CN106084530B - A kind of hydrophilic self-lubricating microballoon and the preparation method and application thereof - Google Patents
A kind of hydrophilic self-lubricating microballoon and the preparation method and application thereof Download PDFInfo
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- CN106084530B CN106084530B CN201610397864.0A CN201610397864A CN106084530B CN 106084530 B CN106084530 B CN 106084530B CN 201610397864 A CN201610397864 A CN 201610397864A CN 106084530 B CN106084530 B CN 106084530B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The present invention relates to a kind of hydrophilic self-lubricating microballoons and the preparation method and application thereof, include the component of following mass fraction：80~99% styrene-acrylonitrile copolymer amide copolymer microballoon, 0.5~20% sulfonated graphene；Grain size 200nm~50 μm of nano particle.The present invention has following advantages：(1) styrene/acrylamide copolymerization microsphere matrix size is controllable, widely applicable, can build the micro-sphere structure of different scale；(2) use sulfonated graphene and styrene/acrylamide copolymerization microsphere compound by self assembly, the hydrophilic radical of microsphere surface and the sulfonated graphene on surface layer act synergistically, with more superior lubrication and hydrophilic effect, and wearability, persistence are more prominent；(3) aqueous self-lubricating material, has the characteristics that safety and environmental protection, has huge market prospects.
Description
Technical field
The present invention relates to a kind of functional microsphere, specifically a kind of hydrophilic self-lubricating microballoon and preparation method thereof with answer
With.
Background technology
Self-lubricating function material is the important source material in the fields such as composite material, functional paint, laminated film, to holding surface
Cleaning, release plays an important roll at anti-pickup.Wherein hydrophilic self-lubricating technology is by keeping the lasting hydrophilic of body surface
Property, it is easy to be washed away by water using surface contaminant, to have self-cleaning function.Conventional route is by improving surface hydrophilic
Groups density, such as hydroxyl, carboxyl, amino or surfactant are realized.But it is maximum existing for such self-lubricating material
Problem is protracted hydrophilicity, since polymer itself wears no resistance, larger fretting wear is caused on continuous contact surface, to lose
Effect.Graphite material itself is a kind of very outstanding solid lubricating material, the unique selection of even many high-temperature lubricating materials.
But graphite C-C covalent bonds itself become a kind of typical hydrophobic material, can not be good compound with hydrophilic substrate acquisition, and
Excessive scale itself also can not be used largely as packing material.Therefore, the exploitation hydrophilic self-lubricating material of high-performance still has
There is very big challenge.
Graphene can be regarded as the graphite material of single layer or few layer, have the excellent lubrication property of graphite, especially
After making its surface-functionalized a large amount of hydrophilic radical, hydrophilic dispersibility will greatly improve.Especially in combination with the hydroxyl that surface is abundant
After base, sulfonate radical, graphene has superior hydrophily with superpower wear-resisting lubricity.Therefore, graphene oxide
And sulfonated graphene, there will be important application in solid-state self-lubricating material.
Invention content
Defect in view of the above technology, a kind of hydrophilic self-lubricating microballoon of present invention proposition and the preparation method and application thereof.
A kind of hydrophilic self-lubricating microballoon, includes the component of following mass fraction：
Styrene-co-acrylamide microballoon 80~99%
Sulfonated graphene 0.5~20%；
Wherein Styrene-co-acrylamide microballoon is copolymerized by styrene monomer and acrylamide monomers, and two
Person's ratio is 20：1~5：2, grain size 200nm~50 μm of Styrene-co-acrylamide microballoon.
A kind of preparation method of hydrophilic self-lubricating microballoon, steps are as follows for the method：
Step 1：In the there-necked flask equipped with thermometer and reflux condensing tube be added emulsifier, buffer, 1/2 benzene second
Alkene monomer and acrylamide monomers, soluble in water, to be emulsified dose of all dissolving；
Step 2：Initiator is dissolved in the water simultaneously, the half of this dissolving is poured into the there-necked flask of reaction, is stirred,
It is heated to assigned temperature, remaining styrene and acrylamide monomers are then added dropwise；
Step 3：Remaining initiator is added in the there-necked flask of reaction after adding, is heated to reflux temperature, reaction terminates
Postcooling obtains styrene-propene amide copolymerization microsphere dispersion liquid to that can terminate building-up process after 50 DEG C；
Step 4：At the same time, sulfonated graphene is dispersed in water, sulfonated graphene dispersion liquid is prepared；
Step 5：Wait for that styrene-propene amide copolymerization microsphere dispersion liquid is cooled to room temperature, in whipping process, by sulfonation
Graphene dispersing solution is added thereto, and Styrene-co-acrylamide/sulfonated graphene complex microsphere dispersion liquid is prepared,
Using sulfonated graphene and styrene-propene amide copolymerization microsphere electrostatic assembly, sulfonated graphene is wrapped in microsphere surface；
Step 6：Final Styrene-co-acrylamide/sulfonated graphene is obtained after separation, washing, drying
Complex microsphere, i.e. hydrophilic lubrication microballoon powder.
The hydrophilic lubrication microballoon of the present invention is using styrene and acrylamide monomers copolymer microsphere as core, sulfonated graphite
Alkene package is assembled in its surface, forms a kind of nucleocapsid.
Acrylamide monomers can be acrylamide, N hydroxymethyl acrylamide, methacryl in the step 1
Amine, N- octyl acrylamides, acrylyl oxy-ethyl-trimethyl salmiac, dimethyl diallyl ammonium chloride any one and appoint
Meaning ratio combines, and dosage is the 5~40% of styrene monomer total amount；
Buffer described in step 1 can be sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide any one or
Person combines, and dosage is the 0.01~1% of styrene monomer total amount；
Emulsifier described in step 1 can be alkylsulfonate, alkylbenzene sulfonate, cetyl trimethylammonium bromide, gather
Ethylene glycol, hydroxymethyl cellulose, sodium carboxymethylcellulose pyce, ethyl cellulose, methylcellulose, carboxymethyl cellulose, hydroxypropyl first
Logical any one of base cellulose, polyvinylpyrrolidone, polyvinyl alcohol, Qula or two or more combinations, dosage are benzene second
The 0.5~5% of alkene monomer total amount；
Stir speed (S.S.) described in step 1 is 100~600 revs/min, is stirred 5~30 minutes.
Initiator can be potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, azo-bis-isobutyl cyanide, azo in the step 2
Two isobutyl dimethyl phthalates, azobisisoheptonitrile, benzoyl peroxide, cumyl peroxide, methyl ethyl ketone peroxide, peroxidating two
Any one in two hexamethylene fat of carbonic acid, tert-butyl hydroperoxide or combination, dosage are the 0.5~10% of styrene monomer total amount；
Reaction temperature described in step 2 is 50~70 degree, keeps the temperature 30 minutes~2 hours, and the monomer dropping time is 10-50 points
Clock.
Reflux temperature described in step 3 is 70~100 degree, 10 minutes~2 hours time.
Ultrasound, grinding, height can be used in the aqueous dispersions that sulfonated graphene dispersion liquid concentration described in step 4 is 1~40%
The techniques such as homogeneous, high speed shear are pressed to realize that dispersion, addition are the 1~20% of styrene monomer total amount.
Mixing speed described in step 5 is 100~500 revs/min, is stirred 30 minutes~5 hours.
Separating technology described in step 6, which may be used, to be added inorganic salts demulsification precipitation, centrifuges, the method for filtering, preferably
It is more efficient for sodium chloride or Klorvess Liquid break milk separation is added；The washing process is repeatedly washed using deionized water,
It is finally washed with ethyl alcohol, removes foreign ion；Vacuum drying, spray drying etc., drying temperature may be used in the drying process
40~70 degree.
A kind of hydrophilic self-lubricating microballoon functional paint, composite material, function film hydrophilic Self-lubricating Stuffing in answer
With the functional paint, composite material, the hydrophilic Self-lubricating Stuffing of function film are compatible with various water-base resins, obtained from clear
Clean, anti-pollution prevents adhesion, is antifog, anti-freeze function.
Material made of the present invention has excellent water dispersible, can be mutually compatible with various water-base resins.This is hydrophilic from profit
Sliding microballoon can be widely applied to aqueous self-lubricating, automatically cleaning, anti-pollution, freezing, anti-freezing mist functional paint, it is also possible to various resins
Based composites, film obtain the functions such as self-lubricating, resist blocking and that, release, have the advantages such as wear-resisting, permanent hydrophilic, have important
Commercial application value.
Compared with currently used hydrophilic Self-lubricating Stuffing, the present invention is copolymerized to be formed using the rich amino-containing acryloyl in surface
Sulfonated graphene assembling is wrapped in its surface, is formed while taking into account hydrophilic and lubricating function microballoon by electropositive microballoon.Its
In acrylamide modification phenylethylene micro ball, have size controllable, the high feature of yield can be that Subsequent sulfonation graphene is negative
It carries and facility is provided.Sulfonate radical is enriched possessed by the sulfonated graphene of outer layer, itself there is very superior hydrophily, while its
Graphene-structured forms solid-state self-lubricating property, and the complex microsphere is made to have lubrication stability more superior than conventional filler,
Wearability has well solved the deficiency of current hydrophilic lubricating material, it can be achieved that permanent hydrophilic lubrication.
The beneficial effects of the invention are as follows：Compared with prior art, the present invention has following advantages：
(1) styrene/acrylamide copolymerization microsphere matrix size is controllable, on probation wide, can build the micro- of different scale
Spherical structure；
(2) use sulfonated graphene and styrene/acrylamide copolymerization microsphere compound by self assembly, the sulfonation stone on surface layer
Black alkene has more superior lubrication and hydrophilic effect；
(3) aqueous self-lubricating material, has the characteristics that safety and environmental protection, has huge market prospects.
Specific implementation mode
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand, below it is right
The present invention is expanded on further.
A kind of hydrophilic self-lubricating microballoon, includes the component of following mass fraction：
Styrene-co-acrylamide microballoon 80~99%
Sulfonated graphene 0.5~20%；
Wherein Styrene-co-acrylamide microballoon is copolymerized by styrene monomer and acrylamide monomers, and two
Person's ratio is 20：1~5：2, grain size 200nm~50 μm of Styrene-co-acrylamide microballoon.
A kind of preparation method of hydrophilic self-lubricating microballoon, steps are as follows for the method：
Step 1：In the there-necked flask equipped with thermometer and reflux condensing tube be added emulsifier, buffer, 1/2 benzene second
Alkene monomer and acrylamide monomers, soluble in water, to be emulsified dose of all dissolving；
Step 2：Initiator is dissolved in the water simultaneously, the half of this dissolving is poured into the there-necked flask of reaction, is stirred,
It is heated to assigned temperature, remaining styrene and acrylamide monomers are then added dropwise；
Step 3：Remaining initiator is added in the there-necked flask of reaction after adding, is heated to reflux temperature, reaction terminates
Postcooling obtains styrene-propene amide copolymerization microsphere dispersion liquid to that can terminate building-up process after 50 DEG C；
Step 4：At the same time, sulfonated graphene is dispersed in water, sulfonated graphene dispersion liquid is prepared；
Step 5：Wait for that styrene-propene amide copolymerization microsphere dispersion liquid is cooled to room temperature, in whipping process, by sulfonation
Graphene dispersing solution is added thereto, and Styrene-co-acrylamide/sulfonated graphene complex microsphere dispersion liquid is prepared,
Using sulfonated graphene and styrene-propene amide copolymerization microsphere electrostatic assembly, sulfonated graphene is wrapped in microsphere surface；
Step 6：Final Styrene-co-acrylamide/sulfonated graphene is obtained after separation, washing, drying
Complex microsphere, i.e. hydrophilic lubrication microballoon powder.
The microballoon of the present invention is using styrene and acrylamide monomers copolymer microsphere as core, sulfonated graphene package group
Mounted in its surface, a kind of nucleocapsid is formed.
Acrylamide monomers can be acrylamide, N hydroxymethyl acrylamide, methacryl in the step 1
Amine, N- octyl acrylamides, acrylyl oxy-ethyl-trimethyl salmiac, dimethyl diallyl ammonium chloride any one and appoint
Meaning ratio combines, and dosage is the 5~40% of styrene monomer total amount；
Buffer described in step 1 can be sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide any one or
Person combines, and dosage is the 0.01~1% of styrene monomer total amount；
Emulsifier described in step 1 can be alkylsulfonate, alkylbenzene sulfonate, cetyl trimethylammonium bromide, gather
Ethylene glycol, hydroxymethyl cellulose, sodium carboxymethylcellulose pyce, ethyl cellulose, methylcellulose, carboxymethyl cellulose, hydroxypropyl first
Logical any one of base cellulose, polyvinylpyrrolidone, polyvinyl alcohol, Qula or two or more combinations, dosage are benzene second
The 0.5~5% of alkene monomer total amount；
Stir speed (S.S.) described in step 1 is 100~600 revs/min, is stirred 5~30 minutes.
Initiator can be potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, azo-bis-isobutyl cyanide, azo in the step 2
Two isobutyl dimethyl phthalates, azobisisoheptonitrile, benzoyl peroxide, cumyl peroxide, methyl ethyl ketone peroxide, peroxidating two
Any one in two hexamethylene fat of carbonic acid, tert-butyl hydroperoxide or combination, dosage are the 0.5~10% of styrene monomer total amount；
Reaction temperature described in step 2 is 50~70 degree, keeps the temperature 30 minutes~2 hours, and the monomer dropping time is 10-50 points
Clock.
Reflux temperature described in step 3 is 70~100 degree, 10 minutes~2 hours time.
Ultrasound, grinding, height can be used in the aqueous dispersions that sulfonated graphene dispersion liquid concentration described in step 4 is 1~40%
The techniques such as homogeneous, high speed shear are pressed to realize that dispersion, addition are the 1~20% of styrene monomer total amount.
Mixing speed described in step 5 is 100~500 revs/min, is stirred 30 minutes~5 hours.
Separating technology described in step 6, which may be used, to be added inorganic salts demulsification precipitation, centrifuges, the method for filtering, preferably
It is more efficient for sodium chloride or Klorvess Liquid break milk separation is added；The washing process is repeatedly washed using deionized water,
It is finally washed with ethyl alcohol, removes foreign ion；Vacuum drying, spray drying etc., drying temperature may be used in the drying process
40~70 degree.
A kind of hydrophilic self-lubricating microballoon functional paint, composite material, function film hydrophilic Self-lubricating Stuffing in answer
With the functional paint, composite material, the hydrophilic Self-lubricating Stuffing of function film are compatible with various water-base resins, obtained from clear
Clean, anti-pollution prevents adhesion, is antifog, anti-freeze function.
In order to prove technical scheme of the present invention, spy uses following embodiment：
Embodiment one：
Various composition proportioning is as follows：
(1) in the there-necked flask equipped with thermometer and reflux condensing tube be added emulsifier, buffer, 1/2 styrene list
Body and acrylamide monomers, soluble in water, to be emulsified dose of all dissolving；
(2) while by initiator it is dissolved in the water, the half of this dissolving is poured into the there-necked flask of reaction, 300 revs/min
Stirring, is heated to 60 degree, remaining styrene and acrylamide monomers is then added dropwise；
(3) remaining initiator is added in the there-necked flask of reaction after adding, is heated to 80 degree of reflux, it is cold after reaction
But to building-up process can be terminated after 50 DEG C, styrene-propene amide copolymerization microsphere dispersion liquid is obtained；
(4) at the same time, sulfonated graphene is dispersed in water, sulfonated graphene dispersion liquid, concentration 10% is prepared；
(5) near waiting for that styrene-propene amide copolymerization microsphere dispersion liquid is cooled to room temperature, in 300 revs/min of whipping process
In, sulfonated graphene dispersion liquid is added thereto, it is compound micro- that Styrene-co-acrylamide/sulfonated graphene is prepared
Ball dispersion liquid；
(6) precipitation is precipitated in microballoon by the sodium chloride solution demulsification that 0.1M is then added, through filtering, water and ethyl alcohol washing, and 40
Degree vacuum drying 3 hours, obtains final Styrene-co-acrylamide/sulfonated graphene complex microsphere powder, i.e., hydrophilic profit
Sliding microballoon powder.
It observes after tested, microsphere diameter 500nm or so.Aqueous acrylamide then is added in the hydrophilic self-lubricating microballoon powder
In acid resin, self-lubricating hydrophilic coating is prepared, roller coating is coated on 70um aluminium foils, through 140 degree of baking-curings, obtained from profit
Sliding coating, by test, skin-friction coefficient 0.5 impregnates 200 hours in water, and 15.2 degree of hydrophilic angle rises to 16.3 degree.
Embodiment two：
Various composition proportioning is as follows：
(1) in the there-necked flask equipped with thermometer and reflux condensing tube be added emulsifier, buffer, 1/2 styrene list
Body and acrylamide monomers, soluble in water, to be emulsified dose of all dissolving；
(2) while by initiator it is dissolved in the water, the half of this dissolving is poured into the there-necked flask of reaction, 300 revs/min
Stirring, is heated to 60 degree, remaining styrene and acrylamide monomers is then added dropwise；
(3) remaining initiator is added in the there-necked flask of reaction after adding, is heated to 80 degree of reflux, it is cold after reaction
But to building-up process can be terminated after 50 DEG C, styrene-propene amide copolymerization microsphere dispersion liquid is obtained；
(4) at the same time, sulfonated graphene is dispersed in water, sulfonated graphene dispersion liquid, concentration 10% is prepared；
(5) near waiting for that styrene-propene amide copolymerization microsphere dispersion liquid is cooled to room temperature, in 300 revs/min of whipping process
In, sulfonated graphene dispersion liquid is added thereto, it is compound micro- that Styrene-co-acrylamide/sulfonated graphene is prepared
Ball dispersion liquid；
(6) precipitation is precipitated in microballoon by the sodium chloride solution demulsification that 0.1M is then added, through filtering, water and ethyl alcohol washing, and 40
Degree vacuum drying 3 hours, obtains final Styrene-co-acrylamide/sulfonated graphene complex microsphere powder, i.e., hydrophilic profit
Sliding microballoon powder.
It observes after tested, microsphere diameter 500nm or so.Aqueous acrylamide then is added in the hydrophilic self-lubricating microballoon powder
In acid resin, self-lubricating hydrophilic coating is prepared, roller coating is coated on 70um aluminium foils, through 140 degree of baking-curings, obtained from profit
Sliding coating, by test, skin-friction coefficient 0.34, flowing water immersion 200 hours in water, 12.5 degree of hydrophilic angle rises to
13.5 degree.
Embodiment three：
Various composition proportioning is as follows：
(1) in the there-necked flask equipped with thermometer and reflux condensing tube be added emulsifier, buffer, 1/2 styrene list
Body and acrylamide monomers, soluble in water, to be emulsified dose of all dissolving；
(2) while by initiator it is dissolved in the water, the half of this dissolving is poured into the there-necked flask of reaction, 300 revs/min
Stirring, is heated to 60 degree, remaining styrene and acrylamide monomers is then added dropwise；
(3) remaining initiator is added in the there-necked flask of reaction after adding, is heated to 80 degree of reflux, it is cold after reaction
But to building-up process can be terminated after 50 DEG C, styrene-propene amide copolymerization microsphere dispersion liquid is obtained；
(4) at the same time, sulfonated graphene is dispersed in water, sulfonated graphene dispersion liquid, concentration 10% is prepared；
(5) near waiting for that styrene-propene amide copolymerization microsphere dispersion liquid is cooled to room temperature, in 300 revs/min of whipping process
In, sulfonated graphene dispersion liquid is added thereto, it is compound micro- that Styrene-co-acrylamide/sulfonated graphene is prepared
Ball dispersion liquid；
(6) precipitation is precipitated in microballoon by the sodium chloride solution demulsification that 0.1M is then added, through filtering, water and ethyl alcohol washing, and 40
Degree vacuum drying 3 hours, obtains final Styrene-co-acrylamide/sulfonated graphene complex microsphere powder, i.e., hydrophilic profit
Sliding microballoon powder.
It observes after tested, microsphere diameter 500nm or so.Aqueous acrylamide then is added in the hydrophilic self-lubricating microballoon powder
In acid resin, self-lubricating hydrophilic coating is prepared, roller coating is coated on 70um aluminium foils, through 140 degree of baking-curings, obtained from profit
Sliding coating, by test, skin-friction coefficient 0.5, flowing water immersion 200 hours in water, hydrophilic angle rises due to 15.6 degree
To 18.7 degree.
Example IV：
Reaction system formula
(1) in the there-necked flask equipped with thermometer and reflux condensing tube be added emulsifier, buffer, 1/2 styrene list
Body and acrylamide monomers, soluble in water, to be emulsified dose of all dissolving；
(2) while by initiator it is dissolved in the water, the half of this dissolving is poured into the there-necked flask of reaction, 300 revs/min
Stirring, is heated to 60 degree, remaining styrene and acrylamide monomers is then added dropwise；
(3) remaining initiator is added in the there-necked flask of reaction after adding, is heated to 80 degree of reflux, it is cold after reaction
But to building-up process can be terminated after 50 DEG C, styrene-propene amide copolymerization microsphere dispersion liquid is obtained；
(4) at the same time, sulfonated graphene is dispersed in water, sulfonated graphene dispersion liquid, concentration 10% is prepared；
(5) near waiting for that styrene-propene amide copolymerization microsphere dispersion liquid is cooled to room temperature, in 300 revs/min of whipping process
In, sulfonated graphene dispersion liquid is added thereto, it is compound micro- that Styrene-co-acrylamide/sulfonated graphene is prepared
Ball dispersion liquid；
(6) precipitation is precipitated in microballoon by the sodium chloride solution demulsification that 0.1M is then added, through filtering, water and ethyl alcohol washing, and 40
Degree vacuum drying 3 hours, obtains final Styrene-co-acrylamide/sulfonated graphene complex microsphere powder, i.e., hydrophilic profit
Sliding microballoon powder.
It observes after tested, microsphere diameter 500nm or so.Aqueous acrylamide then is added in the hydrophilic self-lubricating microballoon powder
In acid resin, self-lubricating hydrophilic coating is prepared, roller coating is coated on 70um aluminium foils, through 140 degree of baking-curings, obtained from profit
Sliding coating, by test, skin-friction coefficient 0.5, flowing water immersion 200 hours in water, 15 degree of hydrophilic angle is without significant change.
Comparative example one, basic recipe technique and embodiment one are essentially identical, and difference is the unassembled sulfonation of microsphere surface
Graphene is prepared into 0.7,200 hours flowing water of hydrophilic lubrication coating friction coefficient using same process and impregnates.
As seen from the above embodiment, the present invention has more superior lubrication and hydrophilic effect, safety and environmental protection.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these variation and
Improvement is both fallen in claimed invention.The claimed scope of the invention is by appended claims and its equivalent circle
It is fixed.
Claims (11)
1. a kind of hydrophilic self-lubricating microballoon, it is characterised in that：Include the component of following mass fraction：
Styrene-co-acrylamide microballoon 80~99%
Sulfonated graphene 0.5~20%；
Wherein Styrene-co-acrylamide microballoon is copolymerized by styrene monomer and acrylamide monomers, the two ratio
Example is 20：1~5：2；
The hydrophilic self-lubricating microballoon is using styrene and acrylamide monomers copolymer microsphere as core, sulfonated graphene package
It is assembled in its surface, forms a kind of nucleocapsid.
2. a kind of hydrophilic self-lubricating microballoon according to claim 1, it is characterised in that：Styrene-co-acrylamide
Grain size 200nm~50 μm of microballoon.
3. a kind of preparation method of hydrophilic self-lubricating microballoon according to any one of claim 1 to 2, it is characterised in that：
Steps are as follows for the method：
Step 1：In the there-necked flask equipped with thermometer and reflux condensing tube be added emulsifier, buffer, 1/2 styrene list
Body and acrylamide monomers, soluble in water, to be emulsified dose of all dissolving；
Step 2：Initiator is dissolved in the water simultaneously, the half of this dissolving is poured into the there-necked flask of reaction, is stirred, heating
It is warming up to assigned temperature, remaining styrene and acrylamide monomers are then added dropwise；
Step 3：Remaining initiator is added in the there-necked flask of reaction after adding, is heated to reflux temperature, it is cold after reaction
But to building-up process can be terminated after 50 DEG C, styrene-propene amide copolymerization microsphere dispersion liquid is obtained；
Step 4：At the same time, sulfonated graphene is dispersed in water, sulfonated graphene dispersion liquid is prepared；
Step 5：Wait for that styrene-propene amide copolymerization microsphere dispersion liquid is cooled to room temperature, in whipping process, by sulfonated graphite
Alkene dispersion liquid is added thereto, and Styrene-co-acrylamide/sulfonated graphene complex microsphere dispersion liquid is prepared；
Step 6：It is compound that final Styrene-co-acrylamide/sulfonated graphene is obtained after separation, washing, drying
Microballoon, i.e. hydrophilic lubrication microballoon powder.
4. a kind of preparation method of hydrophilic self-lubricating microballoon according to claim 3, it is characterised in that：In the step 1
Acrylamide monomers be acrylamide, N hydroxymethyl acrylamide, Methacrylamide, N- octyl acrylamides it is any one
Kind and arbitrary proportion combination, dosage are the 5~40% of styrene monomer total amount；
Buffer described in step 1 is any one or combination of sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide,
Dosage is the 0.01~1% of styrene monomer total amount；
Emulsifier described in step 1 be alkylsulfonate, alkylbenzene sulfonate, cetyl trimethylammonium bromide, polyethylene glycol,
Hydroxymethyl cellulose, sodium carboxymethylcellulose pyce, ethyl cellulose, methylcellulose, carboxymethyl cellulose, hydroxypropyl methyl fiber
Logical any one of element, polyvinylpyrrolidone, polyvinyl alcohol, Qula or two or more combinations, dosage are styrene monomer
The 0.5~5% of total amount；
Stir speed (S.S.) described in step 1 is 100~600 revs/min, is stirred 5~30 minutes.
5. a kind of preparation method of hydrophilic self-lubricating microballoon according to claim 3, it is characterised in that：In the step 2
Initiator is potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, azo-bis-isobutyl cyanide, azo-bis-iso-dimethyl, two different heptan of azo
Nitrile, benzoyl peroxide, cumyl peroxide, methyl ethyl ketone peroxide, two hexamethylene fat of dicetyl peroxydicarbonate, tert-butyl hydroperoxide
Any one in hydrogen or combination, dosage are the 0.5~10% of styrene monomer total amount；
Reaction temperature described in step 2 is 50~70 degrees Celsius, keeps the temperature 30 minutes~2 hours, and the monomer dropping time is 10-50 points
Clock.
6. a kind of preparation method of hydrophilic self-lubricating microballoon according to claim 3, it is characterised in that：It is returned described in step 3
It is 70~100 degrees Celsius to flow temperature, 10 minutes~2 hours time.
7. a kind of preparation method of hydrophilic self-lubricating microballoon according to claim 3, it is characterised in that：Sulphur described in step 4
The aqueous dispersions that graphite alkene dispersion liquid concentration is 1~40%, using ultrasound, grinding, high-pressure homogeneous, in high speed shear one kind
Technique realizes that dispersion, addition are the 1~20% of styrene monomer total amount.
8. a kind of preparation method of hydrophilic self-lubricating microballoon according to claim 3, it is characterised in that：It is stirred described in step 5
It is 100~500 revs/min to mix speed, is stirred 30 minutes~5 hours.
9. a kind of preparation method of hydrophilic self-lubricating microballoon according to claim 3, it is characterised in that：Divide described in step 6
Separating process is using addition inorganic salts demulsification precipitation, the method for centrifugation, filtering；The washing process is multiple using deionized water
Washing, is finally washed with ethyl alcohol, removes foreign ion；The drying process uses any one of vacuum drying, spray drying,
40~70 degrees Celsius of drying temperature.
10. a kind of preparation method of hydrophilic self-lubricating microballoon according to claim 9, it is characterised in that：Separating technology is adopted
With addition sodium chloride or Klorvess Liquid.
11. a kind of hydrophilic self-lubricating microballoon according to any one of claim 1 to 2 is in functional paint, composite material, work(
Application in the hydrophilic Self-lubricating Stuffing of energy film, it is characterised in that：The parent of the functional paint, composite material, function film
Water Self-lubricating Stuffing is compatible with various water-base resins, obtains automatically cleaning, anti-pollution, prevents adhesion, is antifog, anti-freeze function.
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