CN107573817A - A kind of preparation method of composite water soluble anticorrosive paint - Google Patents
A kind of preparation method of composite water soluble anticorrosive paint Download PDFInfo
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Abstract
The invention belongs to chemistry painting industry field, more particularly to a kind of preparation method of composite water soluble anticorrosive paint.The present invention uses polyaniline aeroge (PA) and conducting metal organic backbone ((Cr)@of MIL 101 TiO2) as filler be added in aqueous epoxy resins be made water corrosion-resistant epoxy paint.Using polyaniline aeroge and conducting metal organic backbone as anticorrosive packing; not only mutually it can transmit electronics by synergistic; corrosion reaction is set to occur above coating rather than metal surface; antiseptic effect is reached so as to play protection metal anode; and the multi-pore channel structure of the two has delayed to corrode the time that particle reaches metal surface jointly; while the aqueous epoxy resins is had antiseptic power, the barrier property of aqueous epoxy resins is added again, so as to be obviously improved the antiseptic property of corrosion-inhibiting coating.
Description
Technical field
The invention belongs to chemistry painting industry field, more particularly to a kind of preparation method of composite water soluble anticorrosive paint.
Background technology
At present, it is in anti-corrosion of metal to use solvent-borne type anticorrosive paint more, as main component is phenol aldehyde modified epoxy resin
TY3318, TY3319, because different resins has each unique performance, it can be selected in construction according to the difference of use environment
Select different resins to be dissolved in organic solvent, as polyurethane has excellent weathering and chemical resistance, high glaze, wearability, have
There is machine silicones extremely outstanding heat resistance can be used as heat-resisting, weathering coating base-material etc., at the same solvent based coating can with place,
The change of weather carries out the control of solvent ratios, to obtain high-quality film；But it must be used in the construction of solvent based coating big
High volatile solvent is measured, and construction tool must also be cleaned with solvent, coating smell is excessive, harmful to human body and environment；
In addition, when environment temperature is less than 15 DEG C, organic solvent mobile is poor, and difficulty is brought to construction.Water paint is last century six
The technology that the ten's grew up, with water as solvent, save ample resources；Fire risk when water paint eliminates construction,
Reduce improves operating environmental condition to atmosphere pollution, water paint only with a small amount of hypotoxicity alcohol ethers organic solvent；But
For a long time, water-based anticorrosive paint is in addition to environmental protection is advantageous to, and other performances are not as good as in solvent-borne type anticorrosive paint.In recent years, by
There are excellent physical and chemical properties in aqueous epoxide resin paint, such as good adhesive force, chemical proofing and resistance to molten
Agent, and its hardness is high, good heat stability, it is shown one's talent in numerous water paints.However, in actual applications
Aqueous epoxy resins there is also it is certain the defects of, the micropore that brings causes antiseptic property to decline after solidifying such as Water-borne modification, barrier
It is deteriorated, intensity decreases etc., therefore need badly and develop a kind of water-based anticorrosive paint of superior performance.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of preparation method of composite water soluble anticorrosive paint, the party
Method can effectively lift the antiseptic property of water-based matrix coating, improve the barrier of coating.
To achieve these goals, the preparation method of composite water soluble anticorrosive paint provided by the invention, comprises the following steps.
Step 1. weighs 3-8g anilinechlorides and added in there-necked flask, adds 15-40mL deionized waters, stirs 20-
40min, mixing speed are 300-500 r/min, obtain solution I；Weigh 6-13g ammonium persulfates to add in beaker, add 20-
In 60mL deionized waters, 20-40min is stirred, mixing speed is 300-500 r/min, obtains solution II；In ice-water bath condition
Under, solution I and solution II are placed into 20-40min, its temperature is reduced to 5-10 DEG C；Then by solution II with 5-10mL/s
Speed add solution I in, be stirred vigorously 0.5-2min rapidly, mixing speed 1000-1500r/min, obtain solution III；Room
Under the conditions of temperature, solution III is stood into 10-15h, obtains polyaniline hydrogel, the polyaniline hydrogel 200-500mL that will be obtained
0.1-0.2 mol/L HCl cleaning, every 8-10h change a HCl, clean 4-6 days；Then it is anhydrous with 300-500mL
Ethanol carries out solvent displacement, changes an absolute ethyl alcohol every 8-10h, after replacing 4-6 days, resulting product is placed in super
Critical CO2In drying kettle, drying process 6-8h, 40-60 DEG C of drying temperature, drying pressure 10-15MPa, polyaniline airsetting is obtained
Glue.
The titanium tetrachloride that step 2. weighs 0.2-0.4mL is dissolved in 70-100mL cold water, and adding 0.2-0.4g metals has
Machine skeleton（MIL-101(Cr)）, stir 20-40 min, mixing speed 200-400r/min, centrifugal treating 5- after stirring
10min, speed 2500-3000r/min, supernatant, obtained sediment are removed, and add 80-120mL deionized waters, so
After be transferred in reactor, under the conditions of 160-200 DEG C, hydro-thermal reaction 8-12h；Centrifuge washing again, speed 2500-
3000r/min, sediment dry 10-16 h, obtain conducting metal organic backbone under 30-50 DEG C of vacuum condition（MIL-101
(Cr)@TiO2）.
Step 3. weighs 10-40 part polyaniline aeroges and 10-40 part conducting metal organic backbones in parts by weight, adds
Into the mixed liquor of 100-200 parts water and 100-200 part aqueous epoxy resins, 1-2h is disperseed in ball mill, produces Compound Water
The mother liquor of property anticorrosive paint.
After step 4. takes 25-50 parts waterborne curing agent to be well mixed with 50-100 part water in parts by weight, then with Compound Water
The mother liquor by weight proportion 1 of property anticorrosive paint：3-5 is mixed, and is produced.
The metal organic framework（MIL-101(Cr)）Preparation method it is as follows：Weigh chromic nitrate 3-5g and 5-10g graphite
Alkene is placed in beaker, adds 10-30ml water, stirs 30-40min, mixing speed 50-150r/min；Weigh 2-3gH2BDC
（1,4- phthalic acids）It is put into reactor, the aqueous solution of chromic nitrate and graphene is transferred to reactor, then with 5-10mL water
Rinse beaker is simultaneously transferred to reactor, stirs 30-60min, mixing speed 50-150r/min, is injected with plastic injector
0.1-0.5mlHF（Hydrofluoric acid）, it is put into 200-250 DEG C of baking oven and reacts 1-3h；Room temperature is cooled to, by products therefrom hot ethanol
Backflow is washed three times, then is flowed back 5-15h with fluorination ammonia spirit, then with alcohol reflux once；By product after drying at room temperature 10-15h
It is put into 100-200 DEG C of baking oven and dries, time 10-15h, obtains metal organic framework（MIL-101(Cr)）.
The aqueous epoxy resins be E20 epoxies breast, E44 epoxy emulsions, Ar555 epoxy resin, E51 epoxy emulsions or
H228A epoxy resin.
The waterborne curing agent is Aq419, W651, W650 or H228B.
The remarkable result of the present invention.
Composite water soluble anticorrosive paint prepared by the present invention is successfully by polyaniline aeroge and conducting metal organic backbone electricity
Sub- transmittability collaboration gets up to transmit electronics, cathode reaction in corrosion reaction is no longer occurred in metal surface, so that corrosion
Product is not regenerated in metal surface；Due to corrosion product Fe3(OH)3Iron rust Fe can be decomposed into2O3While form fluffy knot
Structure, so corrosion of metal can be further exacerbated by, metal erosion is avoided when corrosion product no longer metal surface occurs
Aggravation, so as to play a part of protecting anode metal, solves Anticorrosion from root.Composite water soluble anti-corrosion prepared by the present invention
The anticorrosion mechanism of coating is after metal loses electronics, electronic capability is transmitted because conductive filler has, by electric transmission to coating
Top and corrosive medium H2O, O2Deng generation OH-, due to the OH of generation-In coating surface, avoid and generate corruption in metal surface
Lose sediment（Crud can promote metal erosion）, so as to play a part of protecting anode metal.
In coating prepared by the present invention, the polyaniline aeroge of use is made of polyaniline and aeroge combine
A kind of new three-dimensional network porous structure material, the more of the good electronic transmission performance of polyaniline and aeroge have been provided simultaneously with it
The excellent properties such as pore structure, big specific surface area, are with a wide range of applications in terms of electrochemical energy storage；Conducting metal
Organic backbone（MIL-101(Cr)@TiO2）It is nano-TiO2Modified metal organic backbone（MIL-101(Cr)）The one kind three on surface
Skeleton crystal structure materials are tieed up, there is high porosity and certain electronic transmission performance, one is possessed in terms of electrochemical energy storage
Fixed application value.
For the present invention in the preparation method of new composite water soluble anticorrosive paint, the filler added is not simple mechanical
Blending, but the epoxy-functional on the carboxyl and epoxy resin on the amino and conducting metal organic backbone on aniline aeroge
React to each other, form cross-linked structure and reunite so as to avoid, make filler well dispersed in coating.The present invention successfully utilizes polyphenyl
Amine aeroge is different with the aperture of conducting metal organic backbone, makes corrosion impregnation of different sizes to the time of metallic matrix
It is elongated, it is common to improve aqueous epoxy resins barrier, make the antiseptic property, barrier property and intensity of waterborne epoxy coatings significantly
Degree lifting.
Brief description of the drawings
The anticorrosion mechanism of Fig. 1 composite water soluble anticorrosive paints.
Photo of Fig. 2 aqueous epoxy resins coating after salt spray test 500h.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1.
The preparation method of composite water soluble anticorrosive paint, comprises the following steps.
1. the preparation of conductive filler.
（1）Weigh 8g anilinechlorides to add in there-necked flask, add 40mL deionized waters, stir 40min, mixing speed is
500 r/min, obtain solution I；Weigh 13g ammonium persulfates to add in beaker, add in 60mL deionized waters, stir 40min, stir
It is 500 r/min to mix speed, obtains solution II；Solution I and solution II are positioned over 40min in ice-water bath, make the reduction of its temperature
To 10 DEG C；Then solution II is added in solution I with 5mL/s speed, is stirred vigorously 2min rapidly, mixing speed is
1500r/min, obtain solution III；Solution III is stood into 15h at room temperature, obtains polyaniline hydrogel, the polyaniline that will be obtained
Hydrogel is cleaned with 500mL 0.2 mol/L HCl, is changed a HCl every 10h, is cleaned 6 days；Then the anhydrous second of 500mL is used
Alcohol carries out solvent displacement, changes an absolute ethyl alcohol every 10h, after replacing 6 days, resulting product is placed in into supercritical CO2
Processing 8h is dried in drying kettle, 60 DEG C of drying temperature, drying pressure 15MPa, obtains polyaniline aeroge.
Weigh chromic nitrate 3g and 5g graphene to be placed in beaker, add 25mL water, stir 30min, mixing speed 100r/
min；Weigh 3gH2BDC（1,4- phthalic acids）It is put into reactor, the aqueous solution of chromic nitrate and graphene is transferred to reaction
Kettle, then with 8.6mL water rinse beakers and reactor is transferred to, 30min is stirred, mixing speed 100r/min, uses plastic injection
Device injects 0.31mLHF, is put into 220 DEG C of baking ovens and reacts 2h；Room temperature is cooled to, the backflow of products therefrom hot ethanol is washed three times,
Fluorination ammonia spirit backflow 10h is used again, then with alcohol reflux once；Product is put into 150 DEG C of baking ovens after drying at room temperature 12h and dried
It is dry, time 12h, obtain metal organic framework（MIL-101(Cr)）.
（2）The titanium tetrachloride for weighing 0.2mL is dissolved in 70mL cold water, adds 0.3g metal organic frameworks（MIL-101
(Cr)）, 30min, mixing speed 300r/min are stirred, 5min, speed 3000r/min are centrifuged after stirring, removes supernatant
Obtained sediment simultaneously adds 100mL deionized waters, is then transferred into reactor, the hydro-thermal reaction 8h under the conditions of 160 DEG C；
Centrifuge washing again, centrifugal speed 3000r/min, sediment dry 10h under 40 DEG C of vacuum conditions, it is organic to obtain conducting metal
Bone（MIL-101(Cr)@TiO2）.
2. the preparation of anticorrosive paint.
（1）100 parts of Ar555 aqueous epoxy resins and 100 parts of water are taken, is well mixed, obtains resin system.
（2）20 parts of polyaniline aeroges and 20 parts of conducting metal organic backbone fillers are taken, are added in above-mentioned resin system,
Disperse 1h in ball mill, obtain the mother liquor of water-base epoxy composite anticorrosion coating.
（3）50 parts of H228B waterborne curing agents are taken to be well mixed with 100 parts of water；By the mother of water-base epoxy composite anticorrosion coating
Liquid and the waterborne curing agent by weight proportion 4 diluted：1 mixing, is produced.
By obtained anti-corrosion paint on the metal substrate through handling well, control thickness is solid in 30-200um, room temperature
Change 24h.
Embodiment 2.
The preparation method of the water-based anticorrosive paint of any filler is not added, is comprised the following steps.
（1）100 parts of Ar555 aqueous epoxy resins and 100 parts of water, it is well mixed, obtains resin system.
（2）50 parts of H228B waterborne curing agents are taken to be well mixed with 100 parts of water；Resin system is water-based solid with having diluted
Agent by weight proportion 4：1 mixing, is produced.
By obtained anti-corrosion paint on the metal substrate through handling well, control thickness is solid in 30-200um, room temperature
Change 24h.
Embodiment 3.
The individually preparation method of the water-based anticorrosive paint of addition conducting metal organic backbone, comprises the following steps.
1. the preparation of conductive filler.
（1）The titanium tetrachloride for weighing 0.2mL is dissolved in 70mL cold water, and it is organic to add metal prepared by 0.3g embodiments 1
Skeleton（MIL-101(Cr)）, 30min, mixing speed 300r/min are stirred, 5min is centrifuged after stirring, centrifugal speed is
3000r/min, remove the sediment that supernatant obtains and add 100mL deionized waters, be then transferred into reactor, 160
Hydro-thermal reaction 8h under the conditions of DEG C；Centrifuge washing again, centrifugal speed 3000r/min, sediment are dried under 40 DEG C of vacuum conditions
10h, obtain the organic bone of conducting metal（MIL-101(Cr)@TiO2）.
2. the preparation of anticorrosive paint.
（1）100 parts of Ar555 aqueous epoxy resins and 100 parts of water are taken, is well mixed, obtains resin system.
（2）40 parts of conducting metal organic backbone fillers are taken, are added in above resin system, 1h is disperseed in ball mill, is obtained
To the mother liquor of water-base epoxy composite anticorrosion coating.
（3）50 parts of H228B waterborne curing agents are taken to be well mixed with 100 parts of water；By the mother of water-base epoxy composite anticorrosion coating
Liquid and the waterborne curing agent by weight proportion 4 diluted：1 mixing, is produced.
By the water paint of preparation coated on the metal substrate through handling well, control thickness is solid in 30-200um, room temperature
Change 24h.
Embodiment 4.
The individually preparation method of the water-based anticorrosive paint of addition polyaniline aeroge, comprises the following steps.
1. the preparation of conductive filler.
Weigh 8g anilinechlorides to add in there-necked flask, add 40mL deionized waters, stir 40min, mixing speed 500
R/min, obtain solution I；Weigh 13g ammonium persulfates to add in beaker, add in 60mL deionized waters, stir 40min, stirring speed
Spend for 500 r/min, acquisition solution II；Solution I and solution II are positioned over ice-water bath 40min, its temperature is reduced to 10 DEG C
Below；Then solution II is slowly added in solution I, 2min is stirred vigorously rapidly, mixing speed 1500r/min, obtains
Solution III；Solution III is stood into 15h at room temperature, obtains polyaniline hydrogel, by obtained polyaniline hydrogel 500mL's
0.2 mol/L HCl are cleaned, and are changed once every 10h, are cleaned 6 days；Then solvent displacement is carried out with 500mL absolute ethyl alcohols, often
An absolute ethyl alcohol is changed every 10h, after replacing 6 days, resulting product is placed in supercritical CO2It is dried in drying kettle
8h, 60 DEG C of drying temperature, drying pressure 15MPa, obtains polyaniline aeroge.
2. the preparation of anticorrosive paint.
（1）100 parts of Ar555 aqueous epoxy resins and 100 parts of water are taken, is well mixed, obtains resin system.
（2）40 parts of polyaniline aeroge fillers are taken, are added in above resin system, 1h is disperseed in ball mill, obtains water
The mother liquor of property epoxy composite anticorrosive paint.
（3）50 parts of H228B waterborne curing agents are taken to be well mixed with 100 parts of water；By the mother of water-base epoxy composite anticorrosion coating
Liquid and the waterborne curing agent that has diluted are by 4：1 part by weight mixing, is produced.
By the water paint of preparation coated on the metal substrate through handling well, control thickness is solid in 30-200um, room temperature
Change 24h.
Embodiment 5.
Add metal organic framework（MOF-5）Water-based anticorrosive paint preparation method, comprise the following steps.
1. metal organic framework（MOF-5）Preparation.
Weigh 0.2g terephthalic acid solid powder（99%）With 1.09g zinc nitrates（AR）Crystal, two kinds of medicines are added respectively
Enter stand-by in flask, then measure 30ml DMF（AR）Add in the flask equipped with medicine, treat in flask
During the substantially all dissolving of medicine, flask is placed in thermostatical oil bath and heated, until its temperature reaches 120 DEG C, stop heating, it is permanent
Temperature handles 4h, and crystal occurs in about 45min or so in thermostatic process；After reacting 4h after crystallization, take out flask and outwell upper solution,
Products therefrom is put into 50 DEG C of vacuum drying chambers with after chloroform 2 times and dries 24h, by dried product by bottom crystalline
Bottling, it is stand-by.
2. the preparation of conductive filler polyaniline aeroge.
Weigh 8g anilinechlorides to add in there-necked flask, add 40mL deionized waters, stir 40min, mixing speed 500
R/min, obtain solution I；Weigh 13g ammonium persulfates to add in beaker, add in 60mL deionized waters, stir 40min, stirring speed
Spend for 500 r/min, acquisition solution II；Solution I and solution II are positioned over ice-water bath 40min, its temperature is reduced to 10 DEG C
Below；Then solution II is slowly added in solution I, 2min is stirred vigorously rapidly, mixing speed 1500r/min, obtains
Solution III, solution III is stood into 15h at room temperature, obtains polyaniline hydrogel, by obtained polyaniline hydrogel 500mL's
0.2 mol/L HCl are cleaned, and are changed once every 10h, are cleaned 6 days；Then solvent displacement is carried out with 500mL absolute ethyl alcohols, often
An absolute ethyl alcohol is changed every 10h, is replaced 6 days；Resulting product is placed in supercritical CO28h is dried in drying kettle,
60 DEG C of drying temperature, drying pressure 15MPa, obtains polyaniline aeroge.
3. the preparation of anticorrosive paint.
（1）100 parts of Ar555 aqueous epoxy resins and 100 parts of water are taken, is well mixed, obtains resin system.
（2）Take 20 parts of metal organic frameworks（MOF-5）With 20 parts of polyaniline aeroge fillers, above resin system is added
In, 1h is disperseed in ball mill, obtains the mother liquor of water-base epoxy composite anticorrosion coating.
（3）50 parts of H228B waterborne curing agents are taken to be well mixed with 100 parts of water；By the mother of water-base epoxy composite anticorrosion coating
Liquid and the waterborne curing agent by weight proportion 4 diluted：1 mixing, is produced.
By obtained anti-corrosion paint on the metal substrate through handling well, control thickness is solid in 30-200um, room temperature
Change.
Embodiment 6.
Add metal organic framework（MIL-101(Cr)）Water-based anticorrosive paint preparation method, comprise the following steps.
1. metal organic framework（MIL-101(Cr)）Preparation.
Weigh chromic nitrate 2.8g and 5g graphene to be placed in beaker, add 25mL water, stir 30min, mixing speed is
100r/min；Weigh 1.15gH2BDC（1,4- phthalic acids）It is put into reactor, the aqueous solution of chromic nitrate and graphene is turned
Reactor is moved on to, then with 8.6mL water rinse beakers and is transferred to reactor, stirs 30min, mixing speed 100r/min, is used
Plastic injector injects 0.31mLHF, is put into 220 DEG C of baking ovens and reacts 2h；Room temperature is cooled to, products therefrom is returned with hot ethanol
Stream is washed three times, then with fluorination ammonia spirit backflow 10h, then with alcohol reflux once；Product is put into 150 after drying at room temperature 12h
Dried in DEG C baking oven, time 12h, obtain metal organic framework（MIL-101(Cr)）.
2. the preparation of conductive filler polyaniline aeroge.
Weigh 8g anilinechlorides to add in there-necked flask, add 40mL deionized waters, stir 40min, mixing speed 500
R/min, obtain solution I；Weigh 13g ammonium persulfates to add in beaker, add in 60mL deionized waters, stir 40min, stirring speed
Spend for 500 r/min, acquisition solution II；Solution I and solution II are positioned over ice-water bath 40min, its temperature is reduced to 10 DEG C
Below；Then solution II is slowly added in solution I, 2min is stirred vigorously rapidly, mixing speed 1500r/min, obtains
Solution III, solution III is stood into 15h at room temperature, obtains polyaniline hydrogel, by obtained polyaniline hydrogel 500mL's
0.2 mol/L HCl are cleaned, and are changed once every 10h, are cleaned 6 days；Then solvent displacement is carried out with 500mL absolute ethyl alcohols, often
An absolute ethyl alcohol is changed every 10h, is replaced 6 days；Resulting product is placed in supercritical CO28h is dried in drying kettle,
60 DEG C of drying temperature, drying pressure 15MPa, obtains polyaniline aeroge.
3. the preparation of anticorrosive paint.
（1）100 parts of Ar555 aqueous epoxy resins and 100 parts of water are taken, is well mixed, obtains resin system.
（2）Take 20 parts of metal organic frameworks（MIL-101(Cr)）With 20 parts of polyaniline aeroge fillers, above resin is added
In system, 1h is disperseed in ball mill, obtains the mother liquor of water-base epoxy composite anticorrosion coating.
（3）50 parts of H228B waterborne curing agents are taken to be well mixed with 100 parts of water；By the mother of water-base epoxy composite anticorrosion coating
Liquid and the waterborne curing agent by weight proportion 4 diluted：1 mixing, is produced.
By obtained anti-corrosion paint on the metal substrate through handling well, control thickness is solid in 30-200um, room temperature
Change.
The preparation method of compounded mix of the present invention filling water-based anticorrosive paint, filler used are a kind of new conductive compound
Material, the anticorrosion mechanism of composite water soluble anticorrosive paint of the present invention, is shown in Fig. 1.
Testing inspection is done to other filler anticorrosive paints simultaneously, obtained aqueous epoxy resins coating is through salt spray test
Photo after 500h, is shown in Fig. 2；Wherein, Fig. 2 a are the aqueous epoxy resins coating that embodiment 2 does not add any filler, through salt fog
Test the photo after 500h；Fig. 2 b are the individually independent aqueous epoxy resins for adding conducting metal organic backbone of addition of embodiment 3
Coating, the photo after salt spray test 500h；Fig. 2 c are the aqueous epoxy resins painting that embodiment 4 individually adds polyaniline aeroge
Layer, the photo after salt spray test 500h；Fig. 2 d are that embodiment 5 adds polyaniline aeroge and metal organic framework simultaneously
（MOF-5）Photo of the aqueous epoxy resins coating after salt spray test 500h；Fig. 2 e are that embodiment 6 adds polyaniline gas simultaneously
Photo of gel and metal organic framework MIL-101 (Cr) the aqueous epoxy resins coating after salt spray test 500h；Fig. 2 f are
Embodiment 1 adds conducting metal organic backbone simultaneously（MIL-101(Cr)@TiO2）With the aqueous epoxy resins of polyaniline aeroge
Photo of the coating after salt spray test 500h.A components is add any anticorrosive packing so antiseptic property is worst, and two groups of b, c
Conductive filler is with the addition of, antiseptic property is better than a groups；D, two groups of e not only has a conductive filler polyaniline aeroge, and also metal is organic
Skeleton, the barrier of coating is added, so antiseptic property is slightly better than two groups of b, c；F group antiseptic properties are optimal, almost without obvious
Corrosion change, and antiseptic property is better than two groups of d, e, exactly because conducting metal organic backbone is organic compared to nonconducting metal
Skeleton, antiseptic property is more excellent, the two two kinds of conductive filler collective effect, antiseptic property is reached optimal.
Amino on polyaniline aeroge can also make its open loop and then enhancing with the epoxide group reaction in epoxy resin
The crosslink density of coating and improve the mechanical property of coating, be shown in Table 1.
The adhesion performance test of the aqueous epoxy resins coating of table 1.
| Group | Mechanical property (Mpa) | Group | Mechanical property (Mpa) |
| Embodiment 1 | 8.20 | Embodiment 4 | 8.12 |
| Embodiment 2 | 7.58 | Embodiment 5 | 8.05 |
| Embodiment 3 | 7.91 | Embodiment 6 | 8.10 |
The present invention can improve the mechanical property of coating.
Claims (4)
1. a kind of preparation method of composite water soluble anticorrosive paint, it is characterised in that comprise the following steps：
Step 1. weighs 3-8g aniline hydrochloric acid and added in there-necked flask, adds 15-40mL deionized waters, stirs 20-40min, stirring
Speed is 300-500 r/min, obtains solution I；Weigh 6-13g ammonium sulfate to add in beaker, add 20-60mL deionized waters
In, 20-40min is stirred, mixing speed is 300-500 r/min, obtains solution II；Under the conditions of ice-water bath, by solution I and molten
Liquid II places 20-40min, its temperature is reduced to 5-10 DEG C；Then solution II is slowly added in solution I, it is rapid violent
0.5-2min is stirred, mixing speed 1000-1500r/min, obtains solution III；Under room temperature condition, solution III is stood into 10-
15h, polyaniline hydrogel is obtained, obtained polyaniline hydrogel 200-500mL 0.1-0.2 mol/L HCl is clear
Wash, change a HCl every 8-10h, clean 4-6 days；Then solvent displacement is carried out with 300-500mL absolute ethyl alcohols, every 8-
10h changes an absolute ethyl alcohol, and after replacing 4-6 days, resulting product is placed in into supercritical CO2In drying kettle, drying process
6-8h, 40-60 DEG C of drying temperature, drying pressure 10-15MPa, obtain polyphenyl ammonia gel；
The titanium chloride that step 2. weighs 0.2-0.4mL is dissolved in 70-100mL cold water, adds 0.2-0.4g metal organic frameworks
（MIL-101(Cr)）, stir 20-40 min, mixing speed 200-400r/min, centrifugal treating after stirring, speed 2500-
3000r/min, remove the sediment that supernatant obtains and add 80-120mL deionized waters, be then transferred into reactor,
Under the conditions of 160-200 DEG C, hydro-thermal reaction 8-12h；Centrifuge washing again, centrifugal speed 2500-3000r/min, sediment exist
Under 30-50 DEG C of vacuum condition, 10-16 h are dried；Obtain conducting metal organic backbone（MIL-101 (Cr)s@TiO2）；
Step 3. weighs 10-40 part polyaniline aeroges and 10-40 part conducting metal organic backbones, is added to 100-200 part water
In the mixed liquor of 100-200 part aqueous epoxy resins, 1-2h is disperseed in ball mill, produces the mother of composite water soluble anticorrosive paint
Liquid；
After step 4. takes 25-50 parts waterborne curing agent to be well mixed with 50-100 part water, then the mother with composite water soluble anticorrosive paint
Liquid presses 1：3-5 ratio mixing, is produced.
2. the preparation method of composite water soluble anticorrosive paint as claimed in claim 1, it is characterised in that the metal organic framework
（MIL-101(Cr)）Preparation method it is as follows：Weigh chromic nitrate 3-5g and 5-10g graphene to be placed in beaker, add 10-30mL
Water, stir 30-40min, mixing speed 50-150r/min；Weigh 2-3gH2BDC（1,4- phthalic acids）It is put into reactor
In, the aqueous solution of chromic nitrate and graphene is transferred to reactor, then with 5-10mL water rinse beakers and reactor is transferred to, stir
30-60min, mixing speed 50-150r/min are mixed, 0.1-0.5mLHF is injected with plastic injector, is put into 200-250 DEG C of baking
1-3h is reacted in case；Be cooled to room temperature, by products therefrom hot ethanol backflow wash three times, then with fluorination ammonia spirit flow back 5-
15h, then with alcohol reflux once；Product is put into 100-200 DEG C of baking oven after drying at room temperature 10-15h and dried, time 10-
15h, obtain metal organic framework（MIL-101(Cr)）.
3. the preparation method of composite water soluble anticorrosive paint as claimed in claim 1, it is characterised in that the aqueous epoxy resins
For E20 epoxies breast, E44 epoxy emulsions, Ar555 epoxy resin, E51 epoxy emulsions and H228A epoxy resin.
4. the preparation method of composite water soluble anticorrosive paint as claimed in claim 1, it is characterised in that the waterborne curing agent is
Aq419, W651, W650 or H228B.
Priority Applications (1)
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