CN110318056B - A kind of water-based metal galvanic corrosion inhibitor and preparation method thereof - Google Patents
A kind of water-based metal galvanic corrosion inhibitor and preparation method thereof Download PDFInfo
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- 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
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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Abstract
本发明提供了一种水基金属电偶腐蚀抑制剂及制备方法，其中，水基金属电偶腐蚀抑制剂，包括以下重量份的各组分：羧酸型防锈剂5‑40份，磷酸酯缓蚀剂5‑40份，有机硅缓蚀剂3‑35份，醇胺型硼酸酯10‑50份，甲基苯并三氮唑2‑20份，Tween80 0‑20份，水5‑20份。本发明所述的水基金属电偶腐蚀抑制剂，可作为防锈水单独使用，亦可做添加剂用于金属加工液的配方设计，用量少，具有优异的防锈缓蚀性能，可显著抑制异金属接触面之间的电偶腐蚀，提升金属表面的光亮度，尤其对钛合金及铝合金的电偶腐蚀抑制作用尤为明显。The invention provides a water-based metal galvanic corrosion inhibitor and a preparation method, wherein the water-based metal galvanic corrosion inhibitor comprises the following components in parts by weight: 5-40 parts of a carboxylic acid type rust inhibitor, phosphoric acid 5-40 parts of ester corrosion inhibitor, 3-35 parts of silicone corrosion inhibitor, 10-50 parts of alcohol amine borate, 2-20 parts of methylbenzotriazole, 0-20 parts of Tween80, 5 parts of water ‑20 servings. The water-based metal galvanic corrosion inhibitor of the present invention can be used alone as anti-rust water, and can also be used as an additive for formula design of metal working fluids. It inhibits galvanic corrosion between dissimilar metal contact surfaces and improves the brightness of metal surfaces, especially for titanium alloys and aluminum alloys.
Description
Technical Field
The invention belongs to the technical field of metal rust prevention and protection, and particularly relates to a water-based metal galvanic corrosion inhibitor and a preparation method of a component polyalcohol phosphate ester thereof.
Background
Corrosion of metals is an inevitable problem in their production, processing, transportation, storage and use. The loss of metal due to corrosion is surprising. The performance of the metal workpiece is deteriorated and the precision is reduced due to corrosion, so that the metal workpiece cannot be normally used for special equipment, the safety performance cannot be guaranteed, and serious people even scrap or have safety accidents. Statistically, the worldwide quantity of metals scrapped due to corrosion reaches several million tons every year.
The corrosion forms of metals mainly include chemical corrosion and galvanic corrosion, wherein the chemical corrosion refers to corrosion caused by chemical reaction between metals and substances (oxygen, water, acid and the like) contacted with the metals.
Galvanic corrosion refers to corrosion caused by electrochemical reactions that occur when dissimilar metals or alloys come into contact with an electrolyte solution. Galvanic corrosion is more prone to form than chemical corrosion and has a faster corrosion rate, which is the main type of corrosion in practical corrosion processes.
Titanium alloy and aluminum alloy are widely used in the fields of aviation and aerospace, and the proportion of titanium alloy and aluminum alloy is increasing day by day. In the actual processing process, the phenomena of contact between titanium alloy and aluminum alloy and a machine tool, stacking of dissimilar metals and the like generally exist, galvanic corrosion is caused, the precision of a workpiece is reduced, the surface quality is deteriorated, the strength performance is reduced, the product percent of pass is seriously influenced, the safety in the aviation and aerospace fields is further threatened, and the influence is huge.
The existing metal corrosion inhibitor can better solve the problems of chemical corrosion of metal and galvanic corrosion of alloy, but has little effect on retarding the galvanic corrosion between dissimilar metals. Therefore, the research and development of the galvanic corrosion inhibitor, especially the galvanic corrosion inhibitor aiming at titanium alloy and aluminum alloy, have very important significance.
Disclosure of Invention
In view of the above, the present invention aims to provide a water-based metal galvanic corrosion inhibitor, which overcomes the defects of the prior art, can be used alone as an antirust water, can also be used as an additive for the formulation design of a metal working fluid, has a small amount and excellent antirust corrosion inhibition performance, can significantly inhibit galvanic corrosion between dissimilar metal contact surfaces, improves the brightness of metal surfaces, and particularly has an obvious effect on inhibiting galvanic corrosion of titanium alloys and aluminum alloys.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a water-based metal galvanic couple corrosion inhibitor comprises the following components in parts by weight: 5-40 parts of carboxylic acid type antirust agent, 5-40 parts of phosphate corrosion inhibitor, 3-35 parts of organic silicon corrosion inhibitor, 10-50 parts of alcohol amine type borate, 2-20 parts of methyl benzotriazole, 800-20 parts of Tween and the balance of water. Wherein the amount of water added is generally 5 to 20 parts by weight, based on the fact that the galvanic corrosion inhibitor maintains a stable transparent state and has good flow properties.
Preferably, the carboxylic acid type antirust agent is at least one of dicarboxylic acid antirust agent and tricarboxylic acid antirust agent; preferably, the carboxylic acid type antirust agent is a tricarboxylic acid antirust agent with a sulfonic group in a molecular structure. The inventor finds that the polar group in the antirust agent can be firmly adsorbed on the metal surface to form a compact antirust film.
Preferably, the phosphate ester corrosion inhibitor is a mixture of polyalcohol phosphate ester and imidazoline phosphate ester; more preferably, the mixing mass ratio of the polyol phosphate and the imidazoline phosphate is (1 ± 0.2): (2. + -. 0.2). The inventor finds that the polyol phosphate has strong chelating capacity for metal ions in an aqueous solution, can reduce the number of charged particles and reduce the conductivity of the solution; the imidazoyl phosphate is an anode corrosion inhibitor and can slow down the anodization reaction in galvanic corrosion, and the combination of the imidazoyl phosphate and the anode corrosion inhibitor can effectively inhibit the galvanic corrosion.
Preferably, the polyalcohol phosphate ester is a mixture of isomeric tridecyl ester, polyoxyethylene glycerol mixed ester and beta-hydroxyethyl ethylene glycol ester; preferably, the mixing mass ratio of the isomeric tridecyl ester, the polyoxyethylene glycerol mixed ester and the beta-hydroxyethyl ethylenediamine ester is (29 +/-2): (27 +/-2): 36 +/-2).
Preferably, the polyalcohol phosphate is synthesized by isomeric tridecenol, glycerol polyoxyethylene ether, hydroxyethyl ethylenediamine and phosphorus pentoxide.
Preferably, the mass ratio of isomeric tridecenol, glycerol polyoxyethylene ether, hydroxyethyl ethylenediamine and phosphorus pentoxide is (29 +/-2): (27 ± 2): (36 ± 2): (8. + -.1).
Preferably, the organosilicon corrosion inhibitor is one or more of organosilane, organosiloxane and organosilazane. The inventor finds that the corrosion inhibitor has strong film forming capability, and the formed antirust film has excellent insulating property and can effectively slow down galvanic corrosion between dissimilar metals.
Preferably, the alkanolamine borate is one or more than two of ethanolamine borate, diethanolamine borate and triethanolamine borate; preferably, the alkanolamine borate is triethanolamine borate. The inventor finds that the hydramine type boric acid ester has excellent antirust performance, and in addition, the strong polar group in the hydramine type boric acid ester can play a bridging role with the antirust agent and the corrosion inhibitor used in the invention, so that a high-strength net-shaped antirust film is formed, and the antirust and corrosion inhibition effects are improved.
Another object of the present invention is to provide a method for preparing polyol phosphate in a water-based metal galvanic corrosion inhibitor, which is used for preparing the water-based metal galvanic corrosion inhibitor.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for preparing polyol phosphate in the water-based metal galvanic couple corrosion inhibitor as described above, comprising the steps of:
(1) uniformly mixing isomeric tridecanol, glycerol polyoxyethylene ether and hydroxyethyl ethylenediamine to obtain a mixture A;
(2) heating the mixture A while stirring, slowly adding phosphorus pentoxide, and continuously stirring for 1-2h when the heating temperature is 110 +/-5 ℃;
(3) and (2) continuously stirring, distilling the mixture of the phosphorus pentoxide and the mixture A under reduced pressure, distilling water generated by the reaction until the solid completely reacts and no water is distilled, and stopping the reaction to obtain the polyol phosphate.
Preferably, the reaction is carried out in a double-layer glass reaction kettle; the stirring speed is 200-600 rad/min.
The researchers found that the polyol phosphate synthesized by the method is a mixture of isomeric tridecyl alcohol ester, polyoxyethylene glycerol mixed ester and beta-hydroxyethyl ethylene glycol ester, and the system is clear and transparent. The polyoxyethylene-glycerin mixed ester synthesized by the method has extremely strong surface adsorption performance and can effectively improve corrosion inhibition.
The formula for the reaction of glycerol polyoxyethylene ether and phosphorus pentoxide to produce polyoxyethylene glycerol mixed ester is as follows:
compared with the prior art, the water-based metal galvanic couple corrosion inhibitor has the following advantages:
the water-based metal galvanic couple corrosion inhibitor can be used as antirust water alone or used as an additive for the formula design of metal working fluid, is low in dosage, has excellent dissimilar metal antirust corrosion inhibition performance, can obviously inhibit galvanic couple corrosion between dissimilar metal contact surfaces, improves the brightness of metal surfaces, and particularly has an obvious effect of inhibiting the galvanic couple corrosion of titanium alloys and aluminum alloys.
According to the water-based metal galvanic corrosion inhibitor, the methylbenzotriazole adopted can improve the ion dissociation potential of anode metal, inhibit metal anodization reaction and slow down galvanic corrosion between dissimilar metals. Furthermore, Tween80 acts as an emulsifier, helping to maintain the galvanic corrosion inhibitor in a stable transparent state.
The preparation method of the polyol phosphate in the water-based metal galvanic couple corrosion inhibitor is simple to operate, raw materials are easy to obtain, the polyol phosphate synthesized by the method is a mixture of isotridecanol ester, polyoxyethylene glycerol mixed ester and beta-hydroxyethyl ethylenediamine ester, wherein the polyoxyethylene glycerol mixed ester has extremely strong surface adsorption performance and can effectively improve corrosion inhibition, and the isotridecanol and the beta-hydroxyethyl ethylenediamine ester can be used as auxiliary corrosion inhibitors to play a role in improving corrosion inhibition performance in cooperation with the polyoxyethylene glycerol mixed ester.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Method for synthesizing mono-polyol phosphate
(1) Isomeric tridecanol, glycerol polyoxyethylene ether and hydroxyethyl ethylenediamine are mixed according to the mass ratio (29 +/-2): (27 ± 2): (36 ± 2): (8 +/-1) adding the mixture into a double-layer glass reaction kettle, and starting stirring at the stirring speed of 200-600 rad/min;
(2) setting the temperature in the reaction kettle to be 110 +/-5 ℃, starting heating, and slowly adding phosphorus pentoxide according to a proportion;
(3) and (3) after the temperature is raised to 110 +/-5 ℃, continuously stirring for 1-2 hours, starting a reduced pressure distillation device in the stirring process, evaporating water generated by the reaction until the solid completely reacts and no water is evaporated, and stopping the reaction to obtain the product, namely the polyol phosphate.
The material proportions and the operating conditions of the examples and the comparative examples are as follows:
example 1, example 5, comparative examples 1-2: the mass ratio of isomeric tridecanol, glycerol polyoxyethylene ether and hydroxyethyl ethylenediamine is 30: 28: 37: 8.5; the stirring speed is 400rad/min, the temperature of the reaction kettle is set to be 110 ℃, and the stirring is continued for 1.5 h.
Example 2, comparative example 2-1: the mass ratio of isomeric tridecanol, glycerol polyoxyethylene ether and hydroxyethyl ethylenediamine is 28: 28: 35: 7; the stirring speed is 300rad/min, the temperature of the reaction kettle is set to be 113 ℃, and the stirring is continued for 1.2 h.
Example 3, comparative example 3-1: the mass ratio of isomeric tridecanol, glycerol polyoxyethylene ether and hydroxyethyl ethylenediamine is 31: 29: 38: 9; the stirring speed is 500rad/min, the temperature of the reaction kettle is set to be 108 ℃, and the stirring is continued for 1.8 h.
Example 4, comparative example 4-1: the mass ratio of isomeric tridecanol, glycerol polyoxyethylene ether and hydroxyethyl ethylenediamine is 29: 27: 36: 8; the stirring speed is 450rad/min, the temperature of the reaction kettle is set to be 110 ℃, and the stirring is continued for 2 h.
In all examples and comparative examples relating to polyol phosphates, the mixing mass ratio of isomeric tridecanol ester, polyoxyethylene glycerol mixed ester and β -hydroxyethylethylene diamine ester in polyol phosphate was the same as the mixing mass ratio of isomeric tridecanol, polyoxyethylene glycerol, and hydroxyethylethylene diamine in their respective synthetic materials.
Preparation method of galvanic corrosion inhibitor
1) Putting a carboxylate antirust agent, alcohol amine type boric acid ester, methylbenzotriazole and deionized water into a reaction kettle, heating to 70-80 ℃, and stirring at constant temperature until the solid is completely dissolved to obtain clear liquid A;
2) and (3) cooling to 40-60 ℃, adding a phosphate ester corrosion inhibitor, an organic silicon corrosion inhibitor and Tween80 into the A, and stirring at constant temperature until the system is uniform and clear, thus obtaining the water-based metal couple corrosion inhibitor.
III,Detection method
1) Example 1, example 2, example 3, example 4 and comparative examples 1-1, 1-2, 2-1, 3-1, 4-1 were diluted to 2 wt% with deionized water, respectively;
2) example 5 and comparative example 5-1 were each diluted to 5 wt% with deionized water;
3) couple pairs consisting of TC4 titanium test piece, gray cast iron test piece, 7075 aluminum test piece and gray cast iron test piece are respectively taken, and the contact surfaces are respectively coated with the diluents of the examples and the comparative examples;
4) placing the couple pair with the contact surfaces coated with the diluents of the examples and the comparative examples in an oven at 55 ℃ for 24 hours;
5) and (4) taking out each couple pair, observing the corrosion condition of the contact surface, and referring to national standard GB/T6144-2010 for the evaluation standard of the corrosion inhibition grade.
Fourthly,Selection of raw materials
The tricarboxylic acid used in this example and comparative example was basf L190; the dicarboxylic acid is Tianjin Hao Rui Sen chemical CI-02; imidazoline phosphate is Shanghai Ruibo chemical RP 720; the alkyl phosphate is Shanghai chess chemical industry P50; fatty acid alkanolamide phosphate is Shanghai macroze chemical 3260; the organosiloxane is Acksonobel P15; ethanolamine borate, diethanolamine borate, triethanolamine borate, methylbenzotriazole and Tween80 are all common commercial products.
V, V,Example 1, comparative examples 1 to 1, and comparative examples 1 to 2
Using the above preparation method, example 1, comparative examples 1 to 1 and comparative examples 1 to 2 were prepared as shown in Table 1, respectively.
TABLE 1 example 1, comparative examples 1-2 inhibitor compositions
The galvanic corrosion inhibitions of example 1 and comparative examples 1-1 and 1-2 are shown in tables 2 and 3.
TABLE 2 galvanic corrosion inhibition of example 1 and comparative examples 1-1, 1-2 titanium alloys
As can be seen from Table 2, the titanium alloy of example 1, which was prepared using polyol phosphate and imidazoline phosphate, exhibited better galvanic corrosion inhibition than comparative examples 1-1, which were prepared using alkyl phosphate and imidazoline phosphate, and comparative examples 1-2, which were prepared using polyol phosphate and fatty acid alkanolamide phosphate.
TABLE 3 galvanic corrosion inhibition of the aluminum alloys of example 1 and comparative examples 1-1, 1-2
As can be seen from Table 2, the aluminum alloy of example 1, which was prepared using the polyol phosphate and imidazoline phosphate, exhibited better galvanic corrosion inhibition than comparative examples 1-1, which were prepared using the alkyl phosphate and imidazoline phosphate, and comparative examples 1-2, which were prepared using the polyol phosphate and fatty acid alkanolamide phosphate.
Sixthly,Example 2, comparative example 2-1
Using the above preparation method, example 2 and comparative example 2-1 were prepared as shown in Table 3, respectively.
TABLE 4 inhibitor composition of example 2, comparative example 2-1
The galvanic corrosion inhibition of example 2 and comparative example 2-1 are shown in tables 5 and 6.
TABLE 5 galvanic corrosion inhibition of example 2 and comparative examples 2-1 titanium alloys
As can be seen from Table 5, the aluminum alloy of example 2 containing a silicone corrosion inhibitor exhibits better galvanic corrosion inhibition than the aluminum alloy of comparative example 2-1 which does not contain a silicone corrosion inhibitor.
TABLE 6 galvanic corrosion inhibition of example 2 and comparative examples 2-1 aluminum alloys
As can be seen from Table 6, the aluminum alloy of example 2 containing a silicone corrosion inhibitor exhibits better galvanic corrosion inhibition than the aluminum alloy of comparative example 2-1 which does not contain a silicone corrosion inhibitor.
Seven, seven,Example 3, comparative example 3-1
Using the above preparation method, example 3 and comparative example 3-1 were prepared as shown in Table 7, respectively.
TABLE 7 inhibitor compositions of example 3, comparative example 3-1
The galvanic corrosion inhibitions of example 3 and comparative example 3-1 are shown in tables 8 and 9.
TABLE 8 galvanic corrosion inhibition of example 3 and comparative examples 3-1 titanium alloys
As can be seen from Table 8, the titanium alloy of example 3 containing the olamine type borate ester has better galvanic corrosion inhibition than that of comparative example 3-1 containing no olamine type borate ester.
TABLE 9 galvanic corrosion inhibition of example 3 and comparative examples 3-1 aluminum alloys
As can be seen from Table 9, the aluminum alloy of example 3, which contains the olamine type borate ester, has better galvanic corrosion inhibition than the aluminum alloy of comparative example 3-1, which does not contain the olamine type borate ester.
Eight,Example 4, comparative example 4-1
Using the above preparation methods, example 4 and comparative example 4-1 were prepared as shown in Table 10, respectively.
TABLE 10 inhibitor compositions of example 4, comparative example 4-1
The galvanic corrosion inhibitions of example 4 and comparative example 4-1 are shown in tables 11 and 12.
TABLE 11 galvanic corrosion inhibition of example 4 and comparative examples 4-1 titanium alloys
As can be seen from Table 11, the titanium alloy of example 4 containing tolyltriazole has better galvanic corrosion inhibition than that of comparative example 4-1 containing no tolyltriazole.
TABLE 12 galvanic corrosion inhibition of example 4 and comparative examples 4-1 aluminum alloys
As can be seen from Table 12, the aluminum alloy of example 4 containing tolyltriazole has better galvanic corrosion inhibition than that of comparative example 4-1 containing no tolyltriazole.
Nine components,Example 5, comparative example 5-1
Comparative example 5-1: an imported high-end fully synthetic aluminum alloy processing fluid, in particular to Jiashiduo Syntilo 9913.
Example 5 was obtained by adding example 1 to comparative example 5-1 in an amount of 6 parts by weight and stirring at a constant temperature of 60 ℃ until the system was clear and transparent.
The galvanic corrosion inhibitions of example 5 and comparative example 5-1 are shown in tables 13 and 14.
TABLE 13 galvanic corrosion inhibition of example 5 and comparative examples 5-1 titanium alloys
TABLE 14 galvanic corrosion inhibition of example 5 and comparative examples 5-1 aluminum alloys
As can be seen from tables 13 and 14, example 5 has good galvanic corrosion inhibition for TC4 titanium/gray cast iron and 7075 aluminum/gray cast iron couple pairs as compared with comparative example 5-1, which shows that when the present invention is added to a metal working fluid, the galvanic corrosion inhibition of the metal working fluid can be significantly improved, and the corrosion of the contact surface can be effectively prevented.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
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| WO2006068790A2 (en) * | 2004-12-21 | 2006-06-29 | Hercules Chemical Company Incorporated | Corrosion inhibiting heat transfer materials |
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