CN110592594B - Quaternary carboxylic acid metal antirust agent and preparation method and application thereof - Google Patents
Quaternary carboxylic acid metal antirust agent and preparation method and application thereof Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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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
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Abstract
The invention provides a quaternary carboxylAn acid metal antirust agent belongs to the technical field of metal antirust. The structural formula of the tetrabasic carboxylic acid metal antirust agent is as follows:
Description
Technical Field
The invention relates to the technical field of metal rust prevention, in particular to a tetracarboxylic acid metal rust inhibitor (also called a tetracarboxylic acid metal rust inhibitor single product or a tetracarboxylic acid metal rust inhibitor single product), and a preparation method and application thereof.
Background
With the improvement of environmental protection consciousness of various countries in the world and the active implementation of sustainable development strategy of China, the metal antirust market puts more attention on environmental protection, which means that higher requirements are put forward on metal antirust agents. It is known that metal materials are rusted in a short time without rust prevention treatment in the processes of production, storage and transportation, which has adverse effects on the appearance and performance of the metal materials, and even the metal materials are scrapped due to serious rusting.
Most of water-based antirust liquid used in China for many years contains sodium nitrite, which has good antirust performance on ferrous metals, and has the obvious advantages of low price, convenient use, easy removal and the like, but the sodium nitrite can irritate human skin and has carcinogenic risk, so the use and the discharge of the sodium nitrite are strictly limited. The antirust oil and the antirust paint form a protective oil film or paint film on the surface of the metal to isolate the corrosion of the surrounding environment medium to the metal, thereby achieving the purpose of rust prevention for a long time. Although the antirust performance is good, the antirust oil or the antirust paint is used, a large amount of oil raw materials are consumed, and the antirust oil or the antirust paint needs to be removed in subsequent metal processing (such as electroplating, painting, welding and assembling) and unsealing, so that a large amount of oily waste liquid is generated to be discharged, the environment is polluted, a large amount of manpower and material resources are consumed for the post-treatment of metal products, and the cost is increased.
In recent years, for reasons of environmental protection and the like, research on environment-friendly water-based antirust agents is widely concerned by researchers at home and abroad, and particularly, development of long-acting water-based antirust agents becomes a trend. In the field of rust prevention of ferrous metals, dibasic acid rust inhibitors and tribasic acid rust inhibitors are two types of water-based rust inhibitors which are widely applied. Dodecanedioic acid is a commonly used dicarboxylic acid rust inhibitor, is mainly prepared by a biosynthesis method, and is described in detail in patents CN201510659020.4 and CN 201610139691.2. However, the biosynthesis method has the problems of complex operation, large wastewater amount, high refining difficulty and the like, so that the cost is high, and the application of the biosynthesis method in the field of metal rust prevention is influenced. The tribasic acid is 2,4, 6-tri (amino caproyl) -1,3, 5-triazine, which is an ashless antirust agent of organic tribasic polycarboxylic acid, and a synthetic method of the tribasic carboxylic acid is introduced in patent CN201010546770.8, namely, the carboxylate of the amino caproic acid is used for replacing chlorine in cyanuric chloride in a water phase, and then the product is obtained by acidification. The tribasic acid has good antirust performance on iron, can be used as an antirust single agent, but has high acid value (dry products are usually more than 365 mgKOH/g), so a large amount of alkaline substances such as liquid alkali, alcohol amine and the like are needed to be neutralized and dissolved in the using process, which greatly increases the difficulty in the preparation of a formula; meanwhile, the corrosion of the alloy on other metals such as aluminum, magnesium and the like is also obvious.
In addition, the rust inhibitor is required to have hard water resistance during the addition and use process, and the hard water contains a large amount of Ca2＋And Mg2＋Plasma, which can react with the carboxylic acid type rust inhibitor to generate corresponding calcium soap and magnesium soap, resulting in the decrease of the concentration of the rust inhibitor, the decrease of the rust-preventive performance, and even the loss of the rust-preventive ability. On the other hand, inorganic ions in hard water are also inorganic nutrients for microorganisms, and the higher the hardness of water, the faster the microorganisms grow and multiply, and the faster the performance of the water-based lubricant and rust inhibitor therein is degraded.
Disclosure of Invention
The invention aims to provide a tetrabasic carboxylic acid metal antirust agent and a preparation method thereof, which solve the defects of poor compatibility and high cost of the conventional antirust single agent; the tetrabasic carboxylic acid metal antirust agent can be used as a water-based antirust agent, has outstanding antirust, antioxidant and anti-tarnish performances on various metals, is low in production cost, simple and convenient in process, suitable for industrialization and application, stable to hard water, environment-friendly and environment-friendly.
The structural formula of the tetrabasic carboxylic acid metal antirust agent provided by the invention is as follows:
wherein R1 is C3-C8 linear chain or branched chain alkyl, and R2 is C0-C8 linear chain or branched chain alkyl.
The invention adopts a simple and easy one-pot method which is environment-friendly to synthesize the tetrabasic carboxylic acid metal antirust agent.
The technical scheme of the invention is as follows: in an aqueous solution, n-amino alkyl carboxylic acid, diamine and liquid alkali are used as raw materials to perform substitution reaction with cyanuric chloride, and finally, inorganic acid is used for acidification to obtain a quaternary carboxylic acid finished product; and simultaneously, carrying out an antirust performance test and a hard water compatibility test on the obtained finished product.
The preparation method of the tetrabasic carboxylic acid metal antirust agent comprises the following preparation steps: (1) mixing water, n-amino alkyl carboxylic acid and diamine, and cooling to-5-10 ℃; (2) adding cyanuric chloride in batches, and simultaneously dropwise adding liquid alkali to maintain the pH value of the reaction system at 9-12; (3) heating to 75-100 ℃, and reacting for 2-5 h; preferably reacting for 2-3 h; (4) acidifying with inorganic acid until the pH is = 1-6, and filtering to obtain a solid product, namely the tetrabasic carboxylic acid metal antirust agent.
In the above method for preparing a tetrabasic carboxylic acid metal rust inhibitor, preferably, the structure of the n-aminoalkyl carboxylic acid in the step (1) is:
wherein R1 is a C3-C8 linear or branched alkyl group.
In the above method for preparing the tetrabasic carboxylic acid metal antirust agent, preferably, the structure of the diamine in the step (1) is
Wherein R2 is a linear or branched alkyl group having 0-8 carbon atoms.
In the above preparation method of the tetracarboxylic acid metal antirust agent, preferably, in the preparation method, the molar ratio of (total) cyanuric chloride, n-amino alkyl carboxylic acid and diamine is 1: 2.0-2.2: 0.50 to 0.52.
The invention also provides an application method of the tetrabasic carboxylic acid metal antirust agent, and the tetrabasic carboxylic acid metal antirust agent is added into the water-based lubricating liquid and is used as an antirust additive of the water-based lubricating liquid.
The invention relates to a tetrabasic carboxylic acid metal antirust agent, which belongs to an ashless antirust single product of organic tetrabasic carboxylic acid, has simple and convenient preparation method, is applied to an antirust additive of a water-based lubricating liquid, and at least has the following beneficial effects:
the antirust agent can be used as a water-based antirust agent, and has outstanding antirust, antioxidant and anti-discoloration performances on various metals;
the tetrabasic carboxylic acid metal antirust agent has good compatibility with hydraulic fluid, cutting fluid, metal processing fluid and the like, and can be used as a water-based antirust agent;
the tetrabasic carboxylic acid has a nonpolar group and a polar group at the same time, and utilizes the directional adsorption effect to realize rust prevention by preventing or delaying the contact of oxygen and hydrogen with the surface of a metal part, in particular, the tetrabasic carboxylic acid contains stronger polar group carboxyl, so that antirust molecules are favorably adsorbed on the surface of the part, and hydrophobic alkyl is directionally arranged on the side opposite to the polar group on the surface of the part to form a protective film, so that water molecules, other substances related to corrosion reaction and charges are prevented from moving to the metal surface to corrode the surface of the part, the corrosion speed is reduced, and the rust prevention effect is realized; experiments prove that the prepared tetracarboxylic acid antirust agent has antirust performance equivalent to or even better than that of a tricarboxylic acid antirust agent L190Plus widely used in the industry;
meanwhile, as the nitrogen atom in the heterocyclic molecule of the tetracarboxylic acid has lone pair electrons, the tetracarboxylic acid can react with the metal surface of an iron atom with a vacant orbit to generate a complex, prevent molecules such as oxygen, water and the like from contacting with the metal, and have antioxidation and anti-discoloration properties;
the antirust, antioxidant and antitarnish agent has outstanding antirust, antioxidant and antitarnish performances on various metals such as cast iron, carbon steel and alloy metal, and has less corrosiveness on other metals such as nonferrous metals such as aluminum, magnesium and the like;
secondly, the production cost is low, the flow is simple and convenient, and the method is suitable for industrialization and application
The tetrabasic carboxylic acid metal antirust agent is prepared by adopting a simple and feasible one-pot synthesis method, raw materials are easy to obtain, production equipment is easy to manufacture or purchase, the tetrabasic carboxylic acid metal antirust agent can be produced and obtained only by controlling reaction conditions and a charging sequence, the process is simple and convenient, the production cost is low, and the tetrabasic carboxylic acid metal antirust agent is suitable for large-scale industrial production; the acid value of the prepared tetrabasic carboxylic acid metal antirust agent is obviously lower than that of tribasic carboxylic acid, so that a large amount of alkaline substances such as liquid alkali and alcohol amine are prevented from being neutralized and dissolved in the using process, the formula is convenient to prepare, and the application is facilitated;
thirdly, green application is realized, and the environment is friendly
The tetrabasic carboxylic acid metal antirust agent does not contain toxic and harmful substances forbidden in industries such as sodium nitrite, phosphate, hexavalent chromium, trivalent chromium, boric acid system and the like; experiments prove that the quaternary carboxylic acid metal antirust agent water solution neutralized by triethanolamine salt keeps clear in hard water solutions with different hardness, and shows that the quaternary carboxylic acid metal antirust agent has excellent hard water compatibility and strong adaptability to water quality; the tetrabasic carboxylic acid antirust agent also has extremely low foam tendency in the use process, and the treated metal surface has no floating ash, grease or jelly and no greasy feeling, belongs to a clean antirust product, and is an environment-friendly ashless antirust agent.
Detailed Description
The present invention is further described below with reference to examples. It should be noted that the present invention is not limited to the following embodiments.
The invention relates to a tetrabasic carboxylic acid metal antirust agent, which comprises the following preparation steps: (1) mixing water, n-amino alkyl carboxylic acid and diamine, and cooling to-5-10 ℃; (2) adding cyanuric chloride in batches, and simultaneously dropwise adding liquid alkali to maintain the pH value of the reaction system at 9-12; (3) heating to 75-100 ℃, and reacting for 2-5 h; (4) acidifying with inorganic acid until the pH is = 1-6, and filtering to obtain a solid product, namely the tetrabasic carboxylic acid metal antirust agent; the structural formula is as follows:
in particular embodiments, step (1), the n-aminoalkylcarboxylic acid has the structure:
wherein R1 is a C3-C8 linear or branched alkyl; in the present invention, the n-aminoalkylcarboxylic acid is a compound in which the amino group is located at the end of the longest carbon chain containing a carboxyl group, wherein n represents the number of carbon atoms in the compound; in the following specific examples 1 to 8 and 10, the alkyl group R1 is a straight-chain alkyl group; in specific example 9, alkyl R1 is branched alkyl;
in specific implementation, the diamine in the step (1) has the structure:
wherein R2 is a linear or branched alkyl group having 0-8 carbon atoms; in the diamine, two amine groups are respectively positioned at the end of an alkyl R2, and in specific examples 1-2 and 4-9, an alkyl R2 is a straight-chain alkyl group; in specific example 10, alkyl R2 is a branched alkyl;
the following is a specific example of the preparation of a tetracarboxylic acid metal rust inhibitor. In the specific implementation, during the preparation process, the molar ratio of cyanuric chloride to n-aminoalkyl carboxylic acid to diamine is preferably 1: 2.0-2.2: 0.50 to 0.52. In specific application, the tetracarboxylic acid metal antirust agent is added into the water-based lubricating liquid in an addition amount of 0.5-2.0 wt%.
Example 1
A tetrabasic carboxylic acid metal antirust agent A is synthesized by the following steps:
a) mixing 50g of water, 10.3g (0.1 mol) of 4-aminobutyric acid and 1.5g (0.025 mol) of ethylenediamine in a flask provided with a thermometer and a condenser under the stirring condition, cooling to 5 ℃ in an ice-water bath, and adjusting the pH to 11 by using 32% liquid alkali;
b) 9.2g (0.05 mol) of cyanuric chloride is alternately added in batches, 32% liquid alkali is added dropwise at the same time, the temperature of the system is controlled below 10 ℃ in the feeding process, and the pH value of the system is 11-12. After the feeding is finished, stirring in an ice water bath for 30min, heating to 75 ℃, and preserving heat for 2 h;
c) and filtering to obtain a transparent solution after the reaction is finished, acidifying to pH =1-1.5 by using 20% hydrochloric acid, performing suction filtration to obtain a tetracarboxylic acid metal antirust agent A, and drying to obtain a dry product 13.6 g.
Example 2
A tetrabasic carboxylic acid metal antirust agent B is synthesized by the following steps:
a) mixing 50g of water, 11.3g (0.11 mol) of 4-aminobutyric acid and 2.9g (0.025 mol) of hexamethylenediamine in a flask provided with a thermometer and a condenser under the stirring condition, cooling to 5 ℃ in an ice-water bath, and adjusting the pH to 11 by using 32% liquid alkali;
b) 9.2g (0.05 mol) of cyanuric chloride is alternately added in batches, 32% liquid alkali is added dropwise at the same time, the temperature of the system is controlled below 10 ℃ in the feeding process, and the pH value of the system is 11-12. After the feeding is finished, stirring in an ice water bath for 30min, heating to 85 ℃, and preserving heat for 2 h;
c) and filtering to obtain a transparent solution after the reaction is finished, acidifying to pH =1-2 by using 20% hydrochloric acid, performing suction filtration to obtain a tetrabasic carboxylic acid metal antirust agent B, and drying to obtain a dry product of 14.9 g.
Example 3
A tetrabasic carboxylic acid metal antirust agent C is synthesized by the following steps:
a) mixing 50g of water, 13.1g (0.1 mol) of 6-aminocaproic acid and 1.6g (0.026 mol) of 80% hydrazine hydrate in a flask provided with a thermometer and a condenser under stirring, cooling to 0 ℃ in an ice-water bath, and adjusting the pH to 10 by using 32% liquid alkali;
b) 9.2g (0.05 mol) of cyanuric chloride is alternately added in batches, 32% liquid alkali is added dropwise at the same time, the temperature of the system is controlled below 10 ℃ in the feeding process, and the pH value of the system is 10-11. After the feeding is finished, stirring in an ice water bath for 30min, heating to 85 ℃, and preserving heat for 2 h;
c) and filtering to obtain a transparent solution after the reaction is finished, acidifying to pH =1-2 by using 20% hydrochloric acid, performing suction filtration to obtain a tetrabasic carboxylic acid metal antirust agent C, and drying to obtain a dry product 15.8 g.
Example 4
A tetrabasic carboxylic acid metal antirust agent D is synthesized by the following steps:
a) mixing 50g of water, 13.1g (0.1 mol) of 6-aminocaproic acid and 2.3g (0.026 mol) of butanediamine in a flask provided with a thermometer and a condenser pipe under the condition of stirring, cooling to 5 ℃ in an ice-water bath, and adjusting the pH to 10 by using 32% liquid alkali;
b) 9.2g (0.05 mol) of cyanuric chloride is alternately added in batches, 32% liquid alkali is added dropwise at the same time, the temperature of the system is controlled below 10 ℃ in the feeding process, and the pH value of the system is 10-11. After the feeding is finished, stirring in an ice water bath for 30min, heating to 95 ℃, and preserving heat for 3 h;
c) and filtering to obtain a transparent solution after the reaction is finished, acidifying to pH =2-3 by using 20% hydrochloric acid, performing suction filtration to obtain a tetrabasic carboxylic acid metal antirust agent D, and drying to obtain a dry product of 17.0 g.
Example 5
A tetrabasic carboxylic acid metal antirust agent E is synthesized by the following steps:
a) mixing 50g of water, 17.5g (0.11 mol) of 8-aminocaprylic acid and 1.5g (0.025 mol) of ethylenediamine in a flask provided with a thermometer and a condenser under the stirring condition, cooling to 0 ℃ in an ice-water bath, and adjusting the pH to 10 by using 32% liquid alkali;
b) 9.2g (0.05 mol) of cyanuric chloride is alternately added in batches, 32% liquid alkali is added dropwise at the same time, the temperature of the system is controlled below 10 ℃ in the feeding process, and the pH value of the system is 9-10. After the feeding is finished, stirring in an ice water bath for 30min, heating to 80 ℃, and preserving heat for 3 h;
c) and filtering to obtain a transparent solution after the reaction is finished, acidifying to pH =2-3 by using 20% hydrochloric acid, performing suction filtration to obtain a tetrabasic carboxylic acid metal antirust agent E, and drying to obtain a dry product of 18.6 g.
Example 6
A tetrabasic carboxylic acid metal antirust agent F is synthesized by the following steps:
a) mixing 50g of water, 17.5g (0.11 mol) of 8-aminocaprylic acid and 3.6g (0.025 mol) of octanediamine in a flask provided with a thermometer and a condenser pipe under the condition of stirring, cooling to 10 ℃ in an ice-water bath, and adjusting the pH to 10 by using 32% liquid alkali;
b) 9.2g (0.05 mol) of cyanuric chloride is alternately added in batches, 32% liquid alkali is added dropwise at the same time, the temperature of the system is controlled below 15 ℃ in the feeding process, and the pH value of the system is 9-10. After the feeding is finished, stirring in an ice water bath for 30min, heating to 90 ℃, and preserving heat for 3 h;
c) and filtering to obtain a transparent solution after the reaction is finished, acidifying to pH =3-4 by using 20% hydrochloric acid, performing suction filtration to obtain a tetrabasic carboxylic acid metal antirust agent F, and drying to obtain a dry product of 20.0 g.
Example 7
A tetrabasic carboxylic acid metal antirust agent G is synthesized by the following steps:
a) mixing 50g of water, 17.3g (0.1 mol) of 9-aminononanoic acid and 1.6g (0.026 mol) of 80% hydrazine hydrate in a flask with a thermometer and a condenser under stirring, cooling to 0 ℃ in an ice-water bath, and adjusting the pH to 9 with 32% liquid alkali;
b) 9.2g (0.05 mol) of cyanuric chloride is alternately added in batches, 32% liquid alkali is added dropwise at the same time, the temperature of the system is controlled below 10 ℃ in the feeding process, and the pH value of the system is 9-10. After the feeding is finished, stirring in an ice water bath for 30min, heating to 95 ℃, and preserving heat for 2 h;
c) and filtering to obtain a transparent solution after the reaction is finished, acidifying to pH =4-5 by using 20% hydrochloric acid, performing suction filtration to obtain a tetrabasic carboxylic acid metal antirust agent G, and drying to obtain 19.7G of a dry product.
Example 8
A tetrabasic carboxylic acid metal antirust agent H is synthesized by the following steps:
a) mixing 50g of water, 17.3g (0.1 mol) of 9-aminononanoic acid and 2.9g (0.025 mol) of hexamethylenediamine in a flask with a thermometer and a condenser under stirring, cooling to-5 ℃ in an ice-water bath, and adjusting the pH to 11 by using 32% liquid alkali;
b) 9.2g (0.05 mol) of cyanuric chloride is alternately added in batches, 32% liquid alkali is added dropwise at the same time, the temperature of the system is controlled below 10 ℃ in the feeding process, and the pH value of the system is 11-12. After the feeding is finished, stirring in an ice water bath for 30min, heating to 100 ℃, and preserving heat for 2 h;
c) and filtering to obtain a transparent solution after the reaction is finished, acidifying to pH =5-6 by using 20% hydrochloric acid, performing suction filtration to obtain a tetrabasic carboxylic acid metal antirust agent H, and drying to obtain a dry product of 20.8 g.
Example 9
A tetrabasic carboxylic acid metal antirust agent I is synthesized by the following steps:
a) mixing 50g of 3-amino-4-methylpentanoic acid (13.1 g) and ethylenediamine (1.5 g, 0.025 mol) in a flask equipped with a thermometer and a condenser while stirring, cooling to 0 ℃ in an ice-water bath, and adjusting the pH to 10 with 32% liquid alkali;
b) 9.2g (0.05 mol) of cyanuric chloride is alternately added in batches, 32% liquid alkali is added dropwise at the same time, the temperature of the system is controlled below 10 ℃ in the feeding process, and the pH value of the system is 10-11. After the feeding is finished, stirring in an ice water bath for 30min, heating to 85 ℃, and preserving heat for 5 h;
c) and filtering to obtain a transparent solution after the reaction is finished, acidifying to pH =1-2 by using 20% hydrochloric acid, performing suction filtration to obtain a tetrabasic carboxylic acid metal antirust agent I, and drying to obtain a dry product 15.4 g.
Example 10
A tetrabasic carboxylic acid metal antirust agent J is synthesized by the following steps:
a) 50g of 4-aminobutyric acid (11.3 g, 0.11 mol) and 2.9g of 2-methylpentamethylenediamine (diamine with branched alkyl groups, 0.025 mol) are mixed with stirring in a flask equipped with a thermometer and a condenser, cooled to 5 ℃ in an ice-water bath, and adjusted to pH 11 with 32% liquid base;
b) 9.2g (0.05 mol) of cyanuric chloride is alternately added in batches, 32% liquid alkali is added dropwise at the same time, the temperature of the system is controlled below 10 ℃ in the feeding process, and the pH value of the system is 11-12. After the feeding is finished, stirring in an ice water bath for 30min, heating to 85 ℃, and preserving heat for 4 h;
c) and filtering to obtain a transparent solution after the reaction is finished, acidifying to pH =1-2 by using 20% hydrochloric acid, performing suction filtration to obtain a tetrabasic carboxylic acid metal antirust agent B, and drying to obtain a dry product of 14.7 g.
Comparative example
In order to compare with the tetrabasic carboxylic acid metal antirust agent prepared by the invention, a tribasic carboxylic acid antirust agent commonly used in the metal working fluid industry is selected as a comparison. The comparative sample was obtained from L190Plus from Ciba, Switzerland and has the formula:
table 1 shows the acid value data of the products obtained in the examples, which were measured by the experiments, and the acid value of the products was measured by the national Standard GB 264-1983 (2004) for measuring the acid value of petroleum products.
TABLE 1 acid value of the products of examples and comparative examples
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | Comparative example |
| Metal antirust agent | A | B | C | D | E | F | G | H | I | J | L190 Plus |
| Acid value mgKOH/g | 325 | 314 | 295 | 283 | 265 | 240 | 250 | 233 | 320 | 322 | 369 |
| Number of carbons in R1 | 3 | 3 | 5 | 5 | 7 | 7 | 8 | 8 | 5 | 3 | - |
| Number of carbons in R2 | 2 | 6 | 0 | 4 | 2 | 8 | 0 | 6 | 2 | 6 | - |
The experiments in Table 1 show that the acid value of the prepared tetracarboxylic acid metal antirust is obviously lower than that of a tricarboxylic acid antirust L190Plus commonly used in the industry; as the carbon chains of R1 and R2 become longer, the acid value of the resulting tetracarboxylic acid metal rust inhibitor tends to decrease.
The following application examples were conducted for the rust inhibitors prepared in examples 1 to 10 and comparative examples, respectively, and the procedures and results thereof are as follows.
And (3) testing the antirust performance:
the rust inhibitive performance of each rust inhibitive agent on cast iron powder was determined according to the rust inhibitive experiment provided by the PRC mechanical industry standard JB-T9189-1999. Preparing a diluent with the antirust agent content of 10% and the pH value of 8.5 from the antirust agent, triethanolamine and distilled water, preparing the diluent into distilled water solutions with the mass fractions of 0.5%, 1.0% and 2.0%, and measuring the antirust property of the distilled water solutions at the temperature of 20-30 ℃. The results of the experiment are shown in table 2.
TABLE 2 Rust protection rating
As can be seen from Table 2, the prepared tetracarboxylic acid antirust property has antirust performance equivalent to or even better than that of the tricarboxylic acid antirust agent L190Plus, the antirust performance of the tricarboxylic acid antirust agent L190Plus is 0-1 grade at a lower mass concentration (0.5%), and other antirust agents B, C, D, E, F, G except the antirust agent A, H, I, J are 0-1 grade in the prepared tetracarboxylic acid antirust property. And at both mass concentrations of 1.0% and 2.0%, the test piece showed a 0-grade. Overall, the rust inhibitive effect of the quaternary carboxylic acid rust inhibitive agent with a branched alkyl group is slightly inferior to that of the quaternary carboxylic acid rust inhibitive agent with a straight alkyl group.
Hard water compatibility test:
hard water solutions with hardness of 200, 300, 400, 500 and 600 ppm were prepared. The tetracarboxylic acid metal rust inhibitor B prepared in example 2, the tetracarboxylic acid metal rust inhibitor D prepared in example 4, and the comparative rust inhibitor were prepared as diluents having a rust inhibitor content of 10% and a pH of 8.5, and were dissolved in water having different hardness in a mass fraction of 1%, 2.0%, 3.0%, 4.0%, and 5.0%, respectively, and the solution conditions were observed, and the experimental results are shown in table 3.
Table 3 hard water resistance test of three additives
1: -is clear and transparent; 2: turbidity appeared in the solution.
As can be seen from the experimental results of Table 3, in a series of additive aqueous solutions of different hardness at each concentration of the tetracarboxylic acid metal rust inhibitors B and D prepared by the present invention, except for being turbid at 600 ppm and at 500ppm of 4.0% and 5.0%, the rest is clear and transparent, while a 1.0% solution of L190Plus can be used only at 500ppm, and as the concentration thereof increases, the hardness of hard water which can stably exist gradually decreases; the compatibility of the tetrabasic carboxylic acid metal rust inhibitors B and D with hard water is far stronger than that of L190, and excellent hard water compatibility is shown;
in order to verify the stability and thermal stability of a hard water solution of a tetracarboxylic acid metal antirust, several antirust additives are respectively prepared into diluents with the antirust content of 10% and the pH value of 8.5, then the diluents are respectively added into hard water with different hardness in a mass fraction of 1.0%, 3.0% and 5.0%, and the diluents are respectively placed at 25 ℃ and 70 ℃ for 7 days to observe the solution condition. The results of the experiment are shown in table 4.
TABLE 4 hard water stability and Heat stability of three rust inhibitors
1: -is clear and transparent; 2: turbidity appeared in the solution; 3. - -is an experiment not performed.
As can be seen from the experimental results of Table 4, the hard water resistance stability and the thermal stability of the metal rust inhibitors C and E provided by the invention are good, and except that the 400 ppm solution with the mass concentration of 5.0% of the metal rust inhibitor C is turbid after being placed at 70 ℃ for 7 days, the rest solutions with different hardness and different concentrations are still clear and transparent after being placed at two temperatures for 7 days. While the 400 ppm solution with the mass concentration of 1% and the 300 ppm solution with the mass concentration of 3% of the comparative additive L190Plus have turbidity after being placed at 25 ℃ and 70 ℃ for 7 days, the comparative antirust agent is proved to have far lower hard water resistance stability and thermal stability than the tetrabasic carboxylic acid metal antirust agent provided by the invention except that the comparative antirust agent is not compatible with hard water.
The experimental results show that the tetrabasic carboxylic acid metal antirust agent prepared by the invention has excellent antirust performance and is a water-based antirust additive with excellent performance.
The present invention is not described in detail in the prior art.
Claims (4)
1. A tetrabasic carboxylic acid metal antirust agent is characterized in that: the structural formula of the tetrabasic carboxylic acid metal antirust agent is as follows:
wherein R1 is C3-C8 linear chain or branched chain alkyl, and R2 is C0-C8 linear chain or branched chain alkyl.
2. A method for preparing a tetracarboxylic acid metal rust inhibitor according to claim 1, characterized in that: the preparation method comprises the following preparation steps: (1) mixing water, n-amino alkyl carboxylic acid and diamine, and cooling to-5-10 ℃; (2) adding cyanuric chloride in batches, and simultaneously dropwise adding liquid alkali to maintain the pH value of the reaction system at 9-12; (3) heating to 75-100 ℃, and reacting for 2-5 h; (4) acidifying with inorganic acid until the pH is = 1-6, and filtering to obtain a solid product, namely the tetrabasic carboxylic acid metal antirust agent;
the structure of the n-aminoalkyl carboxylic acid in the step (1) is as follows:
wherein R1 is a C3-C8 linear or branched alkyl;
the diamine in the step (1) has a structure as follows:
wherein R2 is a linear or branched alkyl group having 0-8 carbon atoms.
3. The method for preparing a tetracarboxylic acid metal rust inhibitor according to claim 2, wherein: in the preparation method, the molar ratio of cyanuric chloride to n-amino alkyl carboxylic acid to diamine is 1: 2.0-2.2: 0.50 to 0.52.
4. The tetracarboxylic acid metal rust inhibitor according to claim 1, wherein: the tetrabasic carboxylic acid metal antirust agent is added into water-based lubricating liquid and is used as an antirust additive of the water-based lubricating liquid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS62270785A (en) * | 1986-05-19 | 1987-11-25 | Chiyoda Kagaku Kenkyusho:Kk | Heat resistant anticorrosive for copper and copper alloy |
| CN102250029A (en) * | 2011-05-16 | 2011-11-23 | 修建东 | Preparation method of triazine hydroxyethyl ethylenediamine polycarboxylic acid |
| CN104213124A (en) * | 2014-09-04 | 2014-12-17 | 徐立庶 | Method for manufacturing water-based metal antirust agents |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62270785A (en) * | 1986-05-19 | 1987-11-25 | Chiyoda Kagaku Kenkyusho:Kk | Heat resistant anticorrosive for copper and copper alloy |
| CN102250029A (en) * | 2011-05-16 | 2011-11-23 | 修建东 | Preparation method of triazine hydroxyethyl ethylenediamine polycarboxylic acid |
| CN104213124A (en) * | 2014-09-04 | 2014-12-17 | 徐立庶 | Method for manufacturing water-based metal antirust agents |
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