CN111500170A - Amino functionalized graphene modified polyurea long-acting anticorrosive coating and preparation method thereof - Google Patents
Amino functionalized graphene modified polyurea long-acting anticorrosive coating and preparation method thereof Download PDFInfo
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Abstract
The amino-functionalized graphene modified polyurea long-acting anticorrosive coating provided by the invention comprises a semi-prepolymer component A terminated by isocyanate, graphene can be uniformly dispersed in an amino polyether mixture to obtain a component B through functionalized modification of an amino compound, the component B further reacts with the isocyanate-terminated prepolymer component A, the amino-functionalized modified graphene and graphene oxide are well dispersed in a polyurea matrix, and the functionalized graphene is connected into a polyurea matrix molecular chain, so that the low permeability of the polyurea coating to a corrosive medium can be ensured, the interface combination of the polyurea coating and the polyurea matrix is stronger, the mechanical property is improved, the low permeability of the coating is ensured, and the long-acting anticorrosive function of polyurea is realized.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to an amino functionalized graphene modified polyurea long-acting anticorrosive coating and a preparation method thereof.
Background
Some common methods for preventing corrosion of metals include the use of corrosion inhibitors, electrochemical cathodic protection, surface treatment, and coatings. Among these anti-corrosion methods, the use of anti-corrosion coatings is emphasized by their ease of application and good protective properties. Polyurea resins have good adhesion, chemical resistance, and durability at high and low temperatures, and thus are widely used. The graphene modified polyurea is difficult to disperse in the resin matrix, so that microcracks and pores in the coating are generated, corrosive media in the marine environment can penetrate into the substrate through the pores, the organic coating fails, and the corrosion of metal equipment in the marine environment is accelerated. The graphene has a large specific surface area and a strong shielding effect, and can effectively prevent corrosive media from permeating into a coating through pores and cracks when being added into the polyurea coating as a filler. However, the poor dispersibility of the graphene in the polyurea coating makes the corrosion resistance of the polyurea coating not be well reflected.
Chinese patent CN110117453A A polyurea composite modified waterproof coating and a processing technology thereof. The invention discloses a polyurea composite modified waterproof coating and a processing technology thereof, wherein the polyurea composite modified waterproof coating comprises a component A, a component B and a catalyst, the weight ratio of the component A to the component B to the catalyst is 12:4:1, the waterproof agent is contained in the raw materials, the possibility that the coating is affected by environmental moisture and water can be reduced, the service life of the coating can be prolonged, the corrosion resistance and the ageing resistance of the coating can be improved by adopting modified lithopone, the foam eliminating agent is added, the possibility of occurrence of foam is reduced, the quality of the coating is improved, the catalyst can enable the component A and the component B to react completely, and the utilization rate of the coating is improved.
Chinese patents CN107793901A, CN104231703A, CN108237063A CN106784915A, CN106995653A, CN109909131A, and CN108047792A CN110183939A report that graphene modified epoxy resin anticorrosive paint has poor dispersibility in paint and fails to achieve long-acting heavy-duty anticorrosive effect because graphene is not modified by functional modification.
Disclosure of Invention
Therefore, it is necessary to provide an amino-functionalized graphene-modified polyurea long-acting anticorrosion coating capable of realizing a polyurea long-acting anticorrosion function, aiming at the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an amino functionalized graphene modified polyurea long-acting anticorrosive coating comprises the following steps:
heating polyether polyol to 95-100 ℃ in an inert environment, dehydrating for 1-1.5 hours under the vacuum of-0.1-0.5 MPa, relieving the vacuum, cooling to below 40 ℃, adding polyisocyanate, heating to 80 ℃ for reacting for 2 hours, measuring the NCO value after the reaction is finished, discharging, filtering and packaging to obtain a semi-prepolymer A component blocked by isocyanate, wherein the mass ratio of the polyether polyol to the polyisocyanate is 100: (66-155);
the mass ratio of (55-65): (20-30): (10-15): (2-5): (0.5-1): (1-1.5) stirring, grinding and filtering the amino polyether, the amine chain extender, the aminated graphene, the color paste, the wetting dispersant and the anti-settling wax to obtain a component B. In some preferred embodiments, the isocyanate prepolymer of component A has a-NCO content of 14% to 17%; the isocyanate index of the component A and the isocyanate index of the component B are 1.05-1.10.
In some preferred embodiments, the isocyanate index of the A component and the B component is 1.05 to 1.10.
Specifically, the content of-NCO in the component A is 10-16.5%, the solid content is more than or equal to 99%, the viscosity is 500-800 mPa.s at 25 ℃, and the density is 1.08-1.12 g/ml at 25 ℃.
In some preferred embodiments, the polyether polyol comprises a polyoxypropylene glycol or a polytetrahydrofuran ether glycol.
Specifically, the polyoxypropylene diol is called voranol2120, and has a hydroxyl value of 54.5-57.5 mgKOH/g or voranol 2110 relative to a molecular weight of 2000, and a hydroxyl value of 110 + -5 mgKOH/g or a hydroxyl value of 33.5-36.5 mgKOH/g TEP-330N relative to a molecular weight of 1000.
Specifically, the polytetrahydrofuran ether glycol grade PTMG1000 has a relative molecular mass of 1000 +/-50, a hydroxyl value of 107-118 mgKOH/g or PTMG2000, a relative molecular mass of 2000 +/-50, a hydroxyl value of 54.7-57.5 mgKOH/g or PTMG3000, a relative molecular mass of 3000 +/-50 and a hydroxyl value of 36.2-38.7 mgKOH/g.
In some preferred embodiments, the polyisocyanate comprises 4,4 '-diphenylmethane diisocyanate or a mixture of 2,4' -diphenylmethane diisocyanate and 4,4 '-diphenylmethane diisocyanate or toluene diisocyanate or isophorone diisocyanate or 4,4' -dicyclohexylmethane diisocyanate or naphthalene diisocyanate.
Specifically, the purity of 4,4 '-diphenylmethane diisocyanate (MDI-100) is more than or equal to 99.6%, the freezing point is more than or equal to 38 ℃, the NCO mass fraction is 33.5%, the purity of a mixture of 2,4' -diphenylmethane diisocyanate and 4,4 '-diphenylmethane diisocyanate (MDI-50) is more than or equal to 99.6%, the freezing point is less than or equal to 15 ℃, the NCO mass fraction is 33.5%, the purity of toluene diisocyanate (TDI-100, TDI-65, TDI-80) is more than or equal to 99.5%, the purity of isophorone diisocyanate (IPDI) is more than or equal to 99.5%, the NCO mass fraction is 37.5% -37.8%, the freezing point is-60 ℃, the purity of 4,4' -dicyclohexylmethane diisocyanate (HMDI) is more than or equal to 99.5%, the NCO mass fraction is 31.8% -32.1%, the freezing point is 10-15 ℃, the purity of Naphthalene Diisocyanate (NDI) is more than or equal to 99%, the NCO mass fraction is 40.8 +/-1.0%, and the liquefied MDI (L-MDI) has the mass fraction of 28%, and.
In some preferred embodiments, the aminopolyether comprises a difunctional aminopolyether or a polytetramethylene ether di-p-aminobenzoate or a trifunctional aminopolyether.
In particular, difunctional aminopolyethers, under the designation Jeffamine D-2000 or Jeffamine D-400 or Jeffamine D-4000 or THF-140 or THF-170 or SD-2001 or ST-404.
In particular, polytetramethylene ether di-P-aminobenzoate is available under the brand name P-650 or P-1000 or P-2000.
Specifically, the grade of the trifunctional amino polyether is Jeffamine T-3000, Jeffamine T-5000 or Jeffamine T-403.
In some preferred embodiments, the amine chain extender comprises an aromatic diamine or an aliphatic diamine;
the aromatic diamine comprises at least one of 3, 5-diethyltoluenediamine, 3' -dichloro-4, 4' -diaminodiphenylmethane, 3' -diethyl-4, 4' -diaminodiphenylmethane, 3, 5-dimethylthiotoluenediamine, 2, 4-diamino-3, 5-dimethylthiochlorobenzene (TX-2), bis-sec-butylaminodiphenylmethane and N, N ' -dialkylphenylenediamine;
the aliphatic diamine comprises at least one of isophorone diamine (IPDA), dimethyl-diamino-dicyclohexylmethane, 4' -bis-sec-butylaminodicyclohexylmethane or 3,3' -dimethyl-4, 4' -bis-sec-butylaminodicyclohexylmethane.
In some preferred embodiments, the aminated graphene is prepared by the following method:
stripping graphite oxide into graphene oxide: dispersing graphite oxide in water, and performing ultrasonic cleaning to obtain a graphene oxide aqueous solution;
preparing amino polyether modified graphene-NH 2-GOs: dissolving aminopolyether in DMF, adding NaOH and the aqueous solution of graphene oxide, mixing the dispersed aqueous solution to obtain a mixture, refluxing and stirring the mixture at the temperature of 100 ℃ under a protective atmosphere, cooling to room temperature after the reaction is finished, washing the mixture with DMF to remove impurities, and drying in vacuum to remove DMF solvent to obtain the aminated graphene-NH 2-rGO.
In some preferred embodiments, zinc powder is further added into the aminated graphene-NH 2-rGO, the fineness of the zinc powder is 1000-1500 meshes, and the mass ratio of the zinc powder to the aminated graphene is 20: 0.5 to 1.0.
It can be understood that in the above embodiments, the addition of zinc powder as a negative electrode material to the amino-functionalized graphene can also play a role in protection even if the coating is damaged.
In some preferred embodiments, the color paste is a color paste common to the polyurethane industry, and the color of the color paste comprises: red, yellow, blue, green, white and black pulp, the water content of which is less than or equal to 0.5 percent, and the wetting dispersant is polyether ester phosphate.
In addition, the invention also provides an amino functionalized graphene modified polyurea long-acting anticorrosive coating which is prepared by any preparation method of the amino functionalized graphene modified polyurea long-acting anticorrosive coating.
The invention adopts the technical scheme that the method has the advantages that:
the amino-functionalized graphene modified polyurea long-acting anticorrosive coating provided by the invention comprises a semi-prepolymer component A terminated by isocyanate, graphene can be uniformly dispersed in an amino polyether mixture to obtain a component B through functionalized modification of an amino compound, the component B further reacts with the isocyanate-terminated prepolymer component A, the amino-functionalized modified graphene and graphene oxide are well dispersed in a polyurea matrix, and the functionalized graphene is connected into a polyurea matrix molecular chain, so that the low permeability of the polyurea coating to a corrosive medium can be ensured, the interface combination of the polyurea coating and the polyurea matrix is stronger, the mechanical property is improved, the low permeability of the coating is ensured, and the long-acting anticorrosive function of polyurea is realized.
The amino functionalized graphene modified polyurea long-acting anticorrosive coating provided by the invention has important value in the practical application of the anticorrosive field, provides important basis for the industrial application of graphene, and has important practical significance for improving the seawater corrosion resistance of ocean engineering equipment in China.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of an amino functionalized graphene modified polyurea long-acting anticorrosive coating, which comprises the following steps:
step S110: heating polyether polyol to 95-100 ℃ in an inert environment, dehydrating for 1-1.5 hours under vacuum of-0.1 MPa, relieving the vacuum, cooling to below 40 ℃, adding polyisocyanate, heating to 80 ℃ for reacting for 2 hours, measuring the NCO value after the reaction is finished, discharging, filtering and packaging to obtain an isocyanate-terminated semi-prepolymer A component, wherein the mass ratio of the polyether polyol to the polyisocyanate is 100: (66-155);
the mass ratio of (55-65): (20-30): (10-15): (2-5): (0.5-1): (1-1.5) stirring, grinding and filtering the amino polyether, the amine chain extender, the aminated graphene, the color paste, the wetting dispersant and the anti-settling wax to obtain a component B. In some preferred embodiments, the isocyanate prepolymer of component A has a-NCO content of 14% to 17%; the isocyanate index of the component A and the isocyanate index of the component B are 1.05-1.10.
The amino-functionalized graphene modified polyurea long-acting anticorrosive coating provided by the invention comprises a semi-prepolymer component A terminated by isocyanate, graphene can be uniformly dispersed in an amino polyether mixture to obtain a component B through functionalized modification of an amino compound, the component B further reacts with the isocyanate-terminated prepolymer component A, the amino-functionalized modified graphene and graphene oxide are well dispersed in a polyurea matrix, and the functionalized graphene is connected into a polyurea matrix molecular chain, so that the low permeability of the polyurea coating to a corrosive medium can be ensured, the interface combination of the polyurea coating and the polyurea matrix is stronger, the mechanical property is improved, the low permeability of the coating is ensured, and the long-acting anticorrosive function of polyurea is realized.
Example 1-preparation of DETDA modified graphene oxide GOS-DETDA:
(1) preparing graphite oxide:
preparing graphite oxide by adopting a modified Hummers method:
adding 10g of flake graphite into 230ml of concentrated sulfuric acid in an ice water mixture, slowly adding 30g of potassium permanganate while stirring by using an electric stirrer, controlling the reaction temperature to be less than 5 ℃ all the time, and keeping the reaction temperature for 96 hours; adding the obtained dark green liquid into 460ml of deionized water;
stirring the obtained solution at 35 ℃ for reaction for 1.5h, then heating to 95 ℃, reacting for 1h, adding 30ml of 30% hydrogen peroxide while the solution is hot, standing for 12h, filtering, washing with 1000ml of 5% hydrochloric acid, washing with 3000ml of deionized water until no sulfate ions exist, and drying the obtained sample at 70 ℃.
(2) Preparation of diethyl toluene diamine modified graphene oxide:
adding 4g of graphite oxide into 200DMF, carrying out ultrasonic treatment for 2.5h by using an ultrasonic cleaning machine to obtain a Graphene Oxide Suspension (GOS), then adding 20g of DETDA, carrying out ultrasonic treatment for 5min, reacting for 48h at 120 ℃, adding 60ml of absolute ethyl alcohol, standing overnight, removing the supernatant, filtering the lower-layer precipitate, washing with ethanol and deionized water, and drying the obtained sample at 70 ℃ to obtain GOS-DETDA.
Example 2-preparation of aminopolyether D-400 modified graphene D-400-rGO:
(1) stripping graphite oxide into graphene oxide:
50g of graphite oxide is dispersed in 100ml of water, the power of an ultrasonic cleaner is 300W, and the water solution (GO) of graphene oxide of 0.5g/ml is prepared after ultrasonic treatment for 50 min.
(2) Preparation of amino polyether D-400 modified graphene D-400-rGO:
2g D-400 is dissolved in DMF of 80m L, 80mg NaOH and 160m L0.5.0 g/m L GO which are dispersed in water are added, the mixture is refluxed and stirred at the temperature of 100 ℃ for 24h under the protection of nitrogen atmosphere, after the reaction is finished, the mixture is cooled to room temperature, the impurities are removed by washing with DMF, and the DMF solvent is removed by vacuum drying.
Example 3
The formula composition and the preparation process of the amino functionalized graphene modified polyurea long-acting anticorrosive coating in the embodiment are as follows:
the polyurea elastomer coating formula consists of a component A and a component B, wherein the component A is a prepolymer of polyoxypropylene glycol voranol2120 and MDI diisocyanate; the component B consists of amino polyether Jeffamine D-2000 and Jeffamine T-5000, a functionalized graphene/zinc powder blend, an amine chain extender DETDA, color paste and a wetting dispersant. The components of the substances are as follows:
the alpha values of the component A and the component B are 1.05-1.10.
(1) And (3) synthesizing a component A of the isocyanate-terminated semi-prepolymer:
adding voranol2120 into a reaction kettle protected by nitrogen, heating to 95-100 ℃ under stirring, dehydrating for 1-1.5 hours under vacuum-0.1 MPa, relieving the vacuum, reducing the temperature to be below 40 ℃, adding MDI-50, reacting for 2 hours at 80 ℃, cooling to be below 60 ℃ after the reaction is finished, measuring the NCO value, discharging, filtering and packaging to obtain the isocyanate-terminated semi-prepolymer A component.
(2) Preparation of the component B:
and weighing the component B according to the formula sequence in the table, sequentially putting the component B into a storage vat of a high-speed dispersion machine, stirring for 30 minutes at room temperature, and filtering and packaging by using a 200-mesh filter screen to obtain the component B.
Example 4
The formula composition and the preparation process of the amino functionalized graphene modified polyurea long-acting anticorrosive coating in the embodiment are as follows:
the polyurea elastomer coating formula consists of a component A and a component B, wherein the component A is a prepolymer of polytetrahydrofuran ether glycol PTMG-1000 and HMDI diisocyanate; the component B consists of amino polyether Jeffamine D-2000, THF-170, Jeffamine T-5000, amine chain extender DETDA, Unilink 4200, aminated graphene/zinc powder, color paste, wetting dispersant and anti-settling wax.
The components A and B comprise the following components in parts by weight:
the a value of the A component and the B component is 1.05.
(1) Preparation of component A:
putting PTMG-1000 into a reaction kettle with nitrogen protection, heating to 95-100 ℃ under stirring, dehydrating for 1-1.5 hours under vacuum-0.1 MPa, relieving vacuum, reducing the temperature to be below 40 ℃, adding 4,4' -dicyclohexylmethane diisocyanate (HMDI), reacting for 2 hours at 80 ℃, reducing the temperature to be below 60 ℃ after the reaction is finished, adding a propyl carbonate diluent, stirring for 10 minutes, measuring the NCO value, discharging, filtering and packaging to obtain the isocyanate-terminated semi-prepolymer A component.
(2) Preparation of the component B: weighing the component B according to the formula sequence, sequentially putting the component B into a storage vat of a high-speed dispersion machine, stirring for 30 minutes at room temperature, filtering and packaging by a 200-mesh filter screen to obtain the component B.
Example 5
Spray polyurea elastomer anticorrosive coating and performance test
Adopting GUSMER XM-70 high-pressure spraying equipment and a high-pressure manual spray gun for spraying, wherein the spraying process parameters are as follows:
the temperature of the spray coating of the component A and the component B is kept between 65 and 70 DEG C
The performance parameters of the graphene modified polyurea long-acting anticorrosive coating are as follows:
of course, the long-acting anticorrosive coating of amino-functionalized graphene-modified polyurea of the present invention may have various changes and modifications, and is not limited to the specific structure of the above embodiments. In conclusion, the scope of the present invention should include those changes or substitutions and modifications which are obvious to those of ordinary skill in the art.
Claims (10)
1. A preparation method of an amino functionalized graphene modified polyurea long-acting anticorrosive coating is characterized by comprising the following steps:
heating polyether polyol to 95-100 ℃ in an inert environment, dehydrating for 1-1.5 hours under the vacuum of-0.1-0.5 MPa, relieving the vacuum, cooling to below 40 ℃, adding polyisocyanate, heating to 80 ℃ for reacting for 2 hours, measuring the NCO value after the reaction is finished, discharging, filtering and packaging to obtain a semi-prepolymer A component terminated by isocyanate, wherein the mass ratio of the polyether polyol to the polyisocyanate is 100: (66-155);
the mass ratio of (55-65): (20-30): (10-15): (2-5): (0.5-1): (1-1.5) stirring, grinding and filtering the amino polyether, the amine chain extender, the aminated graphene, the color paste, the wetting dispersant and the anti-settling wax to obtain a component B.
2. The preparation method of the amino-functionalized graphene-modified polyurea long-acting anticorrosive coating according to claim 1, wherein the isocyanate index of the component A and the isocyanate index of the component B are 1.05-1.10.
3. The method for preparing the amino-functionalized graphene-modified polyurea long-lasting corrosion protective coating according to claim 1, wherein the polyether polyol comprises polyoxypropylene glycol or polytetrahydrofuran ether glycol.
4. The method for preparing the amino-functionalized graphene-modified polyurea long-acting anticorrosion coating according to claim 1, wherein the polyisocyanate comprises 4,4 '-diphenylmethane diisocyanate or a mixture of 2,4' -diphenylmethane diisocyanate and 4,4 '-diphenylmethane diisocyanate or toluene diisocyanate or isophorone diisocyanate or 4,4' -dicyclohexylmethane diisocyanate or naphthalene diisocyanate.
5. The method for preparing the amino-functionalized graphene-modified polyurea long-acting anticorrosion coating according to claim 1, wherein the amino polyether comprises difunctional amino polyether or polytetramethylene ether di-p-aminobenzoate or tri-functional amino polyether.
6. The method for preparing the amino-functionalized graphene-modified polyurea long-acting anticorrosion coating according to claim 1, wherein the amine chain extender comprises an aromatic diamine or an aliphatic diamine;
the aromatic diamine comprises at least one of 3, 5-diethyltoluenediamine, 3' -dichloro-4, 4' -diaminodiphenylmethane, 3' -diethyl-4, 4' -diaminodiphenylmethane, 3, 5-dimethylthiotoluenediamine, 2, 4-diamino-3, 5-dimethylthiochlorobenzene (TX-2), bis-sec-butylaminodiphenylmethane and N, N ' -dialkylphenylenediamine;
the aliphatic diamine comprises at least one of isophorone diamine (IPDA), dimethyl-diamino-dicyclohexylmethane, 4' -bis-sec-butylaminodicyclohexylmethane or 3,3' -dimethyl-4, 4' -bis-sec-butylaminodicyclohexylmethane.
7. The method for preparing the amino functionalized graphene-modified polyurea long-acting anticorrosive coating according to claim 1, wherein the amino functionalized graphene is prepared by the following method:
stripping graphite oxide into graphene oxide: dispersing graphite oxide in water, and performing ultrasonic cleaning to obtain a graphene oxide aqueous solution;
preparing amino polyether modified graphene-NH 2-GOs: dissolving aminopolyether in DMF, adding NaOH and the aqueous solution of graphene oxide, mixing the dispersed aqueous solution to obtain a mixture, refluxing and stirring the mixture at the temperature of 100 ℃ under a protective atmosphere, cooling to room temperature after the reaction is finished, washing the mixture with DMF to remove impurities, and drying in vacuum to remove DMF solvent to obtain the aminated graphene-NH 2-rGO.
8. The preparation method of the amino-functionalized graphene-modified polyurea long-acting anticorrosive coating as claimed in claim 7, wherein zinc powder is further added into the amino-functionalized graphene-NH 2-rGO, the fineness of the zinc powder is 1000-1500 meshes, and the mass ratio of the zinc powder to the amino-functionalized graphene is 20: 0.5 to 1.0.
9. The method for preparing the long-acting anticorrosive coating of amino-functionalized graphene-modified polyurea, according to claim 1, wherein the color paste is a color paste commonly used in polyurethane industry, and the color of the color paste comprises: red, yellow, blue, green, white and black pulp, the water content of which is less than or equal to 0.5 percent, and the wetting dispersant is polyether ester phosphate.
10. An amino-functionalized graphene-modified polyurea long-acting anticorrosive coating which is characterized by being prepared by the preparation method of the amino-functionalized graphene-modified polyurea long-acting anticorrosive coating according to any one of claims 1 to 9.
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