CN109370361A - Graphene silicone acrylic emulsion corrosion-resistant finishes material and preparation method thereof - Google Patents
Graphene silicone acrylic emulsion corrosion-resistant finishes material and preparation method thereof Download PDFInfo
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- CN109370361A CN109370361A CN201811197592.5A CN201811197592A CN109370361A CN 109370361 A CN109370361 A CN 109370361A CN 201811197592 A CN201811197592 A CN 201811197592A CN 109370361 A CN109370361 A CN 109370361A
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The invention belongs to resistant material technical fields, more particularly to a kind of graphene silicone acrylic emulsion corrosion-resistant finishes material and preparation method thereof, graphene is prepared by using Hummers method first, then prepares organosilicon performed polymer using octamethylcy-clotetrasiloxane, KOH, silane coupling agent, dimethyl sulfoxide, hexamethyldisiloxane；Graphene silicone acrylic emulsion corrosion-resistant finishes material is finally prepared using butyl acrylate, methyl acrylate, acrylic acid, styrene, N hydroxymethyl acrylamide, organosilicon prepolymer solution etc..The present invention by acid resistance, alkali resistance, salt tolerance measurement it can be concluded that, joined the film corrosion resistance that the silicone acrylic emulsion of graphene is prepared into is enhanced than simple silicone acrylic emulsion, when being corroded by acid-alkali salt, the mass loss of film reduces, and the content of black alkene, when being 5%, the corrosion resistance of graphene silicone acrylic emulsion corrosion-resistant finishes material is best.
Description
Technical field
The invention belongs to resistant material technical fields, and in particular to a kind of graphene silicone acrylic emulsion corrosion-resistant finishes material
And preparation method thereof.
Background technique
Engineering material is occurred harmful chemical change, electrochemical change etc. by the effect of ambient enviroment and loses material
Original excellent performance becomes the corrosion of material.Commonly metallic material corrosion and carbon steel material corrosion.Iron material is application
Maximum metal material, therefore the corrosive liquid of ironwork is most commonly seen.Although carbon steel material has, cheap, manufacturing process is simple
It is single, the advantages that plasticity is good, good toughness, workability, but carbon steel material generally existing perishable weakness.In order to solve this
One problem, domestic and foreign scholars develop many corrosion-resistant finishes materials to improve the corrosion resistance of steel material.
Graphene is the monoatomic layer thickness that the carbon atom of sp2 hydridization is formed, and is arranged in the crystal of bi-dimensional cellular shape, is had
There are biggish surface area and lower preparation cost, the exploitation suitable for functional composite material.Common graphene composite wood
Material has: graphene/inorganic material, graphene/polymer etc., can be used for preparing after graphene and inorganic metallic materials are compound super
Capacitive vessel and lithium battery etc., graphene and the compound performance that original polymer can be improved of polymer.Than if any scholar in acid
Property under the conditions of chemical remediation is prepared using the in-situ polymerization of graphite oxide and aniline monomer graphene/PANI nanofiber it is compound
Material is up to 480F/g in the specific capacitance for the PANI doped graphene composite material that current density is 0.1A/g.
The graphene/silicon of huge great wave et al. (document: the preparation and performance of graphene and silicone acrylic emulsion composite material) preparation
Acrylic emulsion composite material, when the dosage of graphene is 0.6-0.9%, the dispersity in macromolecule matrix is preferable, with
The silicone acrylic emulsion film that graphene is not added is compared, and the corrosion resistance of composite material improves, and when the dosage of graphene is matter
When measuring score 0.7%, acid resistance reaches 470h, and alkali resistance reaches 320h, and salt tolerance reaches 520h.Though such corrosion-resistant time
So the silicone acrylic emulsion than being not added with graphene improves a lot, but in actual application or there is an urgent need to corrosion resistances more
High coating material, therefore we need the new material of continual exploitation more highly corrosion resistant.
Summary of the invention
A kind of graphene silicone acrylic emulsion corrosion-resistant finishes material provided by the invention and preparation method thereof provides a kind of resistance to
The higher coating material of corrosivity.
The present invention provides a kind of preparation methods of graphene silicone acrylic emulsion corrosion-resistant finishes material, comprising the following steps:
S1, Hummers method prepare graphene；
S2 prepares organosilicon performed polymer；
Octamethylcy-clotetrasiloxane, KOH are mixed, reacted 1~1.5 hour for 90~100 DEG C under stirring condition；Silane is added
Coupling agent, dimethyl sulfoxide, hexamethyldisiloxane obtain organosilicon performed polymer isothermal reaction 2.5~3 hours at 85~95 DEG C
Solution；
S3 prepares graphene silicone acrylic emulsion corrosion-resistant finishes material:
S31 prepares butyl acrylate, methyl acrylate, acrylic acid, styrene, N hydroxymethyl acrylamide, S2
Organosilicon prepolymer solution mixes, and obtains mix monomer；
S32 mixes distilled water, neopelex, nonylphenol polyoxyethylene ether, diethanol amine, obtains pre- anti-
Answer system；
The mix monomer of sodium hydrogensulfite and partial volume is added into pre-reaction system by S33, is added and causes after mixing
Agent obtains intermediate reaction system；Graphene is added in the mix monomer of residual volume, then joined residual volume
The mix monomer of graphene is added in intermediate reaction system, obtains late phase reaction system；Finally add again to later period reaction system
Enter silane coupling agent, continues polymerization reaction, obtain graphene silicone acrylic emulsion coating material.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant finishes material, the step of S1 specifically such as
Under:
S11 prepares graphene oxide
Ratio into the container for be placed in ice-water bath according to 23mL:2g:1g sequentially add volume fraction 98% the concentrated sulfuric acid,
Graphite powder, sodium nitrate stir 3~5 minutes, and potassium permanganate is added, and control system temperature is reacted 1.5~2 hours less than 20 DEG C；
35 DEG C are warming up to, continues stirring 25~30 minutes；Cleaning solution is added, raises the temperature to 98 DEG C, continuous heating 15~20 minutes；
The hydrogen peroxide of volume fraction 30% is added, mixes, filters while hot, filter cake and drying is taken out, obtains graphene oxide；Wherein nitre
Sour sodium, potassium permanganate, cleaning solution, hydrogen peroxide ratio be 1g:6g:46mL:5mL；
S12 prepares graphene
Graphene oxide and distilled water are mixed according to the ratio of 1mg:1mL, obtain brown color suspension, ultrasonic disperse,
80% hydrazine hydrate solution of volume fraction is added dropwise under the conditions of 80 DEG C, and reacts 24 hours, filters, filter wash cake, it is dry, obtain graphite
Alkene, wherein the ratio of graphene oxide and hydrazine hydrate solution is 100mg:1mL.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant finishes material, in S11, the washing
Liquid is to be mixed by tap water and distilled water according to the volume ratio of 1:1；Alternatively, the cleaning solution is distilled water.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant finishes material, the reaction of S11 and S12
The temperature respectively needed is maintained by way of water-bath.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant finishes material, in S12 using methanol,
Distilled water or methanol-distillation water mixed liquid filter wash cake.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant finishes material, in S2, prestox ring four
Siloxanes, KOH, silane coupling agent, dimethyl sulfoxide, hexamethyldisiloxane ratio be 20mL:0.10g:3mL:1mL:
0.1mL。
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant finishes material, in S31, by acrylic acid
The organosilicon prepolymer solution that butyl ester, methyl acrylate, acrylic acid, styrene, N hydroxymethyl acrylamide, S2 are prepared according to
15mL:5mL:1mL:4mL:0.5g:2mL is mixed；
In S32, by distilled water, neopelex, nonylphenol polyoxyethylene ether, diethanol amine according to 70mL:
The ratio of 0.75g:0.25mL:2mL mixes；
In S33, diethanol amine, sodium hydrogensulfite, initiator, graphene, silane coupling agent amount ratio be 2mL:0.1g:
10mL:0.03~0.23g:1mL.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant finishes material, diethanol amine, Asia in S3
Sodium bisulfate, initiator, graphene, silane coupling agent amount ratio be 2mL:0.1g:10mL:0.16g:1mL.
Initiator described in S3 is by the ammonium persulfate solution of 2g/100mL, and solvent is distilled water；Or the initiator
It is made in accordance with the following methods: 0.2g solution of zinc sulfate, 0.05g zinc sulfate being dissolved in the distilled water of 10mL, initiator is configured to.
The present invention also provides a kind of graphene silicone acrylic emulsion corrosion-resistant finishes materials being prepared by the above method.
Compared with prior art, graphene silicone acrylic emulsion corrosion-resistant finishes material of the invention and preparation method thereof have with
It is lower the utility model has the advantages that
(1) present invention prepares graphene by using Hummers method first, carries out XRD inspection to graphite powder, graphene
It surveys, because there is strong diffraction maximum at 26.8 °, the crystal layer spatial arrangement regular smooth of graphite, angle of this peak in graphite lattice
It spends in range, so being graphite.The diffraction maximum that has the last one of the graphene at 25.6 °, compares the XRD diffraction pattern of graphite, and 2 θ are angular
It moves left, the peak of graphene broadens, the weakened at peak, it can thus be concluded that graphene is the graphite of single layer.
(2) pass through the silicone acrylic emulsion for preparing to comparative example 1, the infrared spectroscopy of the machine silicon performed polymer of 1 method of embodiment preparation
Analysis, it can be deduced that silicone acrylic emulsion, performed polymer are relatively pure.In 1726cm-1There is the stretching vibration peak of a C=O at place,
1600cm-1~1700cm-1When place, there is not the characteristic peak of stretching vibration in C=C double bond, illustrates that C=C double bond is not present.?
2948cm-1Occurs-CH when place3Stretching vibration peak, in 3000cm-1C h bond without occurring being connected with C=C double bond above
Stretching vibration peak, be pure silicon acrylic emulsion.In 3486cm-1There is the stretching vibration peak of-OH in-Si-OH key in place,
2963cm-1Appearance-CH3Stretching vibration peak, in 3004cm-1There is the stretching vibration peak of c h bond in C=C double bond in place,
1621cm-1There is the stretching vibration peak of C=C double bond in place, in 809cm-1There is the stretching vibration peak of organosiloxane in place,
In 1254cm-1Wavelength at be organosilicon performed polymer characteristic spectrum, be machine silicon performed polymer.
(3) by acid resistance, alkali resistance, salt tolerance measurement it can be concluded that, joined graphene silicone acrylic emulsion preparation
At film corrosion resistance enhance than the silicone acrylic emulsion of comparative example 1, when being corroded by acid-alkali salt, the mass loss of film reduces,
And the content (mass fraction that graphene accounts for graphene silicone acrylic emulsion) of black alkene, when being 5%, corrosion resistance is best.This is because stone
Black alkene single layer densification, when graphene is added in silicone acrylic emulsion, being dispersed in silicone acrylic emulsion for graphene uniform is evenly dispersed
Graphene forms netted physical barrier in being film-made and plays the role of shielding protection.So the corrosion resistance of silicone acrylic emulsion increases
By force.By the comparison to acidproof, alkaline-resisting three width figure of salt tolerant, mass loss is smaller than alkali and salt in acid proof detection process, can be with
It show that acid resistance is stronger, this is because the hydroxide ion in alkali adheres into graphene/silicon acrylic emulsion coating surface, keeps surface living
Property enhancing, thus more perishable, and the hydrogen ion in acid is attached to surface and does not increase surface-active, so 5% graphene/silicon
The acid resistance of acrylic emulsion is best.
(4) corrosion test through different samples, we show that the graphene silicone acrylic emulsion of Examples 1 to 8 preparation is corrosion-resistant
The acid and alkali resistance of coating material, salt corrosivity are significantly better than silicone acrylic emulsion and the prior art.Illustrate that method of the invention can be prepared
The higher coating material of corrosion resistance out.
Detailed description of the invention
Fig. 1 is the acid resistance analysis of different samples；
Fig. 2 is the alkali resistance analysis of different samples；
Fig. 3 is the Salt Tolerance Analysis of different samples；
Fig. 4 is mass loss figure of the sample 3 in acid, alkali, salt；
Fig. 5 is the infrared spectrum analysis figure of silicone acrylic emulsion prepared by comparative example 1；
Fig. 6 is the infrared spectrogram of machine silicon performed polymer prepared by embodiment 1；
Fig. 7 is the XRD diffraction spectrogram of graphite powder；
Fig. 8 is the XRD difraction spectrum of the graphene of 1 method of embodiment preparation.
Specific embodiment
The present invention is described in detail combined with specific embodiments below, but should not be construed as limitation of the invention.It is following
The test method of actual conditions is not specified in embodiment, operates usually according to normal condition, due to not being related to inventive point, thus it is not right
Its step is described in detail.
The main agents D4 (octamethylcy-clotetrasiloxane) that uses in the present invention, silane coupling agent is commercially available silane coupled
Agent KH570, DMSO (dimethyl sulfoxide), MM (hexamethyldisiloxane), OP-10 (nonylphenol polyoxyethylene ether) etc. are commercially available.
Embodiment 1
A kind of preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material, comprising the following steps:
S1, Hummers method prepare graphene；
S11 prepares graphene oxide
S111, is packed into 3/5 water equipped with ice cube in the beaker of 250mL, and is put on magnetic stirring apparatus；Prepare one again
The conical flask of a drying is put into beaker, gets out ice-water bath；
S112 measures the concentrated sulfuric acid of 23mL volume fraction 98%, weighs 2g graphite powder, 1g sodium nitrate, 6g potassium permanganate, standby
With；
S113 is put into the conical flask for the drying that S111 prepares, later the concentrated sulfuric acid of measurement by magneton is stirred with tweezers
It pours into conical flask, fixes conical flask with iron stand；
The weighed graphite powder of S111 and sodium nitrate are added in conical flask S114, mixing, are stirred to react 3 minutes, then will
The weighed potassium permanganate of S111 is added in conical flask；Bath temperature is controlled less than 20 DEG C, is stirred to react 2 in thermostat water bath constant temperature
Hour；Then by warming-in-water to 35 DEG C, continue stirring 30 minutes in 35 DEG C, be added the cleaning solution of 46mL, then by bath temperature
Be increased to 98 DEG C, in 98 DEG C continuous heating 20 minutes, liquid be in brown color, red cigarette of emerging；
Wherein, it is configured to cleaning solution after tap water and distilled water being mixed with the volume ratio of 1:1, after preparing 30 minutes again
It uses；
S115, the liquid that S114 is added in the hydrogen peroxide for measuring 5mL volume fraction 30% are mixed in the conical flask of brown color
Substance in conical flask is removed conical flask and is filtered while hot, and the cleaning solution water washing conical flask prepared with S114, exists to remaining solid
After stablizing on filter paper, filter cake is taken out with tweezers, is served as a contrast with clean filter paper in filter cake bottom, is put into 60 DEG C of drying box dry
12 hours, graphene oxide is obtained, it is spare；
S12 prepares graphene
The dry graphene oxide of 200mg is weighed with assay balance, pours into the beaker of 250mL, adds the steaming of 200mL
Distilled water obtains brown color suspension, and the probe of Ultrasound Instrument is put into brown color suspension, and 450W ultrasonic disperse 20 minutes；It will
Solution after ultrasonic disperse is put into water-bath, and 80 DEG C of bath temperature, then 80% hydrazine hydrate solution of volume fraction of 2mL is added dropwise,
Reaction 24 hours；Then it is filtered with vacuum pump, then successively uses methanol and distilled water flushing filter cake, obtained solid is dry at 60 DEG C
It is sufficiently 12 hours dry in dry case, graphene is obtained, is saved backup.
S2 prepares organosilicon prepolymer solution；
S21 prepares a dry 250mL three-necked flask, takes the D4 of 20mL to be added in three-necked flask, use assay balance
The KOH for weighing 0.10g, KOH is poured into three-necked flask, dry stirring magneton is put into three-necked flask with paper groove；Then
Three-necked flask is fixed on magnetic stirring apparatus, the temperature of magnetic stirring apparatus is adjusted to 100 DEG C, magnetic agitation is opened, in magnetic force
Lower 100 DEG C are stirred to react 1 hour；
S22 takes a dry 50mL small beaker, and the MM of DMSO, 0.1mL of KH570,1mL of 3mL is added, and mixing is equal
It is even, it is then added in the three-necked flask after S21 reacts one hour, 3 hours of isothermal reaction, it is pre- to obtain organosilicon at 90 DEG C
Oligomer solution.
S3 prepares graphene silicone acrylic emulsion corrosion-resistant finishes material:
S31, by the butyl acrylate of 15mL, the methyl acrylate of 5mL, the acrylic acid of 1mL, the styrene of 4mL, 0.5g
The organosilicon prepolymer solution that N hydroxymethyl acrylamide, 2mL S2 are prepared mixes, and obtains mix monomer, spare；
0.2g ammonium persulfate is dissolved in the distilled water of 10mL, initiator is configured to, it is spare.
S32, by the distilled water of 70mL, the neopelex of 0.75g, 0.25mL OP-10,2mL diethanol
Amine is added in clean three-necked flask, mixes, clean stirring magneton is put into three-necked flask, and three-necked flask is fixed on
On magnetic stirring apparatus, it is warming up to 60 DEG C under magnetic stirring, obtains pre-reaction system；
The sodium hydrogensulfite of 0.1g and the mix monomer of half volume (36mL), stirring are added into pre-reaction system by S33
The initiator 10mL prepared is uniformly added dropwise afterwards and obtains intermediate reaction system after the reagent in observation there-necked flask is creamy white；It will
The graphene of 0.03g is added in the mix monomer of residual volume (36mL), is allowed graphene and silicone acrylic emulsion to be copolymerized, then will be remained
The mix monomer that joined graphene of remaining volume is added in intermediate reaction system, obtains late phase reaction system；Residual volume
The mix monomer that joined graphene dripped in four times in 20 minutes, initiator drips in six times in 30 minutes
At；1mL KH-570 finally is added to later period reaction system, late phase reaction system temperature is increased to 80 DEG C~85 DEG C automatically, adjusts
The temperature of magnetic stirring apparatus is saved to 85 DEG C, keeps this temperature, constant temperature continues polymerization one and a half hours, after the completion of copolymerization, graphite
Alkene is evenly dispersed in silicone acrylic emulsion, obtains graphene silicone acrylic emulsion coating material, the graphene silicone acrylic emulsion coating material
The mass fraction of middle graphene is 1%.
Embodiment 2
The quality of a kind of preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material, the graphene added in S33 is
0.1g, remaining operation is the same as embodiment 1；The mass fraction of graphene in graphene silicone acrylic emulsion coating material prepared by embodiment 2
It is 3%.
Embodiment 3
The quality of a kind of preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material, the graphene added in S33 is
0.16g, remaining operation is the same as embodiment 1；The mass fraction of graphene in graphene silicone acrylic emulsion coating material prepared by embodiment 2
It is 5%.
Embodiment 4
The quality of a kind of preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material, the graphene added in S33 is
0.23g, remaining operation is the same as embodiment 1；The mass fraction of graphene in graphene silicone acrylic emulsion coating material prepared by embodiment 2
It is 7%.
Embodiment 5
A kind of preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material, cleaning solution described in S11 is distilled water；
In S21, react 1.5 hours for 100 DEG C under magnetic stirring；In S22,2.5 hours of isothermal reaction at 90 DEG C；All reagents
Dosage halves；Remaining operation is the same as embodiment 3.
Embodiment 6
A kind of preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material is operated with embodiment 3, and difference is, will
The step of S1, is changed to:
S11 prepares graphene oxide
The concentrated sulfuric acid, the 2g graphite powder, 1g of 23mL volume fraction 98% are added into the triangular pyramidal bottle bottle for be placed in ice-water bath
Sodium nitrate stirs 5 minutes, and 6g potassium permanganate is added, and control system temperature is reacted 1.5 hours less than 20 DEG C；35 DEG C are warming up to,
Continue stirring 25 minutes in 35 DEG C；46mL cleaning solution is added, then raises the temperature to 98 DEG C, divides in 98 DEG C of continuous heatings 15
Clock；The hydrogen peroxide of 5mL volume fraction 30% is added, mixes, filters while hot, takes out filter cake and the drying in 60 DEG C of drying box
10 hours, obtain graphene oxide；
S12 prepares graphene
200mg graphene oxide and 200mL distilled water are mixed, obtain brown color suspension, 400W ultrasonic disperse 20 divides
80% hydrazine hydrate solution of 2mL volume fraction is added dropwise under the conditions of 80 DEG C, and reacts 24 hours for clock, and vacuum pump filters, with methanol-steaming
Distilled water mixed liquor filter wash cake, the volume fraction of methanol is 15% in methanol-distillation water mixed liquid, dry, obtains graphene.
Embodiment 7
A kind of preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material is operated with embodiment 6, and difference is, S12
It is middle to use distilled water filter wash cake.
Embodiment 8
A kind of preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material, the initiator are made in accordance with the following methods
At: 0.2g solution of zinc sulfate, 0.05g zinc sulfate are dissolved in the distilled water of 10mL, initiator is configured to；Remaining operation is the same as implementation
Example 3.
Comparative example 1
A kind of preparation method of silicone acrylic emulsion, comprising the following steps:
S1 and S2 step is with embodiment 1, and steps are as follows by S3:
S31 takes a clean 100mL beaker, and the butyl acrylate of 15mL, the methyl acrylate of 5mL, 1mL is added
The organosilicon prepolymer solution that acrylic acid, the styrene of 4mL, 0.5g N hydroxymethyl acrylamide, 2mL S2 are prepared, will burn
Reagent in cup stirs and evenly mixs, and obtains mix monomer, spare；
Prepare a new clean small beaker, the distilled water of 0.2g ammonium persulfate, 10mL is added, stirring makes ammonium persulfate
Dissolution, is configured to initiator, spare.
S32 prepares the clean three-necked flask of 250mL, and the distilled water of 70mL, the detergent alkylate sulphur of 0.75g is added
Sour sodium, 0.25mL OP-10,2mL diethanol amine be added three-necked flask in；Clean stirring magneton is put into three-necked flask
In, and three-necked flask is fixed on magnetic stirring apparatus, it is warming up to 60 DEG C under magnetic stirring；
The sodium hydrogensulfite of 0.1g and the mix monomer of half volume (36mL) is added in S33；S31 is added dropwise after stirring and evenly mixing
The mix monomer (36mL) of the initiator and residual volume that prepare, and the mix monomer of residual volume in 20 minutes in four times
It drips, initiator is added dropwise to complete in six times in 30 minutes.After to be triggered dose is added dropwise to complete with remaining mix monomer, system temperature
Degree is increased to 80 DEG C~85 DEG C automatically, and the reagent in three-necked flask is creamy white, and adjusts the temperature of magnetic stirring apparatus to 85 DEG C, protects
This temperature is held, constant temperature continues polymerization one and a half hours, obtains silicone acrylic emulsion.
In order to verify effect of the invention, We conducted following a series of experiments:
One, membrane sample is prepared
Clean glass slide is got out, is prepared by the silicone acrylic emulsion of 1~2 method of comparative example preparation, Examples 1 to 8 method
Graphene silicone acrylic emulsion be uniformly applied on glass slide respectively, drying box temperature is adjusted to 90 DEG C, glass slide is put into baking
In dry case, drying.Prepare membrane sample respectively, comparative example 1, the corresponding membrane sample in Examples 1 to 8 side be respectively designated as sample C,
Sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7, sample 8.Each sample does three parallel laboratory tests.
Two, corrosion resistance detects
(1) chlorination of the hydrochloric acid solution of 5mL/100mL, the sodium hydroxide solution of 5g/100mL, 3g/100mL is prepared respectively
Sample C, sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7, sample 8 are soaked in 5mL/ respectively by sodium solution
In the sodium chloride solution of the hydrochloric acid solution of 100mL, the sodium hydroxide solution of 5g/100mL or 3g/100mL, different samples are observed
Corrosion-resistant (film surface the is corroded completely) time in different solutions.
The graphene prepared with huge great wave et al. (document: the preparation and performance of graphene and silicone acrylic emulsion composite material)/
Silicone acrylic emulsion composite material carry out corrosivity control experiment, the graphene/silicon acrylic emulsion composite material prepared according to " one,
Prepare membrane sample " in method membrane sample, referred to as control group is made.The results are shown in Table 1.
Corrosion-resistant time of the different samples of table 1 in different solutions
(2) sodium chloride of the hydrochloric acid solution of 0.5mol/L, the sodium hydroxide solution of 0.5mol/L, 0.5mol/L are prepared respectively
Sample C, sample 1, sample 2, sample 3, sample 4 are soaked in the hydrogen of the hydrochloric acid solution of 0.5mol/L, 0.5mol/L by solution respectively
In the sodium chloride solution of sodium hydroxide solution or 0.5mol/L, total immersion is steeped 48 hours, is taken out film drying every eight hours and is weighed
The quality of film, and record data.
Fig. 1 is the acid resistance analysis of different samples, be can be observed how from the curvilinear trend in Fig. 1, when in silicone acrylic emulsion plus
When entering graphene, acid resistance enhancing, can be seen that from the mass change size of ordinate can also be from curvilinear slope variation tendency
It can be concluded that and it can be concluded that, the silicone acrylic emulsion acid resistance of 5% graphene containing mass fraction (sample 3) is best, this is because containing
The graphene of mass fraction 5% in silicone acrylic emulsion be copolymerized effect it is best, equally distributed reticular structure is more preferable in film, rise
To bigger protective effect.
Fig. 2 is the alkali resistance analysis of different samples, be can be observed how from the curvilinear trend in Fig. 2, when in silicone acrylic emulsion plus
When entering graphene, alkali resistance enhancing is alkaline-resisting because single-layer graphene, which is uniformly dispersed in lotion, plays the role of isolation
Property enhancing.It can be concluded that, graphene mass fraction is from the mass change size of ordinate and from curvilinear slope variation tendency
Alkali resistance is best when 5% (sample 3).
Fig. 3 is the Salt Tolerance Analysis of different samples, be can be observed how from the curvilinear trend in Fig. 3, when in silicone acrylic emulsion plus
When entering graphene, salt tolerance enhancing, this is because the addition of graphene plays the role of shielding, so salt tolerance enhances.From
The mass change size of ordinate and from curvilinear slope variation tendency it can be concluded that, graphene content be 5% when salt tolerance most
It is good.
Fig. 4 is mass loss figure of the sample 3 in acid, alkali, salt.From Fig. 4 we it can be concluded that its acid resistance is best,
And in 16h~acid resistance is most stable in this period for 24 hours, this is because the hydroxide ion in alkali adhere into graphene/
Silicone acrylic emulsion coating surface, enhances surface-active, thus it is more perishable, and the hydrogen ion in acid is attached to surface and does not increase
Surface-active, so the acid resistance of graphene/silicon acrylic emulsion is best.
Three, the infrared spectrum analysis of silicone acrylic emulsion
Fig. 5 is the infrared spectrum analysis figure of silicone acrylic emulsion prepared by comparative example 1, from fig. 5, it can be seen that infrared wavelength exists
1726cm-1There is the stretching vibration peak of a C=O at place, in 1500cm-1~1600cm-1When place, C=C double bond is not stretched
The characteristic peak of vibration illustrates that C=C double bond is not present.In 2948cm-1Occurs-CH when place3Stretching vibration peak, in 3000cm-1
Above without the stretching vibration peak for the c h bond for occurring being connected with C=C double bond, illustrate there is no double bond presence, table in silicone acrylic emulsion
The polymerization reaction fully reacting of bright organosilicon performed polymer and acrylic resin.Therefore, it can be said that bright, the above are silicone acrylic emulsions.
Four, the infrared spectrum analysis of organosilicon performed polymer
Fig. 6 is the infrared spectrogram of machine silicon performed polymer prepared by embodiment 1.Show that wavelength is in 3486cm by Fig. 6 observation-1
There is the stretching vibration peak of-OH in-Si-OH key, in 2963cm in place-1Appearance-CH3Stretching vibration peak, in 3004cm-1Place
There is the stretching vibration peak of c h bond in C=C double bond, in 1621cm-1There is the stretching vibration peak of C=C double bond in place,
809cm-1There is the stretching vibration peak of organosiloxane in place, in 1254cm-1Wavelength at be organosilicon performed polymer characteristic light
Spectrum.By the analysis of the infrared spectroscopy to the above organosilicon performed polymer, can obtain polymer is organosilicon performed polymer.
Five, the XRD diffraction analysis of graphite powder
Fig. 7 is the XRD diffraction spectrogram of graphite powder, there is strong diffraction maximum, the crystal layer spatial arrangement of graphite at 26.8 °
Regular smooth, this peak is in the angular range in graphite lattice.
Six, the XRD diffraction analysis of graphene
Fig. 8 is the XRD difraction spectrum of the graphene of 1 method of embodiment preparation, and graphene has the last one at 25.6 ° in Fig. 4
Diffraction maximum, compare the XRD diffraction pattern of graphite, 2 θ are angularly moved left, and the peak of graphene broadens, thus the weakened at peak may be used
Obtain the graphite that graphene is single layer.
It should be noted that when the present invention provides numberical range, it should be appreciated that except non-present invention is otherwise noted, every number
Being worth any one numerical value between two endpoints and two endpoints of range can be selected.Unless otherwise defined, make in the present invention
All technical and scientific terms are identical as the normally understood meaning of those skilled in the art of the present technique.Although this hair has been described
Bright preferred embodiment, once a person skilled in the art knows basic creative concepts, then can be to these embodiments
Make other change and modification.So the following claims are intended to be interpreted as including preferred embodiment and falls into the present invention
All change and modification of range.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material, which comprises the following steps:
S1, Hummers method prepare graphene；
S2 prepares organosilicon performed polymer；
Octamethylcy-clotetrasiloxane, KOH are mixed, reacted 1~1.5 hour for 90~100 DEG C under stirring condition；It is added silane coupled
Agent, dimethyl sulfoxide, hexamethyldisiloxane obtain organosilicon prepolymer solution isothermal reaction 2.5~3 hours at 85~95 DEG C；
S3 prepares graphene silicone acrylic emulsion corrosion-resistant finishes material:
S31 prepares butyl acrylate, methyl acrylate, acrylic acid, styrene, N hydroxymethyl acrylamide, S2 organic
Silicon prepolymer solution mixes, and obtains mix monomer；
Distilled water, neopelex, nonylphenol polyoxyethylene ether, diethanol amine are mixed, obtain pre-reaction body by S32
System；
The mix monomer of sodium hydrogensulfite and partial volume is added into pre-reaction system, initiator is added after mixing, obtains by S33
To intermediate reaction system；Graphene is added in the mix monomer of residual volume, residual volume then be joined into graphite
The mix monomer of alkene is added in intermediate reaction system, obtains late phase reaction system；Finally silicon is added to later period reaction system
Alkane coupling agent continues polymerization reaction, obtains graphene silicone acrylic emulsion coating material.
2. the preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material according to claim 1, which is characterized in that S1
The step of it is specific as follows:
S11 prepares graphene oxide
Ratio into the container for be placed in ice-water bath according to 23mL:2g:1g sequentially adds the concentrated sulfuric acid of volume fraction 98%, graphite
Powder, sodium nitrate stir 3~5 minutes, and potassium permanganate is added, and control system temperature is reacted 1.5~2 hours less than 20 DEG C；Heating
To 35 DEG C, continue stirring 25~30 minutes；Cleaning solution is added, raises the temperature to 98 DEG C, continuous heating 15~20 minutes；Again plus
Enter the hydrogen peroxide of volume fraction 30%, mix, filter while hot, takes out filter cake and drying, obtain graphene oxide；Wherein nitric acid
Sodium, potassium permanganate, cleaning solution, hydrogen peroxide ratio be 1g:6g:46mL:5mL；
S12 prepares graphene
Graphene oxide and distilled water are mixed according to the ratio of 1mg:1mL, obtain brown color suspension, ultrasonic disperse, 80 DEG C
Under the conditions of 80% hydrazine hydrate solution of volume fraction is added dropwise, and react 24 hours, filter, filter wash cake is dry, obtain graphene,
In, the ratio of graphene oxide and hydrazine hydrate solution is 100mg:1mL.
3. the preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material according to claim 2, which is characterized in that
In S11, the cleaning solution is to be mixed by tap water and distilled water according to the volume ratio of 1:1；Alternatively, the cleaning solution
It is distilled water.
4. the preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material according to claim 2, which is characterized in that
The reaction of S11 and S12 maintains the temperature respectively needed by way of water-bath.
5. the preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material according to claim 2, which is characterized in that
Methanol, distilled water or methanol-distillation water mixed liquid filter wash cake are used in S12.
6. the preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material according to claim 1, which is characterized in that S2
In, octamethylcy-clotetrasiloxane, KOH, silane coupling agent, dimethyl sulfoxide, hexamethyldisiloxane ratio be 20mL:0.10g:
3mL:1mL:0.1mL.
7. the preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material according to claim 1, which is characterized in that
In S31, organosilicon that butyl acrylate, methyl acrylate, acrylic acid, styrene, N hydroxymethyl acrylamide, S2 are prepared
Prepolymer solution is mixed according to 15mL:5mL:1mL:4mL:0.5g:2mL；
In S32, by distilled water, neopelex, nonylphenol polyoxyethylene ether, diethanol amine according to 70mL:0.75g:
The ratio of 0.25mL:2mL mixes；
In S33, diethanol amine, sodium hydrogensulfite, initiator, graphene, silane coupling agent amount ratio be 2mL:0.1g:
10mL:0.03~0.23g:1mL.
8. the preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material according to claim 7, which is characterized in that S3
Middle diethanol amine, sodium hydrogensulfite, initiator, graphene, silane coupling agent amount ratio be 2mL:0.1g:10mL:0.16g:
1mL。
9. the preparation method of graphene silicone acrylic emulsion corrosion-resistant finishes material according to claim 6, which is characterized in that S3
Described in initiator be by the ammonium persulfate solution of 2g/100mL, solvent is distilled water；Or the initiator is according to lower section
Method is made: 0.2g solution of zinc sulfate, 0.05g zinc sulfate being dissolved in the distilled water of 10mL, initiator is configured to.
10. graphene silicone acrylic emulsion corrosion-resistant finishes material made of any means according to claim 1~9.
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| CN107417867A (en) * | 2017-06-13 | 2017-12-01 | 陕西科技大学 | A kind of graphene oxide is modified the preparation method of composite phase-change microcapsules |
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| CN106280578A (en) * | 2016-07-11 | 2017-01-04 | 国家纳米科学中心 | A kind of limbic function functionalized graphene, its preparation method and for preparing the purposes of anticorrosive paint |
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