CN111187387A - Metal anticorrosion emulsion and preparation method thereof - Google Patents
Metal anticorrosion emulsion and preparation method thereof Download PDFInfo
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- CN111187387A CN111187387A CN201911263124.8A CN201911263124A CN111187387A CN 111187387 A CN111187387 A CN 111187387A CN 201911263124 A CN201911263124 A CN 201911263124A CN 111187387 A CN111187387 A CN 111187387A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a metal anticorrosion emulsion which comprises the following raw materials in parts by weight: 25-35 parts of soft monomer, 65-75 parts of hard monomer, 1-10 parts of adhesive force monomer, 1-5 parts of functional monomer, 1-5 parts of crosslinking monomer, 1-5 parts of emulsifier, 0.1-1 part of initiator, 150 parts of deionized water and 170 parts of ammonia water. According to the invention, the acrylic emulsion with the core-shell structure is synthesized by a semi-continuous pre-emulsification process, the glass transition temperature distribution of the core shell is reasonably controlled, the performance is improved, and the consumption of expensive monomers is reduced. Phosphate ester monomers are introduced to ensure that phosphate ester groups in the polymer and metal base materials form compact phosphate ester salts, so that metal is passivated, and the metal is prevented from contacting water or other media to achieve an excellent anticorrosion effect; the water resistance is improved by adding monomers such as cyclotrimethylolpropane methylal acrylate and the like to improve the adhesion to metal; addition of DAAM and ADH increases crosslinking strength and improves corrosion resistance.
Description
Technical Field
The invention relates to a metal anticorrosion emulsion and a preparation method thereof, belonging to the field of metal anticorrosion.
Background
The corrosion of metal materials is caused by the electrochemical or chemical action of metal with the outside world to produce oxides. From the elemental high energy state of the metal back to the low energy state of the oxide. Thus, metal corrosion is thermodynamically a spontaneous process. Metal corrosion can cause serious damage and loss, which is worldwide in the billions of dollars per year.
The acrylate has excellent adhesion to metals. For example, according to the patent, the preparation method of the water-based acrylate anticorrosive paint (CN108795193A) comprises the following steps of weighing in sequence: 50-60 parts of aqueous acrylate emulsion, 12-18 parts of modified bentonite, 8-14 parts of modified starch, 5-8 parts of additive, 10-15 parts of titanium dioxide, 2-4 parts of dispersing agent, 1-2 parts of defoaming agent and 35-40 parts of water, mixing the water with the dispersing agent, adding the defoaming agent, the additive, the modified starch and the modified bentonite, stirring and mixing to obtain a blank, mixing the blank with the aqueous acrylate emulsion, adding the titanium dioxide, stirring and mixing to obtain the aqueous acrylate anticorrosive paint. The existing acrylic ester anticorrosive emulsion has low density after film formation, high water and oxygen permeability, poor corrosion resistance, poor water resistance after film formation, hot sticking and cold brittleness.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a metal anticorrosion emulsion, which improves the adhesive force of acrylic emulsion to metal and enhances the anticorrosion performance by improving the crosslinking strength. The invention also provides a preparation method of the metal anticorrosion emulsion.
In order to achieve the purpose, the metal anticorrosion emulsion adopted by the invention comprises the following raw materials in parts by weight: 25-35 parts of soft monomer, 65-75 parts of hard monomer, 1-10 parts of adhesive force monomer, 1-5 parts of functional monomer, 1-5 parts of crosslinking monomer, 1-5 parts of emulsifier, 0.1-1 part of initiator, 150 parts of deionized water and 170 parts of ammonia water.
As an improvement, the metal anticorrosion emulsion comprises the following raw materials: 27-33 parts of soft monomer, 67-73 parts of hard monomer, 5-6 parts of adhesive force monomer, 3-4 parts of functional monomer, 2-3 parts of crosslinking monomer, 2-3 parts of emulsifier, 0.4-0.6 part of initiator, 150 parts of deionized water and 170 parts of ammonia water and 2-5 parts of ammonia water.
As a modification, the soft monomer adopts one or more of butyl acrylate, isooctyl acrylate and dibutyl itaconate.
As a modification, the hard monomer adopts one or a mixture of styrene and methyl methacrylate.
As an improvement, the adhesive force monomer adopts one or more of acrylic acid, methacrylic acid and cyclotrimethylolpropane formal acrylate.
As an improvement, the functional monomer adopts one or more of polyethylene glycol monomethacrylate phosphate (PAM-100), polypropylene glycol monomethacrylate phosphate (PAM-200) and 2-hydroxyethyl methacrylate phosphate (PM-2) as a mixture.
As an improvement, the crosslinking monomer adopts one or more of N-methylol acrylamide, diacetone acrylamide and adipic dihydrazide.
As an improvement, the emulsifier adopts one or a mixture of two of nonylphenol ethoxy phosphate (RE-610) and nonylphenol polyoxyethylene ether phosphate (NP-10P).
As a modification, the initiator adopts one or a mixture of ammonium persulfate and sodium persulfate.
In addition, the invention also provides a preparation method of the metal anti-corrosion emulsion, which comprises the following steps:
1) adding 1/3 adhesive force monomers into soft and hard monomers to serve as core layer monomers, wherein the mass of the core layer monomers accounts for 2/3 of the total mass of the monomers, then adding 1/2 emulsifier and deionized water of 1/3 of the total mass of the monomers, dispersing for 10min, emulsifying at high speed, then adding 4/9 initiator, and stirring uniformly to obtain core layer monomer emulsion;
2) adding 1/4 emulsifier into deionized water with the total monomer mass of 1/3, dispersing for 10min, emulsifying the rest monomers, and adding 2/9 initiator to obtain shell layer monomer emulsion;
3) adding the rest of emulsifier and deionized water into a reaction kettle, heating to 80-85 ℃, adding the rest of initiator at constant temperature, then starting to dropwise add the core layer monomer emulsion obtained in the step 1) for 2.5-3h, continuing to dropwise add the core layer monomer emulsion obtained in the step 2) after dropwise adding, and keeping the temperature for 2h after dropwise adding for 1 h;
4) cooling to room temperature, adding ammonia water to adjust the pH value to be alkalescent, and filtering to obtain the metal anticorrosive emulsion.
Compared with the prior art, the acrylic emulsion with the core-shell structure is synthesized by a semi-continuous pre-emulsification process, the glass transition temperature distribution of the core shell is reasonably controlled, the performance is improved, and the consumption of expensive monomers is reduced. Phosphate ester monomers are introduced to ensure that phosphate ester groups in the polymer and metal base materials form compact phosphate ester salts, so that metal is passivated, and the metal is prevented from contacting water or other media to achieve an excellent anticorrosion effect; the water resistance is improved by adding monomers such as cyclotrimethylolpropane methylal acrylate and the like to improve the adhesion to metal; diacetone acrylamide and adipic dihydrazide are added to increase the crosslinking strength and improve the corrosion resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention.
Example 1
The metal anticorrosion emulsion comprises the following raw materials in parts by weight: 27 parts of soft monomer, 67 parts of hard monomer, 5 parts of adhesive force monomer, 3 parts of functional monomer, 2 parts of crosslinking monomer, 2 parts of emulsifier, 0.4 part of initiator, 150 parts of deionized water and 2 parts of ammonia water;
the soft monomer adopts butyl acrylate; the hard monomer is prepared by mixing styrene and methyl methacrylate; the adhesive force monomer adopts acrylic acid; the functional monomer adopts the mixture of PAM-100, PAM-200 and PM-2.
The crosslinking monomer adopts N-methylol acrylamide. The emulsifier adopts the mixture of RE-610 and NP-10P.
The initiator adopts ammonium persulfate.
The preparation method of the metal anticorrosion emulsion is characterized by comprising the following steps:
1) adding 1/3 adhesive force monomers into soft and hard monomers to serve as core layer monomers, wherein the mass of the core layer monomers accounts for 2/3 of the total mass of the monomers, then adding 1/2 emulsifier and deionized water of 1/3 of the total mass of the monomers, dispersing for 10min, emulsifying at high speed, then adding 4/9 initiator, and stirring uniformly to obtain core layer monomer emulsion (the Tg of a core layer is 10-15 ℃);
2) adding 1/4 emulsifier into deionized water with a total monomer mass of 1/3, dispersing for 10min, emulsifying the rest monomers, and adding 2/9 initiator after emulsification to obtain shell layer monomer emulsion (with a shell layer Tg of 30-35 ℃);
3) adding the rest of emulsifier and deionized water into a reaction kettle, heating to 80 ℃, adding the rest of initiator at constant temperature, then beginning to dropwise add the core layer monomer emulsion obtained in the step 1) for 2.5 hours, continuing to dropwise add the core layer monomer emulsion obtained in the step 2) after finishing dripping to obtain a shell layer monomer emulsion, wherein the dropwise adding time is 1 hour, and keeping the temperature for 2 hours after finishing dripping;
4) cooling to room temperature, adding ammonia water to adjust the pH value to be alkalescent, and filtering to obtain the metal anticorrosive emulsion.
Example 2
The metal anticorrosion emulsion comprises the following raw materials in parts by weight: 30 parts of soft monomer, 70 parts of hard monomer, 5 parts of adhesive force monomer, 3 parts of functional monomer, 3 parts of crosslinking monomer, 3 parts of emulsifier, 0.5 part of initiator, 160 parts of deionized water and 3 parts of ammonia water;
the soft monomer adopts isooctyl acrylate; the hard monomer adopts styrene; the adhesive force monomer adopts methacrylic acid; the functional monomer adopts the mixture of PAM-100 and PM-2; the crosslinking monomer adopts N-methylol acrylamide.
The emulsifier adopts RE-610; the initiator adopts sodium persulfate.
The preparation method of the metal anticorrosion emulsion is characterized by comprising the following steps:
1) adding 1/3 adhesive force monomers into soft and hard monomers to serve as core layer monomers, wherein the mass of the core layer monomers accounts for 2/3 of the total mass of the monomers, then adding 1/2 emulsifier and deionized water of 1/3 of the total mass of the monomers, dispersing for 10min, emulsifying at high speed, then adding 4/9 initiator, and stirring uniformly to obtain core layer monomer emulsion (the Tg of a core layer is 10-15 ℃);
2) adding 1/4 emulsifier into deionized water with a total monomer mass of 1/3, dispersing for 10min, emulsifying the rest monomers, and adding 2/9 initiator after emulsification to obtain shell layer monomer emulsion (with a shell layer Tg of 30-35 ℃);
3) adding the rest of emulsifier and deionized water into a reaction kettle, heating to 85 ℃, adding the rest of initiator at constant temperature, then beginning to dropwise add the core layer monomer emulsion obtained in the step 1) for 2.5 hours, continuing to dropwise add the core layer monomer emulsion obtained in the step 2) after finishing dripping to obtain a shell layer monomer emulsion, wherein the dropwise adding time is 1 hour, and keeping the temperature for 2 hours after finishing dripping;
4) cooling to room temperature, adding ammonia water to adjust the pH value to be alkalescent, and filtering to obtain the metal anticorrosive emulsion.
Example 3
The metal anticorrosion emulsion comprises the following raw materials in parts by weight: 35 parts of soft monomer, 75 parts of hard monomer, 10 parts of adhesive force monomer, 5 parts of functional monomer, 5 parts of crosslinking monomer, 5 parts of emulsifier, 1 part of initiator, 170 parts of deionized water and 5 parts of ammonia water;
the soft monomer adopts dibutyl itaconate; the hard monomer adopts methyl methacrylate; the adhesive force monomer adopts cyclotrimethylolpropane formal acrylate; the functional monomer adopts the mixture of PAM-200 and PM-2.
The crosslinking monomer adopts diacetone acrylamide and adipic dihydrazide; the emulsifier adopts RE-610. The initiator adopts ammonium persulfate.
The preparation method of the metal anticorrosion emulsion is characterized by comprising the following steps:
1) adding 1/3 adhesive force monomers into soft and hard monomers to serve as core layer monomers, wherein the mass of the core layer monomers accounts for 2/3 of the total mass of the monomers, then adding 1/2 emulsifier and deionized water of 1/3 of the total mass of the monomers, dispersing for 10min, emulsifying at high speed, then adding 4/9 initiator, and stirring uniformly to obtain core layer monomer emulsion (the Tg of a core layer is 10-15 ℃);
2) adding 1/4 emulsifier into deionized water with a total monomer mass of 1/3, dispersing for 10min, emulsifying the rest monomers, and adding 2/9 initiator after emulsification to obtain shell layer monomer emulsion (with a shell layer Tg of 30-35 ℃);
3) adding the rest of emulsifier and deionized water into a reaction kettle, heating to 83 ℃, adding the rest of initiator at constant temperature, then beginning to dropwise add the core layer monomer emulsion obtained in the step 1), wherein the dropwise adding time is 3 hours, and continuing to dropwise add the core layer monomer emulsion obtained in the step 2) to obtain a shell layer monomer emulsion after dropwise adding the core layer monomer emulsion, wherein the dropwise adding time is 1 hour, and the temperature is kept for 2 hours after dropwise adding;
4) cooling to room temperature, adding ammonia water to adjust the pH value to be alkalescent, and filtering to obtain the metal anticorrosive emulsion.
The relevant properties of the metal corrosion protection emulsions prepared in examples 1-3 above are shown in Table 1 below.
TABLE 1 Properties of the metal corrosion protection emulsions prepared in the examples of the invention
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The metal anticorrosion emulsion is characterized by comprising the following raw materials in parts by weight: 25-35 parts of soft monomer, 65-75 parts of hard monomer, 1-10 parts of adhesive force monomer, 1-5 parts of functional monomer, 1-5 parts of crosslinking monomer, 1-5 parts of emulsifier, 0.1-1 part of initiator, 150 parts of deionized water and 170 parts of ammonia water.
2. The metal anticorrosion emulsion as recited in claim 1, comprising the following raw materials in parts by weight: 27-33 parts of soft monomer, 67-73 parts of hard monomer, 5-6 parts of adhesive force monomer, 3-4 parts of functional monomer, 2-3 parts of crosslinking monomer, 2-3 parts of emulsifier, 0.4-0.6 part of initiator, 150 parts of deionized water and 170 parts of ammonia water and 2-5 parts of ammonia water.
3. The anticorrosive metal emulsion according to claim 1, wherein the soft monomer is one or more selected from butyl acrylate, isooctyl acrylate and dibutyl itaconate.
4. The anticorrosive emulsion for metals according to claim 1, wherein the hard monomer is one or a mixture of styrene and methyl methacrylate.
5. The metal corrosion-resistant emulsion according to claim 1, wherein the adhesion monomer is one or more of acrylic acid, methacrylic acid and cyclotrimethylolpropane formal acrylate.
6. The metal preservative emulsion according to claim 1, wherein the functional monomer is one or more of PAM-100, PAM-200 and PM-2.
7. The anticorrosive metal emulsion according to claim 1, wherein the crosslinking monomer is one or more selected from the group consisting of N-methylol acrylamide, diacetone acrylamide, and adipic dihydrazide.
8. The anticorrosive metal emulsion of claim 1, wherein the emulsifier is RE-610, NP-10P, or a mixture thereof.
9. The metal corrosion-resistant emulsion according to claim 1, wherein the initiator is one or a mixture of ammonium persulfate and sodium persulfate.
10. A method of preparing a corrosion inhibiting emulsion for metals according to any of claims 1 to 9 comprising the steps of:
1) adding 1/3 adhesive force monomers into soft and hard monomers to serve as core layer monomers, wherein the mass of the core layer monomers accounts for 2/3 of the total mass of the monomers, then adding 1/2 emulsifier and deionized water of 1/3 of the total mass of the monomers, dispersing for 10min, emulsifying at high speed, then adding 4/9 initiator, and stirring uniformly to obtain core layer monomer emulsion;
2) adding 1/4 emulsifier into deionized water with the total monomer mass of 1/3, dispersing for 10min, emulsifying the rest monomers, and adding 2/9 initiator to obtain shell layer monomer emulsion;
3) adding the rest of emulsifier and deionized water into a reaction kettle, heating to 80-85 ℃, adding the rest of initiator at constant temperature, then starting to dropwise add the core layer monomer emulsion obtained in the step 1) for 2.5-3h, continuing to dropwise add the core layer monomer emulsion obtained in the step 2) after dropwise adding, and keeping the temperature for 2h after dropwise adding for 1 h;
4) cooling to room temperature, adding ammonia water to adjust the pH value to be alkalescent, and filtering to obtain the metal anticorrosive emulsion.
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| CN113337172A (en) * | 2021-06-15 | 2021-09-03 | 岳阳市格瑞科技有限公司 | Water-based acrylate insulating paint and preparation method thereof |
| CN113372782A (en) * | 2021-07-30 | 2021-09-10 | 常州浩阳新材料科技有限公司 | Metal or oxide evaporation enhanced PET (polyethylene terephthalate) online coating liquid |
| CN113604146A (en) * | 2021-09-10 | 2021-11-05 | 中建安装集团南京建设有限公司 | Large-diameter corrosion-resistant steel pipe for pipe jacking construction and machining process thereof |
| CN116023826A (en) * | 2022-12-26 | 2023-04-28 | 广东银洋环保新材料有限公司 | Acrylic ester rust-coated anticorrosive paint and preparation method thereof |
| CN117964830A (en) * | 2024-03-29 | 2024-05-03 | 广东东方一哥新材料股份有限公司 | Acrylic ester emulsion and application thereof in preparation of waterproof coating |
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| CN117964830A (en) * | 2024-03-29 | 2024-05-03 | 广东东方一哥新材料股份有限公司 | Acrylic ester emulsion and application thereof in preparation of waterproof coating |
| CN117964830B (en) * | 2024-03-29 | 2024-06-04 | 广东东方一哥新材料股份有限公司 | Acrylic ester emulsion and application thereof in preparation of waterproof coating |
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Application publication date: 20200522 |