CN112409896A - Preparation method of long-oil alkyd resin anticorrosive enamel with high corrosion potential - Google Patents
Preparation method of long-oil alkyd resin anticorrosive enamel with high corrosion potential Download PDFInfo
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- CN112409896A CN112409896A CN202011396492.2A CN202011396492A CN112409896A CN 112409896 A CN112409896 A CN 112409896A CN 202011396492 A CN202011396492 A CN 202011396492A CN 112409896 A CN112409896 A CN 112409896A
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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- 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
- 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
- C09D5/23—Magnetisable or magnetic paints or lacquers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/63—Additives non-macromolecular organic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
- C09F9/00—Compounds to be used as driers (siccatives)
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Abstract
The invention discloses a preparation method of a long-oil alkyd resin anticorrosive enamel with high corrosion potential, which takes dry long-oil alkyd resin and zinc abietate synthesized by the method as film forming substances, takes isobutanol as a solvent, and then adds organic kaolin, organic bentonite, carbon black, dimethyl silicone oil and drier aluminum naphthenate salt, and the simple rosin-based long-oil alkyd resin anticorrosive enamel is obtained by high-speed stirring. The enamel has lower corrosion current, higher corrosion potential and larger electrochemical impedance, namely the enamel has good local corrosion resistance, and can be applied to anticorrosion engineering in the fields of house balcony metal-based railings, petrochemical equipment, pipelines, offshore oil platforms, wharf facilities, ships and the like.
Description
Technical Field
The invention relates to the field of enamel, in particular to a preparation method of long-oil alkyd resin anticorrosive enamel with high corrosion potential.
Background
Due to the low potential of metal material equipment such as petrochemical equipment, pipelines, offshore oil platforms, ships and the like, the metal material equipment is extremely easy to corrode in the atmospheric environment, and particularly, the parts of the ship equipment below a waterline are extremely easy to cause serious local corrosion due to long-term immersion in corrosive media such as sodium chloride and the like. The existing treatment method is to add a large amount of heavy metal compounds such as lead tetraoxide and the like into the paint formula, however, the anticorrosive coating is continuously precipitated by ions such as the highly toxic heavy metal lead and the like, seriously pollutes the ocean, the river and the soil environment, and seriously affects the global ecological environment and the human body. However, because no suitable alternative technology exists at present, the search for suitable low-toxicity alternative technology is of great significance.
The alkyd resin is an oil-modified polyester resin obtained by condensation polymerization of a polyol, phthalic anhydride, and a fatty acid or oil (fatty acid triglyceride). A plurality of hydrogen bonds exist in macromolecules of the alkyd resin, the intermolecular force is large, and the alkyd resin anticorrosive paint can be crosslinked with a plurality of compounds to form a film, so that the alkyd resin anticorrosive paint prepared by taking the alkyd resin as a film forming substance has the characteristics of better corrosion resistance, permeability resistance, wear resistance, better adhesive force and the like, but has a plurality of variable factors for crosslinking with the alkyd resin to form a film, at present, because the selected monomer is not properly matched with the alkyd resin, the corrosion potential is lower, at present, because the selected monomer is not properly matched with the alkyd resin, the anticorrosive performance of some newly developed alkyd resin coatings is poor, the requirements of actual severe environments cannot be met, and particularly, the preparation process is complex.
The low toxicity of zinc compounds is relatively low, and at present, the documents about the use of rosin zinc for preparing coatings are as follows: the forest product utilization room coating group of Guangxi Zhuang autonomous region forestry scientific research institute, formaldehyde modified rosin zinc paint, 04 th year in 1981, 6-8. The varnish can not meet the anticorrosive requirements of petrochemical equipment, pipelines, offshore oil platforms and ships, can only play a decorative role, and has a complex preparation method.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of rosin-based long-oil alkyd resin anticorrosive enamel with excellent anticorrosive performance and high corrosion potential.
In order to solve the technical problems, the invention adopts the following technical scheme: the paint is prepared by taking dry long-oil alkyd resin and zinc abietate as film forming substances, taking isobutanol as a solvent, and then adding organic kaolin, organic bentonite, carbon black, dimethyl silicone oil and a drier aluminum naphthenate.
The preparation method of the long-oil alkyd resin anticorrosive enamel with the high corrosion potential comprises the steps of taking dry long-oil alkyd resin and zinc abietate as film forming substances, taking isobutanol as a solvent, adding organic kaolin, organic bentonite, carbon black, dimethyl silicone oil and a drier aluminum naphthenate, and stirring at a high speed in a reaction tank to obtain the enamel.
The preparation method of the long-oil alkyd resin anticorrosive enamel with the high corrosion potential comprises the following steps:
<1> in a molar ratio of 1: 2, adding abietic acid and zinc acetate into a crusher, crushing, dispersing and mixing for 3 minutes at 3000 r/min, transferring into a crucible, reacting for 40 minutes in a reaction box at the temperature of 160-190 ℃, transferring into the crusher while the materials are hot, cooling, crushing for 3 minutes, washing the product by using an ethanol aqueous solution with the volume ratio of 30%, and drying for 1 hour at the temperature of 80 ℃ to obtain zinc abietate;
and (2) adding 20-40 parts by weight of dry long-oil alkyd resin, 0.5-5 parts by weight of zinc abietate and 10-30 parts by weight of isobutanol solvent into a reaction tank, uniformly stirring, and then continuously adding 10-20 parts by weight of organic kaolin, 5-15 parts by weight of organic bentonite, 0.5-4 parts by weight of carbon black, 1-6 parts by weight of simethicone and 0.5-5 parts by weight of aluminum salt of a drier naphthenic acid into the reaction tank, and stirring at a high speed for 20 minutes to obtain the nano-silver-zinc-based paint.
Experiments show that the rosin-based long-oil alkyd resin anticorrosive enamel prepared by taking dry long-oil alkyd resin and zinc abietate as film-forming substances, taking isobutanol as a solvent and adding aluminum salt of organic kaolin, organic bentonite, carbon black, dimethyl silicone oil and a drier naphthenic acid is coated on a Q235 carbon steel electrode, and an electrochemical work test is adopted, so that the exposed area is 1 square centimeter, the corrosion current is remarkably reduced, the corrosion potential is increased by more than 200 mV, and the alternating current impedance is remarkably increased; in addition, the enamel is sprayed on a tinplate, and the experiment shows that the salt spray in a 5% sodium chloride solution does not have local corrosion within 200 hours, and the alkyd resin anticorrosive enamel without zinc abietate has serious local corrosion. Therefore, the prepared alkyd resin anticorrosive enamel has higher local corrosion resistance, is superior to the existing alkyd resin anticorrosive enamel, and has the advantages of simple equipment and simple and easy manufacture.
Drawings
FIG. 1 is an infrared spectrum of zinc abietate prepared in example 1;
FIG. 2 is a plot of the polarization of a long oil alkyd anticorrosion enamel of high corrosion potential of example 1 versus an alkyd anticorrosion enamel without the prepared zinc abietate.
FIG. 3 is a plot of the AC impedance of a long oil alkyd anticorrosion enamel of high corrosion potential of example 1 versus an alkyd anticorrosion enamel without the prepared zinc abietate.
FIG. 4 is a graph of a salt spray corrosion experiment for a long oil alkyd anticorrosion enamel of example 1 with a high corrosion potential.
FIG. 5 is a graph of salt spray corrosion experiments for an alkyd resin anticorrosion enamel in example 1 without the prepared zinc abietate.
Detailed Description
Example 1
Treatment of materials
Polishing the material on polishing cloth with 1.0 μm and 0.3 μm of alumina powder, then placing in 5% hydrochloric acid for 5 min, then placing in deionized water for 3 times of ultrasonic cleaning, each time for 5 min, finally placing in absolute ethyl alcohol for 6 min, and drying for later use.
Preparation of alkyd resin anticorrosive enamel
Adding 1 mol of abietic acid and 2 mol of zinc acetate into a pulverizer, pulverizing, dispersing and mixing for 3 minutes at 3000 r/min, transferring into a crucible, reacting for 40 minutes in a reaction box at the temperature of 180 ℃, transferring into the pulverizer while the materials are hot, pulverizing for 3 minutes after cooling, washing the product by using an ethanol aqueous solution with the volume ratio of 30%, and drying at the temperature of 80 ℃ for 1 hour to obtain zinc abietate;
adding 30 parts by weight of dry long-oil alkyd resin, 2 parts by weight of zinc abietate and 20 parts by weight of isobutanol solvent into a reaction tank together, uniformly stirring, and then continuously putting 20 parts by weight of organic kaolin, 5 parts by weight of organic bentonite, 1 part by weight of carbon black, 3 parts by weight of dimethyl silicone oil and 5 parts by weight of aluminum salt of drier naphthenic acid into the reaction tank together, and stirring at high speed for 20 minutes to obtain the long-oil alkyd resin anticorrosive enamel with high corrosion potential;
and (3) the other part of the anticorrosive enamel is completely the same as the step (2) except that 2 parts by weight of zinc abietate is not added, and the long-oil alkyd resin anticorrosive enamel without the zinc abietate is obtained.
Anticorrosion performance test of long-oil alkyd resin anticorrosion enamel
The two prepared anti-corrosion enamel paints are diluted by isopropanol and isobutanol mixed solvent with the solvent volume ratio of 2:3, then 18 mu L of anti-corrosion enamel paint is respectively coated on two spare Q235 carbon steel electrodes, the exposed area of the coating film is 1 square centimeter, the coating film is dried in the air for 24 hours, then an electrochemical polarization curve test and an alternating current impedance test are carried out in 3.5% sodium chloride solution, and the corrosion current, the corrosion potential and the alternating current impedance are compared, so that the corrosion current is remarkably reduced, the corrosion potential is increased by 263 mV, and the alternating current impedance arc is remarkably increased by about 10 times.
And 2, diluting the prepared anticorrosive enamel containing zinc abietate with a mixed solvent of isopropanol and isobutanol in a solvent volume ratio of 2:1, spraying the diluted anticorrosive enamel on a spare tinplate, and spraying the diluted anticorrosive enamel in a 5% sodium chloride solution for 24 hours to form salt mist, wherein the salt mist is 200 hours, and the anticorrosive enamel containing the zinc abietate has no local corrosion phenomenon. The anticorrosive enamel does not contain zinc abietate and has serious local corrosion.
Therefore, the long-oil alkyd resin anticorrosive enamel prepared by the invention is simple in method, and has higher corrosion potential and better local corrosion resistance.
Claims (4)
1. The preparation method of the long-oil alkyd resin anticorrosive enamel with high corrosion potential is characterized by comprising the following components in parts by weight:
20-40% of dry long-oil alkyd resin;
0.5-5 parts of zinc abietate;
10-30 parts of isobutanol as a solvent;
10-20 parts of organic kaolin;
5-15 parts of organic bentonite;
0.5-4% of carbon black;
1-6 parts of dimethyl silicone oil;
0.5-5% of a drier aluminum naphthenate;
the method specifically comprises the following steps:
<1> in a molar ratio of 1: 2, adding abietic acid and zinc acetate into a crusher, crushing, dispersing and mixing for 3 minutes at 3000 r/min, transferring into a crucible, reacting for 40 minutes in a reaction box at the temperature of 160-190 ℃, transferring into the crusher while the materials are hot, cooling, crushing for 3 minutes, washing the product by using an ethanol aqueous solution with the volume ratio of 30%, and drying for 1 hour at the temperature of 80 ℃ to obtain zinc abietate;
and (2) adding 20-40 parts by weight of dry long-oil alkyd resin, 0.5-5 parts by weight of zinc abietate prepared in the step (1) and 10-30 parts by weight of isobutanol solvent into a reaction tank, uniformly stirring, and then continuously adding 10-20 parts by weight of organic kaolin, 5-15 parts by weight of organic bentonite, 0.5-4 parts by weight of carbon black, 1-6 parts by weight of dimethyl silicone oil and 0.5-5 parts by weight of aluminum salt of a drier naphthenic acid into the reaction tank, and stirring at high speed for 20 minutes to obtain the nano-silver-containing alkyd resin.
2. The preparation method of the high corrosion potential long oil alkyd resin anticorrosive enamel according to claim 1, wherein the preparation method comprises the following steps: the reagents used in the step 1 are abietic acid and zinc acetate, and the molar ratio of the reagents is 1: 2.
3. the preparation method of the high corrosion potential long oil alkyd resin anticorrosive enamel according to claim 1, wherein the preparation method comprises the following steps: in the step 1, heating reaction is carried out for 40 minutes at the temperature of 160-190 ℃.
4. The preparation method of the high corrosion potential long oil alkyd resin anticorrosive enamel according to claim 1, wherein the preparation method comprises the following steps: the product was washed with 30% by volume aqueous ethanol and dried at 80 ℃ for 1 hour.
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| CN202011396492.2A CN112409896A (en) | 2020-12-04 | 2020-12-04 | Preparation method of long-oil alkyd resin anticorrosive enamel with high corrosion potential |
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| CN202011396492.2A CN112409896A (en) | 2020-12-04 | 2020-12-04 | Preparation method of long-oil alkyd resin anticorrosive enamel with high corrosion potential |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242936A (en) * | 2013-04-26 | 2013-08-14 | 河南师范大学 | Solid cutting fluid and preparation method thereof |
| CN108690473A (en) * | 2017-07-25 | 2018-10-23 | 山东科耀化工有限公司 | The preparation method of rosin acid modified alkyd resin zinc salt antifouling paint |
| CN110256944A (en) * | 2019-07-12 | 2019-09-20 | 广西民族大学 | A kind of preparation method of the abietyl long oil alkyd corrosive enamel of high pitting potential |
-
2020
- 2020-12-04 CN CN202011396492.2A patent/CN112409896A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242936A (en) * | 2013-04-26 | 2013-08-14 | 河南师范大学 | Solid cutting fluid and preparation method thereof |
| CN108690473A (en) * | 2017-07-25 | 2018-10-23 | 山东科耀化工有限公司 | The preparation method of rosin acid modified alkyd resin zinc salt antifouling paint |
| CN110256944A (en) * | 2019-07-12 | 2019-09-20 | 广西民族大学 | A kind of preparation method of the abietyl long oil alkyd corrosive enamel of high pitting potential |
Non-Patent Citations (2)
| Title |
|---|
| 杨东海: "《松香再加工及利用》", 30 April 1984, 中国林业出版社 * |
| 胡立红等: ""新型松香缓蚀剂"", 《第十四届全国缓蚀剂学术讨论会论文集》 * |
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