CN103214655A - Modified epoxy resin and high-solid anticorrosive coating prepared therewith - Google Patents
Modified epoxy resin and high-solid anticorrosive coating prepared therewith Download PDFInfo
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- CN103214655A CN103214655A CN2013101009085A CN201310100908A CN103214655A CN 103214655 A CN103214655 A CN 103214655A CN 2013101009085 A CN2013101009085 A CN 2013101009085A CN 201310100908 A CN201310100908 A CN 201310100908A CN 103214655 A CN103214655 A CN 103214655A
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Abstract
The invention discloses modified epoxy resin and high-solid anticorrosive coating prepared therewith. The modified epoxy resin is prepared through a reaction of E-44 epoxy resin and a fluorinated acrylic acid mixed monomer, and styrene. The fluorinated acrylic acid mixed monomer is prepared from the raw materials of methyl methacrylate, butyl acrylate and hexafluoro butyl methacrylate. According to the invention, with the novel components and ratio, the prepared modified epoxy resin reaches the technical indicators that: the modified epoxy resin is light-yellow transparent viscose liquid with acid value of 4.6mgKOH/g, epoxy value of 0.03 equivalents/l00g, and viscosity (25 DEG C) of 0.245Pa.s; the resin has excellent performances in the respects such as water resistance, acid and alkali resistance, high and low temperature resistance, corrosion resistance, adhesion strength, and the like. The invention also provides a high-solid anticorrosive coating prepared with the modified epoxy resin and a novel ratio. As a result, the coating has excellent performances in the respects such as water resistance, acid and alkali resistance, high and low temperature resistance, corrosion resistance, adhesion strength, and the like. The coating can be used on different low-altitude aircraft substrates of aluminum alloy, titanium alloy, magnesium alloy, composite materials, and the like.
Description
Technical field
The present invention relates to a kind of modified epoxy and with the high-solid level protective system of its preparation.
Background technology
Resins, epoxy is used very extensive, and owing to himself structure, it is corrosion-resistant, thermostability etc. is subjected to certain restriction, therefore need carry out modification to Resins, epoxy.Utilize polyester that Resins, epoxy is carried out modification more existing reports, for example Chinese invention patent CN101864236 and CN101885831 etc.; Utilizing Acrylic Acid Monomer to carry out graft modification Resins, epoxy also has some reports, and for example Lee is published in " coatings industry " " based on the preparation of protection against corrosion iron oxide red primer and the performance study of acrylic acid-grafted Resins, epoxy " of 2012 the 42nd volume the 6th phase 1-5 pages or leaves for upright the grade.Existing low flyer ground has the defective that can not be applicable to different low flyer grounds with protective system.
Summary of the invention
The objective of the invention is to, provide a kind of modified epoxy and with the high-solid level protective system of its preparation.The modified epoxy that the present invention makes is in aspect superior performances such as water-fast, high-low temperature resistant, antiseptic property and sticking power; The present invention utilizes the high-solid level protective system that is applicable to different low flyer grounds of above-mentioned modified epoxy preparation, has overcome existing low flyer ground and has had the defective that can not be applicable to different low flyer grounds with protective system.
Technical scheme of the present invention: modified epoxy, the weight proportion of feed composition is as follows, and consumption is a weight part;
60～75 parts of Resins, epoxy, 18～25 parts of perfluoroalkyl acrylate mix monomers,
12～20 parts of vinylbenzene;
Described perfluoroalkyl acrylate mix monomer comprises following component, in massfraction:
Methacrylic acid 25～40%, butyl acrylate 25～40%,
Methacrylic acid hexafluoro butyl ester 25～40%.
In the aforesaid modified epoxy, the weight proportion of feed composition is as follows:
65～70 parts of Resins, epoxy, 20～22 parts of perfluoroalkyl acrylate mix monomers,
15～18 parts of vinylbenzene;
Described perfluoroalkyl acrylate mix monomer comprises following component, in massfraction:
Methacrylic acid 30～36%, butyl acrylate 30～36%,
Methacrylic acid hexafluoro butyl ester 30～36%.
In the aforesaid modified epoxy, described Resins, epoxy is E-44 Resins, epoxy; Described perfluoroalkyl acrylate mix monomer is that methacrylic acid, butyl acrylate and the methacrylic acid hexafluoro butyl ester of 1:1:1 formed by mass ratio.
The method for preparing aforesaid modified epoxy, it is: heating E-44 Resins, epoxy to 105～115 ℃, under agitation drip the perfluoroalkyl acrylate mix monomer, behind insulation reaction 3～4h, survey acid number, when acid number during less than 5 mgKOH/g, be cooled to about 7O ℃, add vinylbenzene and dilute, stir evenly the back cooling discharge, promptly get modified epoxy.
With the high-solid level protective system of aforesaid modified epoxy preparation, it is made up of A component and B component, and the quality proportioning of A component and B component is 100:20～40;
The A component is pressed the preparation of column weight amount proportion raw material:
16～20 parts of modified epoxies, 10～13 parts of 601-75 Resins, epoxy,
24～30 parts of pigment, 0.1～0.3 part of anti-settling agent,
0.05～0.15 part of flow agent, 8～10 parts of fillers,
3～4 parts of matting agents, 4～6 parts of rust-preventive agent,
0.1～0.2 part of defoamer, 1～1.5 part of butyl glycol ether,
3～4 parts of toluene, 18～21 parts of dimethylbenzene;
The B component is pressed the preparation of column weight amount proportion raw material:
60～66 parts in solidifying agent, 19～22 parts of toluene,
4～6 parts of propyl carbinols, 0.5～1.5 part of butyl glycol ether,
4～6 parts of dimethylbenzene, 2～4 parts of siccative.
In the aforesaid high-solid level protective system, the quality proportioning of A component and B component is 100:25～35.
In the aforesaid high-solid level protective system, the quality proportioning of A component and B component is 100:33.
In the aforesaid high-solid level protective system, described pigment is made by titanium dioxide; Described anti-settling agent is a wilkinite; Described filler is made by talcum powder and barium sulfate; Described matting agent is a flatting silica.
In the aforesaid high-solid level protective system, described pigment is made up of by the mass ratio of 1:0.8～1.2 titanium dioxide TR-33 and R902+ titanium dioxide; Described anti-settling agent is a wilkinite 938; Described flow agent is the MAA flow agent; Described filler is made up of by mass ratio 1:0.8～1.2 superfine talcum powder CMS-666 and barium sulfate; Described matting agent is the C906 flatting silica; Described rust-preventive agent is the phosphorus zinc chromate; Described defoamer is 5400 defoamers; Described solidifying agent is a solidifying agent 2015; Described siccative is siccative T-30.
Prepare the method for aforesaid high-solid level protective system, it is characterized in that, it comprises following three steps:
Modified epoxy, 601-75 Resins, epoxy and dimethylbenzene mix in a, elder generation, under agitation slowly add anti-settling agent, the about 5min of high speed dispersion under agitation adds pigment and defoamer to homogeneous, stir 15min, add filler then, stir 15min, under agitation add matting agent, flow agent, rust-preventive agent, butyl glycol ether and toluene again, stir 20min, be uniformly dispersed the back with sand milling grind to fineness less than 40mm, remove by filter abrasive sand, filter and package and obtain the A component;
B, solidifying agent, toluene, propyl carbinol, butyl glycol ether, dimethylbenzene and siccative are mixed, stir 20min, be uniformly dispersed, filter and package and obtain the B component;
C, A component and B component are mixed, after stirring, promptly obtain the high-solid level protective system.
Compared with prior art, the present invention is by adopting new component and proportioning, the modified epoxy that makes reaches following technical indicator: faint yellow transparent thick liquid, acid number 4.6mgKOH/g, oxirane value 0.03 equivalent/l00g, viscosity (under the situation of 25 ° of C) is 0.245 Pa * s, in aspect superior performances such as water-fast, resistance to acids and bases, high-low temperature resistant, antiseptic property and sticking power.The high-solid level protective system that the present invention adopts above-mentioned modified epoxy and new proportioning to make, test-results shows, in aspect superior performances such as water-fast, resistance to acids and bases, high-low temperature resistant, antiseptic property and sticking power, can be used for different low flyer grounds such as aluminium alloy, titanium alloy, magnesium alloy and matrix material.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but not as the foundation to the present invention's restriction.
Embodiment.
Prepare modified epoxy by following step:
A, methacrylic acid, butyl acrylate and the methacrylic acid hexafluoro butyl ester mass ratio by 1:1:1 is mixed, make the perfluoroalkyl acrylate mix monomer.
B, get 67.65 parts of E-44 Resins, epoxy, heat to 110 ℃, under agitation drip 21.18 parts of perfluoroalkyl acrylate mix monomers, behind the insulation reaction 4h, survey acid number, when acid number during less than 5mgKOH/g, be cooled to 7O ℃, add 16.47 parts of vinylbenzene and dilute, stir evenly the back cooling discharge, make modified epoxy.
The performance index of prepared modified epoxy are as follows: the faint yellow transparent thick liquid of outward appearance, and acid number is 4.6 mgKOH/g, and oxirane value is 0.03 equivalent/l00g, and viscosity (under the situation of 25 ° of C) is 0.245 Pa * s.
Follow these steps to prepare the high-solid level protective system:
A, get 18.2 parts of modified epoxies, 601-75 Resins, epoxy resin and 19.45 parts of dimethylbenzene of 11.29 parts earlier, after the mixing, under agitation slowly add 0.2 part of wilkinite 938, the about 5min of high speed dispersion under agitation adds 14.88 parts of TR-33 titanium dioxides, 14.88 parts of R902 to homogeneous
+
Titanium dioxide and 0.13 part of 5400 defoamer, stir 15min, add 4.92 parts of talcum powder 666 and 4.99 parts of barium sulfate then, stir 15min, under agitation add 3.46 parts of C906 flatting silicas, 0.09 part of MAA flow agent, 4.99 parts of phosphorus zinc chromates, 1.32 parts of butyl glycol ethers and 3.29 parts of toluene again, stir 20 min, be uniformly dispersed the back with sand milling grind to fineness less than 40mm, remove by filter abrasive sand, filter and package and obtain the A component.
B, get 2015,21.12 parts of toluene of 64.09 parts of solidifying agent, 5.92 parts of propyl carbinols, 0.99 part of butyl glycol ether, 4.93 parts of dimethylbenzene and 2.96 parts of siccative T-30, after the mixing, stir 20min, be uniformly dispersed, filter and package and obtain the B component.
C, get A component and B component that mass ratio is 100:33, after the mixing, stir, make the high-solid level protective system.
Above-mentioned 601-75 Resins, epoxy and E-44 Resins, epoxy are that Sanmu Group Co., Ltd., Jiangsu produces.
Above-mentioned titanium dioxide TR-33 is that the two sharp titanium dioxide of Dongguan City company limited produces.
Above-mentioned R902+ titanium dioxide Shanghai auspicious titanizing worker company limited produces.
Above-mentioned wilkinite 938 is that Xiamen Ai Kema industrial chemicals company limited produces.
Above-mentioned MAA flow agent is that prosperous titanium digests (China) production.
Above-mentioned superfine talcum powder CMS-666 is that Heshan chemical industry (Liaoning) company limited produces.
Above-mentioned barium sulfate isThe Shanghai river titanium white heavy chemicals company limited that jumps produces.
Above-mentioned C906 flatting silica is that the prosperous Industry Co.,Ltd in Shanghai produces.
Above-mentioned phosphorus zinc chromate is that the prosperous flourish chemical metallization of Lanxi City company limited produces.
Above-mentioned 5400 defoamers are that last sea cowry reaches the production of wrapping material company limited.
Above-mentioned 2015 solidifying agent are that Shanghai Yao Shan chemical industry company limited produces.
Above-mentioned siccative T-30 is that Shanghai hundred mattress chemical industry company limiteds produce.
The above-mentioned high-solid level protective system that makes is tried to be coated with on aluminium alloy, titanium alloy, magnesium alloy and matrix material, and coating performance is as shown in the table.
Above-mentioned testing data shows: the high-solid level protective system that the present invention makes can be used for different low flyer grounds in aspect superior performances such as water-fast, high-low temperature resistant, antiseptic property and sticking power.
Above-mentioned generality to the invention that relates among the application is described and the description of its embodiment be should not be construed as is the restriction that this invention technical scheme is constituted.Those skilled in the art disclose according to the application's, can be under the prerequisite of related invention integrant, to above-mentioned general the description or/and the public technology feature in the embodiment (comprising embodiment) increases, reduces or makes up, formation belongs to other technical scheme of described invention.
Claims (10)
1. modified epoxy, it is characterized in that: the weight proportion of feed composition is as follows, and consumption is a weight part;
60～75 parts of Resins, epoxy, 18～25 parts of perfluoroalkyl acrylate mix monomers,
12～20 parts of vinylbenzene;
Described perfluoroalkyl acrylate mix monomer comprises following component, in massfraction:
Methacrylic acid 25～40%, butyl acrylate 25～40%,
Methacrylic acid hexafluoro butyl ester 25～40%.
2. modified epoxy according to claim 1 is characterized in that, the weight proportion of feed composition is as follows:
65～70 parts of Resins, epoxy, 20～22 parts of perfluoroalkyl acrylate mix monomers,
15～18 parts of vinylbenzene;
Described perfluoroalkyl acrylate mix monomer comprises following component, in massfraction:
Methacrylic acid 30～36%, butyl acrylate 30～36%,
Methacrylic acid hexafluoro butyl ester 30～36%.
3. modified epoxy according to claim 1 and 2 is characterized in that: described Resins, epoxy is E-44 Resins, epoxy; Described perfluoroalkyl acrylate mix monomer is that methacrylic acid, butyl acrylate and the methacrylic acid hexafluoro butyl ester of 1:1:1 formed by mass ratio.
4. the method for preparing claim 1,2 or 3 described modified epoxies, it is characterized in that, it is: heating ring epoxy resins to 105～115 ℃ under agitation drip the perfluoroalkyl acrylate mix monomer, behind insulation reaction 3～4h, survey acid number, when acid number during less than 5 mgKOH/g, be cooled to about 7O ℃, add vinylbenzene and dilute, stir evenly the back cooling discharge, promptly get modified epoxy.
5. with the high-solid level protective system of the described modified epoxy preparation of the arbitrary claim of claim 1 to 4, it is characterized in that: it is made up of A component and B component, and the quality proportioning of A component and B component is 100:20～40;
The A component is pressed the preparation of column weight amount proportion raw material:
16～20 parts of modified epoxies, 10～13 parts of 601-75 Resins, epoxy,
24～30 parts of pigment, 0.1～0.3 part of anti-settling agent,
0.05～0.15 part of flow agent, 8～10 parts of fillers,
3～4 parts of matting agents, 4～6 parts of rust-preventive agent,
0.1～0.2 part of defoamer, 1～1.5 part of butyl glycol ether,
3～4 parts of toluene, 18～21 parts of dimethylbenzene;
The B component is pressed the preparation of column weight amount proportion raw material:
60～66 parts in solidifying agent, 19～22 parts of toluene,
4～6 parts of propyl carbinols, 0.5～1.5 part of butyl glycol ether,
4～6 parts of dimethylbenzene, 2～4 parts of siccative.
6. high-solid level protective system according to claim 5 is characterized in that: the quality proportioning of A component and B component is 100:25～35.
7. high-solid level protective system according to claim 6 is characterized in that: the quality proportioning of A component and B component is 100:33.
8. according to claim 5,6 or 7 described high-solid level protective systems, it is characterized in that: described pigment is made by titanium dioxide; Described anti-settling agent is a wilkinite; Described filler is made by talcum powder and barium sulfate; Described matting agent is a flatting silica.
9. high-solid level protective system according to claim 8 is characterized in that: described pigment is made up of by the mass ratio of 1:0.8～1.2 titanium dioxide TR-33 and R902+ titanium dioxide; Described anti-settling agent is a wilkinite 938; Described flow agent is the MAA flow agent; Described filler is made up of by mass ratio 1:0.8～1.2 superfine talcum powder CMS-666 and barium sulfate; Described matting agent is the C906 flatting silica; Described rust-preventive agent is the phosphorus zinc chromate; Described defoamer is 5400 defoamers; Described solidifying agent is a solidifying agent 2015; Described siccative is siccative T-30.
10. prepare the method for the described high-solid level protective system of the arbitrary claim of claim 5 to 9, it is characterized in that, it comprises following three steps:
Modified epoxy, 601-75 Resins, epoxy and dimethylbenzene mix in a, elder generation, under agitation slowly add anti-settling agent, the about 5min of high speed dispersion under agitation adds pigment and defoamer to homogeneous, stir 15min, add filler then, stir 15min, under agitation add matting agent, flow agent, rust-preventive agent, butyl glycol ether and toluene again, stir 20min, be uniformly dispersed the back with sand milling grind to fineness less than 40 μ m, remove by filter abrasive sand, filter and package and obtain the A component;
B, solidifying agent, toluene, propyl carbinol, butyl glycol ether, dimethylbenzene and siccative are mixed, stir 20min, be uniformly dispersed, filter and package and obtain the B component;
C, A component and B component are mixed, after stirring, promptly obtain the high-solid level protective system.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104327674A (en) * | 2014-11-18 | 2015-02-04 | 江苏科技大学 | Epoxy resin paint composition directly coating rust layer |
| CN104513588A (en) * | 2014-12-18 | 2015-04-15 | 河北科莱冷暖工程有限公司 | Nitrogen-containing flame retardant epoxy resin abrasion proof and water proof coating |
| CN107163645A (en) * | 2017-06-14 | 2017-09-15 | 合肥市旺友门窗有限公司 | A kind of aluminum alloy doors and windows wear-resistant paint and preparation method thereof |
| CN108031404A (en) * | 2017-11-25 | 2018-05-15 | 赖邦德 | surfactant and its preparation method and application |
| CN109749054A (en) * | 2018-12-13 | 2019-05-14 | 珠海宏昌电子材料有限公司 | A kind of extinction powder coating epoxy resin and its preparation method and application |
| CN112341905A (en) * | 2020-11-26 | 2021-02-09 | 沈阳化工研究院有限公司 | High-solid-content rust-conversion acid-resistant anticorrosive paint and preparation method thereof |
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| CN102732124A (en) * | 2012-06-04 | 2012-10-17 | 上海大学 | Fluorine-containing heavy-duty anticorrosive coating and its application |
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| CN1380370A (en) * | 2002-03-25 | 2002-11-20 | 葛明槽 | Fire-resistant powder coating material and its production process |
| CN101125995A (en) * | 2007-09-28 | 2008-02-20 | 王新虎 | Screw thread adhesion abrasion resisting self-lubricating coating and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327674A (en) * | 2014-11-18 | 2015-02-04 | 江苏科技大学 | Epoxy resin paint composition directly coating rust layer |
| CN104327674B (en) * | 2014-11-18 | 2016-06-08 | 江苏科技大学 | The epoxy-resin coating composite of a kind of directly application on rust layer |
| CN104513588A (en) * | 2014-12-18 | 2015-04-15 | 河北科莱冷暖工程有限公司 | Nitrogen-containing flame retardant epoxy resin abrasion proof and water proof coating |
| CN107163645A (en) * | 2017-06-14 | 2017-09-15 | 合肥市旺友门窗有限公司 | A kind of aluminum alloy doors and windows wear-resistant paint and preparation method thereof |
| CN108031404A (en) * | 2017-11-25 | 2018-05-15 | 赖邦德 | surfactant and its preparation method and application |
| CN109749054A (en) * | 2018-12-13 | 2019-05-14 | 珠海宏昌电子材料有限公司 | A kind of extinction powder coating epoxy resin and its preparation method and application |
| CN109749054B (en) * | 2018-12-13 | 2021-07-16 | 珠海宏昌电子材料有限公司 | Epoxy resin for extinction powder coating and preparation method and application thereof |
| CN112341905A (en) * | 2020-11-26 | 2021-02-09 | 沈阳化工研究院有限公司 | High-solid-content rust-conversion acid-resistant anticorrosive paint and preparation method thereof |
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| CN103214655B (en) | 2015-01-07 |
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Effective date of registration: 20210421 Address after: No.11, Shengyang Road, Shangma Industrial Park, Wenling Economic Development Zone, Wenzhou, Zhejiang, 317500 Patentee after: ZHEJIANG YUTONG NEW MATERIAL Co.,Ltd. Address before: Room 633, C building, No. 525 Xixi Road, Xihu District, Zhejiang, Hangzhou 310013, China Patentee before: HANGZHOU RIYAO TECHNOLOGY Co.,Ltd. |
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Address after: No.11, Shengyang Road, Shangma Industrial Park, Wenling Economic Development Zone, Wenling City, Taizhou City, Zhejiang Province, 317500 Patentee after: ZHEJIANG YUTONG NEW MATERIAL Co.,Ltd. Address before: No.11, Shengyang Road, Shangma Industrial Park, Wenling Economic Development Zone, Wenzhou, Zhejiang, 317500 Patentee before: ZHEJIANG YUTONG NEW MATERIAL Co.,Ltd. |