Neutral water-based antirust agent
Technical Field
The invention relates to an antirust agent, in particular to a neutral aqueous antirust agent.
Background
Dodecenylsuccinic acid and barium dinonylnaphthalene sulfonate or calcium dinonylnaphthalene sulfonate are generally added into the traditional rust-preventive oil to improve the salt mist performance of the rust-preventive oil. Since dodecenylsuccinic acid (T746) is an oil-soluble corrosion inhibitor, strong in acidity and poor in water solubility, it can only be used as a lubricating oil or rust preventive oil additive, and its use in aqueous rust preventive systems has limitations. When dodecenylsuccinic acid is used in an aqueous rust preventive liquid, its solubility in water can be improved only by reacting with different amines by utilizing its high acid value (acid value: 250mg KOH/g), but the addition of an alcohol amine to this system increases the content of free amines in the rust preventive, and the free amines are liable to volatilize, thereby not only increasing the pungent taste of the rust preventive, but also affecting the physical health of the operator. Barium dinonyl naphthalene sulfonate or calcium dinonyl naphthalene sulfonate is an oil-soluble antirust additive, when the antirust additive is applied to a water-based antirust agent, an emulsifier is required to be added for dissolution when the antirust additive is dissolved in water, and when the emulsifier and the antirust agent are adsorbed on the surface of metal, the emulsifier and the antirust agent are easy to adsorb moisture in the air, so that the antirust effect of the antirust agent is influenced. In addition, the existing water-based antirust agents are strong in alkalinity and short in antirust time, and the alkaline water-based antirust agents are not only not beneficial to environmental protection, but also not beneficial to the health of operators.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a neutral aqueous antirust agent, aiming at the problems that in the prior art, the aqueous antirust agent has high free amine content and the antirust effect is poor because an emulsifier and the antirust agent are adsorbed on the surface of metal and easily absorb moisture in the air.
The technical scheme is as follows: the neutral water-based antirust agent is prepared by mixing the following components in percentage by mass: 10-20% of amine dodecenyl succinate and/or ammonium dodecenyl succinate salt, 14-20% of ammonium dinonylnaphthalene sulfonate salt and/or ammonium dinonylnaphthalene sulfonate salt, 20-30% of alcohol ether solvent, 0.5-1% of benzotriazole and the balance of water.
Wherein the dodecenylsuccinic acid amine salt is dodecenylsuccinic acid dicyclohexylamine or dodecenylsuccinic acid oleylamine or a mixture of dodecenylsuccinic acid dicyclohexylamine and dodecenylsuccinic acid oleylamine.
Wherein the dodecenyl succinic acid amine salt is prepared by the following method: dodecenylsuccinic acid and fatty amine are mixed according to the mol ratio of 1: 1-1.05, the mixed materials are placed at the temperature of 90-110 ℃ for reaction for 3-4h, and dodecenylsuccinic acid amine salt is obtained after the reaction, wherein the acid value of the dodecenylsuccinic acid amine salt is less than 10mg KOH/g, and free amine is less than 10mg KOH/g. The lower the acid value, the more sufficient the reaction of dodecenylsuccinic acid was. The lower the free amine, the more neutral the solution is after dissolution in water.
Wherein the fatty amine is dicyclohexylamine or oleylamine.
The dodecenyl ammonium succinate is obtained by neutralizing dodecenyl succinic acid and ammonia water, the acid value of the dodecenyl ammonium succinate is less than 10mg KOH/g, and free amine is less than 10mg KOH/g.
Wherein the dinonylnaphthalene sulfonate amine salt is dinonylnaphthalene sulfonate dicyclohexylamine or dinonylnaphthalene sulfonate oleylamine, or a mixture of dinonylnaphthalene sulfonate dicyclohexylamine and dinonylnaphthalene sulfonate oleylamine.
Wherein the alcohol ether solvent is one or the mixture of any two of ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl ether or propylene glycol monophenyl ether.
Wherein the pH value of the antirust agent is 7.0-7.7.
The mechanism of good rust prevention effect of the water-based rust inhibitor is as follows: the aqueous antirust agent uses dinonyl naphthalene sulfonic acid amine salt and/or dinonyl naphthalene sulfonic acid ammonium salt and dodecenyl succinic acid amine salt and/or dodecenyl succinic acid ammonium salt for synergic antirust (aiming at salt mist and atmospheric corrosion), benzotriazole is used for electrochemical anticorrosion, the solubility of dinonyl naphthalene sulfonic acid amine salt in water is far greater than that of barium dinonyl sulfonate or calcium dinonyl naphthalene sulfonate, and the dinonyl naphthalene sulfonic acid amine salt can be dissolved into water by an alcohol ether solvent. The alcohol ether solvent has certain volatility, and when the water-based antirust agent (three antirust substances are deposited on the surface of a metal in a staggered mode and molecules of the three antirust substances are arranged in a staggered and compact mode) is adsorbed on the surface of the metal, a compact protective layer can be formed on the surface of the metal after moisture and the alcohol ether solvent are volatilized, so that a good antirust effect is achieved.
Has the advantages that: compared with the existing rust preventive oil, the aqueous rust preventive disclosed by the invention is low in preparation cost, the existing dodecenylsuccinic acid and barium dinonylnaphthalenesulfonate or calcium dinonylnaphthalenesulfonate rust preventive oil system can be applied to the aqueous rust preventive (dodecenylsuccinic acid reacts with oil-soluble fatty amine, so that two oil-soluble substances can be well dissolved in water, free amine in the solution is reduced, and the problems that the free amine is high and an emulsifier and the rust preventive agent are adsorbed on the metal surface and easily absorb moisture in the air to cause poor rust preventive effect when the rust preventive oil system is applied to the aqueous rust preventive agent can be solved; in addition, compared with the existing aqueous antirust agent, the aqueous antirust agent is neutral (low in free amine and neutral), so that the aqueous antirust agent is better in environmental protection, less in stimulation to operators and longer in antirust time; the water-based antirust agent can be used as a long-term antirust agent alone, and can also be diluted by adding water for use according to the antirust time requirement.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to specific examples.
The amine dinonylnaphthalenesulfonate salts and ammonium dinonylnaphthalenesulfonate salts used in the formulations of the present invention are commercially available.
Example 1
The neutral aqueous antirust agent is prepared by mixing the following components in parts by mass: 10kg of dodecenyl succinic acid ammonium salt, 10kg of dodecenyl succinic acid oleylamine, 10kg of dinonyl naphthalene sulfonic acid ammonium salt, 30kg of ethylene glycol monobutyl ether, 0.5kg of benzotriazole and 39.5kg of water.
The neutral aqueous antirust agent is prepared by the following method: fully stirring dodecenyl ammonium succinate, dodecenyl oleyl ammonium succinate, dinonyl naphthalene sulfonic acid ammonium salt and ethylene glycol monobutyl ether in a formula amount at normal temperature (the stirring time is more than 1h), then adding water in a formula amount, continuously stirring for more than 2h, finally adding benzotriazole in a formula amount, and stirring for 30min to obtain the neutral aqueous antirust agent with the pH value of 7.5.
The preparation method of dodecenyl succinic acid oleylamine comprises the following specific steps: 284g of dodecenyl succinic acid and 260g of oleylamine are mixed, stirring is started, heating is carried out to 100 ℃ while stirring, reaction is carried out for 4 hours, stirring is continuously carried out in the reaction process, dodecenyl succinic acid oleylamine is obtained, the acid value of the dodecenyl succinic acid oleylamine is 2mg KOH/g according to the detection of a GB/T4945 method, and the free amine is 5mg KOH/g according to the detection of a GB/T6365 method.
The neutral aqueous rust inhibitor stock solution of example 1 was taken for rust inhibition test:
and performing a salt spray test according to SH/T0081, wherein the rust prevention time is 48h and is 0 grade.
The damp-heat test is carried out according to GB/T2361, and the rust prevention time is 240h and 0 grade.
The commercial Jiashiduo Rustilo 4175 has a pH value of 9.1, a salt spray experiment of less than 12h, and a damp-heat experiment of less than 72 h.
From the above results, it is understood that the neutral aqueous rust inhibitor stock solution of example 1 has performance equivalent to that of a commercial rust inhibitor oil, and is much higher than that of a commercial alkaline aqueous rust inhibitor.
50g of the neutral aqueous rust inhibitor of example 1 was dissolved in 50g of distilled water, and the obtained rust inhibitor liquid was subjected to a rust inhibition test:
the salt spray test (continuous spraying) is carried out according to SH/T0081, and the rust prevention time is 24h and 0 grade.
And performing a damp-heat test according to GB/T2361, wherein the rust prevention time is 168h and 0 grade.
The commercial Jiashiduo Rustilo 4175 has pH of 9.1, salt spray experiment of less than 12 hr, and damp heat experiment of less than 72 hr.
From the above results, it is found that the rust inhibitive performance of the rust inhibitive liquid is still far higher than that of the commercially available alkaline aqueous rust inhibitive agent.
Example 2
The neutral aqueous antirust agent is prepared by mixing the following components in parts by mass: 5kg of dodecenyl succinic acid ammonium salt, 5kg of dodecenyl succinic acid dicyclohexylamine, 20kg of dinonyl naphthalene sulfonic acid ammonium salt, 30kg of ethylene glycol monophenyl ether, 0.5kg of benzotriazole and 39.5kg of water.
The neutral aqueous antirust agent is prepared by the following method: fully stirring dodecenyl ammonium succinate, dodecenyl dicyclohexylamine succinate, dinonyl naphthalene sulfonic acid ammonium salt and ethylene glycol monophenyl ether in a formula amount at normal temperature (the stirring time is more than 1h), then adding water in a formula amount, continuously stirring for more than 2h, finally adding benzotriazole in a formula amount, and stirring for 30min to obtain the neutral aqueous antirust agent with the pH value of 7.7.
The preparation method of the dodecenylsuccinic acid dicyclohexylamine comprises the following specific steps: 284g of dodecenyl succinic acid and 180g of dicyclohexylamine are mixed, stirring is started, the mixture is heated to 105 ℃ while stirring, reaction is carried out for 3 hours, stirring is continuously carried out in the reaction process, dodecenyl succinic acid dicyclohexylamine is obtained, the acid value of the obtained dodecenyl succinic acid dicyclohexylamine is 5mg KOH/g according to the detection of a GB/T4945 method, and the free amine is 2mg KOH/g according to the detection of a GB/T6365 method.
50g of the neutral aqueous rust inhibitor of example 2 was dissolved in 50g of distilled water, and the obtained rust inhibitor liquid was subjected to a rust inhibition test:
the salt spray test (continuous spraying) is carried out according to SH/T0081, and the rust prevention time is 36h and 0 grade.
And performing a damp-heat test according to GB/T2361, wherein the rust prevention time is 168h and 0 grade.
Example 3
The neutral aqueous antirust agent is prepared by mixing the following components in parts by mass: 10kg of dodecenyl succinic acid oleylamine, 10kg of dodecenyl succinic acid dicyclohexylamine, 5kg of dinonyl naphthalene sulfonic acid ammonium salt, 20kg of ethylene glycol monobutyl ether, 10kg of diethylene glycol monobutyl ether, 0.5kg of benzotriazole and 39.5kg of water.
The neutral aqueous antirust agent is prepared by the following method: fully stirring dodecenyl oleylamine succinate, dodecenyl dicyclohexylamine succinate, dinonyl dicyclohexylamine naphthalene sulfonate, dinonyl ammonium naphthalene sulfonate, ethylene glycol monobutyl ether and diethylene glycol monobutyl ether in a formula amount at normal temperature (the stirring time is more than 1h), then adding water in a formula amount, continuously stirring for more than 2h, finally adding benzotriazole in a formula amount, and stirring for 30min to obtain the neutral aqueous antirust agent with the pH value of 7.3.
50g of the neutral aqueous rust inhibitor of example 3 was dissolved in 50g of distilled water, and the obtained rust inhibitor liquid was subjected to a rust inhibition test:
the salt spray test (continuous spraying) is carried out according to SH/T0081, and the rust prevention time is 48h and 0 grade.
And performing a damp-heat test according to GB/T2361, wherein the rust prevention time is 360h and 0 grade.
Example 4
The neutral aqueous antirust agent is prepared by mixing the following components in parts by mass: 8kg of dodecenyl succinic acid oleylamine, 8kg of dodecenyl succinic acid dicyclohexylamine, 7kg of dinonyl naphthalenesulfonic acid oleylamine, 20kg of ethylene glycol monobutyl ether, 10kg of propylene glycol monomethyl ether, 0.5kg of benzotriazole and 39.5kg of water.
The neutral aqueous antirust agent is prepared by the following method: fully stirring dodecenyl butanedioic acid oleylamine, dodecenyl butanedioic acid dicyclohexylamine, dinonyl naphthalenesulfonic acid oleylamine, ethylene glycol monobutyl ether and propylene glycol monomethyl ether at normal temperature (the stirring time is more than 1h), then adding water with the formula amount, continuously stirring for more than 2h, finally adding benzotriazole with the formula amount, and stirring for 30min to obtain the neutral aqueous antirust agent with the pH value of 7.0.
50g of the neutral aqueous rust inhibitor of example 4 was dissolved in 50g of distilled water, and the obtained rust inhibitor liquid was subjected to a rust inhibition test:
the salt spray test (continuous spraying) is carried out according to SH/T0081, and the rust prevention time is 45h and 0 grade.
The damp-heat test is carried out according to GB/T2361, and the rust prevention time is 336h, grade 0.
The antirust performance differences of the examples 1-4 are that different dodecenyl succinic acid amine salt combinations and different dinonyl sulfonic acid amine salts are used in the formula, and the amine salts are subjected to different chain lengths of fatty amine and end group structures, so that the formed antirust films are different in compactness and hydrophobicity.