CN110655846A - Toughened epoxy resin coating with enhanced corrosion resistance - Google Patents
Toughened epoxy resin coating with enhanced corrosion resistance Download PDFInfo
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- CN110655846A CN110655846A CN201910973113.2A CN201910973113A CN110655846A CN 110655846 A CN110655846 A CN 110655846A CN 201910973113 A CN201910973113 A CN 201910973113A CN 110655846 A CN110655846 A CN 110655846A
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- epoxy resin
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- titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Organic Chemistry (AREA)
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Abstract
The invention relates to the technical field of epoxy coating modification, and discloses a toughened epoxy resin coating with enhanced corrosion resistance, which comprises the following raw materials in parts by weight: 100 parts of epoxy resin E51, 90-98 parts of curing agent, 0.67 part of curing accelerator and 6.5-10 parts of polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosive filler; the preparation of the toughened epoxy resin coating comprises the following steps: preparing polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosive filler, compounding the prepared filler with epoxy resin E51 to obtain epoxy resin E-51 slurry, and finally compounding the epoxy resin E-51 slurry with a curing agent and a curing accelerator to obtain the epoxy resin E-51 coating. The invention solves the technical problem that the prior epoxy resin coating can not effectively toughen the epoxy resin and simultaneously effectively enhance the corrosion resistance of the epoxy resin.
Description
Technical Field
The invention relates to the technical field of epoxy coating modification, in particular to a toughened epoxy resin coating with enhanced corrosion resistance.
Background
The epoxy coating is the most widely used and important anticorrosive coating, the coating has excellent permeability resistance and corrosion resistance to water, alkali and the like, and low-molecular-weight epoxy resin is regarded by people on the basis of two aspects of anticorrosive performance and environmental protection of the coating, but the low-molecular-weight epoxy resin has high crosslinking density and poor toughness and is easy to break when being subjected to mechanical impact, so that the service life of the coating is greatly shortened, and therefore, the improvement of the toughness and the anticorrosive performance of the epoxy resin coating simultaneously is a key problem to be solved for the anticorrosion of the epoxy resin coating.
The inorganic nano oxide particles have a better effect of toughening the epoxy resin, but the incompatibility between the inorganic nano oxide particles and the epoxy resin causes the inorganic nano oxide particles to generate an agglomeration effect in an epoxy resin matrix and reduce the toughening effect, and the inorganic nano oxide particles do not have an anti-corrosion function, so that the technical purpose of improving the anti-corrosion performance of a coating cannot be achieved.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a toughened epoxy resin coating for enhancing the corrosion resistance, which aims to solve the technical problem that the corrosion resistance of the conventional epoxy resin coating cannot be effectively enhanced while the toughening of epoxy resin cannot be effectively realized.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
the toughened epoxy resin coating for enhancing the corrosion resistance comprises the following raw materials in parts by weight: 100 parts of epoxy resin E51, 90-98 parts of curing agent, 0.67 part of curing accelerator and 6.5-10 parts of polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosive filler;
the polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosion filler comprises the following raw materials in parts by weight: 5 parts of silicon dioxide with the average particle size of less than or equal to 100nm, 5 parts of titanium dioxide with the average particle size of less than or equal to 50nm and 9.3 parts of aniline;
the preparation of the toughened epoxy resin coating comprises the following steps: preparing polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosive filler, compounding the prepared filler with epoxy resin E51 to obtain epoxy resin E-51 slurry, and finally compounding the epoxy resin E-51 slurry with a curing agent and a curing accelerator to obtain the epoxy resin E-51 coating.
Further, the curing agent is methylhexahydrophthalic anhydride (MeHHPA).
Further, the curing accelerator was 2-ethyl-4-methylimidazole (2E4 MZ).
Further, the toughened epoxy resin coating comprises the following raw materials in parts by weight: 100g of epoxy resin E51, 95g of methylhexahydrophthalic anhydride (MeHHPA), 0.67g of 2-ethyl-4-methylimidazole (2E4MZ) and 8g of polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosion filler.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the toughened epoxy resin coating is prepared by adding polyaniline-nano silicon dioxide-nano titanium dioxide composite toughened anticorrosive filler into an epoxy resin E-51 resin matrix;
the polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosion filler is prepared by grafting polyaniline with excellent anticorrosion performance on two inorganic nano particles which have excellent toughness and different particle sizes, so that the problem that an inorganic nano toughening component is easy to agglomerate is solved, and the problem that the inorganic nano toughening component does not have anticorrosion performance is solved;
the toughened epoxy resin coating disclosed by the invention has the advantages that the impact resistance is 25-30 cm, the coating is not wrinkled and falls off but has tiny cracks, the impact resistance is obviously better than that of the coating in a comparative example, the impact resistance is 10cm, and the coating is not wrinkled, falls off and has tiny cracks;
the coating resistance of the toughened epoxy resin coating is 1.21-1.42 (multiplied by 10)12Ω·cm2) Coating resistance of 6.43X 10 with the coating layer of the comparative example12Ω·cm2Compared with the prior art, the corrosion resistance is two orders of magnitude higher, namely, the corrosion resistance is better;
therefore, the technical problem that the corrosion resistance of the conventional epoxy resin coating can not be effectively enhanced while the toughening of the epoxy resin can not be effectively realized is solved.
Detailed Description
The following raw materials were used:
epoxy resin E-51, the epoxy equivalent is 185-208 g/eq, the epoxy value is 0.48-0.54 eq/100g, and the viscosity is less than or equal to 2.5 Pa.s (at 25 ℃);
methylhexahydrophthalic anhydride (MeHHPA), acid number 657.32, free acid 0.18%, iodine number 0.87, freezing point-15 deg.C;
the preparation method of the polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosive filler comprises the following steps:
the method comprises the following steps: drying 100g of silicon dioxide with the average particle size of less than or equal to 100nm and 100g of titanium dioxide with the average particle size of less than or equal to 50nm in a 120 ℃ drying oven for 2 hours, and filling the materials into a sealing bag and storing the sealing bag in a drying dish for later use;
step two: dispersing the dried nano silicon dioxide and nano titanium dioxide in 500mL of dimethylbenzene solution simultaneously, performing ultrasonic dispersion for 30min, performing magnetic stirring for 30min, and performing N-phase ultrasonic dispersion2Dropping 100g of r-aminopropyltriethoxysilane coupling agent and 2g of triethylamine under protection, heating to 130 ℃ for reaction for 12h, then extracting with 500mL of absolute ethanol at 100 ℃ for 48h, and drying for later use to obtain surface-modified composite nanoparticles;
step three: dispersing 10g of composite nano particles in 400mL of aniline hydrochloric acid solution (0.25M aniline), performing ultrasonic dispersion for 30min, performing mechanical stirring for 30min in an ice bath, dropwise adding 200mL of 0.5M ammonium peroxodisulfate solution, continuing to react for 5h after dropwise addition, performing vacuum filtration after the reaction is finished, dispersing the product in 400mL of 1M ammonia water solution for 3h, performing vacuum filtration, extracting for 48h at 80 ℃ by using 300mL of tetrahydrofuran, drying the extracted product, adding into 400mL of 0.5M p-toluenesulfonic acid solution, stirring for 8h, washing and drying by using deionized water, and thus obtaining the polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening antiseptic filler.
The first embodiment is as follows:
the toughened epoxy resin coating comprises the following raw materials in parts by weight: 100g of epoxy resin E51, 90g of methylhexahydrophthalic anhydride (MeHHPA) curing agent, 0.67g of 2-ethyl-4-methylimidazole (2E4MZ) curing accelerator and 6.5g of polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosion filler;
the preparation method of the toughened epoxy resin coating comprises the following steps:
the method comprises the following steps: preparation of epoxy resin E-51 slurry
Adding 6.5g of polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosive filler into 100g of epoxy resin E51, and carrying out ball milling for 3h at 300r/min to prepare epoxy resin E-51 slurry;
step two: preparation of epoxy resin E-51 coating
And (3) adding 90g of methylhexahydrophthalic anhydride (MeHHPA) curing agent and 0.67g of 2-ethyl-4-methylimidazole (2E4MZ) curing accelerator into the epoxy resin E-51 slurry prepared in the step one, and performing ball milling until the mixture is uniformly mixed to prepare the epoxy resin E-51 coating.
Example two:
the toughened epoxy resin coating comprises the following raw materials in parts by weight: 100g of epoxy resin E51, 95g of methylhexahydrophthalic anhydride (MeHHPA) curing agent, 0.67g of 2-ethyl-4-methylimidazole (2E4MZ) curing accelerator and 8g of polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosion filler;
the preparation method of the toughened epoxy resin coating comprises the following steps:
the method comprises the following steps: preparation of epoxy resin E-51 slurry
Adding 8g of polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening and anticorrosion filler into 100g of epoxy resin E51, and performing ball milling for 3h at 300r/min to prepare epoxy resin E-51 slurry;
step two: preparation of epoxy resin E-51 coating
And (3) adding 95g of methylhexahydrophthalic anhydride (MeHHPA) curing agent and 0.67g of 2-ethyl-4-methylimidazole (2E4MZ) curing accelerator into the epoxy resin E-51 slurry prepared in the step one, and performing ball milling until the mixture is uniformly mixed to prepare the epoxy resin E-51 coating.
Example three:
the toughened epoxy resin coating comprises the following raw materials in parts by weight: 100g of epoxy resin E51, 98g of methylhexahydrophthalic anhydride (MeHHPA) curing agent, 0.67g of 2-ethyl-4-methylimidazole (2E4MZ) curing accelerator and 10g of polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosion filler;
the preparation method of the toughened epoxy resin coating comprises the following steps:
the method comprises the following steps: preparation of epoxy resin E-51 slurry
Adding 10g of polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening and anticorrosion filler into 100g of epoxy resin E51, and performing ball milling for 3h at 300r/min to prepare epoxy resin E-51 slurry;
step two: preparation of epoxy resin E-51 coating
And (3) adding 98g of methylhexahydrophthalic anhydride (MeHHPA) curing agent and 0.67g of 2-ethyl-4-methylimidazole (2E4MZ) curing accelerator into the epoxy resin E-51 slurry prepared in the step one, and performing ball milling until the mixture is uniformly mixed to prepare the epoxy resin E-51 coating.
Comparative example:
the toughened epoxy resin coating comprises the following raw materials in parts by weight: 100g of epoxy resin E51, 95g of methylhexahydrophthalic anhydride (MeHHPA) curing agent, 0.67g of 2-ethyl-4-methylimidazole (2E4MZ) curing accelerator and 8g of nano titanium dioxide filler;
the preparation method of the toughened epoxy resin coating comprises the following steps:
the method comprises the following steps: preparation of epoxy resin E-51 slurry
Adding 8g of nano titanium dioxide filler into 100g of epoxy resin E51, and carrying out ball milling for 3h at 300r/min to prepare epoxy resin E-51 slurry;
step two: preparation of epoxy resin E-51 coating
And (3) adding 95g of methylhexahydrophthalic anhydride (MeHHPA) curing agent and 0.67g of 2-ethyl-4-methylimidazole (2E4MZ) curing accelerator into the epoxy resin E-51 slurry prepared in the step one, and performing ball milling until the mixture is uniformly mixed to prepare the epoxy resin E-51 coating.
And (3) performance testing:
firstly, the preparation method of the epoxy resin coating is carried out according to the standard GB1727-92, and the size of the tinplate is 50 x 120 x 0.3mm3. The pretreatment of the tinplate is carried out according to the standard GB/T9271-2008, 400-mesh sand paper is used for polishing until a model of the original surface can not be seen by naked eyes, absolute ethyl alcohol is used for cleaning sand grains, tin scraps and other dirt on the surface, a blower is used for drying for later use, finally the toughened epoxy resin coating prepared in the above embodiment and comparative example is coated on the tinplate in a brush coating mode and is placed for 5 days, and the test is carried outThe impact resistance is tested, and the test results are shown in table 1;
secondly, sequentially polishing a tinplate for the electrochemical impedance test by 400-mesh, 800-mesh and 1500-mesh sand paper until a model of the original surface cannot be seen by naked eyes, then clearly cleaning surface sand grains, tin scraps and other dirt by absolute ethyl alcohol, then drying for later use by a blower, finally coating the toughened epoxy resin coating prepared in the embodiment and the comparative example on the tinplate in a brush coating mode, standing for 5 days, then soaking in a sodium chloride solution with the mass fraction of 5% for 30 days, and testing the corrosion resistance, wherein the test result is shown in table 1.
TABLE 1
Claims (4)
1. The toughened epoxy resin coating for enhancing the corrosion resistance is characterized by comprising the following raw materials in parts by weight: 100 parts of epoxy resin E51, 90-98 parts of curing agent, 0.67 part of curing accelerator and 6.5-10 parts of polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosive filler;
the polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosion filler comprises the following raw materials in parts by weight: 5 parts of silicon dioxide with the average particle size of less than or equal to 100nm, 5 parts of titanium dioxide with the average particle size of less than or equal to 50nm and 9.3 parts of aniline;
the preparation of the toughened epoxy resin coating comprises the following steps: preparing polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosive filler, compounding the prepared filler with epoxy resin E51 to obtain epoxy resin E-51 slurry, and finally compounding the epoxy resin E-51 slurry with a curing agent and a curing accelerator to obtain the epoxy resin E-51 coating.
2. The toughened epoxy resin coating according to claim 1 wherein said curing agent is methylhexahydrophthalic anhydride (MeHHPA).
3. The toughened epoxy resin coating as claimed in claim 2, wherein the curing accelerator is 2-ethyl-4-methylimidazole (2E4 MZ).
4. The toughened epoxy resin paint as claimed in claim 3, wherein the toughened epoxy resin paint comprises the following raw materials in parts by weight: 100g of epoxy resin E51, 95g of methylhexahydrophthalic anhydride (MeHHPA), 0.67g of 2-ethyl-4-methylimidazole (2E4MZ) and 8g of polyaniline-nano silicon dioxide-nano titanium dioxide composite toughening anticorrosion filler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910973113.2A CN110655846A (en) | 2019-10-14 | 2019-10-14 | Toughened epoxy resin coating with enhanced corrosion resistance |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910973113.2A CN110655846A (en) | 2019-10-14 | 2019-10-14 | Toughened epoxy resin coating with enhanced corrosion resistance |
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| CN110655846A true CN110655846A (en) | 2020-01-07 |
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| CN201910973113.2A Pending CN110655846A (en) | 2019-10-14 | 2019-10-14 | Toughened epoxy resin coating with enhanced corrosion resistance |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401718A (en) * | 2002-09-20 | 2003-03-12 | 西安交通大学 | Process for preparing corrosion-resistant polyaniline paint |
| WO2017101223A1 (en) * | 2015-12-15 | 2017-06-22 | 深圳先进技术研究院 | Fibre-hybridised particle and polymer-based composite |
-
2019
- 2019-10-14 CN CN201910973113.2A patent/CN110655846A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401718A (en) * | 2002-09-20 | 2003-03-12 | 西安交通大学 | Process for preparing corrosion-resistant polyaniline paint |
| WO2017101223A1 (en) * | 2015-12-15 | 2017-06-22 | 深圳先进技术研究院 | Fibre-hybridised particle and polymer-based composite |
Non-Patent Citations (3)
| Title |
|---|
| 刘艳龙: "颗粒改性环氧树脂复合材料拉伸及疲劳性能数值分析", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 * |
| 王德中: "《环氧树脂生产与应用》", 30 June 2001, 化学工业出版社 * |
| 黄玉媛等: "《精细化工配方常用原料手册》", 31 March 1998, 广东科技出版社 * |
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Application publication date: 20200107 |