after dispersion can will not be layered, be settled with stable existence at least one month
Etc. phenomenon.Specifically, using the method can simply and easily by halogenation material with carbon element, such as fluorinated graphite material,
It is scattered in lubricating oil or grease, the lubricating oil or Lubricating Greases frictional property for obtaining is significantly improved.And the method operation letter
It is single, it is convenient, there is no particular/special requirement to equipment and technical staff, it is easy to accomplish, cost is relatively low.
Embodiments in accordance with the present invention, the halogenation material with carbon element include aoxidizing fluorographite, and organic graft modification is fluorinated stone
Ink, fluorographite, fluorinated graphene, fluorographite alkynes are fluorinated carbon nano rod, are fluorinated carbon nanocoils, carbon fluoride nano-tube, fluorination
Nano carbon balls, fluorinated amorphous carbons, at least one in fluorinated carbon fiber and fluorination white carbon black.
Embodiments in accordance with the present invention, the organic media are lube base oil.
In another aspect of the invention, the invention provides a kind of mixture containing halogenation material with carbon element.According to the present invention
Embodiment, should the mixture containing halogenation material with carbon element be using foregoing method prepare.Inventor is found surprisingly that,
It is somebody's turn to do the mixture containing halogenation material with carbon element to remember in nano composite material effective for lubricating oil, grease, especially uses
When in lubricating oil or grease, the lubricating oil containing the mixture or grease have preferable friction resistant.
Description of the drawings
Fig. 1 shows embodiments in accordance with the present invention, the dispersion mechanism schematic diagram of dispersed fluorinated graphite;
Fig. 2 shows embodiments in accordance with the present invention, synthesizes the schematic diagram of oil-soluble polyamine surfactant;
Fig. 3 shows embodiments in accordance with the present invention, and the fluorinated graphite material of variable concentrations is dispersed in the photograph in base oil
Piece;
Fig. 4 shows embodiments in accordance with the present invention, fluorinated graphite material and utilizes the scattered fluorine of polyamine surfactant
The XRD spectra of graphite;
Fig. 5 shows embodiments in accordance with the present invention, ball disk experiment schematic diagram;
Fig. 6 shows embodiments in accordance with the present invention, average friction coefficient<μ>With fluorographite (CF)nIn base oil
Mass fraction functional relationship;
Fig. 7 shows embodiments in accordance with the present invention, coefficientoffrictionμ fluorographite (CF)nQuality in base oil point
Several functional relationships.
Fig. 8 shows embodiments in accordance with the present invention, fluorographite (CF)nStereoscan photograph.
Specific embodiment
The present invention is completed based on the following discovery of inventor:
Inventor is by studying discovery, the electrophilic nucleophilic of the similar bonding force by existing between fluorinated graphite material and amine
Active force, can be effectively by Graphite fluoride Composite Deposition in organic media.And this reaction can cause fluorinated graphite material part
It is dispersed in amine.However, the amine of dispersed fluorinated graphite, such as polyetheramine or alkylamine is traditionally used for, with relatively low amino
Number density, and relatively low amino number density limits the dispersibility of its dispersed fluorinated graphite material.Meanwhile, dispersant and particle
There is the such as gravitation such as Van der Waals force between non-bonding atom in surface group.It is above-mentioned between low-molecular-weight dispersant and particle
Gravitation is not obvious, but then entirely different using polymeric dispersant situation.Construction unit quantity in polymer chain is very
It is huge, and the size of each construction unit ought with a small molecular phase.Above-mentioned gravitation does not have a directivity, and will not saturation, because
This, the graviational interaction between polymer chain and particle is sufficiently large, and polymer can be caused to cover the part surface of particle.Based on upper
Electrophilic-nucleation and the graviational interaction of similar bonding force is stated, inventor devises a series of new oil comprising polyamine structure
Dissolubility polyamine surfactant, the polyamine surfactant can be used for halogenation material with carbon element (including but not limited to fluorographite
Material) it is scattered in organic media.Under room temperature condition, the halogenation material with carbon element after dispersion can with stable existence at least one month when
Between.
In view of this, in one aspect of the invention, the invention provides a kind of oil-soluble polyamine.Reality of the invention
Example is applied, the oil-soluble polyamine is graft polymers, and connect including polyamine backbone and the oil-soluble being connected in the polyamine backbone
Branch chain section, wherein, the chemical constitution of the polyamine backbone includes polyethyleneimine, polyethylene polyamine, polyallylamine, polyethylene
Amine, poly-D-lysine, poly- (4- aminostyryls), poly- (N- (3- aminopropyls) alkyl imino), poly- (2- amino-ethyl acrylic acid
Arrcostab), at least one in polyamidoamine dendrimer and poly- alkyl imino dendritic, the oil soluble
Property grafting segment include at least one in alkyl segment and oxyl segment.Inventor's discovery, can using the oil-soluble polyamine
So that fast and effectively halogenation material with carbon element uniform, stable is scattered in organic media, the halocarbon under room temperature condition, after dispersion
Material the phenomenon such as can will not be layered, settle with stable existence at least one month.Specifically, utilize
The oil-soluble polyamine can simply and easily by halogenation material with carbon element, and such as fluorinated graphite material is scattered in lubricating oil or grease
In, the lubricating oil or Lubricating Greases frictional property for obtaining is significantly improved.It is and the method is simple to operate, convenient, to equipment and technology
Personnel do not have particular/special requirement, it is easy to accomplish, cost is relatively low.
Embodiments in accordance with the present invention, the concrete grammar for synthesizing oil-soluble polyamine surfactant are not particularly limited, can
With the high molecular weight reactive type for adopting can be as amino and isocyanate groups between additive reaction, between amino and anhydride
Substitution reaction, and amidation process etc..Mol ratio between grafted hydrophobic segment and hydrophilic back bone is between 500 and 1, excellent
It is selected between 200 and 2.The schematic diagram of synthesis oil-soluble polyamine surfactant is shown in Fig. 2.Some synthesis oil-soluble polyamine surfaces are lived
Property agent specific example is as follows:
Dendroid polyethyleneimine (PEI) and polyisobutylene butanedioic anhydride (PIBSA) reaction
Dendroid polyethyleneimine (PEI) r and dodecenylsuccinic acid acid anhydride (DDSA) reaction
Polyvinylamine (PVAm) and dodecenylsuccinic acid acid anhydride (DDSA) reaction
Polyvinylamine (PVAm) polyisobutylene butanedioic anhydride (PIBSA) reacts
Embodiments in accordance with the present invention, the chemical constitution of the polyamine backbone that can be adopted include polyethyleneimine, many ethylene
Polyamines, polyallylamine, polyvinylamine, poly-D-lysine, poly- (4- aminostyryls), it is poly- that (N- (3- aminopropyls) alkyl is sub-
Amine), poly- (2- amino-ethyl alkyl acrylates), polyamidoamine dendrimer and poly- alkyl imino dendroid polymerization
At least one in thing.I.e. polyamine backbone can be made up of above-mentioned one or two and two or more structures, and inventor has found,
Using said structure, amino number density is higher, can effectively improve the ability of dispersion halogenation material with carbon element, obtains performance and more preferably divides
Scattered product.During for lubricating oil, its friction resistant performance is significantly improved.
Embodiments in accordance with the present invention, the chemical constitution of the polyamine backbone that can be adopted include following at least one:
Wherein, x is the integer more than 1, and R is hydrogen atom or alkyl.
It should be noted that " * " represents the position being connected with other chemical constitutions in the chemical constitution of this paper.
In some specific embodiments of the present invention, under the chemical constitution of the polyamine backbone that can be adopted is included but is not limited to
Array structure:
Wherein, n is the integer more than 1.
Embodiments in accordance with the present invention, the molecular weight of above-mentioned polyamine backbone are not particularly limited.In some realities of the present invention
Apply in example, the molecular weight of polyamine backbone is 100-20,000,000 dalton.In some preferred embodiments, polyamine backbone point
Son amount is 200-100,000 dalton.Thus, above-mentioned electrophilic-nucleation and graviational interaction are stronger, for halogenation material with carbon element
Dispersion effect and stability it is preferable.
Embodiments in accordance with the present invention, oil-soluble grafting segment are included in alkyl segment and oxyl segment at least
It is a kind of.Specifically, single end-blocking hydrocarbyl chain and oxyalkyl chain are the most frequently used raw materials of grafting/pectinate texture.On the one hand, these
Hydrocarbyl chain and oxyalkyl chain can be small molecule segment such as derivative of fatty acid, unsaturated alhpa olefin derivant.Can be specifically fat
The alhpa olefin of fat acid, aliphatic isocyanate and succinic anhydrides end-blocking.Wherein, fatty acid is preferably C6-C22Fatty acid, fatty isocyanide
Acid esters is preferably C6-C22Aliphatic isocyanate, the alhpa olefin of succinic anhydrides end-blocking are preferably C6-C22Alkylalkenyl succinic anhydrides, example
Dodecenylsuccinic acid acid anhydride, positive octenyl succinic acid anhydride, nonenyl succinic acid acid anhydride, four succinic anhydrides are included but is not limited to such as.By
This, can further improve the dispersion effect of halogenation material with carbon element.On the other hand, these hydrocarbyl chains and oxyalkyl chain can be single envelope
End polymer, such as single end-blocking functional polyolefins, wherein, end functional group can be anhydride, isocyanate groups and carboxylic group.
For single end-blocking functional polyolefins, these end functional groups can be grafted to polymer chain by different synthetic methods
On, such as alkene-anhydride additive reaction, in the functional initiator adopted in conventional radical polymerization reaction, anionic polymerisation
Function terminating reaction, controllable/active free radical polymerization etc..Wherein, it is preferred that the preferable grafting method of versatility and stability
It is the functional initiator used in conventional free radical polymerization.Peroxide initiator and nitrine initiator are that synthesis oil-soluble gathers
The most frequently used initiator of alkene.In building-up process, 4,4 '-azo two (4- cyano group -1- amylalcohols) and 4,4 '-azo, two (4- cyanogen
Valeric acid acid) it is the most frequently used initiator in initiation reaction.Both chemical constitution difference are as follows:
In conventional free radical polymerization, there are the two kinds of chain terminations of coupling termination and disproportionation termination.Unlike most freedom
The base polymerization product that to tend to coupling termination high to obtain Narrow Molecular Weight Distribution and molecular weight, in order to obtain single end-blocking functional poly
Alkene and the product of relatively low molecular weight, need appropriate high temperature to bring it about disproportionation termination reaction.Additionally, in order that discrimination
Change terminating reaction to be smoothed out also needing to select appropriate monomer, 2,4, the 4- trimethyl penta of hydrophobic vinylic monomer that such as body replaces
Alkene, chain alkyl -1- alkene, alpha-olefin, vinyl acetate and its derivant, long chain alkyl methacrylate and chain alkyl propylene
Acid esters etc..
Used as a typical case, the synthesis of poly alpha olefin, such as the following institute of synthetic route of one-ended hydroxy poly- (1- octenes)
Show:
Cause:
Extend,
End-blocking (predominantly disproportionation termination)
Embodiments in accordance with the present invention, single end-blocking functional polyolefins include that single end-blocking functional polyisobutylenes, list are blocked
At least one in sense polybutene and single end-blocking sense polybutadiene.
Embodiments in accordance with the present invention, single end-blocking functional polyolefins include following at least one:
Wherein, m1, m2, n and n1 are each independently the integer more than 1, and i+j+k=1, n1 are preferably the whole of 20-100
Number.Segment is grafted using above-mentioned single functional polyolefins that block as oil-soluble, can effectively improve the dispersion effect of halogenation material with carbon element
Fruit and stability.
The mol ratio of embodiments in accordance with the present invention, the oil-soluble grafting segment and the polyamine backbone is in (200-
1):1, preferably (50-2):1.Within the above range, the dispersion effect of polyamine surfactant is preferable, and the mixture of acquisition is steady
Qualitative good, at least stable existence one month under room temperature condition will not occur layering, sedimentation phenomenon.For lubricating oil or lubrication
During fat, its friction resistant performance can be effectively improved.
In another aspect of this invention, the invention provides a kind of method of dispersion halogenation material with carbon element.It is of the invention
Embodiment, the method include:By foregoing oil-soluble polyamine and the halocarbon material mixing, the first mixture is obtained;
And add first mixture in organic media, and by resulting mixture supersound process, obtain the second mixture.
Inventor's discovery, using the method, fast and effectively can be scattered in halogenation material with carbon element uniform, stable in organic media,
Under room temperature condition, the halogenation material with carbon element after dispersion can will not be layered, settle etc. and be existing with stable existence at least one month
As.Specifically, simply and easily by halogenation material with carbon element, such as fluorinated graphite material can be disperseed using the method
In lubricating oil or grease, the lubricating oil or Lubricating Greases frictional property for obtaining is significantly improved.And the method is simple to operate, side
Just, there is no particular/special requirement to equipment and technical staff, it is easy to accomplish, cost is relatively low.
Specifically, by taking fluorographite as an example, its dispersion mechanism is as shown in Figure 1.Specifically, the crystal structure of fluorographite
Not always preferably, can there are some defects, such as crystal structure edge can have ≡ CF, >=CF ,-CF2- and-CF3Group.
These defects are the break-through point of dispersed fluorinated graphite material.Based on the amino in oil-soluble polyamine surfactant and fluorination stone
Between electrophilic-affine interaction and oil-soluble polyamine surfactant and fluorographite between carbon atom in ink, gravitation is made
With oil-soluble polyamine surfactant is covered in the part surface of fluorographite, is further grafted segment by oil-soluble preferable
It is fat-soluble so that fluorographite is stable, be homogeneously dispersed in organic media.
Embodiments in accordance with the present invention, the concrete species of the halogenation material with carbon element are not particularly limited.The one of the present invention
In a little embodiments, halogenation material with carbon element can include oxidation fluorographite, organic graft modification fluorographite, fluorographite, fluorination
Graphene, fluorographite alkynes are fluorinated carbon nano rod, are fluorinated carbon nanocoils, and carbon fluoride nano-tube is fluorinated Nano carbon balls, is fluorinated nothing
Setting carbon, at least one in fluorinated carbon fiber and fluorination white carbon black.Thus, dispersion effect is preferable, and stability preferably, particularly will
When halogenation material with carbon element after dispersion is used for preparing lubricating oil or grease, the lubricating oil or grease for obtaining has excellent anti-friction
Wipe performance.
Embodiments in accordance with the present invention, the organic media are lube base oil.Thus, have and can effectively obtain friction resistant
The preferable lubricating oil of performance.
In another aspect of this invention, the invention provides a kind of mixture containing halogenation material with carbon element.According to the present invention
Embodiment, should the mixture containing halogenation material with carbon element be using foregoing method prepare.Inventor is found surprisingly that,
During the mixture containing halogenation material with carbon element can be effective for lubricating oil, grease and nano-polymer composite material, especially
When which is in lubricating oil or grease, the lubricating oil containing the mixture or grease have preferable friction resistant.Separately
Outward, it is foregoing dispersion halogenation material with carbon element method all features and a little suitable for this contain halogenation material with carbon element mix
Compound, this is no longer going to repeat them.
Embodiments of the invention are described below in detail.The embodiments described below is exemplary, is only used for explaining this
It is bright, and be not considered as limiting the invention.Unreceipted particular technique or condition in embodiment, according to text in the art
Offer described technology or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument,
For can by city available from conventional products.
Embodiment 1:Synthesis PIBSA- grafting PEI
The dendroid poly- (aziridine) (PEI, BASF product, molecular weight are about 800g/mol) that 10g ethylenediamines are blocked
Dissolved with 250 milliliters of there-necked flasks with 30ml anhydrous propanones.Under stirring condition, nitrogen atmosphere, the there-necked flask containing PEI solution is put
In 58 DEG C of oil baths.Using 150 milliliters of constant pressure funnels, by 47.6g polyisobutylene butanedioic anhydrides (PIBSA), (molecular weight is about
1100g/mol) it is dissolved in 100ml normal hexane.When the hygral equilibrium of solution is at 58 DEG C, PIBSA solution is added drop-wise in there-necked flask,
The rate of addition of solution is that -3 drop of 1 drop is per second.The mixed solution for obtaining keeps 58 DEG C of constant temperature, stirs 12~24 hours.Mixing is molten
Liquid is changed into creamy-white first, and with the carrying out in response time, reaction solution gradually becomes orange red or bronzing.Reaction
Afterwards, the solvent in solution is removed by rotary evaporation in vacuo.Then, obtained viscosity bronzing is liquid or pulpous state is produced
Thing.
Embodiment 2:Synthesis PIBSA- grafting HPA-X
By 5.5g weight polyamines X (hpa-x, Tao Shi chemical products, about 275 grams/mol of molecular weight, a kind of polyethyleneimine
With the mixture of small molecule amine) and 30ml anhydrous propanones dissolving 250 milliliters of there-necked flasks dissolving, stir, under the conditions of nitrogen atmosphere
There-necked flask containing hpa-x solution is placed in 57 DEG C of oil baths.Using 150 milliliters of constant pressure funnels by 44g polyisobutylene fourths
Dicarboxylic anhydride (PIBSA) (about 1100 grams/mol of molecular weight) is dissolved in 100 milliliters of hexanes.When the hygral equilibrium of solution is at 57 DEG C,
PIBSA solution is added drop-wise in there-necked flask, the rate of addition of solution is that -3 drop of 1 drop is per second.The mixed solution for obtaining keeps constant temperature
57 DEG C, stir 12~24 hours.Mixed solution is changed into creamy-white first, and with the carrying out in response time, reaction solution by
Crossfade into orange red or bronzing.After reaction, the solvent in solution is removed by rotary evaporation in vacuo.Then, glued
The bronzing of property is liquid or pulpous state product.
Embodiment 3:Synthesis DDSA- grafting PEI
The dendroid poly- (aziridine) ((PEI, BASF product, molecular weight are about 800g/mol) that 10g ethylenediamines are blocked
Dissolved with 250 milliliters of there-necked flasks with 30ml anhydrous propanones, the there-necked flask containing PEI solution is put under the conditions of stirring, nitrogen atmosphere
In 58 DEG C of oil baths.Using 150 milliliters of constant pressure funnels, by 33.55g dodecenylsuccinic acids acid anhydride, (DDSA, molecular weight are about
268.39g/mol) it is dissolved in 100 milliliters of anhydrous propanones.When the hygral equilibrium of solution is at 58 DEG C, DDSA solution is added drop-wise to into three mouthfuls
In bottle, the rate of addition of solution is that -3 drop of 1 drop is per second.The mixed solution for obtaining keeps 58 DEG C of constant temperature, stirs 12~24 hours.With
The carrying out in response time, reaction solution gradually becomes viscous.After reaction, the solvent in solution is removed by rotary evaporation in vacuo
Go.Then, obtained viscosity bronzing is liquid or pulpous state product.
Embodiment 4:By fluorographite and the oil-soluble grafting/pectination polyamine surfactant for preparing mixing
First, respectively by 2 × 8 × 10-4g,4×8×10-4g,6×8×10-4g,8×8×10-4g,10×8×10-4g,
15×8×10-4g,20×8×10-4g,25×8×10-4g,30×8×10-4g,40×8×10-4g,50×8×10-4g,75
×8×10-4g,100×8×10-4G fluorographites (stereoscan photograph is shown in Fig. 8) and 500 × 8 × 10-4G oil-solubles grafting/comb
Shape polyamine surface activity (25 × 8 × 10-4G PIBSA- grafting PEI, 25 × 8 × 10-4G DDSA- grafting PEI and 450 × 8 ×
10-4G PIBSA- are grafted HPA-X) mix in 10ml vials, then, add base oil in different glass bottle to vial
The weight of middle mixture is 8.0g.And the mixture in vial is uniformly dispersed by ultrasound.
Observation understands, from relatively low solid concentration to higher solid concentration, the fluorination stone of fine dispersion in base oil
Black mixture is at least stable existence one month under stable light yellow transparent solution or microemulsion, and room temperature condition,
The photo that the fluorinated graphite material of variable concentrations is dispersed in base oil is shown in Fig. 3, and wherein, left figure mixes for high fluorographite concentration
Thing, right figure are less fluorinated graphite concentration mixture.Fluorinated graphite material and utilize the scattered fluorographite of polyamine surfactant
XRD spectra see Fig. 4.
Embodiment 5:Ball disk is tested
Experimental subject is the mixture that obtains in embodiment 4, and the experimental standard of ball disk experiment is ASTM G99, the experiment of ball disk
Schematic diagram is shown in Fig. 5.In the experiment of ball disk, lubricating oil is immersed on the surface of ball and disk sample, and test parameter is as shown in table 1.
Table 1:Ball disk experiment test parameter
Fig. 6 is 500 × 10 for the mass fraction concentration of oil-soluble grafting/pectination polyamine surfactant-4Under the conditions of, averagely
Coefficient of friction<μ>With fluorographite (CF)nThe functional relationship of the mass fraction in base oil.It will be evident that with fluorographite
(CF)nThe increase of the mass fraction in base oil,<μ>It is gradually lowered.As seen from Figure 6,<μ>Minimum be about 0.05.Fig. 6
In, average friction coefficient<μ>It is the time average (computational methods see below formula) of coefficient of friction, optimal test period is 900s.
Δ μ is calculated by least absolute deviation method:
Fig. 7 is shown containing fluorographite (CF)nTwo groups of samples of base oil dispersion liquid and base oil coefficientoffrictionμ at any time
Between the functional relationship that changes.Wherein containing fluorographite base oil dispersion liquid in fluorographite mass fraction concentration be 50 ×
10-4, the mass fraction concentration of oil-soluble grafting/pectination polyamine surfactant is 500 × 10-4.Based on the examination in Fig. 6 and Fig. 7
Test result, hence it is evident that it can be seen that the fluorographite of fine dispersion can be effective for lubricating oil or grease additive.
In describing the invention, it is to be understood that term " first ", " second " are only used for describing purpose, and can not
It is interpreted as indicating or implying relative importance or the implicit quantity for indicating indicated technical characteristic.Thus, define " the
One ", the feature of " second " can be expressed or implicitly include one or more this feature.In describing the invention,
" multiple " are meant that two or more, unless otherwise expressly limited specifically.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
Example ", or the description of " some examples " etc. mean specific features with reference to the embodiment or example description, structure, material or spy
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office
Combined in one or more embodiments or example in an appropriate manner.Additionally, in the case of not conflicting, the skill of this area
The feature of the different embodiments or example described in this specification and different embodiments or example can be tied by art personnel
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
1. a kind of oil-soluble polyamine, it is characterised in that the oil-soluble polyamine is graft polymers, and including polyamine backbone and company
The oil-soluble grafting segment being connected in the polyamine backbone,
Wherein, the chemical constitution of the polyamine backbone includes polyethyleneimine, polyethylene polyamine, polyallylamine, polyvinylamine, many
Polylysine, poly- (4- aminostyryls), poly- (N- (3- aminopropyls) alkyl imino), poly- (2- amino-ethyl acrylic acid alkyls
Ester), at least one in polyamidoamine dendrimer and poly- alkyl imino dendritic,
The oil-soluble grafting segment includes at least one in alkyl segment and oxyl segment.
2. oil-soluble polyamine according to claim 1, it is characterised in that the chemical constitution of the polyamine backbone includes following
At least one:
Wherein, x is the integer more than 1, and R is hydrogen atom or alkyl.
3. oil-soluble polyamine according to claim 2, it is characterised in that the molecular weight of the polyamine backbone is 100-20,
000,000 dalton, preferably 200-100,000 dalton.
4. oil-soluble polyamine according to claim 1, it is characterised in that the alkyl segment and oxyl segment are each only
It is on the spot small molecule segment or single terminated polymer segment.
5. oil-soluble polyamine according to claim 4, it is characterised in that the small molecule segment includes derivative of fatty acid
With at least one in unsaturated alhpa olefin derivant,
Preferably, the derivative of fatty acid includes at least one in fatty acid and aliphatic isocyanate, the unsaturated α alkene
Hydrocarbon derivative includes the alhpa olefin of succinic anhydrides end-blocking,
It is highly preferred that the fatty acid is C6-C22Fatty acid, the aliphatic isocyanate are C6-C22Aliphatic isocyanate, it is described
The alhpa olefin of succinic anhydrides end-blocking is C6-C22Alkylalkenyl succinic anhydrides.
6. oil-soluble polyamine according to claim 4, it is characterised in that single terminated polymer segment includes single end-blocking
Functional polyolefins, wherein, end functional group includes at least one in anhydride, isocyanate groups and carboxyl,
Preferably, single end-blocking functional polyolefins include list end-blocking functional polyisobutylenes, single end-blocking sense polybutene and single envelope
At least one in the sense polybutadiene of end,
It is highly preferred that single end-blocking functional polyolefins include following at least one:
Wherein, m1, m2, n and n1 are each independently the integer more than 1, i+j+k=1.
7. oil-soluble polyamine according to claim 1, it is characterised in that the oil-soluble grafting segment and the polyamine bone
The mol ratio of frame is (500-1):1, preferably (200-2):1.
8. it is a kind of dispersion halogenation material with carbon element method, it is characterised in that include:
By the oil-soluble polyamine any one of claim 1-7 and the halocarbon material mixing, the first mixture is obtained;
First mixture is added in organic media, and by resulting mixture supersound process, obtains the second mixture.
9. method according to claim 8, it is characterised in that the halogenation material with carbon element includes, aoxidizes fluorographite, organic
Graft modification fluorographite, fluorographite, fluorinated graphene, fluorographite alkynes are fluorinated carbon nano rod, are fluorinated carbon nanocoils, fluorine
Carbon nano tube, is fluorinated Nano carbon balls, fluorinated amorphous carbons, fluorinated carbon fiber and at least one being fluorinated in white carbon black,
Optionally, the organic media is lube base oil.
10. a kind of mixture containing halogenation material with carbon element, it is characterised in that prepared using the method described in claim 8 or 9
's.
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CN110484020A (en) * | 2019-09-17 | 2019-11-22 | 南方科技大学 | A kind of slurry and its preparation method and application |
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CN104326962A (en) * | 2014-09-30 | 2015-02-04 | 中国科学院宁波材料技术与工程研究所 | Poly alkenyl succinimide ashless dispersant preparation method |
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