CN117702125A - Preparation method of rust-proof master batch composite vapor phase corrosion inhibitor for rust-proof film - Google Patents
Preparation method of rust-proof master batch composite vapor phase corrosion inhibitor for rust-proof film Download PDFInfo
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- CN117702125A CN117702125A CN202311476637.3A CN202311476637A CN117702125A CN 117702125 A CN117702125 A CN 117702125A CN 202311476637 A CN202311476637 A CN 202311476637A CN 117702125 A CN117702125 A CN 117702125A
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- 230000007797 corrosion Effects 0.000 title claims abstract description 99
- 238000005260 corrosion Methods 0.000 title claims abstract description 99
- 239000003112 inhibitor Substances 0.000 title claims abstract description 45
- 239000012808 vapor phase Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical class CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 63
- 230000005764 inhibitory process Effects 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 15
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 32
- 239000012065 filter cake Substances 0.000 claims description 32
- 235000010413 sodium alginate Nutrition 0.000 claims description 29
- 239000000661 sodium alginate Substances 0.000 claims description 29
- 229940005550 sodium alginate Drugs 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003607 modifier Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 12
- 239000012964 benzotriazole Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- IIWXYWWVCBRBCJ-UHFFFAOYSA-N 12-aminododecan-1-ol Chemical compound NCCCCCCCCCCCCO IIWXYWWVCBRBCJ-UHFFFAOYSA-N 0.000 claims description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- GTLQZNKUEFUUIS-UHFFFAOYSA-N carbonic acid;cyclohexanamine Chemical compound OC(O)=O.NC1CCCCC1 GTLQZNKUEFUUIS-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 235000002949 phytic acid Nutrition 0.000 claims description 8
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000008213 purified water Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 230000002401 inhibitory effect Effects 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- 229910052751 metal Inorganic materials 0.000 abstract description 36
- 239000002184 metal Substances 0.000 abstract description 36
- 239000012071 phase Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- VFKZECOCJCGZQK-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCO VFKZECOCJCGZQK-UHFFFAOYSA-M 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 238000006467 substitution reaction Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
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- 239000007769 metal material Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a preparation method of an antirust master batch composite vapor phase inhibitor for an antirust film, and belongs to the technical field of corrosion inhibitor preparation. The invention is used for solving the technical problems that the gas phase corrosion inhibitor in the prior art is difficult to uniformly cover the metal surface, so that corrosion protection is uneven and the corrosion inhibition effect of the conventional gas phase corrosion inhibitor is not stable and durable, and the preparation method of the rust-proof master batch composite gas phase corrosion inhibitor for the rust-proof film comprises the following steps: adding modified sodium alginate, polyethylenimine, mixed antirust master batch and deionized water into a three-neck flask, and stirring until the system is dissolved to obtain a corrosion inhibition solution A; glutaraldehyde and deionized water are added into a three-neck flask and stirred uniformly, so that corrosion inhibition solution B is obtained. The composite vapor phase corrosion inhibitor prepared by the invention can improve the corrosion resistance of metal, has good compatibility with the metal, can not corrode the surface of the metal in the initial stage of use, and has stable corrosion inhibition performance on the metal.
Description
Technical Field
The invention relates to the technical field of corrosion inhibitor preparation, in particular to a preparation method of an antirust master batch composite vapor phase corrosion inhibitor for an antirust film.
Background
Metallic materials are susceptible to corrosion in environments exposed to humidity and oxygen, resulting in damage to the metallic parts and reduced life. To alleviate the metal corrosion problem, rust inhibitive films (also known as corrosion resistant coatings) are widely used to protect metal surfaces. Conventional rust inhibitive films typically include coatings and coverings that provide a protective barrier to reduce metal exposure to corrosive elements of the environment. However, the conventional rust inhibitive film has some disadvantages such as complicated coating process, high cost, easy damage, difficult maintenance, etc.
Vapor phase corrosion inhibitors are a chemical used to prevent corrosion of metals. They are usually in the form of gases or vapors which can be released into the gas phase surrounding the metal surface to form a protective film or chemical barrier on the metal surface in the form of adsorption, complexation, etc. to slow or prevent corrosion of the metal, but existing gas phase corrosion inhibitors tend to have difficulty uniformly covering the metal surface, resulting in uneven corrosion protection. In addition, the corrosion inhibition effect of conventional vapor phase corrosion inhibitors is not stable and durable.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a preparation method of an antirust master batch composite vapor phase inhibitor for an antirust film, which is used for solving the technical problems that the vapor phase inhibitor in the prior art is difficult to uniformly cover the metal surface, so that corrosion protection is uneven and the corrosion inhibition effect of the conventional vapor phase inhibitor is not stable and durable.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the rust-proof master batch composite vapor phase corrosion inhibitor for the rust-proof film comprises the following steps:
s1, adding modified sodium alginate, polyethyleneimine, mixed antirust master batch and deionized water into a three-neck flask, and stirring until the system is dissolved to obtain a corrosion inhibition solution A;
s2, adding glutaraldehyde and deionized water into a three-neck flask, and uniformly stirring to obtain a corrosion inhibition solution B;
s3, mixing the corrosion inhibition solution A and the corrosion inhibition solution B according to a volume ratio of 5:1 by taking compressed air as a carrier, and spraying the mixture from the same nozzle to obtain the composite vapor phase corrosion inhibitor.
Further, in the step S1, the dosage ratio of the modified sodium alginate to the polyethyleneimine to the mixed antirust master batch to the deionized water is 3g to 7g to 4g to 60g, the mixed antirust master batch is composed of benzotriazole, cyclohexylamine carbonate, ammonium phytate and urotropine according to the dosage ratio of 5g to 3g to 2g, wherein the benzotriazole is water-soluble benzotriazole; the dosage ratio of glutaraldehyde to deionized water in step S2 is 1g to 30g.
Further, the modified sodium alginate is processed by the following steps:
a1, adding sodium alginate and absolute ethyl alcohol into a three-neck flask, stirring, dripping an oxidation solution into the three-neck flask, performing light-shielding reaction for 6-8 hours at room temperature, and performing post-treatment to obtain oxidized sodium alginate;
the synthetic reaction principle of the oxidized sodium alginate is as follows:
a2, adding oxidized sodium alginate, a modifier and N, N-dimethylformamide into a three-neck flask, stirring until the system is dissolved, reducing the temperature of the three-neck flask to 8-12 ℃, adding sodium borohydride into the three-neck flask in batches, carrying out heat preservation reaction for 8-10h, and carrying out post treatment to obtain the modified sodium alginate.
The synthetic reaction principle of the modified sodium alginate is as follows:
further, in the step A1, the oxidation solution is 0.1g/mL of sodium periodate aqueous solution, the dosage ratio of sodium alginate, absolute ethyl alcohol and the oxidation solution is 1g:10mL:8mL, and the post-treatment operation comprises: after the reaction is finished, adding ethanolamine into a three-neck flask, stirring for 30-50min, carrying out suction filtration, washing a filter cake with 60vt percent ethanol water solution for three times, then carrying out suction drying, transferring the filter cake into a drying oven with the temperature of 70-80 ℃ and drying to constant weight, thus obtaining oxidized sodium alginate.
Further, in the step A2, the dosage ratio of oxidized sodium alginate, the modifier, the N, N-dimethylformamide to the sodium borohydride is 5g to 2g to 100mL to 1.5g, and the post-treatment operation comprises: and after the reaction is finished, adding absolute ethyl alcohol into the three-neck flask, stirring for 15-25min, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol for three times, then carrying out suction drying, and transferring the filter cake into a drying oven with the temperature of 60-80 ℃ for drying to constant weight, thus obtaining the modified sodium alginate.
Further, the preparation method of the modifier comprises the following steps: adding 12-amino-1-n-dodecanol and acetone into a beaker, stirring until the system is dissolved, and preparing 30wt% of mixed solution of 12-amino-1-n-dodecanol for later use; adding 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide and purified water into a three-neck flask, stirring, heating the three-neck flask to 45-55 ℃, keeping the temperature, stirring for 30-40min, dropwise adding a mixed solution into the three-neck flask, heating the three-neck flask to reflux the system after the dropwise adding is finished, keeping the temperature, reacting for 6-8h, and performing post treatment to obtain the modifier.
The synthetic reaction principle of the modifier is as follows:
further, the dosage ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide, purified water and mixed solution is 10g to 3g to 35mL to 35.7g, and the post-treatment operation comprises: after the reaction is finished, the temperature of the three-mouth flask is reduced to 45-55 ℃, acetone is distilled off under reduced pressure, the temperature of the three-mouth flask is reduced to room temperature, absolute ethyl alcohol is added into the three-mouth flask, a large amount of solids are separated out, suction filtration is carried out, a filter cake is washed three times by the absolute ethyl alcohol and then is pumped to dryness, the filter cake is transferred into a drying box with the temperature of 60-70 ℃, and the filter cake is dried to constant weight, so that the modifier is obtained.
The invention has the following beneficial effects:
1. according to the invention, when the composite gas-phase corrosion inhibitor is prepared, the mixed rust-proof master batch is mixed with the modified sodium alginate and the polyethyleneimine to form the corrosion inhibition solution A, glutaraldehyde solution is used as the corrosion inhibition solution B, the corrosion inhibition solution A and the corrosion inhibition solution B are mixed according to a proportion and then sprayed on the metal surface to form a stable polyethyleneimine/modified sodium alginate rust-proof film on the metal surface, the polyethyleneimine and the modified sodium alginate in the gas-phase corrosion inhibitor can form a stable adhesive film on the metal surface, the mixed rust-proof master batch is uniformly adhered on the metal surface, meanwhile, the high-concentration mixed rust-proof master batch is prevented from directly contacting with the metal surface to corrode the metal surface, and the crosslinking degree of the adhesive film can be effectively controlled by controlling the dosage proportion of glutaraldehyde, so that the air permeability of the adhesive film is improved, the rust-proof master batch can be fully contacted with the metal surface, and the corrosion resistance of the metal is further improved.
2. When the composite vapor phase corrosion inhibitor is prepared, benzotriazole, cyclohexylamine carbonate, ammonium phytate and urotropine are mixed according to a specific proportion to prepare mixed antirust master batch, the benzotriazole is adsorbed to the surface of metal, a protective film is formed on the surface of the metal, contact of oxygen and water molecules on the metal is reduced, and the corrosion rate of the metal is reduced; the cyclohexylamine carbonate and urotropine can neutralize acidic substances and maintain the alkaline pH of the corrosion inhibitor, so that the corrosion of the acidic substances to metals is reduced, and the cyclohexylamine carbonate and the ammonium phytate can form chelates with the surfaces of the metals to form protective films. The film can reduce the contact of metal with oxygen and water molecules, slow down corrosion reaction, supplement benzotriazole, cyclohexylamine carbonate, ammonium phytate and urotropine, improve the corrosion inhibition performance of the whole metal, prolong the service life of the metal and reduce corrosion loss.
3. In the preparation of the composite vapor phase corrosion inhibitor, the hydroxypropyl trimethyl ammonium chloride with dodecylamine modification is prepared by carrying out substitution addition reaction of halogenated hydrocarbon on 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and 12-amino-1-n-dodecanol in an alkaline environment; oxidizing sodium alginate by sodium periodate solution, introducing aldehyde groups into the sodium alginate, and performing nucleophilic addition reaction with amino groups on a modifier to prepare modified sodium alginate; the sodium alginate is subjected to oxidation treatment and then modified, and long alkane linear hydroxypropyl trimethyl ammonium chloride is grafted on modified sodium alginate molecules; the hydroxypropyl trimethyl ammonium chloride of the long alkane straight chain has hydrophobicity, the hydrophilicity of the modified sodium alginate is reduced, the hydrophobicity is enhanced by grafting the long alkane straight chain onto the sodium alginate, the long alkane straight chain with the hydrophobicity can interact with lipid substances, the polyethylenimine is a cationic polymer, the hydroxypropyl trimethyl ammonium chloride is a cationic compound, the modified sodium alginate and the polyethylenimine have similar charged properties, the compatibility of the modified sodium alginate and the polyethylenimine is improved, the modified sodium alginate and the polyethylenimine can form jelly in aqueous solution, the stability of the existence state of corrosion inhibition liquid A is further improved, sedimentation is avoided, and the uniformity of a glue film prepared by the corrosion inhibition liquid A is improved; and the modified sodium alginate after modification has more adsorption sites, and the sites can interact with different functional groups on the surface of the mixed rust-proof master batch, so that the adsorptivity of the sodium alginate and the polyethyleneimine to the mixed rust-proof master batch is improved, and the dispersion uniformity of each component in the corrosion inhibition liquid A is promoted.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the rust-proof master batch composite vapor phase corrosion inhibitor for the rust-proof film provided by the embodiment comprises the following steps:
s1, preparing modifier
Adding 12-amino-1-n-dodecanol and acetone into a beaker, stirring until the system is dissolved, and preparing 30wt% of mixed solution of 12-amino-1-n-dodecanol for later use;
weighing: 30g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 9g of sodium hydroxide and 105mL of purified water are added into a three-neck flask for stirring, the temperature of the three-neck flask is increased to 45 ℃, the three-neck flask is kept warm and stirred for 30min, 107.1g of mixed solution is dripped into the three-neck flask, after the dripping is finished, the temperature of the three-neck flask is increased to the reflux of the system, the temperature of the three-neck flask is kept warm and reacted for 6h, the temperature of the three-neck flask is reduced to 45 ℃, acetone is distilled off under reduced pressure, the temperature of the three-neck flask is reduced to room temperature, 200mL of absolute ethyl alcohol is added into the three-neck flask, a large amount of solids are separated out, the three-neck flask is pumped and filtered, a filter cake is washed three times by the absolute ethyl alcohol and then is pumped out, and the filter cake is transferred into a drying box with the temperature of 60 ℃ and is dried to constant weight, thus obtaining the modifier.
S2, preparing modified sodium alginate
Weighing: adding 20g of sodium alginate and 200mL of absolute ethyl alcohol into a three-necked flask, stirring, dripping 160mL of 0.1g/mL of sodium periodate aqueous solution into the three-necked flask, reacting for 6 hours at room temperature in a dark place, adding 8g of ethanolamine into the three-necked flask, stirring for 30 minutes, carrying out suction filtration, washing a filter cake with 60vt% of ethanol aqueous solution for three times, then pumping, transferring the filter cake into a drying oven with the temperature of 70 ℃ for drying to constant weight, and obtaining oxidized sodium alginate;
weighing: adding 20g of oxidized sodium alginate, 8g of modifier and 400mL of N, N-dimethylformamide into a three-neck flask, stirring until the system is dissolved, reducing the temperature of the three-neck flask to 8 ℃, adding 6g of sodium borohydride into the three-neck flask in batches, carrying out heat preservation reaction for 8h, adding 1600mL of absolute ethyl alcohol into the three-neck flask, stirring for 15min, carrying out suction filtration, washing a filter cake with the absolute ethyl alcohol for three times, then carrying out suction drying, transferring the filter cake into a drying box with the temperature of 60 ℃ and drying to constant weight, thus obtaining the modified sodium alginate.
S3, preparing corrosion inhibition solution A
Weighing: 30g of modified sodium alginate, 70g of polyethylenimine, 16.6g of water-soluble benzotriazole, 10g of cyclohexylamine carbonate, 6.7g of ammonium phytate, 6.7g of urotropine and 600g of deionized water are added into a three-neck flask and stirred until the system is dissolved, so as to obtain a corrosion inhibition solution A.
S4, preparing corrosion inhibition solution B
Weighing: 10g of glutaraldehyde and 300g of deionized water are added into a three-neck flask and stirred uniformly to obtain a corrosion inhibition solution B.
S5, preparing a composite vapor phase corrosion inhibitor
And mixing the corrosion inhibition solution A and the corrosion inhibition solution B according to a volume ratio of 5:1 by taking compressed air as a carrier, and spraying the mixture from the same nozzle to obtain the composite gas-phase corrosion inhibitor.
Example 2
The preparation method of the rust-proof master batch composite vapor phase corrosion inhibitor for the rust-proof film provided by the embodiment comprises the following steps:
s1, preparing modifier
Adding 12-amino-1-n-dodecanol and acetone into a beaker, stirring until the system is dissolved, and preparing 30wt% of mixed solution of 12-amino-1-n-dodecanol for later use;
weighing: 30g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 9g of sodium hydroxide and 105mL of purified water are added into a three-neck flask for stirring, the temperature of the three-neck flask is increased to 50 ℃, the three-neck flask is kept warm and stirred for 35min, 107.1g of mixed solution is dripped into the three-neck flask, after the dripping is finished, the temperature of the three-neck flask is increased to the reflux of the system, the temperature of the three-neck flask is kept warm and reacted for 7h, the temperature of the three-neck flask is reduced to 50 ℃, acetone is distilled off under reduced pressure, the temperature of the three-neck flask is reduced to room temperature, 200mL of absolute ethyl alcohol is added into the three-neck flask, a large amount of solids are separated out, the three-neck flask is pumped and filtered, a filter cake is washed three times by the absolute ethyl alcohol and then is pumped out, and the filter cake is transferred into a drying box with the temperature of 65 ℃ and is dried to constant weight, thus obtaining the modifier.
S2, preparing modified sodium alginate
Weighing: adding 20g of sodium alginate and 200mL of absolute ethyl alcohol into a three-necked flask, stirring, dripping 160mL of 0.1g/mL of sodium periodate aqueous solution into the three-necked flask, reacting for 7 hours at room temperature in a dark place, adding 8g of ethanolamine into the three-necked flask, stirring for 40 minutes, carrying out suction filtration, washing a filter cake with 60vt% of ethanol aqueous solution for three times, then pumping, transferring the filter cake into a drying oven with the temperature of 75 ℃ for drying to constant weight, and obtaining oxidized sodium alginate;
weighing: adding 20g of oxidized sodium alginate, 8g of modifier and 400mL of N, N-dimethylformamide into a three-neck flask, stirring until the system is dissolved, reducing the temperature of the three-neck flask to 10 ℃, adding 6g of sodium borohydride into the three-neck flask in batches, carrying out heat preservation reaction for 9h, adding 1600mL of absolute ethyl alcohol into the three-neck flask, stirring for 20min, carrying out suction filtration, washing a filter cake with the absolute ethyl alcohol for three times, then carrying out suction drying, transferring the filter cake into a drying box with the temperature of 70 ℃ and drying to constant weight, thus obtaining the modified sodium alginate.
S3, preparing corrosion inhibition solution A
Weighing: 30g of modified sodium alginate, 70g of polyethylenimine, 16.6g of water-soluble benzotriazole, 10g of cyclohexylamine carbonate, 6.7g of ammonium phytate, 6.7g of urotropine and 600g of deionized water are added into a three-neck flask and stirred until the system is dissolved, so as to obtain a corrosion inhibition solution A.
S4, preparing corrosion inhibition solution B
Weighing: 10g of glutaraldehyde and 300g of deionized water are added into a three-neck flask and stirred uniformly to obtain a corrosion inhibition solution B.
S5, preparing a composite vapor phase corrosion inhibitor
And mixing the corrosion inhibition solution A and the corrosion inhibition solution B according to a volume ratio of 5:1 by taking compressed air as a carrier, and spraying the mixture from the same nozzle to obtain the composite gas-phase corrosion inhibitor.
Example 3
The preparation method of the rust-proof master batch composite vapor phase corrosion inhibitor for the rust-proof film provided by the embodiment comprises the following steps:
s1, preparing modifier
Adding 12-amino-1-n-dodecanol and acetone into a beaker, stirring until the system is dissolved, and preparing 30wt% of mixed solution of 12-amino-1-n-dodecanol for later use;
weighing: 30g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 9g of sodium hydroxide and 105mL of purified water are added into a three-neck flask for stirring, the temperature of the three-neck flask is increased to 55 ℃, the three-neck flask is kept warm and stirred for 40min, 107.1g of mixed solution is dripped into the three-neck flask, the temperature of the three-neck flask is increased until the system is refluxed after the dripping is finished, the temperature of the three-neck flask is kept warm for 6-8h, the temperature of the three-neck flask is reduced to 55 ℃, acetone is distilled off under reduced pressure, the temperature of the three-neck flask is reduced to room temperature, 200mL of absolute ethyl alcohol is added into the three-neck flask, a large amount of solids are separated out, the three-neck flask is pumped and filtered, a filter cake is washed three times by absolute ethyl alcohol and then pumped to dryness, and the filter cake is transferred into a drying box with the temperature of 70 ℃ and dried to constant weight, and the modifier is obtained.
S2, preparing modified sodium alginate
Weighing: adding 20g of sodium alginate and 200mL of absolute ethyl alcohol into a three-necked flask, stirring, dripping 160mL of 0.1g/mL of sodium periodate aqueous solution into the three-necked flask, reacting for 8 hours at room temperature in a dark place, adding 8g of ethanolamine into the three-necked flask, stirring for 50 minutes, carrying out suction filtration, washing a filter cake with 60vt% of ethanol aqueous solution for three times, then pumping, transferring the filter cake into a drying oven with the temperature of 80 ℃ for drying to constant weight, and obtaining oxidized sodium alginate;
weighing: adding 20g of oxidized sodium alginate, 8g of modifier and 400mL of N, N-dimethylformamide into a three-neck flask, stirring until the system is dissolved, reducing the temperature of the three-neck flask to 12 ℃, adding 6g of sodium borohydride into the three-neck flask in batches, carrying out heat preservation reaction for 10h, adding 1600mL of absolute ethyl alcohol into the three-neck flask, stirring for 25min, carrying out suction filtration, washing a filter cake with the absolute ethyl alcohol for three times, then carrying out suction drying, transferring the filter cake into a drying box with the temperature of 80 ℃ and drying until the weight is constant, thus obtaining the modified sodium alginate.
S3, preparing corrosion inhibition solution A
Weighing: 30g of modified sodium alginate, 70g of polyethylenimine, 16.6g of water-soluble benzotriazole, 10g of cyclohexylamine carbonate, 6.7g of ammonium phytate, 6.7g of urotropine and 600g of deionized water are added into a three-neck flask and stirred until the system is dissolved, so as to obtain a corrosion inhibition solution A.
S4, preparing corrosion inhibition solution B
Weighing: 10g of glutaraldehyde and 300g of deionized water are added into a three-neck flask and stirred uniformly to obtain a corrosion inhibition solution B.
S5, preparing a composite vapor phase corrosion inhibitor
And mixing the corrosion inhibition solution A and the corrosion inhibition solution B according to a volume ratio of 5:1 by taking compressed air as a carrier, and spraying the mixture from the same nozzle to obtain the composite gas-phase corrosion inhibitor.
Comparative example 1
The difference between this comparative example and example 1 is that step S1 is omitted and the modified sodium alginate in step S3 is replaced with an equal amount of oxidized sodium alginate.
Comparative example 2
The difference between this comparative example and example 1 is that step S1 and step S2 are omitted and the modified sodium alginate in step S3 is replaced with an equal amount of sodium alginate.
Example 3
The present comparative example is different from example 1 in that modified sodium alginate was not added in step S3.
Performance test:
the composite vapor phase corrosion inhibitors prepared in examples 1 to 3 and comparative examples 1 to 3 were sprayed on metal samples, and the samples sprayed with the composite vapor phase corrosion inhibitors were tested for vapor phase corrosion inhibition ability (A), vapor phase corrosion inhibition ability after accelerated consumption, compatibility and corrosiveness according to the standard GB/T35491-2017 corrosion inhibitor vapor phase corrosion inhibitor, and specific test results are shown in the following table:
data analysis:
the data in the table are compared and analyzed, the composite gas phase corrosion inhibitor prepared by the invention shows stable corrosion inhibition performance on the gas phase corrosion inhibition capability (A) of metal and the gas phase corrosion inhibition capability after accelerated consumption, and has stable compatibility with the metal, and can not corrode the metal when contacting with the metal.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (7)
1. The preparation method of the rust-proof master batch composite vapor phase corrosion inhibitor for the rust-proof film is characterized by comprising the following steps of:
s1, adding modified sodium alginate, polyethyleneimine, mixed antirust master batch and deionized water into a three-neck flask, and stirring until the system is dissolved to obtain a corrosion inhibition solution A;
s2, adding glutaraldehyde and deionized water into a three-neck flask, and uniformly stirring to obtain a corrosion inhibition solution B;
s3, mixing the corrosion inhibition solution A and the corrosion inhibition solution B according to a volume ratio of 5:1 by taking compressed air as a carrier, and spraying the mixture from the same nozzle to obtain the composite vapor phase corrosion inhibitor.
2. The preparation method of the rust-proof master batch composite vapor phase corrosion inhibitor for the rust-proof film, which is characterized in that in the step S1, the dosage ratio of modified sodium alginate to polyethyleneimine to mixed rust-proof master batch to deionized water is 3g to 7g to 4g to 60g, the mixed rust-proof master batch consists of benzotriazole, cyclohexylamine carbonate, ammonium phytate and urotropine according to the dosage ratio of 5g to 3g to 2g, wherein the benzotriazole is water-soluble benzotriazole; the dosage ratio of glutaraldehyde to deionized water in step S2 is 1g to 30g.
3. The method for preparing the rust-proof master batch composite vapor phase corrosion inhibitor for the rust-proof film according to claim 1, wherein the modified sodium alginate is processed by the following steps:
a1, adding sodium alginate and absolute ethyl alcohol into a three-neck flask, stirring, dripping an oxidation solution into the three-neck flask, performing light-shielding reaction for 6-8 hours at room temperature, and performing post-treatment to obtain oxidized sodium alginate;
a2, adding oxidized sodium alginate, a modifier and N, N-dimethylformamide into a three-neck flask, stirring until the system is dissolved, reducing the temperature of the three-neck flask to 8-12 ℃, adding sodium borohydride into the three-neck flask in batches, carrying out heat preservation reaction for 8-10h, and carrying out post treatment to obtain the modified sodium alginate.
4. The method for preparing the rust-preventive master batch composite vapor phase corrosion inhibitor for the rust-preventive film according to claim 3, wherein the oxidation solution in the step A1 is 0.1g/mL of sodium periodate aqueous solution, the dosage ratio of sodium alginate, absolute ethyl alcohol and oxidation solution is 1g:10mL:8mL, and the post-treatment operation comprises: after the reaction is finished, adding ethanolamine into a three-neck flask, stirring for 30-50min, carrying out suction filtration, washing a filter cake with 60vt percent ethanol water solution for three times, then carrying out suction drying, transferring the filter cake into a drying oven with the temperature of 70-80 ℃ and drying to constant weight, thus obtaining oxidized sodium alginate.
5. The method for preparing the rust-preventive master batch composite vapor phase corrosion inhibitor for the rust-preventive film according to claim 3, wherein the usage amount ratio of oxidized sodium alginate, modifier, N-dimethylformamide and sodium borohydride in the step A2 is 5g:2g:100mL:1.5g, and the post-treatment operation comprises: and after the reaction is finished, adding absolute ethyl alcohol into the three-neck flask, stirring for 15-25min, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol for three times, then carrying out suction drying, and transferring the filter cake into a drying oven with the temperature of 60-80 ℃ for drying to constant weight, thus obtaining the modified sodium alginate.
6. The method for preparing the rust inhibitive master batch composite vapor phase inhibitor for the rust inhibitive film according to claim 3, wherein the preparation method of the modifier is as follows: adding 12-amino-1-n-dodecanol and acetone into a beaker, stirring until the system is dissolved, and preparing 30wt% of mixed solution of 12-amino-1-n-dodecanol for later use; adding 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide and purified water into a three-neck flask, stirring, heating the three-neck flask to 45-55 ℃, keeping the temperature, stirring for 30-40min, dropwise adding a mixed solution into the three-neck flask, heating the three-neck flask to reflux the system after the dropwise adding is finished, keeping the temperature, reacting for 6-8h, and performing post treatment to obtain the modifier.
7. The method for preparing the rust-preventive master batch composite vapor phase corrosion inhibitor for the rust-preventive film according to claim 6, wherein the dosage ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, the sodium hydroxide, the purified water and the mixed solution is 10g:3g:35mL:35.7g, and the post-treatment operation comprises: after the reaction is finished, the temperature of the three-mouth flask is reduced to 45-55 ℃, acetone is distilled off under reduced pressure, the temperature of the three-mouth flask is reduced to room temperature, absolute ethyl alcohol is added into the three-mouth flask, a large amount of solids are separated out, suction filtration is carried out, a filter cake is washed three times by the absolute ethyl alcohol and then is pumped to dryness, the filter cake is transferred into a drying box with the temperature of 60-70 ℃, and the filter cake is dried to constant weight, so that the modifier is obtained.
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