Synthesis and purification process for DOPO

Abstract

The invention discloses a synthesis and purification process for DOPO. The process comprises: 1, sequential adding 2-phenylphenol, anhydrous zinc chloride and phosphorus trichloride to a reactor, then carrying out a heating reaction to generate a CDOP liquid, wherein the phosphorus trichloride is added for three times; 2, adding water and a alcohol organic solvent to the CDOP liquid, the carryingout heating, refluxing, filtering, then adding the water to precipitate crystal, followed by sucking filtering to obtain white crystal; 3, adding a aromatic organic solvent and a metal salt catalyst to the white crystal, then carrying out heating, refluxing, filtering and cooling to precipitate white solid powders; 4, adding a aliphatic hydrocarbon organic solvent to the white solid powders, thencarrying out sucking filtering to obtain the DOPO. According to the present invention, the phosphorus trichloride is added for three times in the process, heating rate is quick, reaction temperature is low, such that generations of side reactions are effectively reduced; HPPA is subjected to a dehydration and a cyclization through a azeotropic distillation method, such that production efficiency is improved, a purity of the prepared DOPO is more than or equal to 99%, and yield of the prepared DOPO is more than or equal to 88%.

Description

technical field

[0001] The invention belongs to the technical field of flame retardants, and in particular relates to a DOPO synthesis and purification process. Background technique

[0002] 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a new type of halogen-free organic phosphorus flame retardant intermediate, which can be used in circuit boards, semiconductor packaging materials, plastics, Flame retardant for photosensitive materials, etc., can also be used as antioxidants, antibacterial agents, precursors for synthetic luminescent materials, etc. Its structural formula is:

[0003]

[0004] So far, foreign countries have done extensive research on the synthesis and application of DOPO. German patent DE2034887 first reported the synthesis method of DOPO, and then German patent DE19505352 and US patents US5717127 and US5481071 all reported the preparation of DOPO. The above-mentioned patents have basically all adopted the same synthetic method: using or...

Examples

Embodiment 1

[0025] Step 1, the synthesis of 6-chloro-(6 hydrogen)-diphenyl(c,e)[1,2]-phosphaphenanthrene: using anhydrous zinc chloride as a catalyst, using o-phenylphenol and phosphorus trichloride As raw materials, o-phenylphenol, anhydrous zinc chloride and phosphorus trichloride were sequentially added to the reactor, heated to 175°C at a heating rate of 3°C / min and reacted for 4 hours to generate 6-chloro-(6 hydrogen) -diphenyl (c, e) [1,2]-phosphaphenanthrene liquid; the mol ratio of the phosphorus trichloride and o-phenylphenol is 1.2:1, and the consumption of anhydrous zinc chloride is o-phenylphenol 0.5% of the mass; among them, phosphorus trichloride is added in the reactor three times, first add 70% of the total amount of phosphorus trichloride at room temperature, and then add 70% of the total amount of phosphorus trichloride when the reaction solution is heated to 105°C 20%, and then add the remaining phosphorus trichloride when the reaction solution is heated to 155°C;

[0...

Embodiment 2

[0031] This example is the same as Example 1, except that the alcoholic organic solvent used is methanol or isopropanol, the aromatic organic solvent used is benzene, toluene, chlorobenzene or dichlorobenzene, and the metal salt catalyst used is Magnesium sulfate, aluminum sulfate, iron sulfate, zinc sulfate, chromium sulfate or manganese sulfate, or magnesium chloride, aluminum trichloride, zinc chloride, chromium chloride or manganese chloride, the aliphatic hydrocarbon organic solvent used is hexane, n-pentane or isopentane.

[0032] In this embodiment, phosphorus trichloride is added in three times, the heating rate is fast, the reaction temperature is low, and the occurrence of side reactions is effectively reduced. phenyl-2-phosphinic acid) for dehydration and cyclization, the cyclization time is short, the operation is simple, and the production efficiency is improved. The prepared DOPO has a purity of ≥99%, a yield of ≥88%, and a melting point of 117.2°C to 118.6°C. E...

Embodiment 3

[0034]Step 1, the synthesis of 6-chloro-(6 hydrogen)-diphenyl(c,e)[1,2]-phosphaphenanthrene: using anhydrous zinc chloride as a catalyst, using o-phenylphenol and phosphorus trichloride As raw materials, o-phenylphenol, anhydrous zinc chloride and phosphorus trichloride were added to the reactor in sequence, heated to 158°C at a heating rate of 0.25°C / min and reacted for 8 hours to generate 6-chloro-(6 hydrogen) -diphenyl (c, e) [1,2]-phosphaphenanthrene liquid; the mol ratio of the phosphorus trichloride and o-phenylphenol is 1.5:1, and the consumption of anhydrous zinc chloride is o-phenylphenol 2.0% of the mass; wherein, phosphorus trichloride is added into the reactor in three times, first adding 85% of the total amount of phosphorus trichloride at room temperature, and then adding 85% of the total amount of phosphorus trichloride when the reaction solution is heated to 130°C 10%, and then add the remaining phosphorus trichloride when the reaction solution is heated to 140...

technical field

[0001] The invention belongs to the technical field of flame retardants, and in particular relates to a DOPO synthesis and purification process. Background technique

[0002] 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a new type of halogen-free organic phosphorus flame retardant intermediate, which can be used in circuit boards, semiconductor packaging materials, plastics, Flame retardant for photosensitive materials, etc., can also be used as antioxidants, antibacterial agents, precursors for synthetic luminescent materials, etc. Its structural formula is:

[0003]

[0004] So far, foreign countries have done extensive research on the synthesis and application of DOPO. German patent DE2034887 first reported the synthesis method of DOPO, and then German patent DE19505352 and US patents US5717127 and US5481071 all reported the preparation of DOPO. The above-mentioned patents have basically all adopted the same synthetic method: using or...

Examples

Embodiment 1

[0025] Step 1, the synthesis of 6-chloro-(6 hydrogen)-diphenyl(c,e)[1,2]-phosphaphenanthrene: using anhydrous zinc chloride as a catalyst, using o-phenylphenol and phosphorus trichloride As raw materials, o-phenylphenol, anhydrous zinc chloride and phosphorus trichloride were sequentially added to the reactor, heated to 175°C at a heating rate of 3°C / min and reacted for 4 hours to generate 6-chloro-(6 hydrogen) -diphenyl (c, e) [1,2]-phosphaphenanthrene liquid; the mol ratio of the phosphorus trichloride and o-phenylphenol is 1.2:1, and the consumption of anhydrous zinc chloride is o-phenylphenol 0.5% of the mass; among them, phosphorus trichloride is added in the reactor three times, first add 70% of the total amount of phosphorus trichloride at room temperature, and then add 70% of the total amount of phosphorus trichloride when the reaction solution is heated to 105°C 20%, and then add the remaining phosphorus trichloride when the reaction solution is heated to 155°C;

[0...

Embodiment 2

[0031] This example is the same as Example 1, except that the alcoholic organic solvent used is methanol or isopropanol, the aromatic organic solvent used is benzene, toluene, chlorobenzene or dichlorobenzene, and the metal salt catalyst used is Magnesium sulfate, aluminum sulfate, iron sulfate, zinc sulfate, chromium sulfate or manganese sulfate, or magnesium chloride, aluminum trichloride, zinc chloride, chromium chloride or manganese chloride, the aliphatic hydrocarbon organic solvent used is hexane, n-pentane or isopentane.

[0032] In this embodiment, phosphorus trichloride is added in three times, the heating rate is fast, the reaction temperature is low, and the occurrence of side reactions is effectively reduced. phenyl-2-phosphinic acid) for dehydration and cyclization, the cyclization time is short, the operation is simple, and the production efficiency is improved. The prepared DOPO has a purity of ≥99%, a yield of ≥88%, and a melting point of 117.2°C to 118.6°C. E...

Embodiment 3

[0034]Step 1, the synthesis of 6-chloro-(6 hydrogen)-diphenyl(c,e)[1,2]-phosphaphenanthrene: using anhydrous zinc chloride as a catalyst, using o-phenylphenol and phosphorus trichloride As raw materials, o-phenylphenol, anhydrous zinc chloride and phosphorus trichloride were added to the reactor in sequence, heated to 158°C at a heating rate of 0.25°C / min and reacted for 8 hours to generate 6-chloro-(6 hydrogen) -diphenyl (c, e) [1,2]-phosphaphenanthrene liquid; the mol ratio of the phosphorus trichloride and o-phenylphenol is 1.5:1, and the consumption of anhydrous zinc chloride is o-phenylphenol 2.0% of the mass; wherein, phosphorus trichloride is added into the reactor in three times, first adding 85% of the total amount of phosphorus trichloride at room temperature, and then adding 85% of the total amount of phosphorus trichloride when the reaction solution is heated to 130°C 10%, and then add the remaining phosphorus trichloride when the reaction solution is heated to 140...

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