CN113214315A - Preparation method of high-performance low-acid-value phosphate - Google Patents
Preparation method of high-performance low-acid-value phosphate Download PDFInfo
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- CN113214315A CN113214315A CN202110473373.0A CN202110473373A CN113214315A CN 113214315 A CN113214315 A CN 113214315A CN 202110473373 A CN202110473373 A CN 202110473373A CN 113214315 A CN113214315 A CN 113214315A
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- organic phase
- phenol
- phosphoric acid
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- phosphate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
Abstract
The invention relates to the field of chemical production, and discloses a preparation method of high-performance low-acid-value phosphate, which has the technical scheme key points that the preparation method comprises the following steps: mixing phenol, phosphoric acid, a water-carrying agent and a catalyst to obtain a first reactant after mixing; heating the first reactant to 80-160 ℃ for esterification reaction, and obtaining a second reactant after the reaction is finished; separating the second reactant to obtain a first organic phase; washing the first organic phase by using an alkaline solution with a first concentration at a first temperature, and separating to obtain a second organic phase after washing is finished; washing the second organic phase with purified water at a second temperature, and separating to obtain a third organic phase after washing; and evaporating the organic solution from the third organic phase and performing filter pressing to obtain the phosphate.
Description
Technical Field
The invention relates to the field of chemical production, in particular to a preparation method of high-performance low-acid-value phosphate.
Background
The phosphate flame retardants are in various types, including triphenyl phosphate, trixylenyl phosphate, tert-butylated triphenyl phosphate, mixed phosphate, and the like, and can be used as a monomer or as a mixture during use.
For example, triphenyl phosphate flame retardant belongs to additive type flame retardant, is monomolecular type and is mainly used for flame retardation of cables, electric wires and engineering plastics. Tri (xylene) phosphate, which is an organic flame retardant, has the advantages of low smoke, low toxicity, no halogen and the like. Because of its low volatility, good water resistance and good flame retardancy, it can be used in flame-resistant turbine oils; because the lubricant has good flame resistance, good thermal oxidation safety and good lubricating property, the lubricant can be used as an extreme pressure antiwear additive and a thickening agent of lubricating grease; it can also be used as flame-retardant, wear-resistant and poison-resistant cable, and polyoxyethylene conveyer belt, foam, floor and other materials; it can also be used as flame-proof hydraulic oil in metallurgy, electric power, mechanical engineering and other fields.
For example, tert-butyl triphenyl phosphate belongs to a new generation of halogen-free organic phosphorus flame retardant and has excellent thermal stability and hydrolysis resistance. The high thermal stability of the flame retardant enables the flame retardant to be used as a flame retardant for engineering plastics and simultaneously can improve the melting property of the plastics. It is widely used for flame-retardant PVC, cellulose resin, synthetic rubber, phenolic resin, epoxy resin, polyester fiber and the like.
For example, CN103224825B discloses a medium-pressure fire-resistant oil using trixylenyl phosphate as base oil and a production method thereof, the ingredients of which are as follows: the weight ratio of the trixylenyl phosphate to the di (tert-butylphenyl) phenylphosphate is = 1.5-1.8: 1.1-1.13, and 0.8-1.0% of epoxidized soybean oil octyl ester and 0.3-0.5% of benzotriazole by total weight are added.
For example, CN104262389A discloses a method for preparing tert-butylated triphenyl phosphate, which adopts a reaction mode that phosphorus trichloride is continuously added dropwise into a solution of phenol, tert-butylphenol and aluminum trichloride under the protection of nitrogen, and hydrogen chloride gas generated in the reaction is absorbed by a hydrochloric acid absorption device. The method comprises four steps of concentrated acid absorption, dilute acid absorption, water absorption and alkali liquor absorption.
For example, CN103214514A discloses a preparation method of triphenyl phosphate, which comprises the following steps: adding a catalyst into molten phenol, putting the molten phenol into a reaction kettle, stirring until the temperature of the material is reduced to be below 50 ℃, stopping stirring, and mixing phosphorus oxychloride; secondly, performing acid discharge under normal pressure and negative pressure under the stirring condition, neutralizing and exhausting to obtain qualified crude ester, wherein the acid value is less than or equal to 6 mgKOH/g; fourthly, heating up the qualified crude ester, carrying out reduced pressure distillation and separation, and collecting a finished product; performing alkali washing and water washing, sampling and analyzing the acid value of the finished product to be less than or equal to 0.05 mgKOH/g, then performing dehydration and purification, sampling and analyzing the acid value of the finished product to be less than or equal to 0.05 mgKOH/g, and filtering to obtain the triphenyl phosphate.
Among the application indexes of phosphate, volume resistivity, chlorine content, acid value, natural point and other indexes are important. In order to make the phosphate ester product have high volume resistivity and high natural point, manufacturers often mix various phosphate esters, and the synthesis steps are multiple, which greatly increases the complexity of the process and the production cost.
Disclosure of Invention
The invention aims to provide a preparation method of high-performance low-acid-value phosphate, which has the advantages of mild reaction conditions, simple and reliable process, convenient operation and preparation and convenient actual production.
The technical purpose of the invention is realized by the following technical scheme: a preparation method of high-performance low-acid-value phosphate ester comprises the following steps:
mixing phenol, phosphoric acid, a water-carrying agent and a catalyst to obtain a first reactant after mixing;
heating the first reactant to 80-160 ℃ for esterification reaction, and obtaining a second reactant after the reaction is finished;
separating the second reactant to obtain a first organic phase;
washing the first organic phase by using an alkaline solution with a first concentration at a first temperature, and separating to obtain a second organic phase after washing is finished;
washing the second organic phase with purified water at a second temperature, and separating to obtain a third organic phase after washing;
evaporating the organic solution from the third organic phase and carrying out pressure filtration to obtain the phosphate.
As a preferred technical scheme of the invention, the phenol comprises cresol, xylenol, ethylphenol, trimethylphenol and tert-butylphenol.
As a preferable technical scheme of the invention, the molar ratio of the phosphoric acid to the phenol is 1: 3-1: 6; the molar ratio of the water-carrying agent to the phosphoric acid is 1: 2-1: 6; the catalyst accounts for 0.5-5% of the total mass of the phosphoric acid and the phenol.
As a preferable technical scheme of the invention, the molar ratio of the phosphoric acid to the phenol is 1: 3-1: 4; the molar ratio of the water-carrying agent to the phosphoric acid is 1: 2-1: 1.45; the catalyst accounts for 1-2% of the total mass of the phosphoric acid and the phenol.
As a preferable technical scheme of the invention, the water-carrying agent comprises petroleum ether, benzene, cyclohexane, toluene and xylene.
As a preferable technical scheme of the invention, the water-carrying agent is toluene and xylene.
As a preferred technical scheme of the invention, the first temperature is 20-50 ℃, and the second temperature is 25 ℃.
As a preferred technical scheme of the invention, the catalyst is SO4 2~/AxOyHZSM-5, wherein A comprises cerium, praseodymium and lanthanum.
As a preferable technical scheme, the alkaline solution comprises a sodium hydroxide solution and a potassium hydroxide solution, the concentration of the alkaline solution is 3-20%, and the mass ratio of the sum of phosphoric acid and phenol to the alkaline solution is 1: 0.3-1: 5.
In a preferred embodiment of the present invention, the mass ratio of the sum of phosphoric acid and phenol to purified water is 1:0.2 to 1:5, and the number of times of washing the second organic phase with purified water at the second temperature is 1 or 2 times.
In conclusion, the invention has the following beneficial effects: a phosphating agent with chlorine is not used, no pollution by-product is generated, and the requirement of green generation is met; the generated phosphate ester product has high purity, low acid value, high volume resistivity, good flame resistance and stable quality, and greatly improves the application performance of the product.
Detailed Description
The invention provides a preparation method of high-performance low-acid-value phosphate, which comprises the following steps:
s1, putting phenol, phosphoric acid, a water-carrying agent and a catalyst into a dry reaction kettle for mixing, wherein the reaction kettle is provided with a water diversion reflux device, and a first reactant is obtained after mixing; wherein the phenol comprises cresol, xylenol, ethylphenol, trimethylphenol and tert-butylphenol; the water-carrying agent comprises petroleum ether, benzene, cyclohexane, toluene and xylene, wherein the toluene and the xylene are more preferable water-carrying agents;
specifically, the molar ratio of phosphoric acid to phenol is 1: 3-1: 6; the molar ratio of the water-carrying agent to the phosphoric acid is 1: 2-1: 6; the catalyst is 0.5-5% of the total mass of phosphoric acid and phenol. More preferred ratios are: the molar ratio of the phosphoric acid to the phenol is 1: 3-1: 4; the molar ratio of the water-carrying agent to the phosphoric acid is 1: 2-1: 1.45; the catalyst accounts for 1-2% of the total mass of the phosphoric acid and the phenol.
Specifically, the catalyst is SO4 2~/AxOyAnd HZSM-5, wherein A comprises cerium, praseodymium and lanthanum, and the proportion of the cerium, the praseodymium and the lanthanum is adjusted according to actual needs.
S2, heating the first reactant to 80-160 ℃ for esterification reaction, and obtaining a second reactant after the reaction is finished;
s3, separating the second reactant to obtain a first organic phase;
s4, washing the first organic phase by using an alkaline solution with a first concentration at a first temperature, and separating to obtain a second organic phase after washing; specifically, the first temperature is 20-50 ℃, the alkaline solution comprises a sodium hydroxide solution and a potassium hydroxide solution, the concentration of the alkaline solution is 3-20%, and the mass ratio of the sum of phosphoric acid and phenol to the alkaline solution is 1: 0.3-1: 5.
S5, washing the second organic phase with purified water at a second temperature, separating to obtain a third organic phase after washing, performing rotary evaporation on washing water and recycling, and saving resources, wherein the mass ratio of the total of phosphoric acid and phenol to the purified water is 1: 0.2-1: 5, the frequency of washing the second organic phase with purified water at the second temperature is 1 or 2 times, and the second temperature is 25 ℃;
s6, evaporating the organic solution from the third organic phase and carrying out pressure filtration to obtain the phosphate.
By the preparation method of the phosphate, no phosphating agent with chlorine is used, no pollution by-product is generated, and the requirement of green generation is met; the generated phosphate ester product has high purity, low acid value, high volume resistivity, good flame resistance and stable quality, and greatly improves the application performance of the product.
Example 1, preparation of a mixed phosphate ester, prepared by the following steps:
115g (85%) of phosphoric acid, 427g of xylenol and 277g of toluene are weighed into a reactor with reflux, and 5.4g of SO are added4 2~/La2O3/PrO2And (4) heating and reacting at 140 ℃ for 8 hours to HZSM-5. After the reaction is finished, separating to obtain a first organic phase, stirring and washing for 2 hours at the temperature of 30 ℃ by using 500g of 10% sodium hydroxide solution, and separating to obtain a second organic phase after washing; then 271g of purified water is used for washing for 1 hour at normal temperature, and after a third organic phase is separated, impurities are removed by distillation to obtain the product. The detected acid value of the product is 0.02mgKOH/g, and the volume resistivity is 6 multiplied by 1010Omega cm, an ignition point of 570 ℃ and a chlorine content of 0 ppm.
Example 2, preparation of a mixed phosphate ester by the following steps:
115g (85%) of phosphoric acid, 366g of a mixture of cresol, xylenol and ethylphenol and 212g of xylene are weighed into a reactor with reflux, 4.8g of SO are added4 2~/La2O3/CeO2And (5) heating and reacting at 150 ℃ for 8 hours under HZSM-5. After the reaction is finished, separating out a first organic phase, stirring and washing the first organic phase for 2 hours at 35 ℃ by using 600g of 5% sodium hydroxide solution, and separating to obtain a second organic phase after the washing is finished;and washing the mixture for 2 hours at normal temperature by using 300g of purified water, separating out a third organic phase, and distilling to remove impurities to obtain the product. The detected acid value of the product is 0.03mgKOH/g, and the volume resistivity is 7 multiplied by 1010Omega. cm, chlorine content 0 ppm.
Example 3, preparation of a mixed phosphate ester by the following steps:
115g (85%) of phosphoric acid, 420g of a mixture of xylenol and tert-butylphenol and 320g of xylene are weighed into a reactor with reflux, 3.0g of SO are added4 2~/PrO2/CeO2And (4) heating and reacting at 145 ℃ for 8 hours to HZSM-5. Separating out a first organic phase after the reaction is finished, stirring and washing the first organic phase for 1.5 hours at the temperature of 30 ℃ by 550g of 8% sodium hydroxide solution, and separating to obtain a second organic phase after the washing is finished; and washing the mixture for 2 hours at normal temperature by using 350g of purified water, separating out a third organic phase, and distilling to remove impurities to obtain the product. The detected acid value of the product is 0.02mgKOH/g, and the volume resistivity is 6.5 multiplied by 1010Omega, cm, the self-ignition point is 600 ℃.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (10)
1. A preparation method of high-performance low-acid-value phosphate ester is characterized by comprising the following steps: the method comprises the following steps:
mixing phenol, phosphoric acid, a water-carrying agent and a catalyst to obtain a first reactant after mixing;
heating the first reactant to 80-160 ℃ for esterification reaction, and obtaining a second reactant after the reaction is finished;
separating the second reactant to obtain a first organic phase;
washing the first organic phase by using an alkaline solution with a first concentration at a first temperature, and separating to obtain a second organic phase after washing is finished;
washing the second organic phase with purified water at a second temperature, and separating to obtain a third organic phase after washing;
evaporating the organic solution from the third organic phase and carrying out pressure filtration to obtain the phosphate.
2. The method for preparing phosphate with high performance and low acid value according to claim 1, wherein the method comprises the following steps: the phenol includes cresol, xylenol, ethylphenol, trimethylphenol and tert-butylphenol.
3. The method for preparing phosphate with high performance and low acid value according to claim 2, which is characterized in that: the molar ratio of the phosphoric acid to the phenol is 1: 3-1: 6; the molar ratio of the water-carrying agent to the phosphoric acid is 1: 2-1: 6; the catalyst accounts for 0.5-5% of the total mass of the phosphoric acid and the phenol.
4. The method for preparing phosphate with high performance and low acid value according to claim 3, wherein the method comprises the following steps: the molar ratio of the phosphoric acid to the phenol is 1: 3-1: 4; the molar ratio of the water-carrying agent to the phosphoric acid is 1: 2-1: 1.45; the catalyst accounts for 1-2% of the total mass of the phosphoric acid and the phenol.
5. The method for preparing phosphate with high performance and low acid value according to claim 4, wherein the method comprises the following steps: the water-carrying agent comprises petroleum ether, benzene, cyclohexane, toluene and xylene.
6. The method for preparing phosphate with high performance and low acid value according to claim 5, wherein: the water-carrying agent is toluene and xylene.
7. The method for preparing phosphate with high performance and low acid value according to claim 6, wherein the method comprises the following steps: the first temperature is 20-50 ℃, and the second temperature is 25 ℃.
8. The method for preparing phosphate with high performance and low acid value according to claim 7, wherein: the catalyst is SO4 2~/AxOyHZSM-5, wherein A comprises cerium, praseodymium and lanthanum.
9. The method for preparing phosphate with high performance and low acid value according to claim 8, wherein: the alkaline solution comprises a sodium hydroxide solution and a potassium hydroxide solution, the concentration of the alkaline solution is 3-20%, and the mass ratio of the sum of phosphoric acid and phenol to the alkaline solution is 1: 0.3-1: 5.
10. The method for preparing phosphate with high performance and low acid value according to claim 9, wherein: the mass ratio of the sum of phosphoric acid and phenol to the purified water is 1: 0.2-1: 5, and the number of times of washing the second organic phase with the purified water at the second temperature is 1 or 2.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2805240A (en) * | 1953-10-29 | 1957-09-03 | Walter H Prahl | Manufacture of aryl phosphates |
| US5097056A (en) * | 1988-02-08 | 1992-03-17 | Bromine Compounds Ltd. | Process for the preparation of triaryl phosphates using H3 PO4 and hard cation as a catalyst |
| CN103214514A (en) * | 2013-04-09 | 2013-07-24 | 天津市联瑞阻燃材料有限公司 | Preparation method of triphenyl phosphate |
| CN103285907A (en) * | 2013-04-25 | 2013-09-11 | 安徽生力农化有限公司 | Mesoporous molecular sieve supported composite metal oxide alcoholysis catalyst, and preparation method of alcoholysis catalyst |
| RU2670105C1 (en) * | 2018-04-06 | 2018-10-18 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Method for obtaining mixed triaryl phosphates |
-
2021
- 2021-04-29 CN CN202110473373.0A patent/CN113214315A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2805240A (en) * | 1953-10-29 | 1957-09-03 | Walter H Prahl | Manufacture of aryl phosphates |
| US5097056A (en) * | 1988-02-08 | 1992-03-17 | Bromine Compounds Ltd. | Process for the preparation of triaryl phosphates using H3 PO4 and hard cation as a catalyst |
| CN103214514A (en) * | 2013-04-09 | 2013-07-24 | 天津市联瑞阻燃材料有限公司 | Preparation method of triphenyl phosphate |
| CN103285907A (en) * | 2013-04-25 | 2013-09-11 | 安徽生力农化有限公司 | Mesoporous molecular sieve supported composite metal oxide alcoholysis catalyst, and preparation method of alcoholysis catalyst |
| RU2670105C1 (en) * | 2018-04-06 | 2018-10-18 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Method for obtaining mixed triaryl phosphates |
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