CN115974926A - Refining method of low-metal-ion low-chroma DOPO flame retardant - Google Patents
Refining method of low-metal-ion low-chroma DOPO flame retardant Download PDFInfo
- Publication number
- CN115974926A CN115974926A CN202211668245.2A CN202211668245A CN115974926A CN 115974926 A CN115974926 A CN 115974926A CN 202211668245 A CN202211668245 A CN 202211668245A CN 115974926 A CN115974926 A CN 115974926A
- Authority
- CN
- China
- Prior art keywords
- low
- dopo
- flame retardant
- chroma
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the technical field of flame retardants, and provides a refining method of a low-metal-ion low-chroma DOPO flame retardant, which comprises the following steps: s1, synthesis: reacting o-phenylphenol with phosphorus trihalide under the action of a catalyst to obtain a reactant; s2, decoloring: dissolving the reactant in toluene, and adding a first decolorizing agent for decolorizing to obtain a decolorized product; s3, hydrolysis: adding water into the decolorized product for hydrolysis to obtain a hydrolysate; s4, refining: dissolving the hydrolysate in toluene, washing the solution obtained by dissolving with water, and decolorizing with a second decolorizing agent to obtain a refined product; s5, crystallizing: adding water into the refined product for crystallization to obtain crystals; s6, dehydration: dehydrating the crystal to obtain the flame retardant DOPO. Through the technical scheme, the problems of high metal ion content, high melting chromaticity and low purity of the DOPO flame retardant in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a refining method of a low-metal-ion low-chroma DOPO flame retardant.
Background
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxa (DOPO) is an organophosphorus flame retardant, the molecular structure of the DOPO not only comprises biphenyl and phosphaphenanthrene ring structures, but also O-P = O bonds exist in a ring form in the molecule, and compared with other acyclic organophosphorus flame retardants, the organophosphorus flame retardant has higher thermal stability and chemical stability.
At present, a toluene solvent method is mostly adopted for synthesizing DOPO, namely, after the reaction of phosphorus trichloride and o-phenylphenol is finished, reactants are dissolved in toluene, and then are filtered and decolored, and then are continuously hydrolyzed to obtain a reaction intermediate DOPO-HPPA, and then the DOPO-HPPA is continuously dehydrated to obtain the DOPO.
In the existing DOPO synthesis method, the DOPO-HPPA intermediate is separated out from toluene along with the hydrolysis, and the separated DOPO-HHPA crystal wraps metal ions, especially zinc ions, so that the metal ions cannot be effectively removed. Therefore, the DOPO prepared by the synthesis method has higher metal ion content, the product can not be applied to electronic materials, and the DOPO product prepared by the method has higher melting chromaticity and low purity.
Disclosure of Invention
The invention provides a refining method of a DOPO flame retardant with low metal ions and low chroma, which solves the problems of high metal ion content, high melt chroma and low purity of the DOPO flame retardant in the related technology.
The technical scheme of the invention is as follows:
a refining method of a low-metal ion and low-chroma DOPO flame retardant comprises the following steps:
s1, synthesis: reacting o-phenylphenol with phosphorus trihalide under the action of a catalyst to obtain a reactant;
s2, decoloring: dissolving the reactant in toluene, and adding a first decolorizing agent for decolorizing to obtain a decolorized product;
s3, hydrolysis: adding water into the decolorized product for hydrolysis to obtain a hydrolysate;
s4, refining: dissolving the hydrolysate in toluene, washing the solution obtained by dissolving with water, and decolorizing with a second decolorizing agent to obtain a refined product;
s5, crystallizing: adding water into the refined product for crystallization to obtain crystals;
s6, dehydration: and dehydrating the crystal to obtain the flame retardant DOPO.
As a further technical scheme, in the S1, the reaction temperature is 170-180 ℃, the phosphorus trihalide is one of phosphorus trichloride, phosphorus tribromide, phosphorus trifluoride and phosphorus triiodide, and the catalyst is Lewis acid.
As a further technical scheme, the Lewis acid is one or more of zinc chloride, aluminum trichloride, aluminum tribromide, ferric trichloride, boron trifluoride and stannic chloride.
The technical scheme is characterized in that in S2, the dissolving temperature is 75-85 ℃, and the dissolving time is 1.5-3h.
The technical scheme is characterized in that in S3, the hydrolysis time is 2.5-3.5h, and the using amount of water is 12% -15% of the mass of the o-phenylphenol.
As a further technical scheme, in the step S2, the first decolorizing agent is one or more of diatomite, alumina and activated carbon, and in the step S4, the second decolorizing agent is one or more of diatomite, alumina and activated carbon.
As a further technical means, in S4, the second decoloring agent is alumina.
As a further technical scheme, in S4, the using amount of toluene is 3.4-3.5 times of the mass of o-phenylphenol, and the dissolving temperature is 87-90 ℃; dissolve until the solution is clear.
In the step S4, water washing is to add water with the temperature of 85-95 ℃ into the solution obtained by dissolving, stir for 0.5-1h, and discharge a water layer after standing for 5-15 min; the number of washing times was 3.
As a further technical scheme, in the step S6, the dehydration is vacuum dehydration, the dehydration temperature is 135-145 ℃, and the vacuum degree is more than or equal to 0.095MPa.
The working principle and the beneficial effects of the invention are as follows:
1. the quality of the dropwise added water is strictly controlled in the hydrolysis process, excessive water is added, excessive water exists in the reaction liquid, excessive hydrolysis can be caused, and the hydrolysis product cannot be completely dissolved in the subsequent refining process. The water addition amount is too little, so that the intermediate product is not completely hydrolyzed, and the product purity is low.
2. In the refining process, after a proper amount of toluene is added, the temperature is raised in a matching way, the dissolution of DOPO-HPPA can be promoted, and finally hot water is added for washing, so that zinc ions and hydrogen chloride in the solution can be removed, metal ions in DOPO are reduced, and the purity of the DOPO product is improved.
3. In the refining process, when the decoloring agent is alumina, trace colored impurities generated in hydrolysis are further removed, and the problem of high melting chromaticity of DOPO is solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.
Example 1
A refining method of a low-metal ion and low-chroma DOPO flame retardant comprises the following steps:
s1, synthesis: mixing 680g of o-phenylphenol and 6.8g of zinc chloride, heating to 175 ℃, slowly dripping 660g of phosphorus trichloride for reaction, wherein the dripping time is 10 hours, keeping the temperature at 175 ℃ for 2 hours after the dripping is finished, and vacuumizing to remove excessive phosphorus trichloride after the reaction is finished to obtain a mixture A;
s2, decoloring: reducing the temperature of the mixture A to 80 ℃, adding 782g of toluene and 6.8g of kieselguhr, stirring for 2 hours, and filtering to obtain a mixture B;
s3, hydrolysis: controlling the temperature of the mixture B to be 60 ℃, slowly dropwise adding 93.6g of water, heating to 80 ℃ after dropwise adding, and reacting for 3 hours to obtain a mixture C;
s4, refining: adding 2346g of toluene into the mixture C, heating to 88 ℃, stirring, adding 390g of 90 ℃ water after the solution is clear, stirring for 0.5h, standing for 10min, discharging a water layer, completing primary washing, repeating the washing for three times to obtain a refined solution, adding 34g of alumina into the refined solution, stirring for 1h at 85 ℃, and filtering to obtain a mixture D;
s5, crystallizing: 780g of water is slowly dripped into the mixture D, white crystals are separated out along with the addition of water, and DOPO-HPPA crystals are obtained after filtration;
s6, dehydration: the DOPO-HPPA crystal is dehydrated for 4 hours in vacuum at 140 ℃ under the vacuum degree of 0.105Mpa, and then poured into an enamel tray to obtain 801.8g DOPO, the yield is 92.8%, the HPLC purity is 99.8%, the zinc ion content is 5ppm, and the melting chromaticity is 70.
Example 2
A refining method of a low-metal ion and low-chroma DOPO flame retardant comprises the following steps:
s1, synthesis: mixing 680g of o-phenylphenol and 6.8g of zinc chloride, heating to 170 ℃, dripping 660g of phosphorus trichloride for reaction, wherein the dripping time is 10 hours, keeping the temperature at 175 ℃ for 2 hours after the dripping is finished, and vacuumizing to remove excessive phosphorus trichloride after the reaction is finished to obtain a mixture A;
s2, decoloring: reducing the temperature of the mixture A to 80 ℃, adding 748g of toluene and 6.8g of diatomite, stirring for 2 hours, and filtering to obtain a mixture B;
s3, hydrolysis: controlling the temperature of the mixture B to be 55 ℃, slowly dropwise adding 86.29g of water, heating to 75 ℃ after dropwise adding, reacting for 3 hours, and obtaining a mixture C;
s4, refining: adding 2312g of toluene into the mixture C, heating to 87 ℃, stirring, after the solution is clear, adding 390g of water at 85 ℃, stirring for 0.6h, standing for 5min, discharging a water layer, finishing primary washing, repeating the washing for three times to obtain a refined solution, adding 34g of alumina into the refined solution, stirring for 1h at 80 ℃, and filtering to obtain a mixture D;
s5, crystallizing: 780g of water is slowly dripped into the mixture D, white crystals are separated out along with the addition of the water, and DOPO-HPPA crystals are obtained after filtration;
s6, dehydration: the DOPO-HPPA crystal is dehydrated for 3 hours in vacuum at 135 ℃ and 0.105Mpa to obtain 796.6g DOPO with the yield of 92.2%, the HPLC purity of 99.3%, the zinc ion content of 8ppm and the melting chroma of 70.
Example 3
A refining method of a low-metal ion and low-chroma DOPO flame retardant comprises the following steps:
s1, synthesis: mixing 680g of o-phenylphenol and 6.8g of zinc chloride, heating to 180 ℃, dripping 660g of phosphorus trichloride for reaction, wherein the dripping time is 10 hours, keeping the temperature at 175 ℃ for 2 hours after the dripping is finished, and vacuumizing to remove excessive phosphorus trichloride after the reaction is finished to obtain a mixture A;
s2, decoloring: reducing the temperature of the mixture A to 80 ℃, adding 816g of toluene and 6.8g of diatomite, stirring for 2 hours, and filtering to obtain a mixture B;
s3, hydrolysis: controlling the temperature of the mixture B to be 65 ℃, slowly dropwise adding 100.68g of water, heating to 85 ℃ after dropwise adding, reacting for 3 hours, and obtaining a mixture C;
s4, refining: adding 2380g of toluene into the mixture C, heating to 90 ℃, stirring, after the solution is clear, adding 390g of water at 95 ℃, stirring for 1h, standing for 15min, discharging a water layer, completing one-time washing, repeating the washing for three times to obtain a refined solution, adding 34g of alumina into the refined solution, stirring for 1h at 90 ℃, and filtering to obtain a mixture D;
s5, crystallizing: 780g of water is slowly dripped into the mixture D, white crystals are separated out along with the addition of water, and DOPO-HPPA crystals are obtained after filtration;
s6, dehydration: the DOPO-HPPA crystal is dehydrated for 3 hours in vacuum at 145 ℃ and 0.107Mpa, 790.6g of DOPO is obtained, the yield is 91.5%, the HPLC purity is 99.6%, the zinc ion content is 5ppm, and the melting chromaticity is 70.
Example 4
A refining method of a low-metal ion and low-chroma DOPO flame retardant comprises the following steps:
s1, synthesis: mixing 680g of o-phenylphenol and 6.8g of zinc chloride, heating to 175 ℃, dripping 660g of phosphorus trichloride for reaction, wherein the dripping time is 10 hours, keeping the temperature at 175 ℃ for 2 hours after the dripping is finished, and vacuumizing to remove excessive phosphorus trichloride after the reaction is finished to obtain a mixture A;
s2, decoloring: reducing the temperature of the mixture A to 80 ℃, adding 795.6g of toluene and 6.8g of diatomite, stirring for 2 hours, and filtering to obtain a mixture B;
s3, hydrolysis: controlling the temperature of the mixture B to be 60 ℃, slowly dropwise adding 93.49g of water, heating to 80 ℃ after dropwise adding, reacting for 3h, and obtaining a mixture C;
s4, refining: adding 2380g of toluene into the mixture C, heating to 88 ℃, stirring, after the solution is clear, adding 390g of water at 90 ℃, stirring for 1h, standing for 10min, discharging a water layer, finishing washing to obtain a refined solution, adding 34g of alumina into the refined solution, stirring for 1h at 85 ℃, and filtering to obtain a mixture D;
s5, crystallizing: 780g of water is slowly dripped into the mixture D, white crystals are separated out along with the addition of the water, and DOPO-HPPA crystals are obtained after filtration;
s6, dehydration: the DOPO-HPPA crystal is dehydrated for 3 hours in vacuum at 140 ℃ under the vacuum degree of 0.103Mpa, 804.4g DOPO is obtained, the yield is 93.1%, the HPLC purity is 98.3%, the zinc ion content is 70ppm, and the melting chromaticity is 140.
Example 5
Example 5 differs from example 4 in that it was washed 6 times in S4 purification; 728.4g DOPO are obtained in a yield of 84.3%, an HPLC purity of 99.8%, a zinc ion content of 5ppm and a melt color of 70.
Example 6
Example 6 was the same as example 1 except that the alumina was replaced with the same amount of diatomaceous earth as in example 1. 798.3g DOPO are obtained in 92.4% yield, an HPLC purity of 99.5%, a zinc ion content of 6ppm and a melt color of 90.
Example 7
Example 7 was conducted in the same manner as example 1 except that alumina was replaced with the same amount of activated carbon as that used in example 1. 799.2g DOPO are obtained in a yield of 92.5%, an HPLC purity of 99.4%, a zinc ion content of 7ppm and a melt color of 100.
Example 8
A refining method of a low-metal ion and low-chroma DOPO flame retardant comprises the following steps:
s1, synthesis: mixing 680g of o-phenylphenol and 6.8g of aluminum trichloride, heating to 175 ℃, slowly dripping 1298.7g of phosphorus tribromide for reaction, wherein the dripping time is 10 hours, keeping the temperature at 175 ℃ for 2 hours after the dripping is finished, and vacuumizing to remove excessive phosphorus trichloride after the reaction is finished to obtain a mixture A;
s2, decoloring: reducing the temperature of the mixture A to 80 ℃, adding 782g of toluene and 6.8g of kieselguhr, stirring for 2 hours, and filtering to obtain a mixture B;
s3, hydrolysis: controlling the temperature of the mixture B to be 60 ℃, slowly dropwise adding 93.6g of water, heating to 80 ℃ after dropwise adding, and reacting for 3 hours to obtain a mixture C;
s4, refining: adding 2346g of toluene into the mixture C, heating to 88 ℃, stirring, adding 390g of 90 ℃ water after the solution is clear, stirring for 0.5h, standing for 10min, discharging a water layer, completing primary washing, repeating the washing for three times to obtain a refined solution, adding 34g of alumina into the refined solution, stirring for 1h at 85 ℃, and filtering to obtain a mixture D;
s5, crystallizing: 780g of water is slowly dripped into the mixture D, white crystals are separated out along with the addition of water, and DOPO-HPPA crystals are obtained after filtration;
s6, dehydration: the DOPO-HPPA crystal is dehydrated for 4 hours in vacuum at 140 ℃ and under the vacuum degree of 0.105Mpa, and then poured into an enamel tray to obtain 800.1g of DOPO, the yield is 92.6%, the HPLC purity is 99.7%, the zinc ion content is 6ppm, and the melting chromaticity is 90.
Comparative example 1
Comparative example 1 differs from example 1 in that the mass of water dropped in the hydrolysis of S3 is 115.06g; 781.1g DOPO are obtained in a yield of 90.4%, an HPLC purity of 99.1%, a zinc ion content of 80ppm and a melt color number of 140.
Comparative example 2
Comparative example 2 differs from example 1 in that the mass of water added dropwise in the hydrolysis of S3 is 72g; 785.4gDOPO are obtained in a yield of 90.9%, an HPLC purity of 97.2%, a zinc ion content of 5ppm and a melt color of 80.
Comparative example 3
Comparative example 3 differs from example 1 in that toluene was added during S4 refining and then the temperature was raised to 82 ℃; 783.6g of DOPO were obtained in a yield of 90.7%, a HPLC purity of 99.6%, a zinc ion content of 90ppm and a melt color of 90.
Comparative example 4
Comparative example 4 is different from example 1 in that the amount of toluene added in S4 purification was 3183g; 771.6g DOPO were obtained in 89.3% yield, 99.8% HPLC purity, 5ppm zinc ion content and 70% melt color.
Comparative example 5
Comparative example 5 is different from example 1 in that the amount of toluene added in S4 refining was 2108g; 801.8gDOPO are obtained in a yield of 92.8%, an HPLC purity of 99.8%, a zinc ion content of 90ppm and a melt color of 80.
As is clear from examples 1 to 6 and comparative examples 1 to 5, example 1 is the most preferable example of the invention, and has a yield of 92.8%, a purity of 99.8%, a zinc ion content of 5ppm, and a melt color of 70. Compared with example 1, the result of example 6 replacing alumina with an equal amount of diatomite and the result of example 7 replacing alumina with an equal amount of activated carbon is that the product has a higher melt color than that of example 1, which shows that alumina has a good effect of removing a small amount of colored impurities in the hydrolysate.
Compared with the example 1, the comparative example 1 increases the mass of the water added in the S3 hydrolysis, and the content of zinc ions in the obtained DOPO is increased, and the melt color is increased, which shows that the mass of the water added in the hydrolysis is increased, so that the proportion of DOPO in the DOPO-HPPA mixture is reduced, the DOPO-HPPA crystal cannot be dissolved in the refining process, and the zinc ions and the colored impurities are wrapped in the crystal and cannot be washed out, so that the content of the zinc ions in the final product is increased, and the melt color is larger; comparative example 2 reduced the mass of water added dropwise during the hydrolysis of S3, and the resulting purity of DOPO was reduced, indicating that reducing the mass of water added dropwise would result in incomplete hydrolysis and affect product purity. Therefore, in the hydrolysis process, the quality of the dropwise added water is strictly controlled, so that the intermediate product can be completely hydrolyzed, the hydrogen chloride generated in the reaction can be removed from the system in a gas form, the hydrogen chloride can be prepared into a byproduct, namely hydrochloric acid, and the difficulty in subsequent waste acid treatment is reduced. Comparative example 3 the temperature of toluene addition was reduced for S4, resulting in a product with a higher zinc ion content.
The comparative example 4 increases the addition of toluene in the S4 refining process, so that the crystal quantity is reduced when S5 is crystallized, and the product yield is reduced, and the comparative example 5 decreases the addition of toluene in the S4 refining process, so that the precipitated DOPO-HPPA cannot be completely dissolved and cannot be thoroughly washed, and the product has large zinc ion content and high melting chromaticity.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A refining method of a low-metal ion and low-chroma DOPO flame retardant is characterized by comprising the following steps:
s1, synthesis: reacting o-phenylphenol with phosphorus trihalide under the action of a catalyst to obtain a reactant;
s2, decoloring: dissolving the reactant in toluene, and adding a first decolorizing agent for decolorizing to obtain a decolorized product;
s3, hydrolysis: adding water into the decolorized product for hydrolysis to obtain a hydrolysate;
s4, refining: dissolving the hydrolysate in toluene, washing the solution obtained by dissolving with water, and decolorizing with a second decolorizing agent to obtain a refined product;
s5, crystallizing: adding water into the refined product for crystallization to obtain crystals;
s6, dehydration: dehydrating the crystal to obtain the flame retardant DOPO.
2. The refining method of a low metal ion, low chroma DOPO flame retardant as claimed in claim 1, wherein the reaction temperature in S1 is 170-180 ℃, the phosphorus trihalide is one of phosphorus trichloride, phosphorus tribromide, phosphorus trifluoride and phosphorus triiodide, and the catalyst is Lewis acid.
3. The refining method of a low metal ion, low chroma DOPO flame retardant as claimed in claim 2, wherein the lewis acid is one or more of zinc chloride, aluminum trichloride, aluminum tribromide, ferric trichloride, boron trifluoride, and tin tetrachloride.
4. The refining method of a low metal ion, low chroma DOPO flame retardant as claimed in claim 1, wherein the dissolving temperature in S2 is 75-85 ℃ and the dissolving time is 1.5-3h.
5. The refining method of a low metal ion and low chroma DOPO flame retardant according to claim 1, wherein in the S3, the hydrolysis time is 2.5-3.5h, and the amount of water is 12-15% of the mass of the o-phenylphenol.
6. The method for refining the low-metal-ion and low-chroma DOPO flame retardant according to claim 1, wherein in the S2, the first decolorizing agent is one or more of diatomite, alumina and activated carbon, and in the S4, the second decolorizing agent is one or more of diatomite, alumina and activated carbon.
7. The method as claimed in claim 6, wherein the second decolorizing agent is alumina in S4.
8. The refining method of a low metal ion and low chroma DOPO flame retardant according to claim 1, wherein in the S4, the using amount of toluene is 3.4 to 3.5 times of the mass of o-phenylphenol, and the dissolving temperature is 87 to 90 ℃; dissolve until the solution is clear.
9. The refining method of a low metal ion, low chroma DOPO flame retardant as claimed in claim 1, wherein in the step S4, the water washing is to add water of 85-95 ℃ to the solution obtained by dissolving, stir for 0.5-1h, and discharge the water layer after standing for 5-15 min; the number of washing times was 3.
10. The refining method of a low metal ion and low chroma DOPO flame retardant according to claim 1, wherein in the step S6, the dehydration is performed in vacuum at a temperature of 135-145 ℃ and a vacuum degree of not less than 0.095MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211668245.2A CN115974926B (en) | 2022-12-23 | 2022-12-23 | Refining method of low-metal ion and low-chromaticity DOPO flame retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211668245.2A CN115974926B (en) | 2022-12-23 | 2022-12-23 | Refining method of low-metal ion and low-chromaticity DOPO flame retardant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115974926A true CN115974926A (en) | 2023-04-18 |
| CN115974926B CN115974926B (en) | 2023-07-07 |
Family
ID=85964276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211668245.2A Active CN115974926B (en) | 2022-12-23 | 2022-12-23 | Refining method of low-metal ion and low-chromaticity DOPO flame retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115974926B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172290A (en) * | 1999-12-15 | 2001-06-26 | Toyobo Co Ltd | Method for producing organophosphorus-based compound |
| CN102617644A (en) * | 2011-01-30 | 2012-08-01 | 南京理工大学 | Synthesizing and refining method of flame retardant intermediate DOPO |
| CN105906666A (en) * | 2016-05-24 | 2016-08-31 | 青岛和新精细化工有限公司 | Method for preparing halogen-free flame retardant |
| CN107556343A (en) * | 2017-10-20 | 2018-01-09 | 利尔化学股份有限公司 | DOPO and its intermediate preparation method |
-
2022
- 2022-12-23 CN CN202211668245.2A patent/CN115974926B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172290A (en) * | 1999-12-15 | 2001-06-26 | Toyobo Co Ltd | Method for producing organophosphorus-based compound |
| CN102617644A (en) * | 2011-01-30 | 2012-08-01 | 南京理工大学 | Synthesizing and refining method of flame retardant intermediate DOPO |
| CN105906666A (en) * | 2016-05-24 | 2016-08-31 | 青岛和新精细化工有限公司 | Method for preparing halogen-free flame retardant |
| CN107556343A (en) * | 2017-10-20 | 2018-01-09 | 利尔化学股份有限公司 | DOPO and its intermediate preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115974926B (en) | 2023-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1063448C (en) | Process for preparation of DOP-containing mixture | |
| CN112457266A (en) | Valsartan mother liquor recovery method | |
| CN115974926B (en) | Refining method of low-metal ion and low-chromaticity DOPO flame retardant | |
| CN110194729B (en) | Preparation method of m-nitro-beta-hydroxyethyl sulfone | |
| JP2001508401A (en) | Method for producing aryl diphosphate esters | |
| CN102127115B (en) | Synthesis method of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide | |
| JPS6233223B2 (en) | ||
| CN108358900A (en) | A kind of preparation method of Afatinib and its maleate | |
| US2262262A (en) | Process of making maleanils | |
| JPH03193793A (en) | Production of tris(trihaloneopentyl)phosphate | |
| CN115850061A (en) | Refining method of diphenyl ether tetracarboxylic acid | |
| US6504050B1 (en) | Process for the preparation of 2-acrylamido-2-methyl-1-propanesulfonic acid | |
| CN112645883B (en) | Preparation method of 3,6-dichloropyridazine | |
| CN112479991A (en) | Preparation method of 2-bromo-5-aldehyde pyridine | |
| JP3938413B2 (en) | Process for producing organophosphorus compounds | |
| WO2013000255A1 (en) | Use of combination of polyphosphoric acid and metallic zinc in decolorizing of tetraacetyl ethylene diamine mother liquid | |
| CN112457287A (en) | Preparation method of E-olopatadine | |
| CN114181078B (en) | Refining method of 3-hydroxy-2-phenyl naphthoate | |
| JP3954121B2 (en) | Process for producing 3-hydroxy-N-benzimidazolone-5-yl-2-naphthamide with high purity required for azo pigments | |
| Rogerson et al. | CLXIV.—Some alkyl derivatives of glutaconic acid and of 2: 6-dihydroxypyridine | |
| CN1159322C (en) | Preparation method of compound triphenyl phosphine | |
| CN115536509B (en) | Synthesis method of 2-bromo-4-hydroxybenzaldehyde | |
| CN117105986A (en) | Preparation method of hexaanilino cyclotriphosphazene | |
| US3140309A (en) | Preparation of isophthalic acid monoester | |
| CN114989130B (en) | Preparation method of vinylene carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB02 | Change of applicant information |
Address after: 061000 south of chemical Avenue East of Jingsi Road, Lingang Economic and Technological Development Zone, Cangzhou City, Hebei Province Applicant after: Xinnuo Lixing (Cangzhou Bohai New Area) Chemical Co.,Ltd. Applicant after: Xinnuo Lixing (Huanghua City) Group Co.,Ltd. Address before: 061000 south of chemical Avenue East of Jingsi Road, Lingang Economic and Technological Development Zone, Cangzhou City, Hebei Province Applicant before: Cangzhou Lingang Fengya Chemical Co.,Ltd. Applicant before: Xinnuo Lixing (Huanghua City) Group Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |