阅读说明：本技术 一种新型n，n-二正丁基氨基苯***的制备方法 (Preparation method of novel N, N-di-N-butylaminobenzotriazole ) 是由 刘亚芳 王学义 范金凤 于 2020-07-07 设计创作，主要内容包括：本发明公开了一种新型N,N-二正丁基氨基苯三唑的制备方法,包括：将苯三唑、甲醛和二正丁胺进行曼尼希反应,制得N,N-二正丁基氨基苯三唑。本发明的制备方法不同于传统的T551的合成工艺,其无需加入催化剂、无溶剂相和水相,副反应少,产率高,制备过程简单；后处理没有引入酸和水,没有三废产生；同时,制备的N,N-二正丁基氨基苯三唑具有优异的油溶性、抑制金属腐蚀性和抗氧化性。(The invention discloses a preparation method of novel N, N-di-N-butylaminobenzotriazole, which comprises the following steps: performing Mannich reaction on benzotriazole, formaldehyde and di-N-butylamine to obtain the N, N-di-N-butylaminobenzotriazole. The preparation method is different from the traditional T551 synthesis process, does not need to add a catalyst, and has no solvent phase and water phase, less side reaction, high yield and simple preparation process; acid and water are not introduced in the post-treatment, and three wastes are not generated; meanwhile, the prepared N, N-di-N-butylaminobenzotriazole has excellent oil solubility, metal corrosion inhibition and oxidation resistance.)

1. A preparation method of novel N, N-di-N-butylaminobenzotriazole is characterized by comprising the following steps:

performing Mannich reaction on benzotriazole, formaldehyde and di-N-butylamine to obtain the N, N-di-N-butylaminobenzotriazole.

2. The method of claim 1, wherein the mannich reaction is of the formula:

3. the method according to claim 1 or 2, wherein the molar ratio of the benzotriazole, formaldehyde and di-n-butylamine is (0.9 to 1.6): (1.0 to 1.7): (0.8 to 1.3).

4. The method of claim 1 or 2, wherein the mannich reaction is carried out at a reaction temperature of 80 to 120 ℃ for 6 to 12 hours.

5. The process according to claim 1 or 2, characterized in that the Mannich reaction comprises in particular:

mixing benzotriazole and di-n-butylamine in a four-neck flask;

heating, stirring for dissolving, keeping the temperature, dropwise adding formaldehyde at a preset reaction temperature for aminomethylation reaction, and finally performing Mannich electrophilic addition reaction under a reflux condition.

6. The method of claim 5, further comprising:

and (3) carrying out reduced pressure distillation on the product after the Mannich reaction, and carrying out suction filtration after reduced pressure distillation.

Technical Field

The invention belongs to the technical field of lubricating oil additives, relates to a preparation method of a lubricating oil metal deactivator, and particularly relates to a preparation method of a novel N, N-di-N-butylaminobenzotriazole.

Background

The metal deactivator is a compound containing S, P, N or other non-metal elements, and the variety mainly includes benzotriazole derivatives, thiadiazole derivatives, and the like. The antioxidant does not have an antioxidant effect per se, but can 'passivate' the activity of metal, thereby playing a role in delaying the oxidation speed of oil products.

The N, N-di-N-butylaminobenzotriazole not only improves the oil solubility of benzotriazole, but also has excellent oxidation resistance, copper corrosion inhibition and metal deactivation performance. The metal deactivator has less consumption (0.01-0.05%), and has outstanding synergistic effect when used in combination with phenolic antioxidant, so that the consumption of the antioxidant can be reduced remarkably, and the antioxidant performance of the oil product can be improved remarkably.

The improved process of T551 metal deactivator, which is published in the papers of Gansu science of journal, mentions that the production process of T551 is as follows: after the raw materials react according to certain conditions, a T551 crude product is generated, and qualified products can be obtained through the production processes of gasoline extraction, solvent removal, normal-temperature static continuous water washing until the pH value is neutral, reduced-pressure distillation, filtration and the like. The preparation method has complex process, and the steps of gasoline extraction, layering, multiple water washing, solvent evaporation reduction and the like are added in the post-treatment, so that a large amount of industrial wastewater is brought, and the preparation method is not environment-friendly and economical; but also requires distillation of large amounts of solvent, increasing costs.

US4376635 discloses a process for the preparation of a metal deactivator by reacting equimolar amounts of an amine and benzotriazole in a reaction vessel containing an excess of solvent. The mixed solvent methanol and benzene used in the preparation method have the following problems: the mixed solvent is not easy to recover, and the solvent benzene has great toxicity, great harm to human bodies and no environmental protection.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a preparation method of novel N, N-di-N-butylaminobenzotriazole.

The invention discloses a preparation method of novel N, N-di-N-butylaminobenzotriazole, which comprises the following steps:

performing Mannich reaction on benzotriazole, formaldehyde and di-N-butylamine to obtain the N, N-di-N-butylaminobenzotriazole.

As a further improvement of the invention, the mannich reaction has the formula:

as a further improvement of the invention, the molar ratio of the benzotriazole to the formaldehyde to the di-n-butylamine is (0.9-1.6): (1.0-1.7): 0.8-1.3).

As a further improvement of the method, the reaction temperature of the Mannich reaction is 80-120 ℃, and the reaction time is 6-12 h.

As a further improvement of the invention, the Mannich reaction specifically comprises:

mixing benzotriazole and di-n-butylamine in a four-neck flask;

heating, stirring for dissolving, keeping the temperature, dropwise adding formaldehyde at a preset reaction temperature for aminomethylation reaction, and finally performing Mannich electrophilic addition reaction under a reflux condition.

As a further improvement of the invention, the method also comprises the following steps:

and (3) carrying out reduced pressure distillation on the product after the Mannich reaction, and carrying out suction filtration after reduced pressure distillation.

Compared with the prior art, the invention has the beneficial effects that:

the preparation method is different from the traditional T551 synthesis process, does not need to add a catalyst, and has no solvent phase and water phase, less side reaction, high yield and simple preparation process; acid and water are not introduced in the post-treatment, and three wastes are not generated; meanwhile, the prepared N, N-di-N-butylaminobenzotriazole has excellent oil solubility, metal corrosion inhibition and oxidation resistance.

Drawings

FIG. 1 is an IR spectrum of N, N-di-N-butylaminobenzotriazole prepared in example 1 of this invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

The invention is described in further detail below with reference to the attached drawing figures:

the invention provides a green preparation method of novel N, N-di-N-butylaminobenzotriazole, which comprises the following steps:

according to the preparation method, on the premise that no catalyst is used and no water phase is introduced, the benzene triazole, the formaldehyde and the di-N-butylamine are subjected to Mannich reaction to prepare the N, N-di-N-butylaminobenzene triazole;

the reaction formula of the reaction is as follows:

wherein the content of the first and second substances,

the molar ratio of benzotriazole, formaldehyde and di-n-butylamine is (0.9-1.6): (1.0-1.7): 0.8-1.3). The benzotriazole has acidity, can provide catalysis for the Mannich reaction, and does not need to introduce an additional acidic catalyst. The final experimental result shows that the reaction is simple and feasible, no solvent is used, no water phase is introduced, the post-treatment is not complex, no three wastes are generated, and the production process is greatly simplified.

The reaction temperature of the Mannich reaction is 80-120 ℃, and the reaction time is 6-12 h.

Further, based on the above reaction conditions, the mannich reaction of the present invention specifically includes:

step 1, weighing benzotriazole, di-n-butylamine and formaldehyde according to a preset molar ratio;

step 2, mixing benzotriazole and di-n-butylamine in a four-neck flask;

step 3, after heating, stirring for dissolving and heat preservation, dropwise adding formaldehyde at a preset reaction temperature for aminomethylation reaction, and finally performing Mannich electrophilic addition reaction under a reflux condition; wherein the content of the first and second substances,

replacing air in the bottle with nitrogen, starting heating, and then starting stirring; the stirring speed is preferably 280-350 rpm; continuously heating to 65 ℃, and keeping the temperature for 40 min; after the heat preservation is finished, slowly dripping formaldehyde at the temperature, and stirring for 1-2 hours at the temperature after finishing dripping.

Step 4, carrying out reduced pressure distillation on the product after the Mannich reaction, and carrying out suction filtration after reduced pressure distillation; wherein the content of the first and second substances,

the water during the reaction is preferably removed by distillation under reduced pressure, and the degree of vacuum of the distillation under reduced pressure is preferably 0.08MPa to 0.095 MPa.

The invention mainly optimizes the synthetic route, determines the optimal feeding ratio and the optimal feeding sequence of the reaction, leads the appearance of the obtained N, N-di-N-butylaminobenzotriazole product to be reddish brown liquid, and the experimental result shows that: the appearance of the product is reddish brown liquid; the residual content of benzotriazole is 0.45-1.10 wt%, and the content of commercial product is 2.56 wt%; the residual content of di-n-butylamine was 0.50 to 1.43% by weight, comparable to the commercial product, 2.20% by weight. The corrosion of the copper sheet (100 ℃, 3h) is less than or equal to 1 b; the water content (m/m) is less than or equal to 0.15; the base number is 202.24-215.85mgKOH/g, the weight loss of the copper sheet per unit area is 0.30-0.60 when the copper sheet is put into a formula of the hydraulic oil complexing agent, and the weight loss of the commercially available product copper sheet is 0.80-1.30.

In order to further illustrate the present invention, the following examples are given to describe the preparation of N, N-di-N-butylaminobenzotriazole according to the present invention in detail, but they should not be construed as limiting the scope of the present invention.