CN110358395A - A kind of corrosion-resistant finishes and preparation method thereof based on graphene - Google Patents
A kind of corrosion-resistant finishes and preparation method thereof based on graphene Download PDFInfo
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- CN110358395A CN110358395A CN201910805257.7A CN201910805257A CN110358395A CN 110358395 A CN110358395 A CN 110358395A CN 201910805257 A CN201910805257 A CN 201910805257A CN 110358395 A CN110358395 A CN 110358395A
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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
- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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
- 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
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Abstract
The invention discloses a kind of corrosion-resistant finishes and preparation method thereof based on graphene, is related to field of metal surface treatment technology.The present invention first uses graphene oxide and 3- aminopropyl triethoxysilane and chloroacetate reaction that modified graphene is made, then improved silica is made with carboxylated mesoporous silicon oxide and potassium tetratitanate and polypyrrole, finally modified graphene is mixed with improved silica, and acrylic emulsion, coalescing agent and water is added, corrosion resistant coating is made, corrosion resistant coating is coated on metal pretreated matrix surface, after to be dried, obtains the corrosion-resistant finishes based on graphene.Corrosion-resistant finishes prepared by the present invention based on graphene has excellent corrosion resistance, and coat fastness is preferable.
Description
Technical field
The present invention relates to field of metal surface treatment technology, specifically a kind of corrosion-resistant finishes and its system based on graphene
Preparation Method.
Background technique
Metal erosion has brought tremendous economic losses to the mankind and social danger, with the development of industry and science and technology, gold
It is increasingly prominent to belong to corrosion-resistant importance, wherein coating technology is the most convenient and economical, therefore plays in the development of the national economy
Increasingly important role.Traditional corrosion-inhibiting coating often uses solvent based coating, containing a large amount of volatile organic matter, and
There is quite a few coating to contain the noxious materials such as tin, lead or chromium, bring serious pollution to environment and endangers the health of the mankind.
Therefore, developing aqueous corrosion-resistant finishes material becomes the target that metal protection area research person lays siege to, and has far-reaching war
Slightly meaning and wide application prospect.
Graphene has excellent as a kind of single layer sheet two-dimension nano materials being made of carbon atom with sp hybridized orbit
Mechanical property, transparency, flexibility, hydrophobicity and chemical stability and outstanding pyroconductivity and electron mobility,
Laminated structure can effectively blocking oxygen, water, ion and electronics pass through, and be very suitable to do coating material, especially ocean
With the metal protection under the adverse circumstances such as saline and alkaline.However, it is extremely difficult that graphene is affixed directly to metallic substrate surface, and
No matter graphene is all difficult stable dispersion in water or in organic solvent, in addition, the poor compatibility of graphene and other materials,
It is easy to happen stacking.Therefore, it is necessary to graphene is modified with improve its dispersibility in water or organic solvent and
With the compatibility of other materials.
Summary of the invention
The purpose of the present invention is to provide a kind of corrosion-resistant finishes and preparation method thereof based on graphene, it is existing to solve
The problems in technology.
To achieve the above object, the invention provides the following technical scheme:
A kind of corrosion-resistant finishes based on graphene, which is characterized in that mainly include the raw material components of following parts by weight: 12 ~
20 parts of modified graphenes, 30 ~ 60 parts of aqueous acrylic emulsions, 2 ~ 3 parts of coalescing agents and 20 ~ 30 parts of water.
A kind of corrosion-resistant finishes based on graphene, which is characterized in that the corrosion-resistant finishes based on graphene also wraps
Include the raw material components of following parts by weight: 10 ~ 15 parts of improved silicas.
As optimization, the solid content of the aqueous acrylic emulsion is 45 ~ 55%, the coalescing agent be decylene glycol ester with
The mixed mixture of 1,2-PD 1:1 in mass ratio.
As optimization, the modified graphene is handled by graphene oxide through 3- aminopropyl triethoxysilane and monoxone
Gained afterwards.
As optimization, the improved silica is made of carboxylated mesoporous silicon oxide, potassium tetratitanate and polypyrrole.
As optimization, the corrosion-resistant finishes based on graphene mainly includes the raw material components of following parts by weight: 20
Part modified graphene, 60 parts of aqueous acrylic emulsions, 3 parts of coalescing agents, 20 parts of water and 15 parts of improved silicas.
As optimization, a kind of preparation method of the corrosion-resistant finishes based on graphene mainly includes following preparation step:
(1) after graphene oxide being mixed with 3- aminopropyl triethoxysilane, then with chloroacetate reaction, be made modified graphite
Alkene；
(2) it by titanium dioxide and potassium carbonate mixed grinding, calcines, washs, it is dry, potassium tetratitanate is obtained, by potassium tetratitanate and positive silicon
Sour second mixing, and pore-foaming agent is added, after being stirred to react under alkaline condition, calcining obtains improved silica；
(3) modified graphene obtained by step (1) is mixed with improved silica obtained by step (2), and three second of 3- aminopropyl is added
The mixed dispersion liquid of oxysilane and succinic anhydride, after being stirred to react, filtering obtains mixture, and mixture is molten with epolamine
Liquid mixing, filtering, then mixed with the hydrochloric acid solution of ferric trichloride, it filters, washs, it is dry, obtain blank；
(4) blank obtained by step (3) is mixed with aqueous acrylic emulsion；And water and coalescing agent is added, it is stirred, obtains stone
Black alkene corrosion resistant coating；
(5) graphene corrosion resistant coating obtained by step (4) metal substrate surface is applied to after dry to obtain based on graphene
Corrosion-resistant finishes；
(6) index analysis is carried out to the corrosion-resistant finishes obtained by step (5) based on graphene.
As optimization, a kind of preparation method of the corrosion-resistant finishes based on graphene mainly includes following preparation step:
(1) graphene oxide is mixed with water 1:100 ~ 1:120 in mass ratio, ultrasonic disperse obtains graphene oxide dispersion, will
Graphene oxide dispersion and 3- aminopropyl triethoxysilane 50:1 ~ 60:1 in mass ratio are mixed in beaker, and stirring hair is anti-
Ying Hou, then 0.1 ~ 0.2 times of graphene oxide dispersion slag charge of monoxone is added into beaker, it after being stirred to react, filters, does
It is dry；
(2) by titanium dioxide, 4:1.2 is mixed in molar ratio with potassium carbonate, and grinding obtains mixed-powder, is in temperature by mixed-powder
After calcining for 24 hours under conditions of 800 DEG C, pretreatment potassium tetratitanate is obtained, hydrochloric acid of the potassium tetratitanate mass fraction for 12% will be pre-processed
It after washing 2 times, then is washed with deionized 3 times, and by the pretreatment potassium tetratitanate after washing under conditions of temperature is 80 DEG C
Dry 3h, obtains potassium tetratitanate, and potassium tetratitanate and ethyl orthosilicate 1:3 in mass ratio are mixed in flask, and adds into flask
Enter 30 times of potassium tetratitanate quality of water and 1 ~ 2 times of potassium tetratitanate quality of cetyl trimethylammonium bromide, adjusts object in flask
The pH to 10 ~ 11 of material, after being stirred to react, filtering obtains improved silica blank, is in temperature by improved silica blank
After calcining 5h under conditions of 500 DEG C, discharging；
(3) step (1) obtained material and step (2) obtained material 2:1 ~ 3:1 in mass ratio are mixed in three-necked flask, and to
The water of 4 ~ 5 times of obtained material quality of step (1) and the 3- ammonia third of 8 ~ 10 times of obtained material quality of step (1) are added in three-necked flask
The mixed dispersion liquid of ethyl triethoxy silicane alkane and succinic anhydride, after being stirred to react, filtering obtains mixture, by mixture and quality
The epolamine solution 1:20 in mass ratio that score is 20% is mixed, and after being stirred, filtering obtains filter cake, by filter cake and tri-chlorination
The hydrochloric acid solution of iron 1:15 in mass ratio mixing, after being stirred to react, filtering obtains pretreatment blank, by pretreatment blank in temperature
Dry 2h under conditions of being 80 DEG C；
(4) step (3) obtained material and acrylic emulsion 1:2 in mass ratio are mixed in blender, and added into blender
Enter the coalescing agent of 0.01 times of obtained material quality of step (3) and the water of 0.8 times of obtained material quality of step (3), is stirred；
(5) step (4) obtained material is applied to metal pretreated substrate surface with 50 μm of smearing thickness, and in temperature be 60
Dry 12 ~ 36h, obtains the corrosion-resistant finishes based on graphene under conditions of DEG C；
(6) corrosion-resistant finishes based on graphene is obtained to step (5) gained and carries out index analysis.
As optimization, the preparation of the mixed dispersion liquid of step (3) the 3- aminopropyl triethoxysilane and succinic anhydride
Method is to mix 3- aminopropyl triethoxysilane and succinic anhydride 1:2 in mass ratio, and 3- aminopropyl-triethoxy is added
The dimethyl sulfoxide that 12 ~ 18 times of silane quality, is stirred, and obtains the mixing point of 3- aminopropyl triethoxysilane and succinic anhydride
Dispersion liquid.
As optimization, the hydrochloric acid solution of step (3) described ferric trichloride is the salt for being 12% by ferric trichloride and mass fraction
Acid 1:50 in mass ratio mixing, obtains the hydrochloric acid solution of ferric trichloride.
As optimization, step (5) the metal pretreated substrate is that metal plate is respectively cleaned 3 with ethyl alcohol and acetone respectively
It is secondary, metal pretreated substrate is obtained, the metal plate is any one in steel plate or copper sheet.
Compared with prior art, the beneficial effects of the present invention are: the present invention is in corrosion-resistant finishes of the preparation based on graphene
Modified graphene and improved silica is added, firstly, graphene is after modification, graphene surface has carboxylic group,
Products can be uniformly distributed in after graphene is added in product, to make the corrosion resistance of product improve, also, in stone
Graphene surface can be improved 3- aminopropyl triethoxysilane and connect with improved silica after black alkene is modified, to improve painting
The consistency of layer, further increases the corrosion resistance of product；Secondly, silica is after modification, silica can be inhaled
Potassium tetratitanate surface is invested, after being connect under the action of with modified graphene in 3- aminopropyl triethoxysilane, can be formed folded
The erosion resistant coating of layer further increases the corrosion resistance of product to improve the density of coating, furthermore two in improved silica
Silica contains meso-hole structure, can be in the mesoporous internal absorption polypyrrole of improved silica, thus into one after modification
Step improves the corrosion resistance of product.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
In order to which clearer explanation method provided by the invention is described in detail by following embodiment, in following implementation
Each indication test method of the corrosion-resistant finishes based on graphene made in example is as follows:
Acid-resistant corrosion: corrosion-resistant finishes and comparative example product by each embodiment gained based on graphene are placed in 10% sulfuric acid
In, corrosion-resistant finishes and comparative example product surface phenomenon after impregnating 200h, obtained by observation embodiment based on graphene.
Alkali corrosion resistance: the corrosion-resistant finishes obtained by each embodiment based on graphene is placed in 10% with comparative example product
Corrosion-resistant finishes and comparative example product table in sodium hydroxide solution, after impregnating 200h, obtained by observation embodiment based on graphene
Face phenomenon.
Impact resistant strength: the corrosion-resistant finishes obtained by each embodiment based on graphene is surveyed with comparative example product by GB1732
Examination.
Embodiment 1
A kind of corrosion-resistant finishes based on graphene mainly includes according to parts by weight the raw material components of following parts by weight: 20
Part modified graphene, 60 parts of aqueous acrylic emulsions, 3 parts of coalescing agents, 20 parts of water, 15 parts of improved silicas.
A kind of preparation method of the corrosion-resistant finishes based on graphene, the preparation of the corrosion-resistant finishes based on graphene
Method mainly includes following preparation step:
(1) graphene oxide is mixed with water 1:100 in mass ratio, the ultrasonic disperse 60min under conditions of frequency is 55kHz
Afterwards, graphene oxide dispersion is obtained, graphene oxide dispersion and 3- aminopropyl triethoxysilane 50:1 in mass ratio are mixed
Together in beaker, it is 60 DEG C in temperature, under conditions of revolving speed is 300r/min after stirring hair reaction 4h, then oxygen is added into beaker
The monoxone that 0.2 times of slag charge of graphite alkene dispersion liquid is 45 DEG C in temperature, and revolving speed is stirred to react 5h under conditions of being 280r/min
Afterwards, it filters, obtains modified graphene blank, dry 2h under conditions of being 80 DEG C in temperature by modified graphene blank；
(2) by titanium dioxide, 4:1.2 is mixed in grinder in molar ratio with potassium carbonate, after mixed grinding 3h, obtains mixed-powder,
After being calcined for 24 hours under conditions of being 800 DEG C in temperature by mixed-powder, pretreatment potassium tetratitanate is obtained, pretreatment potassium tetratitanate is used
After mass fraction is 12% salt acid elution for 2 times, then be washed with deionized 3 times, and by the pretreatment potassium tetratitanate after washing in
Temperature dry 3h under conditions of being 80 DEG C, obtains potassium tetratitanate, and potassium tetratitanate and ethyl orthosilicate 1:3 in mass ratio are mixed in burning
In bottle, and 30 times of potassium tetratitanate quality of water and 1.5 times of potassium tetratitanate quality of cetyl trimethyl bromine are added into flask
Change ammonium, and with mass fraction be 15% ammonium hydroxide adjust flask in material pH to 10, in temperature be 40 DEG C, revolving speed 240r/
After being stirred to react 8h under conditions of min, filtering, obtain improved silica blank, by improved silica blank in temperature be 500
After calcining 5h under conditions of DEG C, discharging；
(3) step (1) obtained material and step (2) obtained material 3:1 in mass ratio are mixed in three-necked flask, and to three mouthfuls
The water of 4 times of obtained material quality of step (1) and three ethoxy of 3- aminopropyl of 10 times of obtained material quality of step (1) are added in flask
The mixed dispersion liquid of base silane and succinic anhydride, in temperature be 40 DEG C, revolving speed be 260r/min under conditions of be stirred to react 5h after,
Filtering, obtains mixture, and mixture is mixed with the epolamine solution 1:20 in mass ratio that mass fraction is 20%, is in temperature
38 DEG C, after revolving speed is stirred 25min under conditions of being 280r/min, filtering obtains filter cake, by the hydrochloric acid of filter cake and ferric trichloride
Solution 1:15 in mass ratio is mixed, and is 45 DEG C in temperature, after revolving speed is stirred to react 40min under conditions of being 280r/min, is filtered,
Blank must be pre-processed, dry 2h under conditions of being 80 DEG C in temperature by pretreatment blank；
(4) step (3) obtained material and acrylic emulsion 1:2 in mass ratio are mixed in blender, and added into blender
Enter the coalescing agent of 0.01 times of obtained material quality of step (3) and the water of 0.8 times of obtained material quality of step (3), is in temperature
40 DEG C, revolving speed is stirred 60min under conditions of being 300r/min；
(5) step (4) obtained material is applied to metal pretreated substrate surface with 50 μm of smearing thickness, and in temperature be 60
Dry 20h, obtains the corrosion-resistant finishes based on graphene under conditions of DEG C；
(6) corrosion-resistant finishes based on graphene is obtained to step (5) gained and carries out index analysis.
As optimization, the preparation of the mixed dispersion liquid of step (3) the 3- aminopropyl triethoxysilane and succinic anhydride
Method is to mix 3- aminopropyl triethoxysilane and succinic anhydride 1:2 in mass ratio, and 3- aminopropyl-triethoxy is added
The dimethyl sulfoxide that 12 ~ 18 times of silane quality, is stirred, and obtains the mixing point of 3- aminopropyl triethoxysilane and succinic anhydride
Dispersion liquid.
As optimization, the hydrochloric acid solution of step (3) described ferric trichloride is the salt for being 12% by ferric trichloride and mass fraction
Acid 1:50 in mass ratio mixing, obtains the hydrochloric acid solution of ferric trichloride.
As optimization, step (5) the metal pretreated substrate is that metal plate is respectively cleaned 3 with ethyl alcohol and acetone respectively
It is secondary, metal pretreated substrate is obtained, the metal plate is steel plate.
Embodiment 2
A kind of corrosion-resistant finishes based on graphene mainly includes according to parts by weight the raw material components of following parts by weight: 20
Part graphene, 60 parts of aqueous acrylic emulsions, 3 parts of coalescing agents, 20 parts of water and 15 parts of improved silicas.
A kind of preparation method of the corrosion-resistant finishes based on graphene, the preparation of the corrosion-resistant finishes based on graphene
Method mainly includes following preparation step:
(1) by titanium dioxide, 4:1.2 is mixed in grinder in molar ratio with potassium carbonate, after mixed grinding 3h, obtains mixed-powder,
After being calcined for 24 hours under conditions of being 800 DEG C in temperature by mixed-powder, pretreatment potassium tetratitanate is obtained, pretreatment potassium tetratitanate is used
After mass fraction is 12% salt acid elution for 2 times, then be washed with deionized 3 times, and by the pretreatment potassium tetratitanate after washing in
Temperature dry 3h under conditions of being 80 DEG C, obtains potassium tetratitanate, and potassium tetratitanate and ethyl orthosilicate 1:3 in mass ratio are mixed in burning
In bottle, and 30 times of potassium tetratitanate quality of water and 1.5 times of potassium tetratitanate quality of cetyl trimethyl bromine are added into flask
Change ammonium, and with mass fraction be 15% ammonium hydroxide adjust flask in material pH to 10, in temperature be 40 DEG C, revolving speed 240r/
After being stirred to react 8h under conditions of min, filtering, obtain improved silica blank, by improved silica blank in temperature be 500
After calcining 5h under conditions of DEG C, discharging；
(2) graphene and step (2) obtained material 3:1 in mass ratio are mixed in three-necked flask, and added into three-necked flask
Enter the mixing dispersion of 4 times of graphene quality of water and 10 times of graphene quality of 3- aminopropyl triethoxysilane and succinic anhydride
Liquid is 40 DEG C in temperature, and after revolving speed is stirred to react 5h under conditions of being 260r/min, filtering obtains mixture, by mixture and matter
It measures the epolamine solution 1:20 in mass ratio that score is 20% to mix, is 38 DEG C in temperature, revolving speed is under conditions of 280r/min
After being stirred 25min, filtering obtains filter cake, filter cake is mixed with the hydrochloric acid solution of ferric trichloride 1:15 in mass ratio, Yu Wendu
Be 45 DEG C, revolving speed be 280r/min under conditions of be stirred to react 40min after, filtering, obtain pretreatment blank, will pretreatment blank in
Temperature dry 2h under conditions of being 80 DEG C；
(3) step (2) obtained material and acrylic emulsion 1:2 in mass ratio are mixed in blender, and added into blender
Enter the coalescing agent of 0.01 times of obtained material quality of step (2) and the water of 0.8 times of obtained material quality of step (2), is in temperature
40 DEG C, revolving speed is stirred 60min under conditions of being 300r/min；
(4) step (3) obtained material is applied to metal pretreated substrate surface with 50 μm of smearing thickness, and in temperature be 60
Dry 20h, obtains the corrosion-resistant finishes based on graphene under conditions of DEG C；
(5) corrosion-resistant finishes based on graphene is obtained to step (4) gained and carries out index analysis.
As optimization, the preparation of the mixed dispersion liquid of step (2) the 3- aminopropyl triethoxysilane and succinic anhydride
Method is to mix 3- aminopropyl triethoxysilane and succinic anhydride 1:2 in mass ratio, and 3- aminopropyl-triethoxy is added
The dimethyl sulfoxide that 12 ~ 18 times of silane quality, is stirred, and obtains the mixing point of 3- aminopropyl triethoxysilane and succinic anhydride
Dispersion liquid.
As optimization, the hydrochloric acid solution of step (2) described ferric trichloride is the salt for being 12% by ferric trichloride and mass fraction
Acid 1:50 in mass ratio mixing, obtains the hydrochloric acid solution of ferric trichloride.
As optimization, step (4) the metal pretreated substrate is that metal plate is respectively cleaned 3 with ethyl alcohol and acetone respectively
It is secondary, metal pretreated substrate is obtained, the metal plate is steel plate.
Embodiment 3
A kind of corrosion-resistant finishes based on graphene mainly includes according to parts by weight the raw material components of following parts by weight: 20
Part modified graphene, 60 parts of aqueous acrylic emulsions, 3 parts of coalescing agents, 20 parts of water and 15 parts of improved silicas.
A kind of preparation method of the corrosion-resistant finishes based on graphene, the preparation of the corrosion-resistant finishes based on graphene
Method mainly includes following preparation step:
(1) graphene oxide is mixed with water 1:100 in mass ratio, the ultrasonic disperse 60min under conditions of frequency is 55kHz
Afterwards, graphene oxide dispersion is obtained, graphene oxide dispersion and 3- aminopropyl triethoxysilane 50:1 in mass ratio are mixed
Together in beaker, it is 60 DEG C in temperature, under conditions of revolving speed is 300r/min after stirring hair reaction 4h, then oxygen is added into beaker
The monoxone that 0.2 times of slag charge of graphite alkene dispersion liquid is 45 DEG C in temperature, and revolving speed is stirred to react 5h under conditions of being 280r/min
Afterwards, it filters, obtains modified graphene blank, dry 2h under conditions of being 80 DEG C in temperature by modified graphene blank；
(2) ethyl orthosilicate is added in flask, and the water of 30 times of ethyl orthosilicate quality of addition and positive silicic acid second into flask
The cetyl trimethylammonium bromide that 1.5 times of ester quality, and with mass fraction be 15% ammonium hydroxide adjust flask in material pH to
10, it is 40 DEG C in temperature, after revolving speed is stirred to react 8h under conditions of being 240r/min, filtering obtains silica blank, by dioxy
After SiClx blank calcines 5h under conditions of being 500 DEG C in temperature, discharging；
(3) step (1) obtained material and step (2) obtained material 3:1 in mass ratio are mixed in three-necked flask, and to three mouthfuls
The water of 4 times of obtained material quality of step (1) and three ethoxy of 3- aminopropyl of 10 times of obtained material quality of step (1) are added in flask
The mixed dispersion liquid of base silane and succinic anhydride, in temperature be 40 DEG C, revolving speed be 260r/min under conditions of be stirred to react 5h after,
Filtering, obtains mixture, and mixture is mixed with the epolamine solution 1:20 in mass ratio that mass fraction is 20%, is in temperature
38 DEG C, after revolving speed is stirred 25min under conditions of being 280r/min, filtering obtains filter cake, by the hydrochloric acid of filter cake and ferric trichloride
Solution 1:15 in mass ratio is mixed, and is 45 DEG C in temperature, after revolving speed is stirred to react 40min under conditions of being 280r/min, is filtered,
Blank must be pre-processed, dry 2h under conditions of being 80 DEG C in temperature by pretreatment blank；
(4) step (3) obtained material and acrylic emulsion 1:2 in mass ratio are mixed in blender, and added into blender
Enter the coalescing agent of 0.01 times of obtained material quality of step (3) and the water of 0.8 times of obtained material quality of step (3), is in temperature
40 DEG C, revolving speed is stirred 60min under conditions of being 300r/min；
(5) step (4) obtained material is applied to metal pretreated substrate surface with 50 μm of smearing thickness, and in temperature be 60
Dry 20h, obtains the corrosion-resistant finishes based on graphene under conditions of DEG C；
(6) corrosion-resistant finishes based on graphene is obtained to step (5) gained and carries out index analysis.
As optimization, the preparation of the mixed dispersion liquid of step (3) the 3- aminopropyl triethoxysilane and succinic anhydride
Method is to mix 3- aminopropyl triethoxysilane and succinic anhydride 1:2 in mass ratio, and 3- aminopropyl-triethoxy is added
The dimethyl sulfoxide that 12 ~ 18 times of silane quality, is stirred, and obtains the mixing point of 3- aminopropyl triethoxysilane and succinic anhydride
Dispersion liquid.
As optimization, the hydrochloric acid solution of step (3) described ferric trichloride is the salt for being 12% by ferric trichloride and mass fraction
Acid 1:50 in mass ratio mixing, obtains the hydrochloric acid solution of ferric trichloride.
As optimization, step (5) the metal pretreated substrate is that metal plate is respectively cleaned 3 with ethyl alcohol and acetone respectively
It is secondary, metal pretreated substrate is obtained, the metal plate is steel plate.
Embodiment 4
A kind of corrosion-resistant finishes based on graphene mainly includes according to parts by weight the raw material components of following parts by weight: 20
Part modified graphene, 60 parts of aqueous acrylic emulsions, 3 parts of coalescing agents, 20 parts of water, 15 parts of improved silicas.
A kind of preparation method of the corrosion-resistant finishes based on graphene, the preparation of the corrosion-resistant finishes based on graphene
Method mainly includes following preparation step:
(1) graphene oxide is mixed with water 1:100 in mass ratio, the ultrasonic disperse 60min under conditions of frequency is 55kHz
Afterwards, graphene oxide dispersion is obtained, graphene oxide dispersion and 3- aminopropyl triethoxysilane 50:1 in mass ratio are mixed
Together in beaker, it is 60 DEG C in temperature, under conditions of revolving speed is 300r/min after stirring hair reaction 4h, then oxygen is added into beaker
The monoxone that 0.2 times of slag charge of graphite alkene dispersion liquid is 45 DEG C in temperature, and revolving speed is stirred to react 5h under conditions of being 280r/min
Afterwards, it filters, obtains modified graphene blank, dry 2h under conditions of being 80 DEG C in temperature by modified graphene blank；
(2) by titanium dioxide, 4:1.2 is mixed in grinder in molar ratio with potassium carbonate, after mixed grinding 3h, obtains mixed-powder,
After being calcined for 24 hours under conditions of being 800 DEG C in temperature by mixed-powder, pretreatment potassium tetratitanate is obtained, pretreatment potassium tetratitanate is used
After mass fraction is 12% salt acid elution for 2 times, then be washed with deionized 3 times, and by the pretreatment potassium tetratitanate after washing in
Temperature dry 3h under conditions of being 80 DEG C, obtains potassium tetratitanate, and potassium tetratitanate and ethyl orthosilicate 1:3 in mass ratio are mixed in burning
In bottle, and 30 times of potassium tetratitanate quality of water and 1.5 times of potassium tetratitanate quality of cetyl trimethyl bromine are added into flask
Change ammonium, and with mass fraction be 15% ammonium hydroxide adjust flask in material pH to 10, in temperature be 40 DEG C, revolving speed 240r/
After being stirred to react 8h under conditions of min, filtering, obtain improved silica blank, by improved silica blank in temperature be 500
After calcining 5h under conditions of DEG C, discharging；
(3) step (1) obtained material and step (2) obtained material 3:1 in mass ratio are mixed in three-necked flask, and to three mouthfuls
The water of 4 times of obtained material quality of step (1) and three ethoxy of 3- aminopropyl of 10 times of obtained material quality of step (1) are added in flask
The mixed dispersion liquid of base silane and succinic anhydride, in temperature be 40 DEG C, revolving speed be 260r/min under conditions of be stirred to react 5h after,
Filtering removes filtrate, dry 2h under conditions of being 80 DEG C in temperature；
(4) step (3) obtained material and acrylic emulsion 1:2 in mass ratio are mixed in blender, and added into blender
Enter the coalescing agent of 0.01 times of obtained material quality of step (3) and the water of 0.8 times of obtained material quality of step (3), is in temperature
40 DEG C, revolving speed is stirred 60min under conditions of being 300r/min；
(5) step (4) obtained material is applied to metal pretreated substrate surface with 50 μm of smearing thickness, and in temperature be 60
Dry 20h, obtains the corrosion-resistant finishes based on graphene under conditions of DEG C；
(6) corrosion-resistant finishes based on graphene is obtained to step (5) gained and carries out index analysis.
As optimization, the preparation of the mixed dispersion liquid of step (3) the 3- aminopropyl triethoxysilane and succinic anhydride
Method is to mix 3- aminopropyl triethoxysilane and succinic anhydride 1:2 in mass ratio, and 3- aminopropyl-triethoxy is added
The dimethyl sulfoxide that 12 ~ 18 times of silane quality, is stirred, and obtains the mixing point of 3- aminopropyl triethoxysilane and succinic anhydride
Dispersion liquid.
As optimization, step (5) the metal pretreated substrate is that metal plate is respectively cleaned 3 with ethyl alcohol and acetone respectively
It is secondary, metal pretreated substrate is obtained, the metal plate is steel plate.
Comparative example
A kind of corrosion-resistant finishes based on graphene mainly includes according to parts by weight the raw material components of following parts by weight: 20
Part graphene, 60 parts of aqueous acrylic emulsions, 3 parts of coalescing agents, 20 parts of water, 15 parts of silica.
A kind of preparation method of the corrosion-resistant finishes based on graphene, the preparation of the corrosion-resistant finishes based on graphene
Method mainly includes following preparation step:
(1) ethyl orthosilicate is added in flask, and the water of 30 times of ethyl orthosilicate quality of addition and positive silicic acid second into flask
The cetyl trimethylammonium bromide that 1.5 times of ester quality, and with mass fraction be 15% ammonium hydroxide adjust flask in material pH to
10, it is 40 DEG C in temperature, after revolving speed is stirred to react 8h under conditions of being 240r/min, filtering obtains silica blank, by dioxy
After SiClx blank calcines 5h under conditions of being 500 DEG C in temperature, discharging；
(2) graphene and step (1) obtained material 3:1 in mass ratio are mixed in three-necked flask, and added into three-necked flask
Enter the mixing dispersion of 4 times of graphene quality of water and 10 times of graphene quality of 3- aminopropyl triethoxysilane and succinic anhydride
Liquid, in temperature be 40 DEG C, revolving speed be 260r/min under conditions of be stirred to react 5h after, filtering, remove filtrate, in temperature be 80 DEG C
Under conditions of dry 2h；
(3) step (2) obtained material and acrylic emulsion 1:2 in mass ratio are mixed in blender, and added into blender
Enter the coalescing agent of 0.01 times of obtained material quality of step (2) and the water of 0.8 times of obtained material quality of step (2), is in temperature
40 DEG C, revolving speed is stirred 60min under conditions of being 300r/min；
(4) step (3) obtained material is applied to metal pretreated substrate surface with 50 μm of smearing thickness, and in temperature be 60
Dry 20h, obtains the corrosion-resistant finishes based on graphene under conditions of DEG C；
(5) corrosion-resistant finishes based on graphene is obtained to step (4) gained and carries out index analysis.
As optimization, the preparation of the mixed dispersion liquid of step (2) the 3- aminopropyl triethoxysilane and succinic anhydride
Method is to mix 3- aminopropyl triethoxysilane and succinic anhydride 1:2 in mass ratio, and 3- aminopropyl-triethoxy is added
The dimethyl sulfoxide that 12 ~ 18 times of silane quality, is stirred, and obtains the mixing point of 3- aminopropyl triethoxysilane and succinic anhydride
Dispersion liquid.
As optimization, step (4) the metal pretreated substrate is that metal plate is respectively cleaned 3 with ethyl alcohol and acetone respectively
It is secondary, metal pretreated substrate is obtained, the metal plate is steel plate.
Effect example
The following table 1 gives the acid corrosion-resistant of the corrosion-resistant finishes based on graphene using the embodiment of the present invention 1 to 4 Yu comparative example
Property, the analysis result of alkali corrosion resistance and impact resistant strength.
Table 1
| Acid-resistant corrosion | Alkali corrosion resistance | Impact strength (Kg/cm) | |
| Embodiment 1 | Surfacing | Surfacing | 260 |
| Embodiment 2 | There is a little crackle on surface | There is a little crackle on surface | 240 |
| Embodiment 3 | There is crackle on surface and generates bubbling | There is crackle on surface and generates bubbling | 235 |
| Embodiment 4 | There is obvious rust spot on surface | There is obvious rust spot on surface | 225 |
| Comparative example | There is more rust spot on surface | There is more rust spot on surface | 180 |
Embodiment 1 can be found compared with the experimental data of comparative example from table 1, when preparing the corrosion-resistant finishes based on graphene
Using modified graphene and after the modified silica of potassium tetratitanate and polypyrrole, the corrosion-resistant finishes based on graphene can be made
Acid-alkali-corrosive-resisting performance greatly improve, while can make product have preferable intensity；From the experiment of embodiment 1 and embodiment 2
Data, which compare, to be found, when being added without modified graphene in the product, graphene can not generate lamination effect with improved silica
Answer, and graphene can not be dispersed in products, and then make the acid-alkali-corrosive-resisting reduced performance of product, from embodiment 1,
The experimental data of embodiment 3 and embodiment 4, which compares, to be found, when be added without in product through potassium tetratitanate and polypyrrole it is modified two
When silica, intensive erosion shield can not be formed in the product, to largely effect on the acid-alkali-corrosive-resisting of product.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
Claims (10)
1. a kind of corrosion-resistant finishes based on graphene, which is characterized in that mainly include the raw material components of following parts by weight: 12
~ 20 parts of modified graphenes, 30 ~ 60 parts of aqueous acrylic emulsions, 2 ~ 3 parts of coalescing agents and 20 ~ 30 parts of water.
2. a kind of corrosion-resistant finishes based on graphene according to claim 1, which is characterized in that described to be based on graphene
Corrosion-resistant finishes further include following parts by weight raw material components: 10 ~ 15 parts of improved silicas.
3. a kind of corrosion-resistant finishes based on graphene according to claim 2, which is characterized in that the water soluble acrylic acid
The solid content of lotion is 45 ~ 55%, and the coalescing agent is that decylene glycol ester and 1,2-PD 1:1 in mass ratio are mixed mixed
Close object.
4. a kind of corrosion-resistant finishes based on graphene according to claim 3, which is characterized in that the modified graphene
By graphene oxide through 3- aminopropyl triethoxysilane and monoxone processing after gained；The improved silica is by carboxylated
Mesoporous silicon oxide, potassium tetratitanate and polypyrrole are made.
5. a kind of corrosion-resistant finishes based on graphene according to claim 4, which is characterized in that described to be based on
The corrosion-resistant finishes of graphene mainly includes the raw material components of following parts by weight: 20 parts of modified graphenes, 60 parts of aqueous acrylamides
Yogurt liquid, 3 parts of coalescing agents, 20 parts of water and 15 parts of improved silicas.
6. a kind of preparation method of the corrosion-resistant finishes based on graphene, which is characterized in that mainly include following preparation step:
(1) after graphene oxide being mixed with 3- aminopropyl triethoxysilane, then with chloroacetate reaction, be made modified graphite
Alkene；
(2) it by titanium dioxide and potassium carbonate mixed grinding, calcines, washs, it is dry, potassium tetratitanate is obtained, by potassium tetratitanate and positive silicon
Sour second mixing, and pore-foaming agent is added, after being stirred to react under alkaline condition, calcining obtains improved silica；
(3) modified graphene obtained by step (1) is mixed with improved silica obtained by step (2), and three second of 3- aminopropyl is added
The mixed dispersion liquid of oxysilane and succinic anhydride, after being stirred to react, filtering obtains mixture, and mixture is molten with epolamine
Liquid mixing, filtering, then mixed with the hydrochloric acid solution of ferric trichloride, it filters, washs, it is dry, obtain blank；
(4) blank obtained by step (3) is mixed with aqueous acrylic emulsion；And water and coalescing agent is added, it is stirred, obtains stone
Black alkene corrosion resistant coating；
(5) graphene corrosion resistant coating obtained by step (4) metal pretreated substrate surface is applied to after dry to obtain based on stone
The corrosion-resistant finishes of black alkene；
(6) index analysis is carried out to the corrosion-resistant finishes obtained by step (5) based on graphene.
7. a kind of preparation method of corrosion-resistant finishes based on graphene according to claim 7, which is characterized in that main
Including following preparation step:
(1) graphene oxide is mixed with water 1:100 ~ 1:120 in mass ratio, ultrasonic disperse obtains graphene oxide dispersion, will
Graphene oxide dispersion and 3- aminopropyl triethoxysilane 50:1 ~ 60:1 in mass ratio are mixed in beaker, and stirring hair is anti-
Ying Hou, then 0.1 ~ 0.2 times of graphene oxide dispersion slag charge of monoxone is added into beaker, it after being stirred to react, filters, does
It is dry；
(2) by titanium dioxide, 4:1.2 is mixed in molar ratio with potassium carbonate, and grinding obtains mixed-powder, is in temperature by mixed-powder
After calcining for 24 hours under conditions of 800 DEG C, pretreatment potassium tetratitanate is obtained, hydrochloric acid of the potassium tetratitanate mass fraction for 12% will be pre-processed
It after washing 2 times, then is washed with deionized 3 times, and by the pretreatment potassium tetratitanate after washing under conditions of temperature is 80 DEG C
Dry 3h, obtains potassium tetratitanate, and potassium tetratitanate and ethyl orthosilicate 1:3 in mass ratio are mixed in flask, and adds into flask
Enter 30 times of potassium tetratitanate quality of water and 1 ~ 2 times of potassium tetratitanate quality of cetyl trimethylammonium bromide, adjusts object in flask
The pH to 10 ~ 11 of material, after being stirred to react, filtering obtains improved silica blank, is in temperature by improved silica blank
After calcining 5h under conditions of 500 DEG C, discharging；
(3) step (1) obtained material and step (2) obtained material 2:1 ~ 3:1 in mass ratio are mixed in three-necked flask, and to
The water of 4 ~ 5 times of obtained material quality of step (1) and the 3- ammonia third of 8 ~ 10 times of obtained material quality of step (1) are added in three-necked flask
The mixed dispersion liquid of ethyl triethoxy silicane alkane and succinic anhydride, after being stirred to react, filtering obtains mixture, by mixture and quality
The epolamine solution 1:20 in mass ratio that score is 20% is mixed, and after being stirred, filtering obtains filter cake, by filter cake and tri-chlorination
The hydrochloric acid solution of iron 1:15 in mass ratio mixing, after being stirred to react, filtering obtains pretreatment blank, by pretreatment blank in temperature
Dry 2h under conditions of being 80 DEG C；
(4) step (3) obtained material and acrylic emulsion 1:2 in mass ratio are mixed in blender, and added into blender
Enter the coalescing agent of 0.01 times of obtained material quality of step (3) and the water of 0.8 times of obtained material quality of step (3), is stirred；
(5) step (4) obtained material is applied to metal pretreated substrate surface with 50 μm of smearing thickness, and in temperature be 60
Dry 12 ~ 36h, obtains the corrosion-resistant finishes based on graphene under conditions of DEG C；
(6) corrosion-resistant finishes based on graphene is obtained to step (5) gained and carries out index analysis.
8. a kind of preparation method with the composite high-molecular conductive material for stablizing conductivity according to claim 8,
It is characterized in that, the preparation method of the mixed dispersion liquid of step (3) the 3- aminopropyl triethoxysilane and succinic anhydride is will
3- aminopropyl triethoxysilane and succinic anhydride 1:2 in mass ratio mixing, and 3- aminopropyl triethoxysilane quality is added
12 ~ 18 times of dimethyl sulfoxide, is stirred, and obtains the mixed dispersion liquid of 3- aminopropyl triethoxysilane and succinic anhydride.
9. a kind of preparation method with the composite high-molecular conductive material for stablizing conductivity according to claim 7,
Be characterized in that, the hydrochloric acid solution of step (3) described ferric trichloride be by ferric trichloride and mass fraction be 12% hydrochloric acid by quality
It is mixed than 1:50, obtains the hydrochloric acid solution of ferric trichloride.
10. a kind of preparation method with the composite high-molecular conductive material for stablizing conductivity according to claim 7,
It is characterized in that, step (5) the metal pretreated substrate is respectively to clean metal plate 3 times with ethyl alcohol and acetone respectively, obtains pre- place
Metallic substrates are managed, the metal plate is any one in steel plate or copper sheet.
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