CN100584911C - High temperature resistant anti-corrosion modified epoxy silicone coating - Google Patents
High temperature resistant anti-corrosion modified epoxy silicone coating Download PDFInfo
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- CN100584911C CN100584911C CN200910008949A CN200910008949A CN100584911C CN 100584911 C CN100584911 C CN 100584911C CN 200910008949 A CN200910008949 A CN 200910008949A CN 200910008949 A CN200910008949 A CN 200910008949A CN 100584911 C CN100584911 C CN 100584911C
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Abstract
The invention relates to a high-temperature resistant anti-corrosion modified epoxy organic silicon coating and a preparation method. The coating uses organic phosphate and fluoropolymer to modify epoxy organic silicon resin which originally has excellent high-temperature resistant and anti-corrosion properties; with organic phosphate group introduced, not only the high-temperature resistance of resin is improved, but also the later anticorrosion property of the coating can be improved to certain extent. In the film forming process of the coating, the organic phosphate group and substrate metal form a compact phosphate protective film, thus passivating metal surface, preventing water molecules and salt ions from being contacted with metal and further leading the coating to have excellent anticorrosion function. With the fluoropolymer with high-temperature resistance and chemical corrosion resistance introduced, the polymerization between the fluoropolymer and active organic silicon group can distinctly improve the high-temperature resistance of resin. The matched use of the modified epoxy organic silicon resin and a high-temperature resistant pigment can lead the coating to not only maintain proper physical mechanical property, but also have excellent anticorrosion performance under the high temperature condition of 350 DEG C.
Description
Technical field
The present invention relates to a kind of fire resistant anticorrosive paint, particularly anti-350 ℃ of pyritous modified epoxy organosilicon anticorrosive coatings and preparation method thereof.
Background technology
In recent years, along with the develop rapidly of new and high technology, more and more higher to the requirement of high-temperature-resistant structure material and high-temperature resistant coating, and facts have proved, high-temperature structural material will be accomplished existing good hot strength, possesses good anti-oxidant, corrosion resistance again and but compares difficulty, and the expense costliness.By contrast, high-temperature resistant coating has but possessed above two kinds of advantages, both can improve the high thermal resistance of material, possesses certain erosion resistance again.So since the 1950's, people are in the ascendant always to the research of high-temperature resistant coating, and obtained remarkable progress.
High-temperature resistant coating generally be meant temperature in paint film nondiscoloration more than 200 ℃, do not come off, still can keep the coating of suitable physical and mechanical properties.High-temperature resistant coating is of a great variety, and the heat resisting temperature of traditional inorganic type high-temperature resistant coating can reach 400-1000 ℃, even higher.Inorganic type high-temperature resistant coating flame resistivity is good, hardness is high, but paint film is more crisp, and water tolerance is bad before completely solidified, and is also strict to the requirement of substrate treatment.At present, generally adopt the organic coating of the method preparation high comprehensive performance that in organic resin, adds mineral filler.That organic anti-corrosive coating commonly used has is epoxide coal bituminous, epoxy glass flake and multi-functional rust-inhibiting paint etc., but heatproof has only 150 ℃ usually, and degraded or carbonization can take place during higher temperature, causes coating to lose efficacy.In former study, mainly lay particular emphasis on the thermotolerance or the erosion resistance of coating, and to both high temperature resistant corrosion resistant coating research was less.Patent 200710098668.4 discloses a kind of epoxy organosilicon anticorrosive coating, and the salt fog cumulative time can reach 360h, be not improved simultaneously aspect thermotolerance and the erosion resistance.
Summary of the invention
The present invention seeks to overcome the shortcoming of coating in the past, a kind of high temperature resistant anticorrosion modified epoxy organosilicon coating and preparation method thereof is provided, this coating can keep suitable physical and mechanical properties can have good Corrosion Protection again under hot environment.Phosphoric acid ester and fluorine modified epoxy organosilicon resin have superpower fire resistant anticorrosive performance.The main body of resin is an epoxy silicone resin, epoxy silicone resin itself has good fire resistant anticorrosive performance, the thermodynamic stability of the Si-O-Si key in its structure is good, can improve coating heat resistance, add epoxide group and improve the snappiness of resin, improve greatly with the sticking power of base material.Introduce bound phosphate groups; active organosilicon group in itself and the epoxy silicone resin reacts; also improved the heat resistance of resin; later stage Corrosion Protection for coating also increases simultaneously; coating is in film process, and bound phosphate groups and substrate metal form fine and close phosphate coating, makes the metallic surface that passivation take place; can prevent water molecules and salt ion and metallic contact, thereby make coating have good corrosion proof function.Introduce fluoro-containing group, the characteristics such as chemical resistance that itself have high temperature resistant, oil resistant, anti-solvent, hydrophobic, excellent electric insulation and height, can significantly improve the resistance to elevated temperatures of resin with the polymerization of active organosilicon group, and fluoro-containing group can reduce the surface tension of coating, improve water tolerance, thereby the corrosion resistance nature of coating is improved greatly.Phosphoric acid ester and fluorine modified epoxy organosilicon resin and high-temperature resisting pigment are used, and can reach the ideal effect.
For realizing this purpose, the present invention has adopted following technical scheme:
Prescription: (following unit is a weight part)
A, phosphoric acid ester and fluorine modified epoxy organosilicon resin formula
Epoxy silicone resin 100
Fluorochemical monomer 1～5
Phosphate ester monomer 2～10
Dimethylbenzene 20～50
B, formulation for coating material
Phosphoric acid ester and fluorine modified epoxy organosilicon resin 30～70
High-temperature resisting pigment 40～70
Filler 10～25
Auxiliary agent 0～5
Solvent 10～25
Coating preparation technology:
A, phosphoric acid ester and fluorine modified epoxy organosilicon resin preparation process
In the reaction vessel that thermometer, stirring, backflow and Dropping feeder are housed, add epoxy silicone resin and fluorochemical monomer, open stirring and be warming up to 70～90 ℃, in 2～3 hours, evenly drip the mixed solution of phosphate ester monomer and dimethylbenzene, after dropwising, be incubated 3～4 hours and finish the synthetic of resin.
The preparation of b, coating
Phosphoric acid ester and fluorine modified epoxy organosilicon resin, high-temperature resisting pigment, filler and solvent etc. are mixed and sand milling below 50 microns, adds auxiliary agent to fineness then, stirring obtains coating.Made coating application behind workpiece, is solidified down at 180 ℃ earlier and dried by the fire under 230 ℃ 0.5 hour then in 1 hour again, can reach optimum performance.
Its structure of described phosphate ester monomer
Described fluorochemical monomer is the perfluor alkyl ethide methacrylic ester, and its structure is CH
2=CR
1COO (CH
2)
m(CF
2CF
2)
nCF
3N=0～5;
Described high-temperature resisting pigment is that enamel is black, the mixture of aluminium powder, zinc powder and carbon black; Described filler is mica powder and talcous mixture; Auxiliary agent is a thermo-stabilizer; Solvent is the mixture of dimethylbenzene and butanols.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but is not limited to this.
In the reaction vessel that thermometer, stirring, backflow and Dropping feeder are housed, add 3 parts of 100 parts of epoxy silicone resin ES-06 and fluorochemical monomers, open stirring and be warming up to 70～90 ℃, in 2～3 hours, evenly drip the mixed solution of 40 parts of phosphate ester monomer PAM-1008 part and dimethylbenzene, after dropwising, be incubated 3～4 hours and finish the synthetic of resin, make phosphoric acid ester and fluorine modified epoxy organosilicon resin ESP-100.
Use phosphate ester monomer PAM-200 and PAM-300 to prepare phosphoric acid ester and fluorine modified epoxy organosilicon resin ESP-200 and ESP-300 respectively, the preparation method is identical with ESP-100.
Table 1 (embodiment unit is a weight part in the table)
| Component | Material name | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples |
| Resin | ESP-100 ESP-200 ESP-300 Es-06 | 40 / 0 / | / 40 / / | / / 40 / | 20 20 / / | 20 / 20 / | / 20 20 / | / / / 40 |
| High-temperature resisting pigment | Enamel is deceived aluminium powder zinc powder carbon black | 30 5 8 2 | 30 5 8 2 | 30 5 8 2 | 30 5 8 2 | 40 5 5 0 | 30 5 8 2 | 30 5 8 2 |
| Filler | The mica powder talcum powder | 12 8 | 12 8 | 12 8 | 12 8 | 12 8 | 12 8 | 12 8 |
| Auxiliary agent | Thermo-stabilizer | 0.5 | 0.5 | 0.5 | 0.5 | 0.3 | 0.5 | 0.5 |
| Solvent | The dimethylbenzene butanols | 12 5 | 12 5 | 12 5 | 12 5 | 12 5 | 12 5 | 12 5 |
The raw material that uses in the embodiment of the invention: phosphate ester monomer (PAM-100, PAM-200, PAM-300), French Rhodia produces; Epoxy silicone resin ES-06, the Wujiang City, Jiangsu Province resin company limited that makes a concerted effort produces; Fluorochemical monomer is the perfluor alkyl ethide methacrylic ester, and too general (Shanghai) fluorine chemical trading company produces; It is that Shanghai Tianguang Chemical Factory produces that enamel is deceived; The barium zinc heat stabilizer is that Changzhou Jia Ren standing grain chemistry company limited produces.
Technology: by above-mentioned prescription requirement resin, pigment, filler and solvent etc. are mixed and sand milling to fineness below 50 microns, add auxiliary agent then, be adjusted to appropriate viscosity, obtain coating.
Made paint spay-coating in steel plate, is solidified 1 hour 0.5 hour (dried film thickness is controlled at 40 ± 5 μ m) of 230 ℃ of bakings then down at 180 ℃, under 350 ℃, carry out 5 hours high temperature resistant experiment then.Model after high temperature resistant experiment is drawn fork by the relevant regulations among standard GB/T 1771-2007 and to model, does salt spray resistance and detects.Detected result sees Table 2.
Table 2
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples |
| Anti-350 ℃ of high temperature coating surface situation after 5 hours | The surface intact, paint film do not have come off, no variable color | The surface intact, paint film do not have come off, no variable color | The surface intact, paint film do not have come off, no variable color | The surface intact, paint film do not have come off, no variable color | The surface intact, paint film do not have come off, no variable color | The surface intact, paint film do not have come off, no variable color | The intact nothing of paint film comes off, a little variable color |
| Salt fog resistance, day | 7 days cut both sides corrosion 2mm | 8 days cut both sides corrosion 2mm | 8 days cut both sides corrosion 2mm | 9 days cut both sides corrosion 2mm | 5 days cut both sides corrosion 2mm | 11 days cut both sides corrosion 2mm | 1 day cut both sides corrosion 2mm |
As can be seen from Table 2, the over-all properties (resistance to elevated temperatures, salt fog resistance) of phosphoric acid ester of being developed and fluorine modified epoxy organosilicon fire resistant anticorrosive paint is better than common epoxy organosilicon coating.
Claims (5)
1. high temperature resistant anticorrosion modified epoxy organosilicon coating, comprise: 30～70 parts of phosphoric acid ester and fluorine modified epoxy organosilicon resins, 40～70 parts of high-temperature resisting pigments, 10～25 parts of fillers, 0～5 part of auxiliary agent, 10～25 parts of solvents, it is characterized in that described phosphoric acid ester and fluorine modified epoxy organosilicon resin be by 100 parts of epoxy silicone resins, 1～5 part of fluorochemical monomer, 2～10 parts of phosphate ester monomers and dimethylbenzene are made for 20～50 parts.
2. coating according to claim 1 is characterized in that, described fluorochemical monomer is the perfluor alkyl ethide methacrylic ester.
3. coating according to claim 1 and 2 is characterized in that the general structure of described phosphate ester monomer is
4. coating according to claim 1 is characterized in that, described auxiliary agent is a zinc barium thermo-stabilizer.
5. the preparation method of each described coating of claim 1-4 is characterized in that, its preparation technology comprises:
The preparation of a, phosphoric acid ester and fluorine modified epoxy organosilicon resin
Thermometer is being housed, add epoxy silicone resin and fluorochemical monomer in the reaction vessel of stirring, backflow and Dropping feeder, open stirring and be warming up to 70～90 ℃, in 2～3 hours, evenly drip the mixture of phosphate ester monomer and dimethylbenzene, after dropwising, be incubated 3～4 hours and finish the synthetic of resin;
The preparation of b, coating
Phosphoric acid ester and the even also sand milling of fluorine modified epoxy organosilicon resin, high-temperature resisting pigment, filler and solvent below 50 microns, are added auxiliary agent to fineness then, and stirring obtains coating.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910008949A CN100584911C (en) | 2009-02-13 | 2009-02-13 | High temperature resistant anti-corrosion modified epoxy silicone coating |
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|---|---|---|---|
| CN200910008949A CN100584911C (en) | 2009-02-13 | 2009-02-13 | High temperature resistant anti-corrosion modified epoxy silicone coating |
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| CN100584911C true CN100584911C (en) | 2010-01-27 |
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| CN102069944A (en) * | 2010-12-13 | 2011-05-25 | 广州龙驰包装材料有限公司 | Process for manufacturing acid- and sulfur-resistant snap lids |
| CN102060126A (en) * | 2010-12-13 | 2011-05-18 | 广州龙驰包装材料有限公司 | Manufacturing process for high temperature-resistant and high pressure-resistant easy-open lid |
| CN102286236B (en) * | 2011-07-25 | 2013-05-01 | 苏州吉人漆业有限公司 | Petroleum resin modified long-acting anticorrosion epoxy zinc-free coating |
| CN102337075A (en) * | 2011-10-09 | 2012-02-01 | 常州豪邦纳米科技涂料有限公司 | High temperature resistant primer for stainless steel |
| CN102391727B (en) * | 2011-10-09 | 2013-12-04 | 常州豪邦纳米科技涂料有限公司 | Transparent paint for stainless steel |
| CN103965776B (en) * | 2013-01-29 | 2016-12-28 | 惠州市华昱美实业有限公司 | A kind of high temperature resistant heat insulation anticorrosive coating |
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| CN109971224A (en) * | 2017-12-28 | 2019-07-05 | 东莞市广信知识产权服务有限公司 | A kind of new Heat Resistant Coating |
| CN108384412A (en) * | 2018-03-22 | 2018-08-10 | 苏州新区特氟龙塑料制品厂 | A kind of high heat-proof epoxy coating |
| CN109266154B (en) * | 2018-07-26 | 2020-08-04 | 广东鑫皇冠新材料有限公司 | Mirror back aluminizing protective coating and preparation method thereof |
| CN111826084A (en) * | 2020-07-17 | 2020-10-27 | 甘肃远东城市管道有限责任公司 | High-temperature-resistant special anticorrosive paint for directly-buried heat-insulating pipe |
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