CN114149729B - Anti-corrosion static-conductive solvent-free polyurea coating and preparation method and application thereof - Google Patents
Anti-corrosion static-conductive solvent-free polyurea coating and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an anticorrosive static-conductive solvent-free polyurea coating and a preparation method and application thereof. The solvent-free polyurea coating with the functions of corrosion prevention and static conduction comprises a component A and a component B, wherein the component A comprises polyaspartic acid ester resin, castor oil-based polyether polyol, amine-terminated polyether, anti-rust pigment and filler, conductive filler, a dispersing agent, a defoaming agent, an anti-settling agent, a wetting agent, a diluting agent and a dewatering agent, the component B comprises an isocyanate curing agent, and the mass ratio of the component A to the component B is (3). The preparation method of the solvent-free polyurea coating with the functions of corrosion resistance and static conduction is very simple, and all the raw materials are mixed uniformly in batches. The anticorrosive static-conductive solvent-free polyurea coating has the highest one-time coating thickness of 1mm, and the coating thickness can be regulated and controlled by changing the construction process, so that the formed paint film has excellent mechanical property, anticorrosive property, static-conductive property and medium-resistant property, and is suitable for being used as an inner wall protective coating of a petroleum storage tank.
Description
Technical Field
The invention relates to the technical field of metal corrosion prevention, in particular to a solvent-free polyurea coating capable of preventing corrosion and conducting static electricity and a preparation method and application thereof.
Background
The oil storage tank is a container for storing oil products and can be divided into a nonmetal oil tank and a metal oil tank according to materials. The metal oil tank has the advantages of low cost, difficult leakage, convenient construction, easy maintenance and the like, and is widely applied. The metal oil tank inevitably has corrosion problems during use, and further has severe problems such as oil pollution, explosion caused by oil leakage and the like. At present, the anticorrosion performance of the metal oil tank is mainly improved by brushing the static conductive anticorrosive paint at home and abroad, the most commonly adopted static conductive anticorrosive paint is epoxy, and conductive graphite and carbon black are mostly used for endowing the coating with a static conductive effect. However, coatings prepared with graphite and carbon black as fillers produce paint films that are dark in color, difficult to observe directly by visual observation of corrosion of the inner wall of oil storage tanks, and carbon-based conductive coatings that, upon defects or breakage, can also cause the steel substrate to act as an anode and accelerate corrosion of the inner wall of oil storage tanks. In addition, the epoxy coating has a limited thickness after being coated once, and is usually repeatedly coated for multiple times to reach the required thickness, so the construction period is long, and the labor cost is high.
Therefore, the development of the anticorrosive static conductive coating with excellent anticorrosive performance and large one-time coating thickness is of great significance.
Disclosure of Invention
The invention aims to provide an anti-corrosion static-conductive solvent-free polyurea coating as well as a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
an anticorrosion static-conductive solvent-free polyurea coating is composed of a component A and a component B:
the component A comprises the following raw materials in parts by mass:
polyaspartic acid ester resin: 10-20 parts;
castor oil based polyether polyol: 20-30 parts;
amino-terminated polyether: 8-12 parts;
antirust pigment and filler: 10-15 parts;
conductive filler: 20-30 parts;
dispersing agent: 0.8 to 1.2 portions;
defoaming agent: 0.5 to 0.9 portion;
anti-settling agent: 0.05 to 0.3 portion;
wetting agent: 0.1 to 0.3 portion;
diluent (b): 3-4 parts;
water removal agent: 4-7 parts;
the component B comprises the following raw materials in parts by mass:
isocyanate curing agent: 20-30 parts;
the mass ratio of the component A to the component B is 3.
Preferably, the ratio of the total equivalents of amine groups and hydroxyl groups in the a component to the equivalents of isocyanate groups in the B component is 1.1 to 1.5.
Preferably, the anti-rust pigment filler is at least one of aluminum tripolyphosphate, aluminum zinc phosphate, molybdate and zinc phosphate.
Preferably, the conductive filler is conductive mica powder. The conductive mica powder has low price, low oil absorption value and low resistivity, and the coating can be endowed with excellent electrostatic conductive performance by adding a small amount of conductive mica powder, and meanwhile, the influence on the viscosity of the coating can be reduced.
Preferably, the dispersant is an alkyl ammonium salt copolymer.
Preferably, the defoamer is a silicone defoamer.
Preferably, the anti-settling agent is BYK-410. The BYK-410 can promote the paint system to establish a three-dimensional structure, can prevent sedimentation and improve the anti-sagging performance, and does not affect the leveling.
Preferably, the wetting agent is polyether modified polydimethylsiloxane. The polyether modified polydimethylsiloxane can obviously reduce the surface tension of the coating, prevent shrinkage cavity, contribute to improving the adhesive force of the coating, and simultaneously can improve the surface smoothness and the glossiness of the coating.
Preferably, the diluent is an ether ester solvent.
Preferably, the water scavenger is a molecular sieve.
Preferably, the isocyanate curing agent is an aromatic isocyanate. Compared with aliphatic isocyanate, the aromatic isocyanate has lower cost and reduces the raw material cost of the coating.
Preferably, the aromatic isocyanate is at least one of polymethylene polyphenyl polyisocyanate and diphenylmethane-4, 4' -diisocyanate.
The preparation method of the corrosion-resistant static-conductive solvent-free polyurea coating comprises the following steps:
1) Uniformly mixing polyaspartic acid ester resin, castor oil-based polyether polyol and amine-terminated polyether, adding a dispersing agent, a defoaming agent, an anti-settling agent, a wetting agent and a diluent, uniformly mixing, adding an anti-rust pigment and filler, uniformly mixing, adding a conductive filler and a water removing agent, uniformly mixing to obtain a component A, and taking an isocyanate curing agent as a component B;
2) And uniformly mixing the component A and the component B to obtain the solvent-free polyurea coating with corrosion resistance and static conduction.
Preferably, the preparation method of the anticorrosive static-electricity-conducting solvent-free polyurea coating comprises the following steps:
1) Mixing polyaspartic acid ester resin, castor oil-based polyether polyol and amino-terminated polyether, dispersing for 5-10 min at the rotation speed of 750-1000 rpm, adding a dispersing agent, a defoaming agent, an anti-settling agent, a wetting agent and a diluent, continuously dispersing for 5-10 min, adding an anti-rust pigment and filler, dispersing for 10-15 min at the rotation speed of 2000-2500 rpm, adding a conductive filler and a water removing agent, uniformly mixing to obtain a component A, and taking an isocyanate curing agent as a component B;
2) And uniformly mixing the component A and the component B to obtain the solvent-free polyurea coating with corrosion resistance and static conduction.
The invention has the beneficial effects that: the anticorrosive static-conductive solvent-free polyurea coating has the highest one-time coating thickness of 1mm, and the coating thickness can be regulated and controlled by changing the construction process, so that the formed paint film has excellent mechanical property, anticorrosive property, static-conductive property and medium-resistant property, and is suitable for being used as an inner wall protective coating of a petroleum storage tank.
Specifically, the method comprises the following steps:
1) The solvent-free polyurea coating for preventing corrosion and conducting static electricity takes polyaspartic acid ester resin, castor oil-based polyether polyol and amine-terminated polyether as film forming substances, the amine-terminated polyether can improve the flexibility of a coating and can react with isocyanate curing agents to form polyurea with the molecular formula of R' -NH-C (= O) -NH-R, and the molecule has excellent acid and alkali resistance, so that the corrosion resistance of the coating can be effectively improved;
2) The anticorrosive static-conducting solvent-free polyurea coating disclosed by the invention forms a paint film with excellent medium resistance, such as: resistant to solvent (93 # gasoline, 62 ℃), salt spray, brine (5% NaCl, normal temperature), alkali (5% NaOH, normal temperature) and acid (5% H) 2 SO 4 Normal temperature) time length can reach more than 800h, boiling water resistance time length can reach more than 50h, and the requirements of acid resistance, alkali resistance, salt water resistance, salt mist resistance, gasoline resistance for 720h and boiling water resistance for 48h in the national standard of steel oil storage tank anticorrosion engineering technology are completely met;
3) The solvent-free polyurea coating with corrosion resistance and static conduction has the highest coating thickness of 1mm, the coating thickness can be regulated and controlled by changing the construction process, the coating thickness can be in a micrometer-millimeter level, the required coating thickness can be obtained by one-time construction, the construction efficiency is obviously improved, and the labor cost is reduced.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
an anti-corrosion static-electricity-conductive solvent-free polyurea coating, the composition of which is shown in the following table:
TABLE 1 composition table of corrosion-resistant static-conductive solvent-free polyurea coating
The preparation method of the corrosion-resistant static-conductive solvent-free polyurea coating comprises the following steps:
1) Mixing polyaspartic acid ester resin F520, castor oil-based polyether polyol D1145 and amino-terminated polyether D2000, dispersing for 10min under the condition of the rotation speed of 1000rpm, adding a dispersant BYK-9076, a defoamer KEPERPLO-768, an anti-settling agent BYK-410, a wetting agent BYK-333 and dipropylene glycol monomethyl ether acetate, continuing to disperse for 10min, adding aluminum tripolyphosphate, dispersing for 15min under the condition of the rotation speed of 2300rpm, adding conductive mica powder YJ and a 3A molecular sieve, and uniformly mixing to obtain a component A, wherein polymethylene polyphenyl polyisocyanate PM-200 is used as a component B;
2) And (3) uniformly mixing the component A and the component B according to the mass ratio of 3.5.
Example 2:
an anti-corrosion static-electricity-conductive solvent-free polyurea coating, the composition of which is shown in the following table:
TABLE 2 composition table of corrosion-resistant static-conductive solvent-free polyurea coating
The preparation method of the corrosion-resistant static-conductive solvent-free polyurea coating comprises the following steps:
1) Mixing polyaspartic acid ester resin F520, castor oil-based polyether polyol D1145 and amino-terminated polyether D2000, dispersing for 10min at the rotation speed of 1000rpm, adding a dispersing agent BYK-9076, a defoaming agent KEPERPLO-768, an anti-settling agent BYK-410, a wetting agent BYK-333 and dipropylene glycol methyl ether acetate, continuing dispersing for 10min, adding zinc phosphate, dispersing for 15min at the rotation speed of 2300rpm, adding conductive mica powder YJ and a 3A molecular sieve, and uniformly mixing to obtain a component A, wherein polymethylene polyphenyl polyisocyanate PM-200 is used as a component B;
2) And (3) uniformly mixing the component A and the component B according to the mass ratio of 3.5.
Example 3:
an anti-corrosion static-conductive solvent-free polyurea coating having the composition shown in the following table:
TABLE 3 composition table of corrosion-resistant static-conductive solvent-free polyurea coating
The preparation method of the anticorrosive static-conducting solvent-free polyurea coating comprises the following steps:
1) Mixing polyaspartic acid ester resin F520, castor oil-based polyether polyol H854 and amino-terminated polyether D2000, dispersing for 10min at the rotation speed of 1000rpm, adding a dispersing agent BYK-9076, a defoaming agent KEPERPLLO-768, an anti-settling agent BYK-410, a wetting agent BYK-333 and dipropylene glycol methyl ether acetate, continuing dispersing for 10min, adding zinc aluminum phosphate, dispersing for 15min at the rotation speed of 2300rpm, adding conductive mica powder YJ and a 3A molecular sieve, uniformly mixing to obtain a component A, and taking polymethylene polyphenyl polyisocyanate PM-200 as a component B;
2) And (3) uniformly mixing the component A and the component B according to the mass ratio of 3.5.
Example 4:
an anti-corrosion static-conductive solvent-free polyurea coating having the composition shown in the following table:
TABLE 4 composition table of corrosion-resistant static-conductive solvent-free polyurea coating
The preparation method of the corrosion-resistant static-conductive solvent-free polyurea coating comprises the following steps:
1) Mixing polyaspartic acid ester resin F520, castor oil-based polyether polyol H870 and amino-terminated polyether D2000, dispersing for 10min at the rotation speed of 1000rpm, adding a dispersant BYK-9076, a defoaming agent KEPERPLLO-768, an anti-settling agent BYK-410, a wetting agent BYK-333 and dipropylene glycol methyl ether acetate, continuing dispersing for 10min, adding zinc phosphate, dispersing for 15min at the rotation speed of 2300rpm, adding conductive mica powder BC-P and a 3A molecular sieve, and uniformly mixing to obtain a component A, wherein polymethylene polyphenyl polyisocyanate PM-200 is used as a component B;
2) And (3) uniformly mixing the component A and the component B according to the mass ratio of 3.5.
Comparative example 1:
a solvent-free polyurea coating having the composition shown in the following table:
TABLE 5 composition table of solvent-free polyurea coatings
The preparation method of the solvent-free polyurea coating comprises the following steps:
1) Mixing polyaspartic acid ester resin F520 and castor oil-based polyether polyol D1145, dispersing for 10min at the rotation speed of 1000rpm, adding a dispersing agent BYK-9076, a defoaming agent KEPERPLO-768, an anti-settling agent BYK-410, a wetting agent BYK-333 and dipropylene glycol methyl ether acetate, continuing dispersing for 10min, adding aluminum tripolyphosphate, dispersing for 15min at the rotation speed of 2300rpm, adding conductive mica powder YJ and a 3A molecular sieve, uniformly mixing to obtain a component A, and taking polymethylene polyphenyl polyisocyanate PM-200 as a component B;
2) And uniformly mixing the component A and the component B according to the mass ratio of 3.5.
Comparative example 2:
a solvent-free polyurea coating having the composition shown in the following table:
TABLE 6 composition table of solventless polyurea coatings
The preparation method of the solvent-free polyurea coating comprises the following steps:
1) Mixing polyaspartic acid ester resin F520 and end amino polyether D2000, dispersing for 10min at the condition of the rotation speed of 1000rpm, adding a dispersant BYK-9076, a defoaming agent KEPERPLO-768, an anti-settling agent BYK-410, a wetting agent BYK-333 and dipropylene glycol methyl ether acetate, continuing to disperse for 10min, adding aluminum tripolyphosphate, dispersing for 15min at the condition of the rotation speed of 2300rpm, adding conductive mica powder YJ and a 3A molecular sieve, uniformly mixing to obtain a component A, and taking polymethylene polyphenyl polyisocyanate PM-200 as a component B;
2) And uniformly mixing the component A and the component B according to the mass ratio of 3.5.
Comparative example 3:
a solvent-free polyurea coating having the composition shown in the following table:
TABLE 7 composition table of solvent-free polyurea coatings
The preparation method of the solvent-free polyurea coating comprises the following steps:
1) Mixing castor oil-based polyether polyol D1145 and amino-terminated polyether D2000, dispersing for 10min at the rotation speed of 1000rpm, adding a dispersant BYK-9076, a defoaming agent KEPERPLO-768, an anti-settling agent BYK-410, a wetting agent BYK-333 and dipropylene glycol methyl ether acetate, continuing to disperse for 10min, adding aluminum tripolyphosphate, dispersing for 15min at the rotation speed of 2300rpm, adding conductive mica powder YJ and a 3A molecular sieve, uniformly mixing to obtain a component A, and taking polymethylene polyphenyl polyisocyanate PM-200 as a component B;
2) And (3) uniformly mixing the component A and the component B according to the mass ratio of 3.5.
Comparative example 4:
a commercially available waterborne epoxy static conductive anticorrosive coating (YHW 2502, guangzhou Jitai chemical Co., ltd.).
Note:
the information on some of the raw materials in examples 1 to 4 and comparative examples 1 to 3 is shown in the following table:
table 8 information on part of raw materials in examples 1 to 4 and comparative examples 1 to 3
And (3) performance testing:
1) The results of performance tests of the solvent-free polyurea coatings of example 1 and comparative examples 1 to 3 (preparation process of paint film: using a film scraper to scrape a solvent-free polyurea coating sample on a steel plate, controlling the thickness of a paint film to be 300 mu m, and drying at room temperature for 1.5h to obtain the paint film) as shown in the following table:
TABLE 9 Performance test results of the solvent-free polyurea coatings of example 1 and comparative examples 1 to 3
Note:
open time and tack-dry time: the test is carried out according to GB/T1728-2020 paint film and putty film drying time measuring method;
flexibility: the test was carried out with reference to "GB/T1731-1993 paint film flexibility assay";
impact resistance: the test is carried out according to GB/T1732-1993 paint film impact resistance test method;
adhesion force: the test is carried out according to the adhesion test of GB/T5210-2006 color paint and varnish by a pull-open method;
boiling water resistance: the test is carried out according to GB/T1733-1993 paint film water resistance test method;
acid, alkali and brine resistance: the test is carried out with reference to the method A in "determination of resistance to liquid media for paints and varnishes GB/T9274-1988";
salt spray resistance: the test is carried out with reference to "determination of the neutral salt spray resistance of the paints and varnishes of GB/T1771-2007".
As can be seen from Table 9:
compared with the prior art, the amino-terminated polyether is not added into the comparative example 1, so that the prepared coating has high brittleness and poor impact strength and flexibility;
comparative example 2 no castor oil based polyether polyol was added, the coating activation period was too short and no practical value was obtained;
compared with the prior art, the preparation method has the advantages that no polyaspartic acid ester resin is added in the comparative example 3, the chain segment flexibility of castor oil-based polyether polyol and amino-terminated polyether is large, the hardness of the prepared coating is too low, and the anti-penetration capability is poor, so that the boiling water resistance and the alkali resistance are poor;
example 1 the activation period of the coating was prolonged by adding castor oil based polyether polyol, the hardness of the coating was improved by adding polyaspartic acid resin containing rigid groups, and the flexibility of the coating was improved by adding amino terminated polyether containing soft segments;
in conclusion, the three resins, namely the polyaspartic acid ester resin, the castor oil-based polyether polyol and the amino-terminated polyether, have synergistic effect, so that the coating has excellent physical property and medium resistance.
2) The results of performance tests of the solvent-free polyurea coatings of examples 1 to 4 and the aqueous epoxy static electricity conductive anticorrosive coating of comparative example 4 (preparation process of paint film: paint samples were knife coated onto steel panels using a film scraper, the thickness of the paint film was controlled at 300 μm, and the paint film was dried at room temperature for 1.5 h) as shown in the following table:
TABLE 10 results of performance test of the coatings of examples 1 to 4 and comparative example 4
Note:
surface dry time and solid dry time: the test is carried out according to GB/T1728-2020 paint film and putty film drying time measuring method;
flexibility: the test was carried out with reference to "GB/T1731-1993 paint film flexibility assay";
impact resistance: the test is carried out by referring to a GB/T1732-1993 paint film impact resistance test method;
adhesion force: the test is carried out according to the GB/T5210-2006 paint and varnish pull-off method adhesion test;
surface resistivity: testing is carried out according to a GB/T1410-2006 test method for the volume resistivity and the surface resistivity of the solid insulating material;
boiling water resistance: the test is carried out according to GB/T1733-1993 paint film water resistance test method;
gasoline resistance: the test is carried out according to the technical standard of the anticorrosive coating in the SY/T0319-2012 steel storage tank liquid coating;
acid, alkali and brine resistance: the test is carried out according to the A method in GB/T9274-1988 determination of the resistance of the colored paint and the varnish to liquid medium;
salt spray resistance: the test is carried out according to the 'determination of the neutral salt spray resistance of GB/T1771-2007 colored paint and varnish';
index value: the performance index of the static conductive anticorrosive coating in the technical standard of the anticorrosion engineering of the GB/T50393-2017 steel oil storage tank.
As can be seen from table 10:
after the anticorrosive static-conductive solvent-free polyurea coating of the embodiments 1 to 4 is formed into a film, the gasoline, acid, alkali, salt and salt fog resistant time of the film can reach more than 720h, the boiling water resistant time can reach more than 48h, the anticorrosive performance is excellent, and the anticorrosive performance is obviously superior to that of a commercial waterborne epoxy static-conductive anticorrosive coating;
the surface resistivity of the paint film formed by the anticorrosive static-conductive solvent-free polyurea paint of the embodiments 1 to 4 is in an index range, and the paint film has excellent static-conductive performance;
the surface drying time and the actual drying time of the corrosion-resistant and static-conductive solvent-free polyurea coating in the embodiments 1 to 4 are shorter than those of the commercial waterborne epoxy static-conductive anticorrosive coating, the time cost is reduced, the thickness of a dry film sprayed by the commercial waterborne epoxy static-conductive anticorrosive coating at one time is only about 50 micrometers, and the specified 250 to 350 micrometers can be achieved only by multiple spraying, while the solid content of the corrosion-resistant and static-conductive solvent-free polyurea coating in the embodiments 1 to 4 is more than 95%, and the viscosity of the coating is moderate, so that the thickness of the dry film subjected to one-time blade coating by using a 300-micrometer film scraper can achieve the specified 250 to 350 micrometers, and the construction efficiency is obviously improved;
in general, the solvent-free polyurea coating for preventing corrosion and conducting static electricity has excellent corrosion resistance and static electricity conducting performance, and has higher construction efficiency and lower time cost than the commercial waterborne epoxy static electricity conducting anticorrosive coating.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. An anticorrosion static-conducting solvent-free polyurea coating is composed of a component A and a component B, and is characterized in that:
the component A comprises the following raw materials in parts by mass:
polyaspartic acid ester resin: 10-20 parts;
castor oil based polyether polyol: 20-30 parts;
amino-terminated polyether: 8-12 parts;
antirust pigment and filler: 10-15 parts;
conductive filler: 20-30 parts;
dispersing agent: 0.8 to 1.2 portions;
defoaming agent: 0.5 to 0.9 portion;
anti-settling agent: 0.05 to 0.3 portion;
wetting agent: 0.1 to 0.3 portion;
diluent agent: 3-4 parts;
and (3) water removal agent: 4-7 parts;
the component B comprises the following raw materials in parts by mass:
isocyanate curing agent: 20-30 parts;
the mass ratio of the component A to the component B is 3;
the ratio of the total equivalents of amino and hydroxyl in the component A to the equivalents of isocyanate groups in the component B is 1.1-1;
the isocyanate curing agent is aromatic isocyanate, and the aromatic isocyanate is at least one of polymethylene polyphenyl polyisocyanate and diphenylmethane-4, 4' -diisocyanate;
the diluent is an ether ester solvent.
2. The corrosion-resistant, static-conductive solvent-free polyurea coating of claim 1, wherein: the anti-rust pigment filler is at least one of aluminum tripolyphosphate, zinc aluminum phosphate, molybdate and zinc phosphate.
3. The solvent-free polyurea coating material according to any one of claims 1 to 2, wherein: the conductive filler is conductive mica powder.
4. The solvent-free polyurea coating material according to any one of claims 1 to 2, wherein: the dispersant is an alkyl ammonium salt copolymer; the defoaming agent is an organic silicon defoaming agent; the wetting agent is polyether modified polydimethylsiloxane.
5. The solvent-free polyurea coating material according to any one of claims 1 to 2, wherein: the water removing agent is a molecular sieve.
6. The method for preparing the corrosion-and static-conductive solvent-free polyurea coating according to any one of claims 1 to 5, comprising the steps of:
1) Uniformly mixing polyaspartic acid ester resin, castor oil-based polyether polyol and amino-terminated polyether, adding a dispersing agent, a defoaming agent, an anti-settling agent, a wetting agent and a diluent, uniformly mixing, adding an anti-rust pigment and filler, uniformly mixing, adding a conductive filler and a water removing agent, uniformly mixing to obtain a component A, and taking an isocyanate curing agent as a component B;
2) And uniformly mixing the component A and the component B to obtain the solvent-free polyurea coating with corrosion resistance and static conduction.
7. Use of the corrosion-and static-conductive solvent-free polyurea coating according to any one of claims 1 to 5 for the corrosion protection of metals.
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| WO2015100583A1 (en) * | 2013-12-31 | 2015-07-09 | 常熟市方塔涂料化工有限公司 | Solvent-free electrostatic conductive paint and preparation method therefor |
| CN103834283A (en) * | 2014-03-05 | 2014-06-04 | 上海正欧实业有限公司 | Polyurea wear-resistant coating material with anti-static function and preparation method thereof |
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