CN107619636A - A kind of high dispersive, impact-resistant graphene anticorrosive paint and preparation method - Google Patents
A kind of high dispersive, impact-resistant graphene anticorrosive paint and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of high dispersive, impact-resistant graphene anticorrosive paint and preparation method, it is characterized in first meeting the rubber grain of water energy volumetric expansion by laser ablation into porous carrier, the mixed-powder of graphene and production of low-temperature foaming agent is equipped in its hole again, after being mixed with water-base resin coating, foaming agent produces gas and promoted in graphene uniform dispersion resin coating in hole, obtains impact-resistant graphene anticorrosive paint.Its remarkable result is in the system that graphene and expanded rubber particle are constructed, it is initially formed and once disperses due to contains hydrophilic component in rubber matrix, gas push forms twice dispersing, solves the uneven problem of graphene dispersion indirectly, improve the antiseptic property of coating, the expanded rubber particle inside coating reaches effective cushioning effect simultaneously, improves the impact resistance of coating.
Description
Technical field
The present invention relates to technical field of coatings, and in particular to a kind of high dispersive, the system of impact-resistant graphene anticorrosive paint
Preparation Method.
Background technology
Graphene is most hard, most thin nanometer new material known to the current mankind, is that one kind is connected by carbon atom with sp2 hydridization
The hexangle type of formation is in the flat film of honeycomb lattice, and 2004 by Univ Manchester UK physics professor AndreGeim
It is successfully separated out from graphite first.Graphene is the hardness and intensity for having intensity superelevation, excellent thermal conductivity.Stone
The Young's modulus of black alkene is about 1100GPa, fracture strength 130GPa, 100 times more taller than best steel.Graphene heat conduction
Coefficient is up to 5000W/ (mK).It is higher more than 10 times than common metal, such as gold, silver, copper.The stable lattice structure of graphene makes
It has excellent electric conductivity, and the movement velocity of wherein electronics has reached the 1/300 of the light velocity, considerably beyond electronics general
Movement velocity in conductor.In addition, graphene also has larger specific surface area and good toughness and shielding.These features
Make it possible that graphene is applied in anticorrosive paint with advantage.
At present, the mode in graphene addition coating has two kinds, first, directly graphene is added in coating, plays anti-corrosion
With the function such as conduction；Second, first by graphene and fluoropolymer resin or other functional nano materials it is compound after, then add
Into coating.But graphene is a kind of loose nano material, and surface energy is big, easily reunites in resin matrix, limitation
Application of the graphene in anticorrosive paint.
Graphene powder is disperseed lubricated through absolute ethyl alcohol and is added to painting by number of patent application CN201610194462.0
In material, final cold coating is obtained by multiple Balrog, ultrasonic disperse.Coating is molten in 10%HCl, 10%NaOH and 10%NaCl
Without actual effect phenomenon after being soaked 1500 hours in liquid, corrosion-resistant purpose is served.But above-mentioned preparation method needs multiple a few hours
Long-time disperse, preparation technology is complicated, and obtained resinous coat combination property is not ideal enough.
Graphene prepared by oxidation stripping method is used to lead to as graphene source in number of patent application CN201510502222.8
Cross three-roll grinder grinding and graphene anticorrosive paint component A is made.Technique is simple, but three-roll grinder process of lapping belongs to open
Formula, solvent volatile quantity is big, not only seriously pollution production space, and be formulated in solvent flashing amount it is uncontrollable, work can not be ensured
Industry production stability.
Made in number of patent application CN201610137270.6 from single bisphenol-A-type epoxy resin and polyamide curing agent
For coating film forming matter, epoxy resin-graphene-zinc powder anticorrosive paint is prepared for using high speed dispersor.Due to film forming matter
Selection it is improper, the standby anticorrosion with coat poor-performing of the patent system, adhesive force be 0~1 grade, salt-fog resistant time there was only 600 hours.
A kind of anti-corrosion of graphene containing zinc based on graphene dispersion body is referred in number of patent application 201610175323.3
7th preparation method, but the mechanical property and antiseptic property data of the priming paint are not provided in patent.
The content of the invention
Applied for the existing graphene of solution in anticorrosive paint and the scattered inequality of graphene itself be present, when it is applied to coating
Reunite, stress concentration is produced inside film, the defects of causing mechanical performance, antiseptic property to decline.The present invention provides a kind of
High dispersive, impact-resistant graphene anticorrosive paint and preparation method.Guard time of the coating to matrix is extended, has been reached long-acting
Corrosion-resistant purpose.
To achieve the above object, the solution of the present invention is as follows：
The preparation method of a kind of high dispersive, impact-resistant graphene anticorrosive paint, preparation process comprise the following steps：
（1）At room temperature, by graphene and production of low-temperature foaming agent in mass ratio 10:0.5~2 is put into stirring container and is stirred until homogeneous,
Obtain graphene mixed-powder；
（2）Enough graphene mixed-powders and expanded rubber particle are put into stirring container, closed container high-speed stirred, stirred
Heat tracing steady temperature, after graphene mixed-powder is loaded with into rubber grain hole, sieves to 50 DEG C through solid during mixing
Separation, removes unnecessary graphene mixed-powder；
（3）Resin, solvent, anti-settling agent are added in stirring container, with 1000~2000r/min rotating speed high-speed stirred, while stirring
Mix side and add the rubber grain for being equipped with graphene mixed-powder, heating water bath to 80 DEG C of constant temperature stirs 1~2 hour；
（4）By step（3）The component being prepared filters by the screen that aperture is 35 μm after grinder is ground, obtains A
Component；
（5）Defoamer, curing agent, levelling agent, solvent are added in stirring container, with uniform under 800~1500r/min rotating speed
Stirring 1~1.5 hour, 40~60 DEG C of whipping temp, is cooled to and obtains B component at room temperature, by A, B component in proportion 100:12~
30, uniformly mixing, obtains graphene anticorrosive paint.
In such scheme, the production of low-temperature foaming agent is sodium acid carbonate, calcium carbonate, AC foaming agents, ammonium hydrogen carbonate, carbamic acid
One kind in ammonium, sodium borohydride, potassium borohydride.
In such scheme, described expanded rubber particle is hydro-expansive rubber, the expanded rubber prepared for laser ablation：
（1）Sheet rubber is cleaned, removes other impurity such as releasing agent, the dust on sheet rubber surface, cleaning chemical solvent is followed successively by three
Chloromethanes, acetone, ethanol and deionized water；
（2）Sheet rubber after cleaning is placed in etching agent, is then scanned laser beam in rubber surface, regulation swashs
Angle between light light beam and sheet rubber is at 30~80 °；
（3）Laser ablation process, by laser beam focusing in sheet rubber surface to be etched, successively processed in a manner of multi-angle, if
It is 100~200mm/s to put laser beam sweep speed, is heated to 30~40 DEG C to the sheet rubber of pre-formed hole, time processing is complete
Bi Hou, processing effect is observed, repeat to etch, until reaching processing request；
（4）After the completion of etching, toward the hole on sheet rubber in blow or air-breathing, caused powder in etching process is all discharged,
Then sheet rubber is crushed using pelleter, obtains expanded rubber particle, particle diameter is 20-50 mesh.
In such scheme, described resin is to include epoxy resin, modified polybutadiene resin, polyester resin, amino tree
One or more in fat, phenolic resin, acrylic resin, polyurethane resin, polyvinyl alcohol ester, PPG.
In such scheme, described anti-settling agent is in polyamide wax, aerosil, organobentonite, polyolefin-wax
One kind.
In such scheme, described defoamer is organic silicon defoamer, polyethers defoamer and mineral oil defoaming agent
Middle one kind.
In such scheme, described solvent is one kind in n-butanol, isobutanol, propandiol butyl ether, ethanol, butyl acetate
Or two kinds of mixtures.
In such scheme, described levelling agent is silicone levelling agent or acrylic compounds levelling agent.
In such scheme, described curing agent is ethylenediamine, diethylenetriamine, beta-hydroxyethyl ethylenediamine, maleic acid
Acid anhydride, glycerine, T-32, TDI-80, it is polyamide-based in one kind.
In such scheme, described component A includes being loaded with 10~20 parts of rubber grain, the resin 60 of graphene mixed-powder
~80 parts, 10~20 parts of solvent, 0.1~2 part of anti-settling agent；Described B component includes 1~10 part of defoamer, curing agent 60~80
Part, 1~10 part of levelling agent, 10~20 parts of solvent.
In such scheme, described laser beam power output is 300mW~1W, and repetition rate is 30kHz~200kHz.
In such scheme, the concentrated sulfuric acid, hydrogen peroxide, deionized water in mass ratio 1 that described etching agent is 98%:1~3:16
~18.
A kind of high dispersive, impact-resistant graphene anticorrosive paint, have the above method to be prepared.
Beneficial effects of the present invention：In the system that graphene and expanded rubber particle are constructed, due to containing in rubber matrix
Hydrophilic component and be initially formed and once disperse, gas push forms twice dispersing, solves the uneven problem of graphene dispersion indirectly,
The antiseptic property of coating is improved, while the expanded rubber particle inside coating reaches effective cushioning effect, improves coating
Impact resistance.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Preparation technology：
Expanded rubber particle preparation：
Etching liquid is 98% H in mass ratio2SO4:H2O2`:H2O=l:l:18 carry out matching somebody with somebody liquid.
（1）Sheet rubber is cleaned, releasing agent, the dust on sheet rubber surface are removed using chloroform, ethanol and deionized water
Etc. other impurity, cleaning chemical solvent is followed successively by chloroform, acetone, ethanol and deionized water.
（2）Sheet rubber after cleaning is placed in etching agent, is then scanned laser beam in rubber surface, is adjusted
The angle between laser beam and sheet rubber is saved at 45 °.
（3）Laser ablation process, by laser beam focusing in sheet rubber surface to be etched, laser beam sweep speed is set
For 120mm/s, 40 DEG C are heated to the sheet rubber of pre-formed hole, is processed in four times, it is 1.6mm to process thickness every time.
（4）After the completion of etching, toward the hole on sheet rubber in blow or air-breathing, caused powder in etching process is all arranged
Go out, then sheet rubber is crushed using pelleter, obtain expanded rubber particle, particle diameter is 20-50 mesh.
The preparation of graphene anticorrosive paint
Component A：
（1）At room temperature, graphene and AC foaming agents are pressed 10:1 is put into stirring container and is stirred until homogeneous, and obtains graphene
Mixed-powder.
（2）Enough graphene mixed-powders and expanded rubber particle are put into stirring container, closed container high-speed stirring
Mix, heat tracing steady temperature, after graphene mixed-powder is loaded with into rubber grain hole, passes through to 50 DEG C in whipping process
Screening solids are from removing unnecessary graphene mixed-powder.
（3）Resin, solvent, anti-settling agent are added in stirring container, with 1500r/min rotating speed high-speed stirred, side stirring
Side adds the rubber grain for being equipped with graphene mixed-powder, and heating water bath to 80 DEG C of constant temperature stirs 2 hours.
（4）By the above-mentioned component being prepared after grinder is ground, filter, obtain by the screen that aperture is 35 μm
Component A.
B component：
Defoamer, curing agent, levelling agent, solvent are added in stirring container, it is small with uniform stirring 1 under 1200r/min rotating speed
When, 50 DEG C of whipping temp.
At room temperature, by AB components in proportion 100:12~30, uniformly mixing.
Embodiment 1
AB components press 100:12.5, which are prepared coating performance parameter, see the table below：
Embodiment 2
AB components press 100:13, which are prepared coating performance parameter, see the table below：
Embodiment 3
AB coating presses 100:15, which are prepared coating performance parameter, see the table below：
Embodiment 4
100：11, which are prepared coating performance parameter, see the table below：
Embodiment 5
AB components press 100:20, which are prepared coating performance parameter, see the table below：
Embodiment 6
AB components press 100:20, which are prepared coating performance parameter, see the table below：
Claims (9)
1. the preparation method of a kind of high dispersive, impact-resistant graphene anticorrosive paint, preparation process comprise the following steps：
（1）At room temperature, by graphene and production of low-temperature foaming agent in mass ratio 10:0.5~2 is put into stirring container and is stirred until homogeneous,
Obtain graphene mixed-powder；
（2）Enough graphene mixed-powders and expanded rubber particle are put into stirring container, closed container high-speed stirred, stirred
Heat tracing steady temperature, after graphene mixed-powder is loaded with into rubber grain hole, sieves to 50 DEG C through solid during mixing
Separation, removes unnecessary graphene mixed-powder；
（3）Resin, solvent, anti-settling agent are added in stirring container, with 1000~2000r/min rotating speed high-speed stirred, while stirring
Mix side and add the rubber grain for being equipped with graphene mixed-powder, heating water bath to 80 DEG C of constant temperature stirs 1~2 hour；
（4）By step（3）The component being prepared filters by the screen that aperture is 35 μm after grinder is ground, obtains A
Component；
（5）Defoamer, curing agent, levelling agent, solvent are added in stirring container, with uniform under 800~1500r/min rotating speed
Stirring 1~1.5 hour, 40~60 DEG C of whipping temp, is cooled to and obtains B component at room temperature, by A, B component in proportion 100:12~
30, uniformly mixing, obtains graphene anticorrosive paint.
2. a kind of high dispersive, the preparation method of impact-resistant graphene anticorrosive paint, its feature exist according to claim 1
In：The production of low-temperature foaming agent is sodium acid carbonate, calcium carbonate, AC foaming agents, ammonium hydrogen carbonate, aminoquinoxaline, sodium borohydride, boron hydrogen
Change one kind in potassium.
3. a kind of high dispersive, the preparation method of impact-resistant graphene anticorrosive paint, its feature exist according to claim 1
In：Described expanded rubber particle is hydro-expansive rubber, is prepared by laser ablation, and specific preparation method is：
（1）Sheet rubber is cleaned, removes other impurity such as releasing agent, the dust on sheet rubber surface, cleaning chemical solvent is followed successively by three
Chloromethanes, acetone, ethanol and deionized water；
（2）Sheet rubber after cleaning is placed in etching agent, is then scanned laser beam in rubber surface, regulation swashs
Angle between light light beam and sheet rubber is at 30~80 °；
（3）Laser ablation process, by laser beam focusing in sheet rubber surface to be etched, successively processed in a manner of multi-angle, if
It is 100~200mm/s to put laser beam sweep speed, is heated to 30~40 DEG C to the sheet rubber of pre-formed hole, time processing is complete
Bi Hou, processing effect is observed, repeat to etch, until reaching processing request；
（4）After the completion of etching, toward the hole on sheet rubber in blow or air-breathing, caused powder in etching process is all discharged,
Then sheet rubber is crushed using pelleter, obtains expanded rubber particle, particle diameter is 20-50 mesh.
4. a kind of high dispersive, the preparation method of impact-resistant graphene anticorrosive paint, its feature exist according to claim 3
In：Described laser beam power output is 300mW~1W, and repetition rate is 30kHz~200kHz.
5. a kind of high dispersive, the preparation method of impact-resistant graphene anticorrosive paint, its feature exist according to claim 3
In：The concentrated sulfuric acid, hydrogen peroxide, deionized water in mass ratio 1 that described etching agent is 98%:1~3:16~18.
6. a kind of high dispersive, the preparation method of impact-resistant graphene anticorrosive paint, its feature exist according to claim 1
In：Described resin is epoxy resin, modified polybutadiene resin, polyester resin, amino resins, phenolic resin, acrylic acid tree
One or more in fat, polyurethane resin, polyvinyl alcohol ester, PPG；Described solvent be n-butanol, isobutanol,
One or both of propandiol butyl ether, ethanol, butyl acetate mixture；Described anti-settling agent is polyamide wax, gas phase dioxy
One kind in SiClx, organobentonite, polyolefin-wax.
7. a kind of high dispersive, the preparation method of impact-resistant graphene anticorrosive paint, its feature exist according to claim 1
In：Described defoamer is middle one kind of organic silicon defoamer, polyethers defoamer and mineral oil defoaming agent；Described stream
Flat agent is silicone levelling agent or acrylic compounds levelling agent；Described curing agent is ethylenediamine, diethylenetriamine, beta-hydroxyethyl
Ethylenediamine, maleic anhydride, glycerine, T-32, TDI-80, it is polyamide-based in one kind.
8. a kind of high dispersive, the preparation method of impact-resistant graphene anticorrosive paint, its feature exist according to claim 1
In：Described component A include being loaded with 60~80 parts of 10~20 parts of rubber grain, the resin of graphene mixed-powder, solvent 10~
20 parts, 0.1~2 part of anti-settling agent；Described B component includes 1~10 part of defoamer, 60~80 parts of curing agent, levelling agent 1~10
Part, 10~20 parts of solvent.
9. a kind of high dispersive, impact-resistant graphene anticorrosive paint, it is characterised in that as the side described in claim any one of 1-8
Method is prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111793413A (en) * | 2020-07-07 | 2020-10-20 | 山东尚核电力科技有限公司 | Powder coating for lining plastic, composite master batch and lining plastic composite pipe |
| CN113024755A (en) * | 2020-03-27 | 2021-06-25 | 江苏国立化工科技有限公司 | Preparation method of resorcinol resin for rubber adhesive and special device thereof |
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| WO2015160764A1 (en) * | 2014-04-14 | 2015-10-22 | The Board Of Regents Of The University Of Texas System | Graphene-based coatings |
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2017
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| WO2015160764A1 (en) * | 2014-04-14 | 2015-10-22 | The Board Of Regents Of The University Of Texas System | Graphene-based coatings |
| CN104877517A (en) * | 2015-05-13 | 2015-09-02 | 沈阳化工大学 | Preparation method of waterborne epoxy composite anticorrosive coating |
Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024755A (en) * | 2020-03-27 | 2021-06-25 | 江苏国立化工科技有限公司 | Preparation method of resorcinol resin for rubber adhesive and special device thereof |
| CN111793413A (en) * | 2020-07-07 | 2020-10-20 | 山东尚核电力科技有限公司 | Powder coating for lining plastic, composite master batch and lining plastic composite pipe |
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