阅读说明：本技术 一种烷基酚类清净剂的制备方法 (Preparation method of alkylphenol detergent ) 是由 万新水 任晓琳 李伟 范金凤 王龙龙 于 2021-08-10 设计创作，主要内容包括：本发明公开了一种烷基酚类清净剂的制备方法,属于清净剂技术领域,以烷基酚为主要原材料,加入氧化钙或氢氧化钙、硫磺、基础油,在促进剂乙二醇作用下进行中和、硫化反应,再加入胺、甲醛进行胺化反应,无需通过碳酸化反应制得高碱值的烷基酚清净剂产品,该产品工艺路线简单,制备出的产品在保证硫化烷基酚钙应有的清净性、酸中和能力、抗氧、抗磨等性能外,还具有游离酚低、碱值高、灰分低的特点。(The invention discloses a preparation method of an alkylphenol detergent, which belongs to the technical field of detergents and is characterized in that alkylphenol is taken as a main raw material, calcium oxide or calcium hydroxide, sulfur and base oil are added, neutralization and vulcanization are carried out under the action of an accelerator glycol, amine and formaldehyde are added for amination, and a high-base-number alkylphenol detergent product is prepared without carbonation.)

1. A method of making an alkylphenol detergent comprising:

adding 1 part of alkylphenol, 0.6-1.5 parts of base oil, 0.05-0.25 part of calcium oxide or calcium hydroxide and 0.1-0.25 part of sulfur in parts by weight into a reaction bottle, and heating to 140-180 ℃;

0.1-0.25 part of accelerator ethylene glycol is dripped into the reaction bottle to carry out neutralization and vulcanization reaction to generate a sulfurized calcium alkyl phenate intermediate;

cooling the sulfurized calcium alkyl phenate intermediate to 30-50 ℃, adding 0.05-0.5 part of amine, 0.5-3 parts of diluent solvent oil and 0.05-0.5 part of aldehyde, heating to 150-250 ℃ to perform amination reaction, and removing water generated by the reaction;

and after the amination reaction is finished, cooling, deslagging, and distilling to remove the solvent to obtain the product.

2. The method of making an alkylphenol detergent of claim 1, wherein the alkylphenol has the formula:

wherein R is a straight chain or branched chain alkyl of C9-30.

3. The method of making an alkylphenol detergent of claim 1, wherein the amine is one or more of a primary amine, a diamine, or a triamine;

the aldehyde is formaldehyde solution, trioxymethylene or paraformaldehyde.

4. The method of claim 1, wherein the neutralization and sulfurization reaction time is 3 to 10 hours, and the reaction formula is:

wherein R is a straight chain or branched chain alkyl of C9-30.

5. The method of preparing an alkylphenol detergent of claim 1, wherein the rate of temperature rise during the amination reaction is 0.5 to 1 ℃/min.

6. The method of claim 1, wherein the deslagging is filtration deslagging or centrifugal deslagging.

Technical Field

The invention belongs to the technical field of detergents, and particularly relates to a preparation method of an alkylphenol detergent.

Background

The conventional preparation method of sulfurized calcium alkyl phenate takes dodecylphenol, base oil, calcium oxide, sulfur and reaction auxiliaries as raw materials, performs neutralization and sulfurization reactions under the action of an accelerator, then charges carbon dioxide for carbonation reaction, and finally obtains the sulfurized calcium alkyl phenate finished product by centrifugation or filtration to remove impurities. The product not only has excellent high-temperature detergency, but also has certain oxidation resistance, corrosion resistance and abrasion resistance, is widely used for preparing medium-high grade internal combustion engine oil and marine oil, and is an indispensable lubricating oil detergent product.

With the increasing awareness of the skilled worker on sulfurized calcium alkyl phenate products, the negative problems associated with sulfurized calcium alkyl phenate detergents have not been ignored. Firstly, the problem of free alkylphenol is solved, the content of free alkylphenol in the finished calcium alkylphenol sulfide product prepared by the conventional process is high, some of the free alkylphenol is even more than 10%, alkylphenol is used as an endocrine disrupting substance, and the reproductive toxicity of alkylphenol is promoted from 2 types to 1B type in 2018 according to a GHS classification system, which means that the residual quantity of alkylphenol is more than or equal to 0.1% of lubricating oil, and GHS pictograms and hazard descriptions are required to be added. Secondly, the problem of ash content is that calcium element is contained in sulfurized calcium alkyl phenolate, and the calcium element is used as a main source for providing base number, so that the calcium alkyl phenolate plays a key role in neutralizing acid substances generated after engine fuel is combusted, high base number means stronger acid neutralizing capacity, and patents CN200810011926.5 and cn200810011927.x do a lot of work in improving the base number of sulfurized calcium alkyl phenolate products, but high base number means higher ash content, and when the ash content is too high, deposits are easily formed at the spark plug of an engine to cause pre-ignition, so that friction and abrasion of moving parts are caused, and engine faults are caused. When the dosage of the sulfurized calcium alkyl phenate in the lubricating oil is reduced or the sulfurized calcium alkyl phenate product with low base number is used, the acid neutralization capacity of the product is reduced.

In recent years, workers in related fields at home and abroad carry out a lot of work on the modification aspect of calcium alkylphenol sulfide products, and in the U.S. Pat. No. 11218390, dodecylphenol is replaced by long-chain linear alkylphenol with low toxicity to prepare calcium alkylphenol sulfide products, but the essence of the calcium alkylphenol sulfide products still belongs to alkylphenol substances, the long-chain alkylphenol has weaker polarity, is difficult to carry out vulcanization and carbonation reactions, is greatly reduced in the aspect of product yield, and is influenced in detergency. In the patent US15301674, free alkylphenol is removed by high-temperature and reduced-pressure extraction, the boiling point of dodecylphenol is usually above 300 ℃, complete removal is difficult by a reduced-pressure distillation method, and the problem of energy consumption caused by the removal is not negligible. Patent CN201210211923.2 describes a formaldehyde condensation type alkyl phenate detergent product, which replaces the sulfuration reaction with formaldehyde condensation, but the base number of the obtained product is lower, and the product does not contain sulfur, and the anti-wear effect of the product is lost.

Disclosure of Invention

In view of the above problems, the present invention provides a method for preparing an alkylphenol type detergent, comprising:

adding 1 part of alkylphenol, 0.6-1.5 parts of base oil, 0.05-0.25 part of calcium oxide or calcium hydroxide and 0.1-0.25 part of sulfur in parts by weight into a reaction bottle, and heating to 140-180 ℃;

0.1-0.25 part of accelerator ethylene glycol is dripped into the reaction bottle to carry out neutralization and vulcanization reaction to generate a sulfurized calcium alkyl phenate intermediate;

cooling the sulfurized calcium alkyl phenate intermediate to 30-50 ℃, adding 0.05-0.5 part of amine, 0.5-3 parts of diluent solvent oil and 0.05-0.5 part of aldehyde, heating to 150-250 ℃ to perform amination reaction, and removing water generated by the reaction;

and after the amination reaction is finished, cooling, deslagging, and distilling to remove the solvent to obtain the product.

Preferably, the alkylphenol has the formula:

wherein R is a straight chain or branched chain alkyl of C9-30.

Preferably, the amine is one or more of a primary amine, a diamine, or a triamine;

the aldehyde is formaldehyde solution, trioxymethylene or paraformaldehyde.

Preferably, the neutralization and vulcanization reaction time is 3-10 hours, and the reaction formula is as follows:

wherein R is a straight chain or branched chain alkyl of C9-30.

Preferably, the rate of slow temperature rise during the amination reaction is from 0.5 to 1 ℃/min.

Preferably, the deslagging is filtering deslagging or centrifugal deslagging.

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

the method does not need to charge carbon dioxide for carbonation reaction to prepare the alkylphenol detergent product with high base number, the product has simple process route, and the prepared product has the characteristics of low free phenol, high base number and low ash content while ensuring the due detergency, acid neutralization capacity, oxidation resistance, abrasion resistance and other properties of the calcium sulfurized alkylphenol.

Drawings

FIG. 1 is a schematic flow chart of a method for preparing an alkylphenol type detergent provided by the present 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.

In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the present invention, it should also be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.

Referring to fig. 1, a method of making an alkylphenol detergent includes:

adding 1 part of alkylphenol, 0.6-1.5 parts of base oil, 0.05-0.25 part of calcium oxide or calcium hydroxide and 0.1-0.25 part of sulfur in parts by weight into a reaction bottle, and heating to 140-180 ℃;

0.1-0.25 part of accelerator ethylene glycol is dripped into the reaction bottle to carry out neutralization and vulcanization reaction to generate a sulfurized calcium alkyl phenate intermediate;

specifically, the neutralization and vulcanization reaction time is 3-10 hours, and the reaction formula is as follows:

wherein R is a straight chain or branched chain alkyl of C9-30.

Cooling the sulfurized calcium alkyl phenate intermediate to 30-50 ℃, adding 0.05-0.5 part of amine, 0.5-3 parts of diluent solvent oil and 0.05-0.5 part of aldehyde, heating to 150-250 ℃ to perform amination reaction, and removing water generated by the reaction;

specifically, the rate of slow temperature rise during amination reaction is 0.5-1 deg.C/min.

And after the amination reaction is finished, cooling, deslagging, and distilling to remove the solvent to obtain the product.

In this example, the alkylphenol has the formula:

wherein R is a straight chain or branched chain alkyl of C9-30; the amine is one or more of primary amine, diamine or triamine; the aldehyde is formaldehyde solution, trioxymethylene or paraformaldehyde.

In this embodiment, the deslagging is filtration deslagging or centrifugal deslagging.

Example 1

100g of dodecylphenol, 100g of 150N base oil, 18g of sulfur and 15g of calcium oxide are added into a 500mL four-mouth bottle, the temperature is raised to 155 ℃, 20g of accelerator ethylene glycol is dropwise added, and the temperature is kept at 150 ℃ for 5 hours after the dropwise addition is finished. Cooling the materials to 30 ℃, adding 18g of paraformaldehyde, 22g of ethylenediamine and 150g of 200# diluted solvent oil, heating to 180 ℃ at the speed of about 1 ℃/min, then cooling, adding 6g of diatomite filter aid for filtration, and distilling the filtrate to remove the solvent to obtain the alkylphenol detergent.

The chemical reaction in this example is as follows:

(1) the dodecylphenol, the calcium oxide and the sulfur are subjected to neutralization and vulcanization reaction under the action of an accelerator ethylene glycol to generate a sulfurized alkylphenol intermediate:

(2) and (3) carrying out amination reaction on the sulfurized alkylphenol intermediate, paraformaldehyde and ethylenediamine:

(3) and (3) carrying out amination reaction on alkylphenol which is not subjected to vulcanization reaction with paraformaldehyde and ethylenediamine:

example 2

100g of dodecylphenol, 100g of 150N base oil, 18g of sulfur and 15g of calcium oxide are added into a 500mL four-mouth bottle, the temperature is raised to 155 ℃, 20g of accelerator ethylene glycol is dropwise added, and the temperature is kept at 170 ℃ for 4 hours after the dropwise addition is finished. Cooling the materials to 40 ℃, adding 19g of trioxymethylene, 34g of N, N-dimethyl-1, 3-propane diamine and 100g of 200# dilution solvent oil, uniformly heating to 210 ℃ at a constant speed of about 0.6 ℃/min, cooling, adding 7g of diatomite filter aid, filtering and removing residues, and distilling the filtrate to remove the solvent to obtain the alkylphenol detergent.

The main chemical reactions of this example are as follows:

(1) the dodecylphenol, the calcium oxide and the sulfur are subjected to neutralization and vulcanization reaction under the action of an accelerator ethylene glycol to generate a sulfurized alkylphenol intermediate:

(2) and (3) carrying out amination reaction on the sulfurized alkylphenol intermediate, trioxymethylene and N, N-dimethyl-1, 3-propane diamine:

(3) unreacted alkylphenol and trioxymethylene,Amination of N, N-dimethyl-1, 3-propanediamine:

example 3

100g of dodecylphenol, 100g of 150N base oil, 18g of sulfur and 15g of calcium oxide are added into a 500mL four-mouth bottle, the temperature is raised to 160 ℃, 20g of accelerator ethylene glycol is dropwise added, and the temperature is kept at 175 ℃ for 3 hours after the dropwise addition is finished. Cooling the materials to 40 ℃, adding 42g of formaldehyde solution (37%), 36g of diethylenetriamine and 100g of 200# diluted solvent oil, uniformly heating to 230 ℃ at a constant speed of 0.5 ℃/min, cooling, centrifuging to remove slag, and distilling clear liquid to remove the solvent to obtain the alkylphenol detergent.

The main chemical reactions of this example are as follows:

(1) the dodecylphenol, the calcium oxide and the sulfur are subjected to neutralization and vulcanization reaction under the action of an accelerator ethylene glycol to generate a sulfurized alkylphenol intermediate:

(2) and (3) carrying out amination reaction on the sulfurized alkylphenol intermediate, formaldehyde solution and diethylenetriamine:

(3) carrying out amination reaction on unreacted alkylphenol, formaldehyde solution and diethylenetriamine:

example 4

100g of dodecylphenol, 100g of 150N base oil, 18g of sulfur and 15g of calcium oxide are added into a 500mL four-mouth bottle, the temperature is raised to 170 ℃, 20g of accelerator ethylene glycol is dropwise added, and the temperature is kept at 180 ℃ for 3 hours after the dropwise addition is finished. Cooling the materials to 50 ℃, adding 9g of trioxymethylene, 4g of ethylenediamine, 8g of N, N-dimethyl-1, 3-propane diamine and 100g of 200# dilution solvent oil, uniformly heating to 210 ℃ at a speed of about 0.8 ℃/min, cooling, centrifuging to remove residues, and distilling clear liquid to remove the solvent to obtain the alkylphenol detergent.

The main chemical reactions of this example are as follows:

(1) the dodecylphenol, the calcium oxide and the sulfur are subjected to neutralization and vulcanization reaction under the action of an accelerator ethylene glycol to generate a sulfurized alkylphenol intermediate:

(2) and (3) carrying out amination reaction on the vulcanized alkylphenol intermediate with trioxymethylene, ethylenediamine and N, N-dimethyl-1, 3-propane diamine:

(3) and (3) carrying out amination reaction on alkylphenol which is not subjected to vulcanization reaction and trioxymethylene, ethylenediamine and N, N-dimethyl-1, 3-propane diamine:

comparative example 1

100g of dodecylphenol, 100g of 150N base oil, 18g of sulfur and 15g of calcium oxide are added into a 500mL four-mouth bottle, the temperature is raised to 155 ℃, 20g of accelerator ethylene glycol is dropwise added, and the temperature is kept at 150 ℃ for 5 hours after the dropwise addition is finished. Then cooling, adding 6g of diatomite filter aid for filtration, and distilling the filtrate to remove the solvent to obtain the sulfurized calcium alkyl phenate detergent.

Comparative example 2

100g of dodecylphenol, 100g of 150N base oil, 18g of sulfur and 15g of calcium oxide are added into a 500mL four-mouth bottle, the temperature is raised to 155 ℃, 20g of accelerator ethylene glycol is dropwise added, the temperature is kept at 150 ℃ for 5 hours after the dropwise addition is finished, 20g of calcium oxide is continuously added, and 22g of carbon dioxide gas is filled. Then cooling, adding 10g of diatomite filter aid for filtration, and distilling the filtrate to remove the solvent to obtain the sulfurized calcium alkyl phenate detergent.

The properties of the products obtained in the above examples and comparative examples are shown in the following table:

the performance detection method in the table comprises the following steps: base number according to ASTM D2896; viscosity according to ASTM D445; sulfur content according to ASTM D1552; detecting free phenol by using an HPLC method; sulfated ash according to ASTM D874; the detergency test is carried out according to SH/T0300-92.

As can be seen from the test results of the samples, compared with the conventional sulfurized calcium alkyl phenate, the prepared alkylphenol detergent product has the characteristics of high base number, good detergency, low free phenol and low ash content, and is a lubricating oil detergent product with excellent performance; the method has the advantages that the high-base-number alkylphenol detergent product is prepared without introducing carbon dioxide for carbonation reaction, the process route of the product is simple, the problems of high ash content, high free phenol content and poor detergency of the conventional high-base-number calcium sulfurized alkylphenol product are solved, and the prepared product has the characteristics of low free phenol content, high base number and low ash content besides the performances of detergency, acid neutralization capacity, oxidation resistance, wear resistance and the like of the calcium sulfurized alkylphenol.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.