CN109097781A - A kind of metal antirusting agent containing modified thiadiazoles - Google Patents
A kind of metal antirusting agent containing modified thiadiazoles Download PDFInfo
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- CN109097781A CN109097781A CN201810982849.1A CN201810982849A CN109097781A CN 109097781 A CN109097781 A CN 109097781A CN 201810982849 A CN201810982849 A CN 201810982849A CN 109097781 A CN109097781 A CN 109097781A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/06—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly alkaline liquids
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Abstract
The invention discloses a kind of metal antirusting agent containing modified thiadiazoles, raw material includes: styrene-acrylic emulsion, polyethylene glycol dimethacrylate, polyaniline, polymaleic anhydride, amino acid, benzotriazole, benzimidazole, modified thiadiazoles, ricinoleic acid, tall oil acid diglycollic amide, sodium molybdate, zirconic acid zinc, propilolic alcohol, cerous nitrate, graphene oxide, triethanolamine, silane coupling agent, potassium hydroxide, natural corrosion inhibiter, ethyl alcohol, water.Metal antirusting agent proposed by the present invention containing modified thiadiazoles, favorable rust preventing effect, antirust time are long.
Description
Technical field
The present invention relates to metal conditioner technical field more particularly to a kind of metal antirusting agents containing modified thiadiazoles.
Background technique
The corrosion of metal is frequently problem in production and living, and the life of product after getting rusty is short, and can not be normal
Use, performance is all affected to some extent, and the metal after excessive erosion not only pollutes environment, but also waste vast resources and energy
Consumption.Therefore antirust treatment has great research significance.Antirust agent is divided into oiliness antirust agent and water-based antirust agent, water-based antirust agent
It is to be added the lye that is made into of water soluble medicament thereto using water as substrate, easy to use, at low cost, safety and removes also very
It is easy, has been favored by people, although existing water-based antirust agent has certain anti-rust action, but rust-proof effect is owed
Good, the antirust period is short, limits its application.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of metal antirusting agent containing modified thiadiazoles,
Its favorable rust preventing effect, antirust time are long.
A kind of metal antirusting agent containing modified thiadiazoles proposed by the present invention, raw material includes: styrene-acrylic emulsion by weight
30-45 parts, 10-20 parts of polyethylene glycol dimethacrylate, 2-3.8 parts of polyaniline, 3-8 parts of polymaleic anhydride, amino acid
0.1-1.2 parts, 0.6-1.2 parts of benzotriazole, 0.2-1.3 parts of benzimidazole, modified thiadiazoles 2-5.3 parts, ricinoleic acid 2-
3.7 parts, 1-2.3 parts of tall oil acid diglycollic amide, 0.3-1.2 parts of sodium molybdate, 1-2 parts of zirconic acid zinc, 2-5 parts of propilolic alcohol, nitric acid
0.5-1.3 parts of cerium, 0.1-0.8 parts of graphene oxide, 0.2-1 parts of triethanolamine, 0.3-1 parts of silane coupling agent, potassium hydroxide
0.1-0.5 parts, corrosion inhibiter 2-3.8 parts natural, 20-35 parts of ethyl alcohol, 150-250 parts of water.
Preferably, the solid content of the styrene-acrylic emulsion is 40-45wt%.
Preferably, the amino acid is the mixed of one or more of cysteine, glycine, alanine, leucine
Close object.
Preferably, the benzimidazole is the benzimidazole of amine-methylated modification.
Preferably, the modified thiadiazoles is prepared according to following technique: Eighteen alkyl acid is mixed with thionyl chloride,
Back flow reaction 100-200min after mixing evenly, is added the alkaline solution of asparatate after vacuum distillation, adjusting pH value is 8-
9, reaction 120-200min is stirred at room temperature, it is acidity that pH is adjusted after cooling, and liquid separation, washing obtain material A；By 2- sulfydryl -5- first
Base -1,3,4- thiadiazoles are mixed with aqueous sulfuric acid, and material A is added at 35-40 DEG C, react 100- at 45-55 DEG C
Water is added after cooling in 200min, filters, and it is 2-3 that pH value is adjusted after filter cake is dissolved with sodium hydrate aqueous solution, be filtered, washed,
Material B is recrystallized to give after drying；Material B is added in dimethylbenzene, triethanolamine is added at 60-70 DEG C, at 100-105 DEG C
Under be stirred to react 2-4h, cool down, rotate after reaction, being dried to obtain the modified thiadiazoles.
Preferably, in the preparation process of modified thiadiazoles, Eighteen alkyl acid, thionyl chloride, asparatate mole
Than for 1:1.3-1.5:0.8-0.9；2- sulfydryl -5- methyl-1,3,4- thiadiazoles, material A molar ratio be 1:1.2-1.5；Object
Expect B, the molar ratio of triethanolamine is 1:1.05-1.3.
Preferably, the silane coupling agent is silane resin acceptor kh-550.
Preferably, the natural corrosion inhibiter is one of Olive leaf P.E, Herba Lysimachiae foenumgraeci extract, watermelon bark extract
Or a variety of mixture.
Metal antirusting agent of the present invention containing modified thiadiazoles, in raw material, using styrene-acrylic emulsion as main film-former,
It joined polyaniline simultaneously, wherein the N on polyaniline imines can interact with each metal ion species, to induce polyaniline
The phenyl group for forming electron rich cooperates with increasing with having after polyethylene glycol dimethacrylate, polymaleic anhydride, amino acid cooperation
Effect effect improves the coverage in substrate surface, and quality of forming film is high, and the adhesive force between metal surface is strong, mentions significantly
The high rust-proof effect and stability of antirust agent, extends the antirust time of antirust agent；In the preparation process of modified thiadiazoles,
First using Eighteen alkyl acid and thionyl chloride as raw material, the chlorine in carboxyl and thionyl chloride in Eighteen alkyl acid has occurred instead
It answers, after mixing with asparatate, chlorine therein is reacted with the amino of asparatate, has obtained material A；With 2- mercapto
Base -5- methyl-1,3,4- thiadiazoles and material A are raw material, control the condition of reaction, make carboxyl and 2- sulfydryl -5- in material A
Methyl-1, the sulfydryl in 3,4- thiadiazoles are reacted, have obtained material B, using material B and triethanolamine as raw material, made two
Person is reacted, and has been obtained modified thiadiazoles, has been added into system, and O, S and N atom are rich in molecule, can be with metal
The hole the d track coordination of ion combines and is formed the octahedral structure of high-spin, and strong adsorption is in metal surface, with three nitrogen of benzo
Azoles, benzimidazole, ricinoleic acid, the cooperation of tall oil acid diglycollic amide form a fine and close protective layer in metal surface, will
Corrosive medium and metal surface separate, and avoid the corrosion of metal material, while improving the greasy property of antirust agent, and be easy to
Biodegrade, the feature of environmental protection are good；In cerous nitrate addition system, with the anion layer of metal surface electrostatic can occur for cerium atom therein
Suction-operated is filled with the gap of metal surface protection layer；Modified thiadiazoles, cerous nitrate and sodium molybdate, zirconic acid zinc, propilolic alcohol and
After natural corrosion inhibiter cooperation, various synergistic effects are played, the rustless property of antirust agent is significantly improved, extends antirust agent
Antirust time, its antirust time is extended to 6 months or more；It, can be with the ethyl alcohol in system in graphene oxide addition system
Forming graphite oxide enester can have an effect under the action of potassium hydroxide with the triethanolamine in system, and it is negative to obtain surface band
The substance of charge can form fine and close protective film in metal surface with the positive charge quick adsorption generated during corrosion of metal,
Prevent the contact with metal surface such as oxygen, hydrone, it is therefore prevented that the generation of corrosion of metal phenomenon.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of metal antirusting agent containing modified thiadiazoles proposed by the present invention, raw material includes: styrene-acrylic emulsion by weight
45 parts, 10 parts of polyethylene glycol dimethacrylate, 3.8 parts of polyaniline, 3 parts of polymaleic anhydride .2 parts of amino acid 1, benzo three
0.6 part of nitrogen azoles, 1.3 parts of benzimidazole, modified 2 parts of thiadiazoles, 3.7 parts of ricinoleic acid, 1 part of tall oil acid diglycollic amide, molybdenum
1.2 parts of sour sodium, 1 part of zirconic acid zinc, 5 parts of propilolic alcohol, 0.5 part of cerous nitrate, 0.8 part of graphene oxide, 0.2 part of triethanolamine, silane
1 part of coupling agent, 0.1 part of potassium hydroxide, 3.8 parts of natural corrosion inhibiter, 20 parts of ethyl alcohol, 250 parts of water.
Embodiment 2
A kind of metal antirusting agent containing modified thiadiazoles proposed by the present invention, raw material includes: styrene-acrylic emulsion by weight
30 parts, 20 parts of polyethylene glycol dimethacrylate, 2 parts of polyaniline, 8 parts of polymaleic anhydride, 0.1 part of amino acid, three nitrogen of benzo
1.2 parts of azoles, 0.2 part of benzimidazole, modified 5.3 parts of thiadiazoles, 2 parts of ricinoleic acid, 2.3 parts of tall oil acid diglycollic amide, molybdenum
0.3 part of sour sodium, 2 parts of zirconic acid zinc, 2 parts of propilolic alcohol, 1.3 parts of cerous nitrate, 0.1 part of graphene oxide, 1 part of triethanolamine, silane are even
Join 0.3 part of agent, 0.5 part of potassium hydroxide, 2 parts of natural corrosion inhibiter, 35 parts of ethyl alcohol, 150 parts of water.
Embodiment 3
A kind of metal antirusting agent containing modified thiadiazoles proposed by the present invention, raw material includes: styrene-acrylic emulsion by weight
43 parts, 16 parts of polyethylene glycol dimethacrylate, 3.2 parts of polyaniline, 5 parts of polymaleic anhydride, amino acid 1 part, three nitrogen of benzo
0.7 part of azoles, 1 part of benzimidazole, modified 2.8 parts of thiadiazoles, 3.5 parts of ricinoleic acid, 1.4 parts of tall oil acid diglycollic amide, molybdenum
1 part of sour sodium, 1.2 parts of zirconic acid zinc, 4.7 parts of propilolic alcohol, 0.7 part of cerous nitrate, 0.7 part of graphene oxide, 0.5 part of triethanolamine, silicon
0.7 part of alkane coupling agent, 0.2 part of potassium hydroxide, 3.5 parts of natural corrosion inhibiter, 28 parts of ethyl alcohol, 210 parts of water；
Wherein, the solid content of the styrene-acrylic emulsion is 40wt%；
The amino acid is the mixture of glycine, leucine；
The benzimidazole is the benzimidazole of amine-methylated modification；
The modified thiadiazoles is prepared according to following technique: Eighteen alkyl acid being mixed with thionyl chloride, stirring is equal
Back flow reaction 100min after even, is added the alkaline solution of asparatate after vacuum distillation, adjusting pH value is 9, is stirred at room temperature anti-
120min is answered, it is acidity that pH is adjusted after cooling, and liquid separation, washing obtain material A；By 2- sulfydryl -5- methyl-1,3,4- thiadiazoles with
Aqueous sulfuric acid mixing, is added material A at 40 DEG C, and 200min is reacted at 45 DEG C, water is added after cooling, is filtered, by filter cake
After being dissolved with sodium hydrate aqueous solution adjust pH value be 2, be filtered, washed, dry after be recrystallized to give material B；Material B is added
In dimethylbenzene, triethanolamine is added at 70 DEG C, 4h is stirred to react at 100 DEG C, it is cooling after reaction, rotate, is dry
To the modified thiadiazoles；
In the preparation process of modified thiadiazoles, Eighteen alkyl acid, thionyl chloride, asparatate molar ratio be 1:
1.3:0.9；2- sulfydryl -5- methyl-1,3,4- thiadiazoles, material A molar ratio be 1:1.2；Mole of material B, triethanolamine
Than for 1:1.3；
The silane coupling agent is silane resin acceptor kh-550；
The natural corrosion inhibiter is Olive leaf P.E.
Embodiment 4
A kind of metal antirusting agent containing modified thiadiazoles proposed by the present invention, raw material includes: styrene-acrylic emulsion by weight
35 parts, 14 parts of polyethylene glycol dimethacrylate, 2.8 parts of polyaniline, 7 parts of polymaleic anhydride, 0.6 part of amino acid, benzo three
1.1 parts of nitrogen azoles, 0.5 part of benzimidazole, modified 5 parts of thiadiazoles, 2.8 parts of ricinoleic acid, 2.1 parts of tall oil acid diglycollic amide,
0.5 part of sodium molybdate, 1.8 parts of zirconic acid zinc, 3.2 parts of propilolic alcohol, 1.2 parts of cerous nitrate, 0.3 part of graphene oxide, triethanolamine 0.8
Part, 0.4 part of silane coupling agent, 0.42 part of potassium hydroxide, 2.8 parts of natural corrosion inhibiter, 32 parts of ethyl alcohol, 170 parts of water；
Wherein, the solid content of the styrene-acrylic emulsion is 45wt%；
The amino acid is cysteine；
The benzimidazole is the benzimidazole of amine-methylated modification；
The modified thiadiazoles is prepared according to following technique: Eighteen alkyl acid being mixed with thionyl chloride, stirring is equal
Back flow reaction 200min after even, is added the alkaline solution of asparatate after vacuum distillation, adjusting pH value is 8, is stirred at room temperature anti-
200min is answered, it is acidity that pH is adjusted after cooling, and liquid separation, washing obtain material A；By 2- sulfydryl -5- methyl-1,3,4- thiadiazoles with
Aqueous sulfuric acid mixing, is added material A at 35 DEG C, and 100min is reacted at 55 DEG C, water is added after cooling, is filtered, by filter cake
After being dissolved with sodium hydrate aqueous solution adjust pH value be 3, be filtered, washed, dry after be recrystallized to give material B；Material B is added
In dimethylbenzene, triethanolamine is added at 60 DEG C, 2h is stirred to react at 105 DEG C, it is cooling after reaction, rotate, is dry
To the modified thiadiazoles；
In the preparation process of modified thiadiazoles, Eighteen alkyl acid, thionyl chloride, asparatate molar ratio be 1:
1.5:0.8；2- sulfydryl -5- methyl-1,3,4- thiadiazoles, material A molar ratio be 1:1.5；Mole of material B, triethanolamine
Than for 1:1.05；
The silane coupling agent is silane resin acceptor kh-550；
The natural corrosion inhibiter is the mixture of Herba Lysimachiae foenumgraeci extract, watermelon bark extract.
Embodiment 5
A kind of metal antirusting agent containing modified thiadiazoles proposed by the present invention, raw material includes: styrene-acrylic emulsion by weight
42 parts, 18 parts of polyethylene glycol dimethacrylate, 3.5 parts of polyaniline, 7 parts of polymaleic anhydride, amino acid 1 part, three nitrogen of benzo
0.9 part of azoles, 0.9 part of benzimidazole, modified 4.7 parts of thiadiazoles, 2.9 parts of ricinoleic acid, 1.8 parts of tall oil acid diglycollic amide,
0.9 part of sodium molybdate, 1.5 parts of zirconic acid zinc, 3.2 parts of propilolic alcohol, 1 part of cerous nitrate, 0.6 part of graphene oxide, 0.7 part of triethanolamine,
0.8 part of silane coupling agent, 0.32 part of potassium hydroxide, 2.9 parts of natural corrosion inhibiter, 28 parts of ethyl alcohol, 200 parts of water；
Wherein, the solid content of the styrene-acrylic emulsion is 43wt%；
The amino acid is the mixture of cysteine, glycine, alanine, leucine；
The benzimidazole is the benzimidazole of amine-methylated modification；
The modified thiadiazoles is prepared according to following technique: Eighteen alkyl acid being mixed with thionyl chloride, stirring is equal
Back flow reaction 150min after even, is added the alkaline solution of asparatate after vacuum distillation, adjusting pH value is 8, is stirred at room temperature anti-
170min is answered, it is acidity that pH is adjusted after cooling, and liquid separation, washing obtain material A；By 2- sulfydryl -5- methyl-1,3,4- thiadiazoles with
Aqueous sulfuric acid mixing, is added material A at 37 DEG C, and 150min is reacted at 50 DEG C, water is added after cooling, is filtered, by filter cake
After being dissolved with sodium hydrate aqueous solution adjust pH value be 2, be filtered, washed, dry after be recrystallized to give material B；Material B is added
In dimethylbenzene, triethanolamine is added at 65 DEG C, 3.2h is stirred to react at 103 DEG C, cooling after reaction, revolving, drying
Obtain the modified thiadiazoles；
In the preparation process of modified thiadiazoles, Eighteen alkyl acid, thionyl chloride, asparatate molar ratio be 1:
1.4:0.85；2- sulfydryl -5- methyl-1,3,4- thiadiazoles, material A molar ratio be 1:1.32；Material B, triethanolamine rub
You are than being 1:1.2；
The silane coupling agent is silane resin acceptor kh-550；
The natural corrosion inhibiter is the mixture of Olive leaf P.E, Herba Lysimachiae foenumgraeci extract, watermelon bark extract.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of metal antirusting agent containing modified thiadiazoles, which is characterized in that its raw material includes: styrene-acrylic emulsion 30- by weight
45 parts, 10-20 parts of polyethylene glycol dimethacrylate, 2-3.8 parts of polyaniline, 3-8 parts of polymaleic anhydride, amino acid 0.1-
1.2 parts, 0.6-1.2 parts of benzotriazole, 0.2-1.3 parts of benzimidazole, modified thiadiazoles 2-5.3 parts, ricinoleic acid 2-3.7
Part, 1-2.3 parts of tall oil acid diglycollic amide, 0.3-1.2 parts of sodium molybdate, 1-2 parts of zirconic acid zinc, 2-5 parts of propilolic alcohol, cerous nitrate
0.5-1.3 parts, 0.1-0.8 parts of graphene oxide, 0.2-1 parts of triethanolamine, 0.3-1 parts of silane coupling agent, potassium hydroxide 0.1-
0.5 part, corrosion inhibiter 2-3.8 parts natural, 20-35 parts of ethyl alcohol, 150-250 parts of water.
2. the metal antirusting agent according to claim 1 containing modified thiadiazoles, which is characterized in that consolidating for the styrene-acrylic emulsion contains
Amount is 40-45wt%.
3. the metal antirusting agent according to claim 1 or claim 2 containing modified thiadiazoles, which is characterized in that the amino acid is half
The mixture of one or more of cystine, glycine, alanine, leucine.
4. the metal antirusting agent containing modified thiadiazoles described in any one of -3 according to claim 1, which is characterized in that the benzo
Imidazoles is the benzimidazole of amine-methylated modification.
5. the metal antirusting agent containing modified thiadiazoles described in any one of -4 according to claim 1, which is characterized in that the modification
Thiadiazoles is prepared according to following technique: Eighteen alkyl acid being mixed with thionyl chloride, after mixing evenly back flow reaction 100-
The alkaline solution of asparatate is added in 200min after vacuum distillation, adjusting pH value is 8-9, and reaction 120- is stirred at room temperature
200min, it is acidity that pH is adjusted after cooling, and liquid separation, washing obtain material A；By 2- sulfydryl -5- methyl-1,3,4- thiadiazoles and sulphur
Aqueous acid mixing, is added material A at 35-40 DEG C, and 100-200min is reacted at 45-55 DEG C, water, mistake is added after cooling
Filter, after filter cake is dissolved with sodium hydrate aqueous solution adjust pH value be 2-3, be filtered, washed, dry after be recrystallized to give material B；
Material B is added in dimethylbenzene, triethanolamine is added at 60-70 DEG C, 2-4h, reaction knot are stirred to react at 100-105 DEG C
It cools down, rotate after beam, being dried to obtain the modified thiadiazoles.
6. the metal antirusting agent according to claim 5 containing modified thiadiazoles, which is characterized in that in the preparation of modified thiadiazoles
In the process, Eighteen alkyl acid, thionyl chloride, asparatate molar ratio be 1:1.3-1.5:0.8-0.9；2- sulfydryl -5- first
Base -1,3,4- thiadiazoles, material A molar ratio be 1:1.2-1.5；Material B, triethanolamine molar ratio be 1:1.05-1.3.
7. the metal antirusting agent containing modified thiadiazoles described in any one of -6 according to claim 1, which is characterized in that the silane
Coupling agent is silane resin acceptor kh-550.
8. the metal antirusting agent containing modified thiadiazoles described in any one of -7 according to claim 1, which is characterized in that described natural
Corrosion inhibiter is the mixture of one or more of Olive leaf P.E, Herba Lysimachiae foenumgraeci extract, watermelon bark extract.
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| CN112899668A (en) * | 2021-01-26 | 2021-06-04 | 温州万虹阀门有限公司 | Surface treatment process for valve body casting part |
| CN115678411A (en) * | 2022-12-19 | 2023-02-03 | 南昌航空大学 | Method for preparing GO/Ce-MOF @ PDA/PU super-hydrophobic self-repairing anti-corrosion coating |
| CN115678411B (en) * | 2022-12-19 | 2023-06-09 | 南昌航空大学 | Method for preparing GO/Ce-MOF@PDA/PU super-hydrophobic self-repairing anti-corrosion coating |
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Application publication date: 20181228 |