CN107337689B

CN107337689B - Synthesis method of alkyl phosphate monoester

Info

Publication number: CN107337689B
Application number: CN201710568277.8A
Authority: CN
Inventors: 张广良; 赵永红
Original assignee: China Daily Chemical Industry Research Institute
Current assignee: China Daily Chemical Industry Research Institute
Priority date: 2017-07-13
Filing date: 2017-07-13
Publication date: 2020-05-05
Anticipated expiration: 2037-07-13
Also published as: CN107337689A

Abstract

The synthesis method of alkyl phosphate monoester is characterized by that it uses phosphoric acid and P₂O₅The mixture is a phosphorylation reagent, fatty alcohol or fatty ether is used as a raw material, and after uniform mixing, the mixture is reacted for 1 to 15 hours under the conditions of vacuum degree of 0.02 to 0.08MPa, reaction temperature of 70 to 120 ℃, and stirring speed of 200 and 700r/min, so as to obtain the product. The method has the advantages of high monoester selectivity, high monoester content and environmental friendliness.

Description

Synthesis method of alkyl phosphate monoester

Technical Field

The invention relates to a method for synthesizing alkyl phosphate monoester.

Background

In recent years, phosphate surfactants have been widely used because of their excellent properties such as low toxicity, no irritation, and remarkable biodegradability. The alkyl phosphate is one of phosphate surfactants, and has better solubility, thermal stability, hard water resistance, acid and alkali resistance, inorganic salt resistance, high temperature resistance, antistatic property and other properties than common surfactants, so the alkyl phosphate is widely applied to chemical fiber oil agents, emulsifiers, antistatic agents, lubricants and the like.

The alkyl phosphate ester comprises monoester, diester and triester, and the alkyl phosphate monoester and the salt thereof have the advantages of mild performance, low toxicity, small irritation, good biodegradability and the like compared with other salts, and simultaneously have various functions of wetting, cleaning, solubilization, emulsification, lubrication and the like, so the alkyl phosphate ester is widely applied to the fields of daily chemicals, textiles, industrial cleaning and the like. However, the content of monoester in the phosphate produced and sold in China is not high at present, the majority of high-content alkyl phosphate monoester needs to be imported, and the commercial product is a mixture of monoester and diester. Because the separation difficulty of the alkyl phosphate monoester and the alkyl phosphate diester is high, the price is also increased sharply along with the increase of the purity of the product and the content of the monoester, and in addition, the safety of the prepared cosmetics and personal care products is higher along with the increase of the purity of the raw materials. Therefore, the research on new species and new technology of the phosphate monoester surfactant is carried out, especially the development of synthesis technology for preparing high-purity alkyl phosphate monoester and alkyl phosphate diester is necessary for promoting the healthy development of the surfactant industry in China and meeting the requirements of various departments of national economy on the surfactant.

The synthesis of the phosphate ester surfactant is divided into two stages, wherein the first stage is the synthesis of phosphate ester, and the second stage is saponification. From the viewpoint of product quality analysis, the synthesis technique is critical. Patent CN 103833785A adopts P₂O₅The alkyl phosphate is synthesized for the phosphorylation reagent, the synthesized product is a mixture of mono-diester and diester, and the content of monoester is 48-52 wt%. The industry adopts the traditional P₂O₅Process for synthesizing phosphoric acid esterThe content of monoester is 35-65%, and P is improved₂O₅The content of the monoester is about 75 percent after the process is hydrolyzed by adding water, and the monoester selectivity is poor because the synthesized product contains diester. Patent CN 104804038A adopts phosphorus oxychloride as a phosphorylation reagent to synthesize alkyl phosphate, the reaction activity is high, the reaction speed is high, but the boiling point of the raw material phosphorus oxychloride is low and is easy to volatilize, the generated byproduct HCl can corrode equipment, and the HCl is easy to react with ROH to generate RCl byproduct, which is not beneficial to the generation of monoester. The patent CN 103012469A adopts phosphoric acid as a phosphorylation reagent, and adds a water-carrying agent to synthesize the alkyl phosphate, and organic solvents such as toluene and dichloroethane are added in the synthesis process of the process, which does not meet the requirements of green process. Patent CN 104804038A describes a preparation method of phosphate, which uses a supergravity rotary reactor, the reactor has a complex structure and high cost, and simultaneously uses a solvent diluent, wherein most of the solvent diluent is a toxic and harmful organic solvent, and is not suitable for industrial production; the method for synthesizing the dodecyl phosphate monoester by the polyphosphoric acid method, such as Wanqing research institute of light chemical engineering in Tianjin, 90 years, has high monoester content, but the polyphosphoric acid process is adopted, so that a large amount of phosphoric acid is contained in the wastewater, which brings great difficulty to the post-treatment. Therefore, the green synthesis of the alkyl phosphate monoester with high content has practical significance and economic value.

Disclosure of Invention

In order to solve the problems in the prior art, the invention aims to provide a synthesis method of alkyl monoester phosphate, which has high monoester selectivity, high monoester content and environmental friendliness.

The invention uses phosphoric acid (85 wt% sold in market) and P₂O₅The mixture is taken as a phosphorylation reagent, fatty alcohol (ether) is taken as a raw material, alkyl phosphate monoester is synthesized by one step through reduced pressure reaction, and the product synthesized by the method has high monoester selectivity, high monoester content and high additional value, can be applied to high-end skin care products such as cosmetics and the like, and simultaneously has the advantages of simple process, mild reaction condition and high reaction speed, thereby being an environment-friendly green synthesis method.

In order to achieve the above object, the present invention is realized by:

with phosphoric acid and P₂O₅The mixture is a phosphorylation reagent, fatty alcohol or fatty ether is used as a raw material, and after uniform mixing, the mixture is reacted for 1 to 15 hours under the conditions of vacuum degree of 0.02 to 0.08MPa, reaction temperature of 70 to 120 ℃, and stirring speed of 200 and 700r/min, so as to obtain the product.

In the process, the molar ratio of the fatty alcohol or the fatty ether to the phosphorylation reagent is 1-1.5: 1;

phosphoric acid and P in the above process₂O₅The mass ratio of (A) to (B) is 0.5-3: 1; the phosphoric acid is commercially available 85wt% phosphoric acid.

The fatty alcohol involved in the process is single carbon chain alcohol or mixed carbon alcohol, and the ether is one of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether.

Compared with the prior art, the technology has the following advantages:

1. with phosphoric acid and P₂O₅The mixture is a phosphorylation reagent, so that the problems of low reaction activity and low conversion rate of phosphoric acid when phosphoric acid is used as the phosphorylation reagent are solved, and the monoester content in the product is improved.

2. With phosphoric acid and P₂O₅The mixture is a phosphorylation reagent, and overcomes the defect of adopting P₂O₅In the case of phosphorylating agents, P₂O₅The high reaction activity causes the product to have the defect of diester generation, and improves the selectivity of monoester in the product.

3. The reaction by-product is only water, so the method has high economical efficiency and is a green synthesis process route.

4. In the synthesized product alkyl phosphate, the monoester content is more than 67wt%, and the monoester selectivity can reach 100%.

5. The reaction condition is mild, the process is simple, and the method is suitable for industrial production.

Detailed Description

Example 1:

weighing 5.6 g, 11.2 g and 38.4g of phosphoric acid, phosphorus pentoxide and dodecanol respectively, uniformly mixing in a reactor, setting the reaction temperature to be 110 ℃, and simultaneously controlling the proper stirring rotation speed and the vacuum degree, wherein the stirring rotation speed is 450r/min, the vacuum degree is 0.05 MPa, and reacting for 4 hours under the reaction conditions. After the reaction is finished, sampling and analyzing for later use. Wherein the content of the dodecyl phosphate monoester is 77wt percent, and the monoester selectivity is 100 percent. The content of the dodecyl phosphate monoester after separation and purification is 92 wt%.

Example 2:

weighing 9.4 g, 8.4g and 54.1g of phosphoric acid, phosphorus pentoxide and octadecanol respectively, uniformly mixing in a reactor, setting the reaction temperature to 120 ℃, simultaneously controlling the appropriate stirring rotation speed and vacuum degree, wherein the stirring rotation speed is 200r/min, and the vacuum degree is 0.06 MPa, reacting for 1h under the reaction conditions, and sampling and analyzing for later use after the reaction is finished. Wherein the content of the octadecyl monoester phosphate is 67wt%, and the monoester selectivity is 100%. The content of the octadecyl monoester phosphate after separation and purification is 88 wt%.

Example 3:

weighing 14.1 g, 4.7 g and 52.6g of phosphoric acid, phosphorus pentoxide and dodecanol respectively, uniformly mixing in a reactor, setting the reaction temperature to be 100 ℃, controlling the appropriate stirring rotation speed and vacuum degree, wherein the stirring rotation speed is 400r/min and the vacuum degree is 0.05 MPa, reacting for 6 hours under the reaction conditions, and sampling and analyzing for later use after the reaction is finished. Wherein the content of the dodecyl phosphate monoester is 83.6wt%, and the monoester selectivity is 100%. The content of the dodecyl phosphate monoester after separation and purification is 94 wt%.

Example 4:

weighing 12.2 g, 11 g and 101.9g of phosphoric acid, phosphorus pentoxide and behenyl alcohol respectively, uniformly mixing in a reactor, setting the reaction temperature to be 90 ℃, controlling the appropriate stirring rotation speed and vacuum degree, wherein the stirring rotation speed is 700r/min, the vacuum degree is 0.05 MPa, reacting for 15h under the reaction conditions, and sampling and analyzing for later use after the reaction is finished. Wherein the monoester content is 74wt% and the monoester selectivity is 100%. The content of the alkyl phosphate monoester after separation and purification is 88 wt%.

Example 5:

weighing 9.4 g, 8.4g and 45.7g of phosphoric acid, phosphorus pentoxide, dodecyl alcohol and tetradecyl alcohol (the mass ratio of the dodecyl alcohol to the tetradecyl alcohol is 3: 1) respectively, uniformly mixing in a reactor, setting the reaction temperature to be 70 ℃, controlling the proper stirring rotation speed and the vacuum degree at the same time, wherein the stirring rotation speed is 500r/min and the vacuum degree is 0.02 MPa, reacting for 15 hours under the reaction conditions, and sampling and analyzing for later use after the reaction is finished. Wherein the content of the alkyl phosphate monoester is 72 wt%, and the monoester selectivity is 100%. The monoester content after separation and purification is 90 wt%.

Example 6:

weighing phosphoric acid, phosphorus pentoxide and AEO₉Respectively 22.2 g, 8.4g and 123.2g, uniformly mixing in a reactor, setting the reaction temperature to 120 ℃, simultaneously controlling the proper stirring rotation speed and the proper vacuum degree, wherein the stirring rotation speed is 400r/min, the vacuum degree is 0.08MPa, reacting for 8 hours under the reaction conditions, and sampling and analyzing for later use after the reaction is finished. Wherein AEO₉The content of the phosphoric monoester was 74wt%, and the monoester selectivity was 100%. The monoester content after separation and purification was 88 wt%.

Claims

1. The method for synthesizing the alkyl phosphate monoester is characterized by comprising the following steps of:

with phosphoric acid and P₂O₅The mixture is a phosphorylation reagent, fatty alcohol is used as a raw material, and after uniform mixing, the mixture is reacted for 1 to 15 hours under the conditions of vacuum degree of 0.02 to 0.08MPa, reaction temperature of 70 to 120 ℃, stirring speed of 200 and 700r/min to obtain a product;

wherein phosphoric acid and P₂O₅The mass ratio of (A) to (B) is 0.5-3: 1.

2. The method for synthesizing the alkyl phosphate monoester is characterized by comprising the following steps of:

with phosphoric acid and P₂O₅The mixture is a phosphorylation reagent, fatty alcohol-polyoxyethylene ether is used as a raw material, and after uniform mixing, the mixture reacts for 1 to 15 hours under the conditions of vacuum degree of 0.02 to 0.08MPa, reaction temperature of 70 to 120 ℃, stirring speed of 200-;

wherein phosphoric acid and P₂O₅The mass ratio of (A) to (B) is 0.5-3: 1.

3. The method for synthesizing an alkyl phosphate monoester according to claim 1 or 2, wherein the molar ratio of the fatty alcohol or fatty alcohol polyoxyethylene ether to the phosphorylating agent is 1-1.5: 1.

4. The method for synthesizing an alkyl monoester phosphate according to claim 1 or 2, wherein the phosphoric acid is commercially available at 85 wt%.

5. The method for synthesizing alkylphosphonate monoester according to claim 1 wherein the aliphatic alcohol is a single carbon chain alcohol or a mixed carbon chain alcohol.