阅读说明：本技术 一种金属硬膜防锈剂及其制备方法 (Metal hard film antirust agent and preparation method thereof ) 是由 刘汐岳 李科发 于 2019-10-31 设计创作，主要内容包括：本发明涉及一种金属硬膜防锈剂及其制备方法,属于防锈剂技术领域。本发明的金属硬膜防锈剂利用石油裂解C5馏分、有机多元醇、硬脂酸咪唑啉季铵盐类化合物、油酸三乙醇胺、钼酸钾及焦磷酸钠来进行合成及复配得到金属硬膜防锈剂,添加12-羟基硬脂酸咪唑啉季铵盐,通过分子中极性原子N、S通过吸附在金属表面形成保护膜,进一步加强保护膜的防锈能力。在金属结构件中实现长效防锈,具有耐蚀性好、成本低廉、使用方便、易施工、易去除、涂层干燥快、防锈效果好、涂膜均匀美观等优势。制备方法所用原料廉价、工艺简单。能够满足工程机械行业装配前早期防护及入库早期防腐防护,可以在工程机械行业推广应用。(The invention relates to a metal hard film antirust agent and a preparation method thereof, belonging to the technical field of antirust agents. The metal hard film antirust agent is synthesized and compounded by utilizing petroleum cracking C5 fraction, organic polyol, a stearic acid imidazoline quaternary ammonium salt compound, triethanolamine oleate, potassium molybdate and sodium pyrophosphate to obtain the metal hard film antirust agent, 12-hydroxystearic acid imidazoline quaternary ammonium salt is added, and a protective film is formed by adsorbing a polar atom N, S in a molecule on the surface of metal, so that the antirust capacity of the protective film is further enhanced. The antirust paint realizes long-acting antirust in a metal structural part, and has the advantages of good corrosion resistance, low cost, convenient use, easy construction, easy removal, fast coating drying, good antirust effect, uniform and attractive coating and the like. The preparation method has the advantages of cheap raw materials and simple process. The early protection before assembly and the early anticorrosion protection in warehousing in the engineering machinery industry can be met, and the method can be popularized and applied in the engineering machinery industry.)

1. A metal hard film antirust agent is synthesized and compounded by petroleum cracking C5 fraction, organic polyol, stearic acid imidazoline quaternary ammonium salt compound, triethanolamine oleate, potassium molybdate and sodium pyrophosphate, and is characterized in that the metal hard film antirust agent is prepared from the following raw materials in parts by mass:

10-20 parts of petroleum cracking C5 fraction;

8-10 parts of organic polyol;

10-25 parts of stearic acid imidazoline quaternary ammonium salt compounds;

8-18 parts of triethanolamine oleate;

3-6 parts of potassium molybdate;

1-3 parts of potassium pyrophosphate.

2. The hard metal film rust inhibitor according to claim 1, characterized in that: wherein the organic polyol is any one or a mixture of more than two of pentaerythritol, 1, 2-propylene glycol, 1, 3-propylene glycol and glycerol.

3. The metal hard film rust inhibitor according to claim 1 or 2, characterized in that: wherein the imidazoline quaternary ammonium stearate compound is 12-imidazoline hydroxystearate quaternary ammonium salt.

4. A method for preparing a hard metal film rust inhibitor according to claim 1, characterized by comprising the steps of:

A. firstly, preparing 12-hydroxystearic acid imidazoline quaternary ammonium salt according to requirements for later use;

B. adding petroleum cracking C5 fraction and organic polyol according to the formula ratio, heating to 50-70 ℃, stirring and dissolving for 0.5-1.5 h; after the materials are completely dissolved, adding triethanolamine oleate, potassium molybdate and sodium pyrophosphate in a formula amount, and stirring for 0.5-1 h at the temperature of 60-70 ℃;

C. and after the metal hard film antirust agent is completely dissolved, adding 12-hydroxystearic acid imidazoline quaternary ammonium salt in a formula amount, preserving heat, stirring for 1-2 h, cooling to room temperature, and discharging to obtain the metal hard film antirust agent.

5. The method for preparing the metal hard film rust inhibitor according to claim 4, wherein the method for preparing the imidazoline quaternary ammonium 12-hydroxystearate in the step A comprises the following steps:

1) adding diethylenetriamine and 12-hydroxystearic acid into a reaction kettle according to a ratio, introducing nitrogen for protection by using dimethylbenzene as a water carrying agent, heating to 140-160 ℃, maintaining for 4-5 hours until no water is distilled off, then heating to 190-210 ℃, reacting for 1.5-2 hours until no water is distilled off, and carrying out reduced pressure distillation to obtain a brownish red oxazoline intermediate liquid;

2) adding the imidazoline intermediate prepared in the step into a reaction kettle, slowly dropwise adding benzyl chloride while stirring, preserving the temperature for reacting for 3 hours after dropwise adding, and slowly cooling to obtain 12-hydroxystearic acid imidazoline quaternary ammonium salt;

the reaction equation is as follows:

6. the method for preparing a rust inhibitor with a hard metal film according to claim 5, characterized in that: the molar ratio of the diethylenetriamine to the 12-hydroxystearic acid in the step 1) is 1.1-1.5: 1.

7. The method for preparing a rust inhibitor with a hard metal film according to claim 5, characterized in that: the reaction temperature of the heat preservation reaction in the step 2) is 90-100 ℃.

8. The method for preparing a rust inhibitor with a hard metal film according to claim 4, wherein: and C, keeping the temperature of the heat preservation in the step C at 60-70 ℃.

9. The metal hard film antirust agent as claimed in claim 3, characterized in that the raw materials are in parts by mass as follows:

petroleum cracking C5 fraction 15.0;

3.0 parts of pentaerythritol;

3.0 parts of 1, 3-propanediol;

3.0 parts of glycerol;

12-hydroxystearic acid imidazoline quaternary ammonium salt 18.5;

triethanolamine oleate 13.0;

4.5 of potassium molybdate;

potassium pyrophosphate 2.0.

Technical Field

The invention relates to a metal antirust agent and a preparation method thereof, in particular to a metal hard film antirust agent and a preparation method thereof, and belongs to the technical field of antirust agents.

Background

The problem of metal corrosion is spread in various industries of national economy, and the performance and the commodity value of metal products and mechanical equipment are lost due to the rust on the surfaces of the metal materials and the mechanical equipment, and even the equipment is scrapped due to serious faults. With the development, transformation and upgrading of equipment manufacturing industry, in order to solve the problems that a water aqua is used for replacing an oil solution to wash or remove oil and rust in the mechanical processing process of metal products or products to be coated and electroplated and rust is generated after oxidation and phosphorization, an antirust agent is needed to carry out antirust treatment on metal parts.

The main component of the traditional antirust agent is a petroleum product as a solvent, and an oil-soluble corrosion inhibitor, an extreme pressure antiwear agent, a detergent dispersant, an antioxidant preservative and other auxiliaries are added. The rust inhibitor in the prior art basically takes gasoline, kerosene or mechanical oil as a solvent, and several rust inhibitors are matched for use to exert the synergistic effect. Commonly used are sulfonates, carboxylates and their soaps, esters, amines and phosphorus-containing compounds. Because the solvent contains aromatic hydrocarbon, the antirust agent has low flash point, is easy to catch fire, pollutes environment and is harmful to health. And the rust-proof protection period is relatively short, the adhesive force is low, metal parts are quickly rusted, and the high-quality requirement of coating protection of engineering machinery is difficult to meet. Moreover, the adhesion between the primer and the substrate is affected if the primer cannot be cleanly treated before coating because the adhesion of the rust inhibitor to the substrate is poor.

Although the metal rust inhibitor product is also improved in view of the above problems, some corrosion inhibitors such as sodium dinonylnaphthalene sulfonate, calcium dinonylnaphthalene sulfonate and the like are added. For example, CN 107699319A is a hard film antirust agent, the formula of which comprises solvent, base oil, lanolin fatty acid polyol ester, hydroxyethyl oleoyl imidazoline, oleoyl sarcosine, calcium dinonylnaphthalenesulfonate and C5 petroleum resin, and fatty acid isopropyl ester is added to form one of the antirust agent components, so that the adhesiveness of the antirust agent and the metal surface can be effectively increased, the adaptability of the antirust agent to temperature is improved, and the antirust effect of the antirust agent is good between-10 ℃ and 50 ℃. Although the dinonyl naphthalene sulfonic acid calcium oil solubility is superior to petroleum barium sulfonate, the antirust performance of the dinonyl naphthalene sulfonic acid calcium oil is similar to that of petroleum barium sulfonate, and the aims of increasing the adhesive force and preventing rust for a long time cannot be achieved when the dinonyl naphthalene sulfonic acid calcium oil is applied to an antirust agent.

Aiming at the defects of relatively short rust prevention period, low adhesion, environmental pollution and harm to health of metal rust inhibitor products in the prior art, a metal rust inhibitor and a preparation method thereof are urgently developed in order to improve the rust prevention function, durability and adhesiveness of the rust inhibitor.

Disclosure of Invention

Aiming at the defects of metal antirust agent products in the prior art, the invention aims to provide the metal hard film antirust agent and the preparation method thereof, which have high corrosion resistance, durability and adhesiveness, do not have the phenomena of hardening, falling off and cracking after use, and are environment-friendly.

The specific technical scheme of the invention is as follows:

the metal hard film antirust agent is synthesized and compounded by petroleum cracking C5 fraction, organic polyol, stearic acid imidazoline quaternary ammonium salt compound, triethanolamine oleate, potassium molybdate and sodium pyrophosphate, and is characterized by comprising the following raw materials in parts by mass:

10-20 parts of petroleum cracking C5 fraction;

8-10 parts of organic polyol;

10-25 parts of stearic acid imidazoline quaternary ammonium salt compounds;

8-18 parts of triethanolamine oleate;

3-6 parts of potassium molybdate;

1-3 parts of potassium pyrophosphate.

Preferably, the organic polyol is any one or a mixture of two or more of pentaerythritol, 1, 2-propanediol, 1, 3-propanediol and glycerol.

Preferably, the imidazoline quaternary ammonium stearate compound is imidazoline quaternary 12-hydroxystearate.

The preparation method of the 12-hydroxystearic acid imidazoline quaternary ammonium salt comprises the following steps:

1) adding diethylenetriamine and 12-hydroxystearic acid into a reaction kettle according to a ratio, introducing nitrogen for protection by using dimethylbenzene as a water carrying agent, heating to 140-160 ℃, maintaining for 4-5 hours until no water is distilled off, then heating to 190-210 ℃, reacting for 1.5-2 hours until no water is distilled off, and carrying out reduced pressure distillation to obtain a brownish red oxazoline intermediate liquid.

2) And adding the imidazoline intermediate prepared in the step into a reaction kettle, slowly dropwise adding benzyl chloride while stirring, preserving the temperature for reaction for 3 hours after dropwise adding, and slowly cooling to obtain the 12-hydroxystearic acid imidazoline quaternary ammonium salt.

Preferably, the molar ratio of the diethylenetriamine to the 12-hydroxystearic acid in the step 1) is 1.1-1.5: 1.

Preferably, the reaction temperature of the heat preservation reaction in the step 2) is 90-100 ℃.

The reaction equation is as follows:

the method for preparing the metal hard film antirust agent comprises the following steps:

A. firstly, preparing 12-hydroxystearic acid imidazoline quaternary ammonium salt according to requirements for later use;

B. adding petroleum cracking C5 fraction and organic polyol according to the formula ratio, heating to 50-70 ℃, stirring and dissolving for 0.5-1.5 h; after the materials are completely dissolved, adding triethanolamine oleate, potassium molybdate and sodium pyrophosphate in a formula amount, and stirring for 0.5-1 h at the temperature of 60-70 ℃;

C. and after the metal hard film antirust agent is completely dissolved, adding 12-hydroxystearic acid imidazoline quaternary ammonium salt in a formula amount, preserving heat, stirring for 1-2 h, cooling to room temperature, and discharging to obtain the metal hard film antirust agent.

Preferably, the temperature of the heat preservation in the step C is 60-70 ℃.

The invention has the beneficial effects that:

(1) the metal hard film antirust agent disclosed by the invention is added with the stearic acid imidazoline quaternary ammonium salt compound, a protective film is formed by adsorbing a polar atom N, S in a molecule on the surface of a metal, meanwhile, a corrosive formed by the metal in a basic liquid is deposited on the protective film on the surface of the metal, and the antirust capacity of the protective film is further enhanced. The antirust agent has a good slow-release antirust function, can prolong the antirust time of the antirust agent, and has a good antirust effect.

(2) According to the invention, petroleum cracking C5 fraction, organic polyol, stearic acid imidazoline quaternary ammonium salt compound, triethanolamine oleate, potassium molybdate and sodium pyrophosphate are used for synthesis and compounding to obtain the metal hard film antirust agent, long-acting rust prevention is realized in a metal structural member, and the metal hard film antirust agent not only has the characteristics of thin coating, excellent adhesion and the like, but also has the advantages of good corrosion resistance, low cost, convenience in use, easiness in construction and removal, quick coating drying, good antirust effect, uniform and attractive coating film and the like.

(3) The preparation method of the metal hard film antirust agent has the advantages of cheap raw materials and simple process, and through tests and field construction operation, the hard film antirust agent can meet the requirements of early protection before assembly and early anticorrosion protection in warehousing in the engineering machinery industry, and can be popularized and applied in the engineering machinery industry.

Detailed Description

In order to better understand the invention, the following examples further illustrate the content of the invention, but the content of the invention is not limited to the following examples, and the examples should not be construed as limiting the scope of the invention.