CN104403387A - Light-cured metal anticorrosive coating - Google Patents
Light-cured metal anticorrosive coating Download PDFInfo
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- CN104403387A CN104403387A CN201410634443.6A CN201410634443A CN104403387A CN 104403387 A CN104403387 A CN 104403387A CN 201410634443 A CN201410634443 A CN 201410634443A CN 104403387 A CN104403387 A CN 104403387A
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- trimethoxy silane
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Abstract
The invention discloses a light-cured metal anticorrosive coating. According to the invention, long-chain alkyl and methacrylate functional group modified one-dimensional nano-attapulgite clay is added into a mixed liquor of acrylate resin, a leveling agent and a photoinitiator, so as to prepare an UV cured nano-composite coating for corrosion protection of metals. The preparation technology of the coating is simple and practical and has high performance cost ratio. The formula contains no organic solvent or reactive diluents and is green and environmentally friendly. Attapulgite fiber is dispersed well in a polymer matrix. The light-cured composite coating has good wet adhesion. Corrosion protection performance of the light-cured composite coating is greatly raised, and its mechanical property and heat resistance are also enhanced obviously. The light-cured composite coating has a wide industrial application prospect.
Description
Technical field
The present invention relates to photocuring metal anti-corrosive paint, belong to protective system field, light-cured acrylate/attapulgite clay nano composite dope that to be specifically related to the fibrous attapulgite clay of modification be addO-on therapy.
Background technology
Metallic corrosion brings huge financial loss and harm to social development, is equivalent to more than 20% of metal production then because corroding the metallic substance scrapped every year according to estimates, accounts for 4.2% of gross national product.Therefore, the anti-corrosive treatment of metal plays very important role in national economy field.Anticorrosion with coat erosion technology is then most economical in numerous anticorrosion technique, most widely used guard method.
Relative to the kind such as solvent based coating, water-borne coatings, the features such as photo-cured coating has that solidification rate is fast, practicality is wide, less energy-consumption and environmental friendliness, receive the extensive concern of society in recent years.Although current industrial widely used esters of acrylic acid photo-cured coating has excellent over-all properties, but specific problem is caused to the coating of metal base, as large in its photocuring post-shrinkage ratio, the string stress produced is difficult to discharge completely, cause film adhesive and impact resistance poor, exist simultaneously hardness low, wear no resistance, the shortcoming such as thermal stability is not enough, make it be extremely restricted in the application in anticorrosive metal field.US Patent No. 5128387, Japanese Patent JP2001172554 and world patent WO03/022945 employ if the acids tackifier such as phosphoric acid are to improve the cohesive force between light solidifying coating and metal base.But the Corrosion Protection of such acid binding agent to coating has negative effect, cause the corrosion protection performance of coating not enough.
Summary of the invention
The object of the invention is to: a kind of photocuring metal anti-corrosive paint is provided, it is the light-cured acrylate/attapulgite clay nano composite dope that is functional stuffing with the attapulgite clay of alkyl and methacrylate based difunctionalization, preparation is simple, low cost, hardness is high, and wear resistance is good, strong adhesion, Corrosion Protection is high, environmental protection.
The technology used in the present invention solution is: first carry out organically-modified to attapulgite clay, obtain the Attapulgite of alkyl and methacrylate based difunctionalization, then added in the mixed solution of acrylate, flow agent and light trigger, obtained photocuring metal anti-corrosive paint; The weight percent of the constitutive material of this protective system is: acrylate resin 79 ~ 94.9%, Attapulgite 2 ~ 10%, flow agent 0.1 ~ 1%, free radical photo-initiation 3 ~ 10%.
Wherein, described acrylate resin is selected from the one in bifunctional acrylate, bifunctional methacrylic ester, trifunctional group acrylate, trifunctional methacrylic ester, four-functional group propenoic acid ester, four-functional group methacrylic ester.
Wherein, described Attapulgite is through alkyl and the two modification of methacrylate functional, and its preparation process is as follows:
(1) >=200 object attapulgite clay 100g are joined in the hydrochloric acid soln of 0.5 ~ 5 mol/L of 2500mL, at 20 ~ 120 DEG C of activation treatment 2 ~ 48h, filter, deionized water wash is to the PH ≈ 7 of filtrate, dry rear pulverizing, obtain activation attapulgite clay for 80 DEG C;
(2) the activation attapulgite clay 10g of step (1) is added alkyl silane, γ-methacryloxypropyl trimethoxy silane (KH-570) and volume of toluene than being (1-10): (1-10): in the 200mL mixing solutions of (180-198), 110 DEG C of backflow 12h, ethanol, washing with acetone, 80 DEG C of vacuum-drying 24h, obtain Attapulgite.
Wherein, described alkyl silane refers to butyl trimethoxy silane, trimethoxysilane, octyl group Trimethoxy silane, isooctyltrimethoxysi,ane, certain herbaceous plants with big flowers base Trimethoxy silane, dodecyltrimethoxysilane, hexadecyl trimethoxy silane, octadecyl trimethoxysilane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, ethyl triethoxysilane, propyl-triethoxysilicane, isopro-pyltriethoxysilane, butyl triethoxyl silane, isobutyl triethoxy silane, octyltri-ethoxysilane, isooctyltriethoxysilane, certain herbaceous plants with big flowers ethyl triethoxy silicane alkane, dodecyl triethoxysilane, hexadecyl, one in octadecyltriethoxy silane and phenyl triethoxysilane.
Wherein, described flow agent refers to the one in Siloxane-Oxyalkylene Copolymers, acrylic polyester modified polyorganosiloxane or reactive organo-siloxane.
Wherein, described free radical photo-initiation refers to 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyciohexyl benzophenone, 2-hydroxy-2-methyl-1-to hydroxyethyl ether phenyl-acetone, 4-to toluene sulfydryl benzophenone, 2; one in 4,6-trimethylbenzoy-dipheny phosphorus oxide, benzophenone, isopropyl thioxanthone.
Compared with prior art, the present invention has the following advantages:
1, the present invention have chosen abundant raw material and low-cost attapulgite clay fills out agent as functional adding, reduce coating cost, make this coating have higher cost performance, the attapulgite clay rod crystalline substance simultaneously with special fiber club shaped structure effectively can improve the fracture toughness property of coating.
2, by carrying out alkyl and methacrylate based difunctionalization to attapulgite clay, improve its dispersiveness in coating, impart its polymerizable characteristic, thus the thermostability of coating and corrosion protection ability increasing greatly.
3, the present invention not only avoids with an organic solvent, does not even use the photocuring reactive thinner with volatility and certain toxicity, makes coating well embody environmental protection characteristic.
Embodiment
Below by embodiment, technical scheme of the present invention is further described, but content not thereby limiting the invention.
Embodiment 1: >=200 object attapulgite clay 100g are joined in the hydrochloric acid soln of 2500mL 0.5 mol/L, at 120 DEG C of activation treatment 24h, filter, deionized water wash is to the PH ≈ 7 of filtrate, 80 DEG C of oven dry, pulverize after take 10g join phenyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane (KH-570) and volume of toluene than be (10:10:180) 200mL mixing solutions in, 110 DEG C of backflow 12h, ethanol, washing with acetone, 80 DEG C of vacuum-drying 24h, obtain Attapulgite; Take 3 grams of Attapulgites, join 86 grams of Bifunctionalized acrylate resin (SARTOMER, SR348C), in the mixed solution of 10 grams of light triggers (2-hydroxy-2-methyl-1-phenyl-acetone) and 1 gram of flow agent (BYK371), stir 20 minutes, obtain photo-cured coating.
Coating performance testing method: under normal temperature and pressure, above-mentioned coating is coated in uniformly on the tinplate base material after ethanol and washing with acetone are also dried; through UV curing solidification (10 ms/min; the paint film of obtained coat-thickness ~ 20 micron; place and to carry out non-corroding protective after 4 hours and can detect (the salt spray test of 5% sodium chloride solution, ISO 9227).
Performance: have no etch pit and coating change after the salt spray test of 48 hours.
Embodiment 2: >=200 object attapulgite clay 100g are joined in the hydrochloric acid soln of 2500mL 1 mol/L, at 110 DEG C of activation treatment 48h, filter, deionized water wash is to the PH ≈ 7 of filtrate, 80 DEG C of oven dry, pulverize after take 10g join n-octyl group Trimethoxy silane, γ-methacryloxypropyl trimethoxy silane (KH-570) and volume of toluene than be (5:5:190) 200mL mixing solutions in, 110 DEG C of backflow 12h, ethanol, washing with acetone, 80 DEG C of vacuum-drying 24h, obtain Attapulgite; Take 2 grams of Attapulgites, join 94.5 grams of Bifunctionalized acrylate resin (SARTOMER, SR802), in the mixed solution of 3 grams of light triggers (2-hydroxy-2-methyl-1-phenyl-acetone) and 0.5 gram of flow agent (BYK 333), stir 20 minutes, obtain photo-cured coating.
Coating performance testing method: under normal temperature and pressure, above-mentioned coating is coated in uniformly on the tinplate base material after ethanol and washing with acetone are also dried; through UV curing solidification (10 ms/min; the paint film of obtained coat-thickness ~ 20 micron; place and to carry out non-corroding protective after 4 hours and can detect (the salt spray test of 5% sodium chloride solution, ISO 9227).
Performance: have no etch pit and coating change after the salt spray test of 48 hours.
Embodiment 3: >=200 object attapulgite clay 100g are joined in the hydrochloric acid soln of 2500mL 2mol/L, at 80 DEG C of activation treatment 12h, filter, deionized water wash is to the PH ≈ 7 of filtrate, 80 DEG C of oven dry, pulverize after take 10g join n-octyl group Trimethoxy silane, γ-methacryloxypropyl trimethoxy silane (KH-570) and volume of toluene than be (1:1:198) 200mL mixing solutions in, 110 DEG C of backflow 12h, ethanol, washing with acetone, 80 DEG C of vacuum-drying 24h, obtain Attapulgite; Take 10 grams of Attapulgites, join 83.5 gram of four functionalized acrylate resins (SARTOMER, SR295), in the mixed solution of 6 grams of light triggers (4-is to toluene sulfydryl benzophenone) and 0.5 gram of flow agent (BYK371), stir 20 minutes, obtain photo-cured coating.
Coating performance testing method: under normal temperature and pressure, above-mentioned coating is coated in uniformly on the tinplate base material after ethanol and washing with acetone are also dried; through UV curing solidification (10 ms/min; the paint film of obtained coat-thickness ~ 20 micron; place and to carry out non-corroding protective after 4 hours and can detect (the salt spray test of 5% sodium chloride solution, ISO 9227).
Performance: have a small amount of etch pit after the salt spray test of 48 hours, but have no coating change.
Embodiment 4: >=200 object attapulgite clay 100g are joined in the hydrochloric acid soln of 2500mL 5 mol/L, at 20 DEG C of activation treatment 2h, filter, deionized water wash is to the PH ≈ 7 of filtrate, 80 DEG C of oven dry, pulverize after take 10g join dodecyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane (KH-570) and volume of toluene than be (10:5:185) 200mL mixing solutions in, 110 DEG C of backflow 12h, ethanol, washing with acetone, 80 DEG C of vacuum-drying 24h, obtain Attapulgite; Take 5 grams of Attapulgites; join 90.8 grams of trifunctional acrylate resin (SARTOMER; SR492), 4 grams of light triggers (2; 4; 6-trimethylbenzoy-dipheny phosphorus oxide) and 0.2 gram of flow agent (KEPER-153) mixed solution in; stir 20 minutes, obtain photo-cured coating.
Coating performance testing method: under normal temperature and pressure, above-mentioned coating is coated in uniformly on the tinplate base material after ethanol and washing with acetone are also dried; through UV curing solidification (10 ms/min; the paint film of obtained coat-thickness ~ 20 micron; place and to carry out non-corroding protective after 4 hours and can detect (the salt spray test of 5% sodium chloride solution, ISO 9227).
Performance: have no etch pit and coating change after the salt spray test of 48 hours.
Coating performance testing method: under normal temperature and pressure, above-mentioned coating is coated in uniformly on the tinplate base material after ethanol and washing with acetone are also dried; through UV curing solidification (10 ms/min; the paint film of obtained coat-thickness ~ 20 micron; place and to carry out non-corroding protective after 4 hours and can detect (the salt spray test of 5% sodium chloride solution, ISO 9227).
Performance: have no etch pit and coating change after the salt spray test of 48 hours.
Comparative example 1: by 89 grams of acrylate resins (SARTOMER, SR348C), 10 grams of light triggers (2-hydroxy-2-methyl-1-phenyl-acetone) and 1 gram of flow agent (BYK371) mixing, stir 20 minutes, obtain photo-cured coating.
Coating performance testing method: under normal temperature and pressure, above-mentioned coating is coated in uniformly on the tinplate base material after ethanol and washing with acetone are also dried; through UV curing solidification (10 ms/min; the paint film of obtained coat-thickness ~ 20 micron; place and to carry out non-corroding protective after 4 hours and can detect (the salt spray test of 5% sodium chloride solution, ISO 9227).
Performance: after the salt spray test of 48 hours, coating is separated with tinplate base material, there is a large amount of rusty stain in tinplate base material.
Comparative example 2: >=200 object attapulgite clay 100g are joined in the hydrochloric acid soln of 2500mL 0.5 mol/L, at 120 DEG C of activation treatment 24h, filter, deionized water wash is to the PH ≈ 7 of filtrate, 80 DEG C of oven dry, pulverize after take 3 grams, join in the mixed solution of 86 grams of acrylate resins (SARTOMER, SR348C), 10 grams of light triggers (2-hydroxy-2-methyl-1-phenyl-acetone) and 1 gram of flow agent (BYK371), stir 20 minutes, obtain photo-cured coating.
Coating performance testing method: under normal temperature and pressure, above-mentioned coating is coated in uniformly on the tinplate base material after ethanol and washing with acetone are also dried; through UV curing solidification (10 ms/min; the paint film of obtained coat-thickness ~ 20 micron; place and to carry out non-corroding protective after 4 hours and can detect (the salt spray test of 5% sodium chloride solution, ISO 9227).
Performance: after the salt spray test of 48 hours, separation phenomenon does not appear in coating and tinplate base material, but some rusty stains appear in tinplate base material.
Claims (6)
1. photocuring metal anti-corrosive paint, is characterized in that the weight percent of the constitutive material of this protective system is: acrylate resin 79 ~ 94.9%, Attapulgite 2 ~ 10%, flow agent 0.1 ~ 1%, free radical photo-initiation 3 ~ 10%.
2. photocuring metal anti-corrosive paint according to claim 1, is characterized in that: described acrylate resin is selected from the one in bifunctional acrylate, bifunctional methacrylic ester, trifunctional group acrylate, trifunctional methacrylic ester, four-functional group propenoic acid ester, four-functional group methacrylic ester.
3. photocuring metal anti-corrosive paint according to claim 1, is characterized in that: described Attapulgite is through alkyl and the two modification of methacrylate functional, and its preparation process is as follows:
(1) >=200 object attapulgite clay 100g are joined in the hydrochloric acid soln of 0.5 ~ 5 mol/L of 2500mL, at 20 ~ 120 DEG C of activation treatment 2 ~ 48h, filter, deionized water wash is to the PH ≈ 7 of filtrate, dry rear pulverizing, obtain activation attapulgite clay for 80 DEG C;
(2) the activation attapulgite clay 10g of step (1) is added alkyl silane, γ-methacryloxypropyl trimethoxy silane (KH-570) and volume of toluene than being (1-10): (1-10): in the 200mL mixing solutions of (180-198), 110 DEG C of backflow 12h, ethanol, washing with acetone, 80 DEG C of vacuum-drying 24h, obtain Attapulgite.
4. photocuring metal anti-corrosive paint according to claim 3, it is characterized in that: described alkyl silane refers to butyl trimethoxy silane, trimethoxysilane, octyl group Trimethoxy silane, isooctyltrimethoxysi,ane, certain herbaceous plants with big flowers base Trimethoxy silane, dodecyltrimethoxysilane, hexadecyl trimethoxy silane, octadecyl trimethoxysilane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, ethyl triethoxysilane, propyl-triethoxysilicane, isopro-pyltriethoxysilane, butyl triethoxyl silane, isobutyl triethoxy silane, octyltri-ethoxysilane, isooctyltriethoxysilane, certain herbaceous plants with big flowers ethyl triethoxy silicane alkane, dodecyl triethoxysilane, hexadecyl, one in octadecyltriethoxy silane and phenyl triethoxysilane.
5. photocuring metal anti-corrosive paint according to claim 1, is characterized in that: described flow agent refers to the one in Siloxane-Oxyalkylene Copolymers, acrylic polyester modified polyorganosiloxane or reactive organo-siloxane.
6. photocuring metal anti-corrosive paint according to claim 1; it is characterized in that: described free radical photo-initiation refers to 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyciohexyl benzophenone, 2-hydroxy-2-methyl-1-to hydroxyethyl ether phenyl-acetone, 4-to toluene sulfydryl benzophenone, 2; one in 4,6-trimethylbenzoy-dipheny phosphorus oxide, benzophenone, isopropyl thioxanthone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410634443.6A CN104403387B (en) | 2014-11-12 | Photocuring metal anti-corrosive paint |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410634443.6A CN104403387B (en) | 2014-11-12 | Photocuring metal anti-corrosive paint |
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| Publication Number | Publication Date |
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| CN104403387A true CN104403387A (en) | 2015-03-11 |
| CN104403387B CN104403387B (en) | 2017-01-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601794A (en) * | 2015-11-16 | 2016-05-25 | 复旦大学 | Sepiolite-acrylic ester compound light curing material, and preparation method thereof |
| CN106111029A (en) * | 2016-07-12 | 2016-11-16 | 淮阴工学院 | A kind of preparation method of clay/polyacrylate composite hollow microsphere |
| CN106894007A (en) * | 2017-02-28 | 2017-06-27 | 河南工程学院 | A kind of Photosensitive chromium-free passivation liquid based on electrospun fibers and preparation method thereof |
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Patent Citations (6)
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| CN101007925A (en) * | 2007-01-18 | 2007-08-01 | 同济大学 | Anticorrosion paint containing aniline copolymer and its preparation and use |
| CN101104750A (en) * | 2007-08-03 | 2008-01-16 | 西安理工大学 | Water anticorrosive paint and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105601794A (en) * | 2015-11-16 | 2016-05-25 | 复旦大学 | Sepiolite-acrylic ester compound light curing material, and preparation method thereof |
| CN106111029A (en) * | 2016-07-12 | 2016-11-16 | 淮阴工学院 | A kind of preparation method of clay/polyacrylate composite hollow microsphere |
| CN106111029B (en) * | 2016-07-12 | 2018-10-02 | 淮阴工学院 | A kind of preparation method of clay/polyacrylate composite hollow microballoon |
| CN106894007A (en) * | 2017-02-28 | 2017-06-27 | 河南工程学院 | A kind of Photosensitive chromium-free passivation liquid based on electrospun fibers and preparation method thereof |
| CN106894007B (en) * | 2017-02-28 | 2018-12-21 | 河南工程学院 | A kind of Photosensitive chromium-free passivation liquid and preparation method thereof based on electrospun fibers |
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