CN108314951B - Preparation method of water-based anticorrosive fireproof coating material for steel structure - Google Patents
Preparation method of water-based anticorrosive fireproof coating material for steel structure Download PDFInfo
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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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- 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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- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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Abstract
A preparation method of a steel structure water-based anticorrosion fireproof coating material relates to a coating preparation method, and adopts a layer-by-layer self-assembly method (LBL) to prepare molybdenum diselenide (MoSe)2) The nano sheets construct a melamine and salt-phytic acid flame-retardant layer thereof, and the functional molybdenum diselenide nano sheets are filled into aqueous epoxy resin to prepare the steel structure aqueous anticorrosion fireproof coating. The method improves the flame retardant property of the water-based epoxy resin by constructing the P-N flame retardant layer; the phytic acid in the nano filler has huge chelating potential energy, so that the phytic acid in the nano filler can be used for connecting the coating and the base material in a stronger way to improve the corrosion resistance and durability of the coating; the problem that the nano material is easy to agglomerate due to the high surface energy of the nano material is also successfully solved.
Description
Technical Field
The invention relates to a preparation method of a coating, in particular to a preparation method of a steel structure water-based anticorrosive fireproof coating material.
Background
Metal corrosion is a phenomenon in which a metal material is destroyed by chemical or electrochemical reaction, and poses a serious threat to national economy and industrial structures. Therefore, corrosion protection plays a very important role in the modern metal working industry. However, corrosion cannot be completely suppressed. Current undisputed methods include cathodic protection, brushing the protective coating and adding corrosion inhibitors, or any combination of the above, with the use of protective coatings being the most widely used method. The current challenge with protective coatings is that novel multifunctional materials act as corrosion inhibitors, which due to their excellent properties can meet different environmental requirements.
Steel structure buildings have achieved a great significance in the current urbanization construction, but no matter what kind of structures are built, the hidden danger of fire exists more or less in the lives of people. Therefore, the fire-proof performance of the steel structure will become more important in the present and future life fields, and the requirement of the fire-proof performance will be further improved.
MoSe2Due to the low price and abundant reserves, the unique structure and physicochemical properties of the plant are attracted extensive attention by researchers. The optical fiber has the characteristics of sandwich-like lamellar structure, adjustability, high carrier mobility, strong interaction with an optical field, strong intrinsic spin-orbit coupling effect, valley degree of freedom and the like, and has great application prospect in the fields of devices such as solid lubricants, electrics, optics, spin electronics and the like. Therefore, adding the molybdenum diselenide with the lamellar structure as a filler into the anticorrosive coating is a good method.
In recent years, phosphorus-nitrogen (P-N) flame retardants have attracted much attention, which exhibit excellent chemical and thermal stability and excellent flame retardancy in a synergistic manner during combustion. The flame retardant has double flame-retardant functions of gas-phase flame retardance and condensed-phase flame retardance, is favorable for forming a carbon layer, blocks the contact between a combustion substrate and air, and releases non-combustible gas to expand the carbon layer. However, the fire-retardant carbon layer formed by adding the P-N flame retardant alone is not continuous, which seriously limits the flame-retardant efficiency of the P-N flame retardant.
Phytic acid as the main component of plant seed accounts for 1-3% of the weight of many grains and oil, and has high phosphorus content. The phytic acid is an organic acid which is easy to obtain and is environment-friendly, has certain biocompatibility, non-toxic and low cost, so that the phytic acid is applied to a plurality of fields of biosensors, nano materials, cation exchange resins, corrosion prevention and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a steel structure water-based anticorrosion fireproof coating material, which is prepared by LBL (Long-layer binding modification) on modified MoSe (MoSe)2The nano sheets construct a P-N flame-retardant layer, and the bonding state of a coating/metal interface is changed through the chelation of phytic acid, so that the coating/metal interface is strongerThe coating and the base material are connected, so that the corrosion resistance and the flame retardance of the coating are improved.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a steel structure water-based anticorrosion fireproof coating material adopts LBL modified MoSe2Constructing a P-N flame-retardant layer by using nanosheets, and then adding functionalized MoSe2The nano sheet and the waterborne epoxy resin are compounded to prepare the steel structure waterborne anticorrosion fireproof coating material, and the specific synthesis steps are as follows:
(1) preparation of functionalized MoSe2 nanosheets: respectively preparing melamine salt and phytic acid into 0.05wt% and 1wt% solutions;
dissolving phytic acid in a solution of ethanol and water (ethanol: water = 95: 5) at room temperature to form a mixed solution with the concentration of 2g/L, soaking MoSe2 nanosheets in the solution at room temperature, centrifuging the solution for 3-5 times by using a centrifugal machine after 2 hours, rinsing the solution for 3-5 times by using deionized water, and finally drying the solution by using nitrogen for later use;
②, standing the MoSe2 nanosheets in the prepared melamine and salt solution thereof for 20-40min, centrifuging the solution for 3-5 times by using a centrifugal machine, rinsing for 3-5 times by using distilled water, and drying by using nitrogen;
standing the MoSe2 nano-sheets adsorbing melamine and melamine salt in a prepared phytic acid solution for 20-40min, centrifuging the solution for 3-5 times by using a centrifugal machine, rinsing for 3-5 times by using distilled water, and drying by using nitrogen;
repeating the step two to ③ for a plurality of times, and reacting for 2 hours at the temperature of 110-130 ℃ to form the functionalized MoSe2 nanosheet;
(2) taking 10-40 parts of the functionalized MoSe2 nanosheet as a filler, adding the filler into a mixed solution of 100-200 parts of water and 100-200 parts of aqueous epoxy resin, and dispersing for 1-2 hours in a ball mill to obtain a mother solution of the steel structure aqueous anticorrosion fireproof coating;
(3) uniformly mixing 25-50 parts of aqueous curing agent and 20-100 parts of water, and mixing with the steel structure aqueous anticorrosion fireproof coating mother liquor according to the proportion of 1: 3-4, and mixing uniformly.
According to the preparation method of the steel structure water-based anticorrosive and fireproof coating material, the melamine and the salt thereof are melamine, melamine sulfate, melamine phosphate or melamine borate.
The preparation method of the steel structure water-based anticorrosive fireproof coating material comprises the step of preparing the MoSe2The number of the P-N flame-retardant layers constructed by the nanosheets is 3-5.
The preparation method of the steel structure water-based anticorrosive fireproof coating material comprises the step of preparing a water-based epoxy resin E51 epoxy emulsion or E44 epoxy emulsion.
According to the preparation method of the steel structure water-based anticorrosive and fireproof coating material, the water-based curing agent is Aq419 or H228B.
The invention has the advantages and effects that:
1. the functionalized MoSe2 nanosheets prepared by the method are added into epoxy resin, electrons on a d orbit are fed back to Fe element through the empty d orbit of Se atoms in MoSe2, the electron cloud density of the Fe element is reduced, and the MoSe2 lamellar structure blocks pores generated in the epoxy resin in the curing process, so that the metal surface is not easy to oxidize or corrode; the phytic acid used as an environment-friendly antirust agent can eliminate the microscopic rust generated by incomplete rust removal in the rust removal process during coating, so that the coating cannot be internally rotted in the later use process, and the phytic acid is easy to form a compact protective film on the surface of the metal due to chelation, so that oxygen and water in the air are isolated from being in contact with the surface of steel, the time for corrosion particles to reach a metal matrix through the coating is blocked and prolonged, and the corrosion of the metal is slowed down.
2. The invention is realized by adding MoSe2Constructing a P-N flame-retardant layer on the surface of the nano sheet, and adding MoSe2MoSe combined use of nano sheet and P-N flame-retardant system2The nano-sheet structure can support a carbon layer formed after the P-N flame-retardant system is combusted, so that a continuous and compact high-strength carbon layer is generated, and the defect that a fireproof carbon layer formed by independently adding a P-N flame retardant is discontinuous is overcome.
3. Functionalized MoSe prepared in the invention2The nano-sheets have good compatibility by using phytic acid, the dispersibility of the filler in resin is improved, and functionalized MoSe is avoided2Restacking and aggregation of the nanoplatelets in the resin, fromThe water-based anticorrosive fireproof coating material for the steel structure is obtained, and has the advantage of simple construction.
Drawings
FIG. 1 shows a diagram of nano-MoSe2Constructing a P-N flame-retardant system structure schematic diagram.
Detailed Description
The present invention will be described in detail with reference to examples.
(1) Preparation of functionalized MoSe2 nanosheets: melamine and phytic acid were prepared as 0.05wt% and 1wt% solutions, respectively.
at room temperature, dissolving phytic acid in a solution of ethanol and water (ethanol: water = 95: 5) to form a mixed solution with the concentration of 2g/L, soaking the MoSe2 nanosheets in the solution at room temperature, centrifuging the solution for 2 hours for 3 times by using a centrifugal machine, rinsing the solution for 3 times by using deionized water, and finally drying the solution by using nitrogen for later use.
②, standing the MoSe2 nanosheets in a prepared melamine solution for 30min, centrifuging the solution for 3 times by using a centrifugal machine, rinsing the solution for 3 times by using distilled water, and drying the solution by using nitrogen;
standing the MoSe2 nanosheets adsorbing the melamine in a prepared phytic acid solution for 30min, centrifuging the solution for 3 times by using a centrifugal machine, rinsing for 3 times by using distilled water, and drying by using nitrogen;
and (4) repeating the step (II) and the step (III) for a plurality of times, and reacting for 2 hours at 120 ℃ to form the functionalized MoSe2 nanosheet.
(2) And (3) taking 30 parts of the functionalized MoSe2 nanosheet as a filler, adding the filler into a mixed solution of 100 parts of water and 100 parts of aqueous epoxy resin, and dispersing for 1 hour in a ball mill to obtain a mother solution of the steel structure aqueous anticorrosion fireproof coating.
(3) And (3) uniformly mixing 50 parts of water-based curing agent and 100 parts of water, and then uniformly mixing the mixture with the steel structure water-based anticorrosive fireproof coating mother liquor according to the proportion of 1-4 to obtain the steel structure water-based anticorrosive fireproof coating paint.
The performance test of the steel structure water-based anticorrosive fireproof coating material prepared by the invention is divided into three groups, wherein the first group is a coating material obtained by adding MoSe2 nano sheets into water-based epoxy resin through mechanical blending, the second group is a coating material obtained by adding phytic acid-melamine (PHAM) into epoxy resin, and the third group is the coating material prepared by the invention. According to the detection standard of the coating material, the adhesion, the corrosion resistance and the flame retardant property are mainly considered, and the specific results are shown in table 1.
| First group | Second group | Third group | |
| 700h salt spray test | Severe corrosion of | Moderate corrosion | No corrosion spots |
| Flame-retardant time of large-plate combustion method | 9min | 22min | 38min |
| Carbon layer Strength/N | 10 | 9 | 13 |
| Adhesion test | 7.3MPa | 7.5MPa | 8.7MPa |
As can be seen from Table 1, the coating material prepared by the method has various performances superior to those of the other two coating materials, mainly because the PHAM/MoSe2 nanosheets prevent the penetration of corrosive media through chelation and blocking of natural pores of epoxy resin, the bonding strength of the coating and a matrix is improved, and the corrosion resistance of the coating is improved; and the flame retardant property of the coating is improved by constructing the PHAM, so that the protective capability of the coating is improved.
Claims (5)
1. The preparation method of the steel structure water-based anticorrosion fireproof coating material is characterized in that LBL modified MoSe is adopted in the method2Constructing a P-N flame-retardant layer by using nanosheets, and then adding functionalized MoSe2Compounding the nanosheets and the waterborne epoxy resin to obtain a steel structure waterborne anticorrosion fireproof coating material; the specific synthesis steps are as follows:
functionalized MoSe2Preparing a nano sheet: respectively preparing melamine salt and phytic acid into 0.05wt% and 1wt% solutions;
dissolving phytic acid in a solution of ethanol and water at room temperature, wherein the ratio of ethanol: water = 95:5, forming a mixed solution with a concentration of 2 g/L; at room temperature, adding MoSe2Soaking the nanosheets into the solution, centrifuging the solution for 3-5 times by using a centrifugal machine after 2 hours, rinsing the solution for 3-5 times by using deionized water, and finally drying the solution for later use by using nitrogen;
then adding the above MoSe2Standing the nanosheets in the prepared melamine and salt solution thereof for 20-40min, centrifuging the solution for 3-5 times by using a centrifugal machine, rinsing the solution for 3-5 times by using distilled water, and drying the solution by using nitrogen;
adsorbing MoSe of melamine and salt thereof2Standing the nanosheets in the prepared phytic acid solution for 20-40min, centrifuging the solution for 3-5 times by using a centrifugal machine, rinsing for 3-5 times by using distilled water, and drying by using nitrogen;
repeating the step two to ③ for a plurality of times, and reacting for 2 hours at the temperature of 110-130 ℃ to form the functionalized MoSe2Nanosheets;
taking 10-40 parts of the functionalized MoSe2Adding the nanosheets serving as fillers into a mixed solution of 100-200 parts of water and 100-200 parts of waterborne epoxy resin, and dispersing for 1-2h in a ball mill to obtain a mother solution of the steel structure waterborne anticorrosive fireproof coating;
(3) uniformly mixing 25-50 parts of aqueous curing agent and 20-100 parts of water, and mixing with the steel structure aqueous anticorrosion fireproof coating mother liquor according to the proportion of 1: 3-4, and mixing uniformly.
2. The method for preparing the water-based anticorrosion and fireproof coating material for the steel structure as claimed in claim 1, wherein the melamine and the salt thereof are melamine, melamine sulfate, melamine phosphate or melamine borate.
3. The method for preparing the water-based anticorrosion and fireproof coating material for the steel structure according to claim 1, wherein the MoSe is used as a base material2The number of the P-N flame-retardant layers constructed by the nanosheets is 3-5.
4. The method for preparing the water-based anticorrosion and fireproof coating material for the steel structure as claimed in claim 1, wherein the water-based epoxy resin is E51 epoxy emulsion or E44 epoxy emulsion.
5. The method for preparing the water-based anticorrosion and fireproof coating material for the steel structure as claimed in claim 1, wherein the water-based curing agent is Aq419 or H228B.
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| CN109486348B (en) * | 2018-11-07 | 2020-08-21 | 沈阳顺风新材料有限公司 | Preparation method of fireproof anticorrosive paint |
| CN111117431B (en) * | 2020-01-08 | 2021-04-27 | 沈阳市津浩科技有限公司 | Water-based epoxy flame-retardant coating and preparation method thereof |
| CN114230805A (en) * | 2021-12-23 | 2022-03-25 | 河北三棵树涂料有限公司 | Organic polymer flame retardant, water-based fireproof flame-retardant coating and preparation method thereof |
| CN116023851A (en) * | 2022-08-19 | 2023-04-28 | 成都启新戎盾新材料有限公司 | Primer-free melamine nano sheet anticorrosive paint |
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Effective date of registration: 20221012 Address after: Liaohe Street, Chengnan Development Zone, Diaobingshan City, Tieling City, Liaoning Province 112000 Patentee after: Liaoning Maggie New Material Group Co.,Ltd. Address before: 110142 No. 11 economic and Technological Development Zone, Liaoning, Shenyang Patentee before: SHENYANG University OF CHEMICAL TECHNOLOGY |