CN110343455A - Aqueous heavy anti-corrosion paint, preparation method and the purposes of the coupling agent modified graphene of silane-containing - Google Patents
Aqueous heavy anti-corrosion paint, preparation method and the purposes of the coupling agent modified graphene of silane-containing Download PDFInfo
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- CN110343455A CN110343455A CN201810290270.9A CN201810290270A CN110343455A CN 110343455 A CN110343455 A CN 110343455A CN 201810290270 A CN201810290270 A CN 201810290270A CN 110343455 A CN110343455 A CN 110343455A
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- aqueous
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- corrosion paint
- heavy anti
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 37
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a kind of aqueous heavy anti-corrosion paints, include A) aqueous industrial resin；And B) silane coupler modified graphene, wherein, be based on component A) meter, component B) amount be 0.1-1.0 weight %, and component A) and amount B) add up to 100 weight %, wherein the weight ratio of silane coupling agent and graphene is 2.0-7.0:1.The invention further relates to the purposes of the method for preparing the aqueous heavy anti-corrosion paint and the aqueous heavy anti-corrosion paint in infrastructure, oil gas and power industry and industrial tank, ship and chemical industry.
Description
Technical field
The invention belongs to paint fields, more specifically, are related to a kind of industrial antisepsis coating, especially aqueous heavy antisepsis applies
Material, and its preparation method and application.
Background technique
Industrial antisepsis coating is widely used to the fields such as modern industry, traffic, the energy, ocean engineering.In recent ten years,
Many industrial antisepsis coating products have successfully been developed in China.Currently, the market scale of China's industrial antisepsis coating has been only second to
Building coating and occupy second.According to statistics, China's industrial antisepsis coating total output in 2017 has reached 6,000,000 tons or so, and
In future, this data is also in sustainable growth.Though there are products currently, Chinese industrial anticorrosive paint market application range is wide
The limitations such as the degree of homogenization is high, technology content is low, and as the mankind are to the pay attention to day by day of environment and health problem, solvent type work
The use of industry coating will have become increasingly limited, therefore following industrial antisepsis coating will refine towards product, is clear
Clean production, paint spraying integration, Water-borne modification, high solidification and solvent free direction develop.
An important species of the aqueous industrial anticorrosive paint as environment-friendly type industrial coating, has been developed tens in foreign countries
The time in year just applies to the traditional solvent-bornes industry such as automobile, steel construction, bridge, household electrical appliances at an unprecedented rate at present
Expect application field infiltration, and is completely replaced trend greatly.With European Union and North America Free Trade Agreement (NAFTA) national environmental protection regulation
Implementation, the technology growth rate of the technology growth rate of aqueous industrial coating significantly more than solvent based coating.
Although the research and development of China's aqueous industrial coating and large-scale production have also had the time of more than ten years, still have
Very big room for improvement.In recent years, external advanced water-base resin product and coating technology enter China's Coating Market, add
Attention of the country to water paint new product development, driven the development of China's water paint, particularly aqueous industrial coating and
Using.
Anticorrosive paint for referring to relatively conventional anticorrosive paint, can be applied, and have in relatively harsh corrosive environment
There is a kind of anticorrosive paint that can reach the protection period longer than conventional anticorrosive paint.Aqueous heavy anti-corrosion paint is aqueous industrial coating hair
One important branch of exhibition, the heavy antisepsis fields such as previous similar petrochemical industry, shipbuilding and bridge are all by solvent type heavy antisepsis
Coating is monopolized, and aqueous heavy anti-corrosion paint product is almost without application, main reason is that the performance of aqueous industrial coating at present
With solvent type anticorrosive paint, there are also a certain distance.
Have literature research in the prior art and prepare aqueous industrial coating using graphene, so as to improve the coating
Some performances.105670474 A of CN is related to a kind of graphene aqueous industrial coating, including following substance: lotion, graphene point
Dispersion liquid, ammonia neutralizer, defoaming agent, wetting agent, levelling agent, mill base, thickener and water utilize graphene itself wherein clearly referring to
Many performances, such as huge specific surface area and special two-dimensional structure, high stability and high-intensitive ability and excellent
Electric conductivity, so that prepared aqueous industrial coating has excellent performance；But it is carried out without any about to graphene
Modified introduction, needless to say it is modified using silane coupling agent.
107523201 A of CN discloses a kind of method using graphene preparation light resistance water paint, it is disclosed that
Improve light resistance, the wearability of aqueous industrial coating using graphene, and improves the film forming extension at break of product water paint
Rate, and disclosing the graphene is the graft grapheme solution using preparations such as graphene oxide and silane coupling agents；But
Without referring to aqueous industrial resin, needless to say the water paint for preparing of graft grapheme and aqueous industrial resin is excellent
Gesture.The condition for preparing graft grapheme is wherein loosely described using graphene oxide and silane coupling agent, however, this
Part can be further improved, to obtain the graft grapheme for being used to prepare the superior water paint of performance.
Aqueous industrial coating is prepared accordingly, with respect to graphene is used can still be further improved, to obtain at least existing
Certain aspect of performance are able to improved water paint.
Summary of the invention
The present invention is intended to provide a kind of aqueous heavy anti-corrosion paint with excellent properties, especially strong with excellent machinery
The aqueous heavy anti-corrosion paint of degree, salt fog resistance and chemical-resistant.
The purpose of the present invention realized and providing a kind of new aqueous heavy anti-corrosion paint, the aqueous heavy anti-corrosion paint packet
Contain:
A) aqueous industrial resin；
B) silane coupler modified graphene,
Wherein, be based on component A) meter, component B) amount be 0.1-1.0 weight %,
And component A) and amount B) add up to 100 weight %,
Wherein, the weight ratio of silane coupling agent and graphene is 2.0-7.0:1.
It is a further object of the present invention to provide a kind of methods for preparing above-mentioned aqueous heavy anti-corrosion paint, comprising:
1) pass through following processes and prepare component B) silane coupler modified graphene:
A) in the dispersion in 45-70 DEG C of graphene oxide in solvent, silane coupling agent is added, is warming up to 90-110
DEG C and at such a temperature keep the temperature 20-40 hours, obtain mixture a；
B) the mixture a obtained by step a) is cooled at 50-70 DEG C, reducing agent is added thereto, and keep the temperature 1.5-
3.5 hours, obtain product b；
C) solvent by the obtained product b of step b) is removed, required silane coupler modified graphene is obtained；
2) will be based on component A) meter 0.1-1.0 weight % the component B obtained by step 1)) it is silane coupler modified
Graphene be added to component A) in aqueous industrial resin, to obtain a kind of aqueous heavy anti-corrosion paint.
Aqueous heavy anti-corrosion paint of the invention has splendid adhesive force, resistance to acid and alkali, salt fog resistance and chemicals-resistant
Property, especially in salt fog resistance, performance and its excellent, it is common water borne work that it is unchanged, which to can achieve 1000 hours or more paint films,
2-3 times of industry coating, antiseptic property are excellent, lasting.
Therefore, the present invention also provides aqueous heavy anti-corrosion paints of the invention in infrastructure, oil gas and power industry, and
Purposes in industrial tank, ship and chemical industry.
Specific embodiment
Hereinafter, the present invention will be described in further detail.
Herein, if all percentages are weight percent without opposite explanation；If without opposite explanation, operation exists
It is carried out under room temperature, normal pressure.
Herein, if without opposite explanation, all amounts are by weight.
Herein, if all proportions are weight ratio without opposite explanation.
The present invention provides a kind of aqueous heavy anti-corrosion paint, it includes:
A) aqueous industrial resin；With
B) silane coupler modified graphene,
Wherein, be based on component A) meter, component B) amount be 0.1-1.0 weight %,
And component A) and amount B) add up to 100 weight %,
Wherein, the weight ratio of silane coupling agent and graphene is 2.0-7.0:1.
In a preferred embodiment, be based on component A) meter, component B) amount be preferably 0.12-0.8 weight %,
More preferably 0.15-0.6 weight %.
In a preferred embodiment, in silane coupler modified graphene, silane coupling agent and graphene
Weight ratio is 3.0-5.5:1.
In a preferred embodiment, resulting silane coupler modified graphene is dissolved in isopropanol, then
Mastersizer 2000 (being purchased from Malvern Instruments Ltd) measurement graphene is utilized by static laser diffraction
Granularity D90, three times, the average value of resulting D90 is less than 3.0 μm, more preferably less than 1.1 μm, more preferably less than 0.6 μ for repetitive operation
m。
Wherein, D90The granularity for representing 90% graphene particles is less than the granularity.
In a preferred embodiment, in prepared aqueous heavy anti-corrosion paint, there is following relationship:
0.03g/μm3≤M/D90 3≤9.30g/μm3,
It is preferred that 0.75g/ μm3≤M/D90 3≤4.85g/μm3,
Wherein M represents the amount of the graphene contained in aqueous heavy anti-corrosion paint.
According to the present invention, component A) aqueous industrial resin is well known by persons skilled in the art to be suitble to prepare any of coating
Resin.Preferably, the number-average molecular weight (Mn) of the aqueous industrial resin is in the range of 5000 to 20000, preferably 8000
To in the range of 15000, more preferably in the range of 9000 to 12000, the Mn is according to GB/T 21863-2008, using solidifying
Glue penetration chromatography (GPC) (wherein doing leacheate using tetrahydrofuran) measurement.
Specifically, the example of aqueous industrial resin includes, but are not limited to aqueous alkide resin, aqueous epoxy resins, aqueous
Amino resins, water-based acrylic resin, water based acrylic resin, water-base epoxy asphaltic resin, waterborne polyurethane resin and
Any one of aqueous inorganic resin or its two or more mixture.Preferably, in the present invention water alcohol acid is used
Resin.
Particularly, in the present invention, the component B) silane coupler modified graphene is made by following processes:
A) in the dispersion in 45-70 DEG C of graphene oxide in solvent, silane coupling agent is added, is warming up to 90-110
DEG C and at such a temperature keep the temperature 20-40 hours, obtain mixture a；
B) the mixture a obtained by step a) is cooled at 50-70 DEG C, reducing agent is added thereto, and keep the temperature 1.5-
3.5 hours, obtain product b；
C) solvent in the product b obtained by step b) is removed, required silane coupler modified graphene is obtained.
In one embodiment of the invention, in step a), added silane coupling agent and graphene oxide
Ratio is 30-65:1, more preferably 40-60:1.
In one embodiment of the invention, in step a), after silane coupling agent is added, preferably it is warming up to 95-100
At DEG C, preferably 24-36 hours are kept the temperature at such a temperature.
Preferably, in step a), the reaction condition should meet following formula, so that silane is even in the modified graphene of preparation
The weight ratio of connection agent and graphene is in the range of 2.0-7.0:1:
5.5≤0.01×R×ln(T+273.15)×ln(t)≤14；
Preferably 7.5≤0.01 × R × ln (T+273.15) × ln (t)≤12,
Wherein, R represents the weight ratio of added silane coupling agent and graphene oxide,
T represent be added silane coupling agent after holding temperature, unit be DEG C, and
T represents the soaking time after silane coupling agent is added, and unit is hour.
Preferably, solvent used in step a) can for methanol, ethyl alcohol, butanol, carbon tetrachloride, acetone, dichloroethanes or
Its mixture, but not limited to this.In the present invention, it is preferred to methanol or methanol: butanol=0.3-2:1, preferably 0.5-1.5:1's is mixed
Close object.The dosage of the solvent can be 50-80 weight %, more preferably 60-70 weight %, based on the molten of the middle addition of step a)
The total amount meter of agent, graphene oxide and silane coupling agent.
In one embodiment of the invention, in step a), the graphene oxide of addition passes through those skilled in the art
The preparation of method known to member, such as prepared by hummers method, more specifically pass through potassium permanganate and graphite in the concentrated sulfuric acid
After oxidation reaction, obtain brown edge have derivative carboxyl and in the plane be mainly phenolic hydroxyl group and epoxy group graphite
Thin slice, it is graphene oxide that this graphene layers can be vigorously stirred removing through ultrasound or high shear.
The silane coupling agent being added in step a) has logical formula (I)
YSiX3(I)
Wherein,
Y is non-hydrolytic group, including C1-6Alkenyl, substituted or unsubstituted C1-6Alkyl or C1-6Alkoxy；And
X is hydrolyzable groups, including halogen, C1-6Alkoxy and acetoxyl group.
Preferably, Y be end by halogen, amino, sulfydryl, contain at least one be selected from N, O or S heteroatomic C1-6It is miscellaneous
The C that ring group, (methyl) acryloxy, isocyanate group replace1-6Alkyl or C1-6Alkoxy.
It is highly preferred that Y is end by amino, the C containing an O atom1-4The C that heterocycle replaces1-4Alkyl or C1-4Alcoxyl
Base.
Especially preferably, Y is the propyl and butoxy that end is replaced by amino, the heterocycle propyl containing O atom.
Preferably, X C1-6Alkoxy.
It is highly preferred that X is methoxyl group and ethyoxyl.
In one embodiment of the invention, used silane coupling agent be gamma-aminopropyl-triethoxy-silane and
γ-glycidyl ether oxygen propyl trimethoxy silicane.
In step b), preferably it is cooled at 55-65 DEG C.
In one embodiment of the invention, in step b), the reducing agent being added can be for metal simple-substance (such as
Sodium, magnesium, aluminium)；Non-metal simple-substance (such as hydrogen, carbon)；(such as sulfuric acid is sub- for metalloid anion (such as ferrous ion) and its compound
Iron).In the present invention, it is preferred to use ferrous sulfate as reducing agent, dosage is 10-30 weight %, preferably 15-25 weight
Measure %, by step a) and b) in the solvent of addition, graphene oxide, silane coupling agent and reducing agent total amount based on.
In step b), 2-3 hours are preferably kept the temperature after reducing agent is added.
In step c), the mode for removing solvent is any suitable way well known by persons skilled in the art, such as will
Temperature rises to 90-120 DEG C, is then evaporated in vacuo.After removing solvent, residue is washed, is centrifuged and is dried, later
Obtain required silane coupler modified graphene.
Optionally, the aqueous heavy anti-corrosion paint also includes component C) additive.The example of the additive includes dispersion
Agent, defoaming agent, thickener, cosolvent, filler and other auxiliary agents, but not limited to this.
Dispersing agent used can be in the present invention, but be not limited to fatty acid；Aliphatic amide；Ester, such as vinyl are double
Stearmide, glyceryl monostearate, glyceryl tristearate；Paraffin, such as atoleine, microcrystalline wax；Metallic soap, such as
Barium stearate, zinc stearate, calcium stearate；Low-molecular-weight wax, such as polyethylene wax, polyethylene glycol 200.The dosage of the dispersing agent
It can be 0.3-1.0 weight %, preferably 0.5-0.8 weight %, the meter based on component A) aqueous industrial resin.
Defoaming agent used can be in the present invention, but be not limited to the fatty acid ester compounded object of silicone emulsion, higher alcohols, polyoxy
Ethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxyethylene polyoxypropylene
Glycerin ether, dimethyl silicone polymer.The dosage of the defoaming agent can be 0.3-1.0 weight %, preferably 0.5-0.8 weight %,
Meter based on component A) aqueous industrial resin.
Thickener used can be in the present invention, but be not limited to inorganic thickening agent, such as bentonite, attapulgite, silicon
Sour aluminium；Cellulose, such as methylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hypromellose；Polyacrylic acid
Ester, such as polyacrylate, acrylic acid and the homopolymer of methacrylic acid etc.；Polyurethane thickener.The dosage of the thickener
Can 0.0-1.0 weight %, preferably 0.3-0.7 weight %, be based on component A) aqueous industrial resin meter.Preferably, at this
Thickener is not used in invention.
Cosolvent used can be the not only compound containing ehter bond but also containing hydroxyl in the present invention.The example is, but not
It is limited to the low-carbon alcohol ether compound of ethylene glycol and propylene glycol, such as butyl glycol ether, propylene glycol monomethyl ether, propandiol butyl ether, diethyl
Glycol methyl ether and its mixture.It is preferable to use one kind of butyl glycol ether or butyl or its two kinds in the present invention
Mixture, most preferably with butyl glycol ether.The amount of cosolvent used is 5-18 weight %, preferably 8-15 in the present invention
Weight %, the meter based on component A) aqueous industrial resin.
Filler used in the present invention can be, but be not limited to titanium white, calcium carbonate, trbasic zinc phosphate, mica, mill base, talcum and
Its mixture.Preferably, the titanium white that the present invention uses is rutile titanium dioxide, and dosage is 10-60 weight, preferably 15-55
Weight, the meter based on component A) aqueous industrial resin.Preferably, the present invention uses calcium carbonate, trbasic zinc phosphate, mica, mill base,
Talcum is any suitable product well known by persons skilled in the art.Wherein, calcium carbonate dosage is 5-60 weight %, preferably
10-55 weight %；The dosage of trbasic zinc phosphate is 10-35 weight %, preferably 15-30 weight %；The dosage of mica is 5-30 weight
Measure %, preferably 10-25 weight %；The dosage of mill base be 13-35 weight %, preferably 15-30 weight %, in each case
It is based on component A) meter of aqueous industrial resin.
Other auxiliary agents used can be in the present invention, but be not limited to industrial drier, such as metal oxide is as aoxidized
Cobalt, metal salt such as lead naphthenate, metallic soap such as lead soap and its mixture.Preferably, in the present invention cobalt drier is used, is used
Amount is 0.2-1.0 weight %, preferably 0.4-0.8 weight %, the meter based on component A) aqueous industrial resin.
Wherein, it should be noted that component A), B) and (if present) optional component C) amount add up to 100 weights
Measure %.
In another aspect of this invention, the method for preparing aqueous heavy anti-corrosion paint of the present invention is provided, comprising:
1) pass through following processes and prepare component B) silane coupler modified graphene:
A) in the dispersion in graphene oxide in solvent, silane coupling agent is added, is warming up to 90-110 DEG C and at this
At a temperature of keep the temperature 20-40 hours, obtain mixture a；
B) the mixture a obtained by step a) is cooled at 45-70 DEG C, reducing agent is added thereto, and keep the temperature 1.5-
3.5 hours, obtain product b；
C) solvent in the product b obtained by step b) is removed, required silane coupler modified graphene is obtained,
2) will be based on component A) meter 0.1-1.0 weight % the component B obtained by step 1)) it is silane coupler modified
Graphene be added to component A) in aqueous industrial resin, to obtain a kind of aqueous heavy anti-corrosion paint.
Optionally, it in aqueous industrial resin is added in the silane coupler modified graphene for obtaining step 1)
Before, further include following procedure: dispersing agent described above, defoaming agent, cosolvent and other auxiliary agents amount described herein above are added
Enter into aqueous industrial resin, stir evenly, titanium white described above, trbasic zinc phosphate, calcium carbonate, cloud is then added into system again
Female and mill base, keep its pre-dispersed and fineness i.e. granularity≤80 micron as defined in being ground to, preferably≤50 micron after, then into system
The silane coupler modified graphene of amount described above is added, stirring is until observe the transparent grainless of system；It
Afterwards, viscosity is adjusted to >=100s, preferably >=50s, obtains required target product, i.e. aqueous heavy anti-corrosion paint.The viscosity is logical
The QND-4 coating -4 viscosity meter (at 23 DEG C) for crossing Shanghai evil spirit space experimental instruments and equipment limited measures.
In still another aspect of the invention, aqueous heavy anti-corrosion paint of the invention is also provided in infrastructure, oil gas and electric power
Purposes in industry, and industrial tank, ship and chemical industry.For example, by aqueous heavy anti-corrosion paint of the invention with this field
Common coating method (such as spraying, roller coating and brushing) is coated on base material, based on the base material to be coated
Common substrate in construction, oil gas and power industry and industrial tank, ship and chemical industry, such as concrete；Timber；Gold
Belong to, such as tinplate (also known as tinplate) and steel；And resin layer.In a preferred embodiment, the resin layer includes
Cement base resin layer, epoxy layer, polyurethane-based resin layer, acrylate based resin layer, polyethylene layer, polypropylene layer,
Polyvinyl chloride layer, rubber layer, bitumen layer and polymer modified asphalt layer.The application temperature of the aqueous heavy anticorrosive material can be 5
DEG C to 40 DEG C, preferably 10 DEG C to 30 DEG C.In addition, the application relative humidity of the aqueous heavy anticorrosive material is 15% to 85%, it is excellent
Select 20% to 80%.
It should be noted that above to aqueous heavy anti-corrosion paint product in terms of described each feature, parameter, condition
And combinations thereof be suitable for preparation method and use in terms of.
The present invention, however, the present invention is not limited thereto are further described by following embodiment.
Embodiment
Used raw material:
Silane coupling agent: KH550 (i.e. gamma-aminopropyl-triethoxy-silane) purchased from Xuan Hao new material Co., Ltd and
KH560 (i.e. γ-glycidyl ether oxypropyltrimethoxysilane)；
Aqueous alkide resin: the alkyd resin 3530 purchased from DSM N. V.；
Dispersing agent: 755 purchased from Digao company；
Defoaming agent: 830 purchased from Digao company；
Drier: the cobalt drier purchased from Guang Shu chemical company；
Titanium white: the titanium white 996 purchased from Sichuan Lomon Titanium Industry Co., Ltd.；
Calcium carbonate: the 1250 mesh product of calcium carbonate purchased from Guangxi Cologne powder company；
Trbasic zinc phosphate: the phosphoric acid zinc product PHOSPHORIC ACID TECH.GRADE zinc purchased from Shijiazhuang elder brother's member chemical industry；
Mica: 600 mesh wet process mica products of Hebei Lingshou Baofeng mica processing Co., Ltd；
Mill base: Guangdong section enlightening general color paste product is bright red, iron oxide red, phthalocyanine blue, carbon black color paste.
Used test method:
Appearance of film: prepared product is coated in tinplate substrate with spraying method, film is obtained, by 7 days
After drying time, the appearance of film is observed；
Impact strength: it is measured according to GB/T 18178-2000.
Flexibility: it is measured according to GB/T 1731-1993.
Adhesive force: it is measured according to GB/T 18178-2000.
Surface drying time: refer to the surface of the paint film dry time, measured according to GB/T 1728-1979.
It does solid work the time: referring to the time of paint film actual drying, measured according to GB/T 1728-1979.
Salt fog resistance: it is measured according to GB/T 18178-2000.
Chemicals-resistant (such as acid, alkali): it is measured according to JSCE-E 549-2000.
Resistance to gasoline, kerosene, diesel oil: it is measured according to GB/T 9274-1988.
I. embodiment is prepared
Prepare silane coupler modified graphene
Embodiment 1
Under nitrogen protection, the merging of 565g methanol solvate is equipped with to the 2L of blender, thermometer, distiller, condenser
In four-hole bottle, and it is added slowly with stirring 5g graphene oxide, and be slowly stirred 30 minutes, is warming up to 55 DEG C and (be known as in table 1
First temperature).Then, it is slowly dropped into 250g silane coupling agent KH560 thereto, 90 DEG C are warming up to after being added dropwise to complete and (is claimed in table 1
For second temperature), heat preservation 24 hours (being known as the first soaking time in table 1), obtain mixture a.Then 65 DEG C of (tables 1 are cooled to
In be known as third temperature), 180g ferrous sulfate reducing agent is slowly added under stirring, and keep the temperature 2.5 hours and (be known as in table 1
Second soaking time), obtain product b.Then, vacuum pump is opened, system temperature is risen to 100 DEG C and (is known as the 4th temperature in table 1
Degree), the solvent in product b is distilled off, finally obtains product c.Later, c is washed using deionized water, is carried out later
Centrifugation obtains the silane coupler modified graphene of solid form after being dried, and is as a result listed in the table below in 1.
Embodiment 2-5
The process of embodiment 1 is repeated, difference is using raw material dosage and experiment condition listed in table 1.
Embodiment 6-7 (is used as comparative example)
The process of embodiment 4 is repeated, difference is using raw material dosage and experiment condition listed in table 1.
Table 1: the experimental data and result of embodiment 1-7
Note: in 0.01 × R of formula × ln (T+273.15) × ln (t), R represents added silane coupling agent and oxidation stone
The ratio between black alkene；T represents second temperature, and unit is DEG C；And t represents the first soaking time, unit is hour.
It is tested with capillary chromatography and remains silane coupling agent in prepared silane coupler modified graphene
Content, to extrapolate the optimal proportion of silane coupling agent and graphene in prepared modified graphene, trial scale is as follows
Shown in table 2:
Table 2
From testing result as can be seen that using silane coupled system and stone in the modified graphene of specified conditions of the present invention preparation
The weight ratio of black alkene can further improve the same substrate of water-base resin in the range of 2.0-7.0:1, using this graphene being modified
Adhesive force.
It takes graphene silane coupler modified obtained by 0.1g to be dissolved in 20g isopropanol, then passes through static laser
Diffraction is repeated using the granularity D90 of Mastersizer 2000 (being purchased from Malvern Instruments Ltd) measurement graphene
Three times, the average value of resulting D90 is listed in the table below in 3 for operation.
Table 3
Seen from table 3, compared with embodiment 6 and 7, what is prepared in 1-5 of the embodiment of the present invention is silane coupler modified
The partial size of graphene is smaller.
Prepare aqueous heavy anti-corrosion paint
Embodiment 9-15
The silane coupler modified graphene obtained by embodiment 1-7 is added separately in aqueous alkide resin, is matched
With corresponding additive, it is prepared into the aqueous heavy anti-corrosion paint of embodiment 9-15, the proportion situation of each raw material is listed in the table below in 4.
Embodiment 16-17
The process of embodiment 12 is repeated, difference is the amount and implementation of the silane coupler modified graphene wherein added
Example 12 is different, and concrete condition is as shown in table 4 below.
Table 4
Note: calcium carbonate, trbasic zinc phosphate, mica and mill base are the production that embodiment beginning (i.e. raw materials used part) is described in detail
Product.
II. purposes embodiment
By the aqueous heavy anti-corrosion paint of 200g embodiment of the present invention 9-17, at room temperature, Ma Kou is coated in spraying method
On iron-based bottom, the film with a thickness of 23 ± 2 microns is obtained, then the film is tested for the property, is as a result listed in the table below in 5.
Table 5:
Note: about the adhesive force in table, 0 grade means that adhesive force effect is best, and 1 grade means that adhesive force effect is preferable, 2 grades of meanings
Refer to that adhesive force effect is qualification.
By embodiment 12 it can be seen from the result of table 5 compared with the result of embodiment 14-15, illustrate using the present invention
Aqueous heavy anti-corrosion paint obtained by the silane coupler modified graphene prepared under specified conditions have excellent salt fog resistance,
Adhesion strength and mechanical strength.
With embodiment 16 (being wherein free of silane coupler modified graphene) and embodiment 17 (wherein containing the silicon of more amount
The coupling agent modified graphene of alkane) aqueous heavy anti-corrosion paint of preparation compares, and the aqueous heavy antisepsis of 9-13 of the embodiment of the present invention applies
Material has excellent mechanical strength, salt fog resistance, resistance to acid and alkali and resistance to gasoline, kerosene and diesel oil.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Art technology
Personnel in the case where not departing from the objective and range of technical solution of the present invention, to technical solution of the present invention carry out modification or
Person's equivalent replacement, is intended to be within the scope of the claims of the invention.
Claims (10)
1. a kind of aqueous heavy anti-corrosion paint, includes
A) aqueous industrial resin；With
B) silane coupler modified graphene,
Wherein, be based on component A) meter, component B) amount be 0.1-1.0 weight %, preferably 0.12-0.8 weight %, it is more excellent
It is selected as 0.15-0.6 weight %,
And component A) and amount B) add up to 100 weight %,
Wherein, the weight ratio of silane coupling agent and graphene is 2.0-7.0:1, preferably 3.0-5.5:1.
2. aqueous heavy anti-corrosion paint according to claim 1, wherein the D90 average value of silane coupler modified graphene
Less than 3.0 μm, preferably smaller than 1.1 μm, more preferably less than 0.6 μm；
And 0.03g/ μm3≤M/D90 3≤9.30g/μm3, preferably 0.75g/ μm3≤M/D90 3≤4.85g/μm3, wherein M is represented
The amount of graphene contained in aqueous heavy anti-corrosion paint.
3. aqueous heavy anti-corrosion paint according to claim 1 or 2, wherein component A) it is at least one to be selected from water alcohol acid tree
Rouge, aqueous epoxy resins, water-compatible amino resin, water-based acrylic resin, water based acrylic resin, water-base epoxy pitch tree
Rouge, waterborne polyurethane resin, aqueous inorganic resin and its mixture aqueous industrial resin, preferred aqueous alkide resin；And
The number-average molecular weight Mn of the aqueous industrial resin in the range of 5000 to 20000, preferably 8000 to 15000 range
It is interior, more preferably in the range of 9000 to 12000, measured according to GB/T21863-2008 using gel permeation chromatography.
4. aqueous heavy anti-corrosion paint according to any one of claim 1 to 3, wherein component B) it is silane coupler modified
Graphene is made by following processes:
A) in the dispersion in 45-70 DEG C of graphene oxide in solvent, silane coupling agent is added, be warming up to 90-110 DEG C and
It is preferred that 95-100 DEG C, and heat preservation 20-40 hours and preferably 24-36 hours at such a temperature, obtain mixture a；
B) the mixture a obtained by step a) is cooled at 50-70 DEG C, reducing agent is added thereto, and it is small to keep the temperature 1.5-3.5
When, obtain product b；
C) solvent in the product b obtained by step b) is removed, required silane coupler modified graphene is obtained.
5. aqueous heavy anti-corrosion paint according to claim 4, wherein in step a), added silane coupling agent and oxygen
The weight ratio of graphite alkene is 30-65:1, more preferably 40-60:1.
6. aqueous heavy anti-corrosion paint according to claim 5, wherein the reaction condition in step a) meets following formula:
5.5≤0.01×R×ln(T+273.15)×ln(t)≤14；
Preferably 7.5≤0.01 × R × ln (T+273.15) × ln (t)≤12,
Wherein, R represents the weight ratio of added silane coupling agent and graphene oxide in step a),
T represent be added silane coupling agent after holding temperature, unit be DEG C, and
T represents the soaking time after silane coupling agent is added, and unit is hour.
7. aqueous heavy anti-corrosion paint according to any one of claim 3 to 6, wherein solvent used in step a) is first
One of alcohol, ethyl alcohol, butanol, carbon tetrachloride, acetone, dichloroethanes or its two or more mixture, preferably methanol
Or methanol: the mixture of butanol=0.3-2:1, preferably 0.5-1.5:1；The dosage of the solvent is 50-80 weight %, more preferably
For 60-70 weight %, based on the total amount of the solvent, graphene oxide and the silane coupling agent that are added in step a).
8. the aqueous heavy anti-corrosion paint according to any one of claim 3 to 7, wherein the silane being added in step a) is even
Joining agent has logical formula (I)
YSiX3(I),
Wherein, Y is non-hydrolytic group, including C1-6Alkenyl, C1-6Alkyl or C1-6Alkoxy, preferably end are by halogen, amino, mercapto
Base, the heteroatomic C that N, O or S are selected from containing at least one1-6Heterocycle, (methyl) acryloxy, isocyanate group replace
C1-6Alkyl or C1-6Alkoxy, more preferably end are by amino, the C containing an O atom1-4The C that heterocycle replaces1-4Alkyl
Or C1-4Alkoxy, particularly preferred end is by amino, the propyl and butoxy that replace containing O atom cyclopropyl；
X is hydrolyzable groups, including halogen, C1-6Alkoxy and acetoxyl group, preferably C1-6Alkoxy, especially methoxyl group and
Ethyoxyl.
9. a kind of method for the aqueous heavy anti-corrosion paint for preparing any one of claim 1-8, comprising:
1) pass through following processes and prepare component B) silane coupler modified graphene:
A) in the dispersion in 45-70 DEG C of graphene oxide in solvent, silane coupling agent is added, be warming up to 90-110 DEG C and
It is preferred that 95-100 DEG C, and heat preservation 20-40 hours and preferably 24-36 hours at such a temperature, obtain mixture a；
B) the mixture a obtained by step a) is cooled at 50-70 DEG C, reducing agent is added thereto, and it is small to keep the temperature 1.5-3.5
When, obtain product b；
C) solvent in the product b obtained by step b) is removed, required silane coupler modified graphene is obtained,
2) component A will be based on) meter 0.1-1.0 weight %, preferably 0.12-0.8 weight %, more preferable 0.15-0.6 weight %
The component B obtained by step 1)) silane coupler modified graphene is added to component A) in aqueous industrial resin, thus
To a kind of aqueous heavy anti-corrosion paint.
10. aqueous heavy anti-corrosion paint as claimed in one of claims 1-8 is in infrastructure, oil gas and power industry and work
Purposes in industry tank, ship and chemical industry.
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