CN111793092A - Purification method of hexaphenoxycyclotriphosphazene - Google Patents
Purification method of hexaphenoxycyclotriphosphazene Download PDFInfo
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000746 purification Methods 0.000 title claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000012065 filter cake Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 10
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- MPAHZJBGSWHKBJ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octaphenoxy-1,3,5,7-tetraza-2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraphosphacycloocta-1,3,5,7-tetraene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 MPAHZJBGSWHKBJ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- 229920007019 PC/ABS Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 hexaphenoxycyclotriphosphazene chlorobenzene Chemical compound 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The patent discloses a purification method of hexaphenoxycyclotriphosphazene. The process is as follows: adding a 5-10% sodium hydroxide solution into a hexaphenoxycyclotriphosphazene synthetic solution, stirring at room temperature for 10-30 min, standing to separate out a water phase, adding water, stirring at room temperature for 10-30 min, standing to separate out the water phase, adding a 5-10% hydrochloric acid solution, stirring at room temperature for 10-30 min, standing to separate out the water phase, adding water, stirring at room temperature for 10-30 min, and standing to separate out the water phase. Finally, evaporating chlorobenzene in the washed oil phase to obtain a crude hexaphenoxycyclotriphosphazene product; and heating and dissolving the crude product by using absolute ethyl alcohol, then cooling to-10-0 ℃, crystallizing for 4-8 hours, filtering, washing a filter cake for 2 times by using absolute ethyl alcohol, and drying at 90-100 ℃ to constant weight to obtain hexaphenoxycyclotriphosphazene. The purification method provided by the invention obviously improves the yield of hexaphenoxycyclotriphosphazene.
Description
Technical Field
The invention relates to a method for purifying hexaphenoxycyclotriphosphazene, in particular to a method for purifying hexaphenoxycyclotriphosphazene from a hexaphenoxycyclotriphosphazene synthetic solution by washing with a sodium hydroxide solution, washing with a hydrochloric acid solution and recrystallizing, belonging to the field of chemical industry and high polymer material auxiliaries.
Background
Hexaphenoxy cyclotriphosphazene is a widely used phosphorus flame retardant [ Xuzhong, Duwei, Wangchun, etc.. Hexaphenoxy cyclotriphosphazene flame retardant PC/ABS alloy and pyrolysis research thereof, Chinese plastics, 2011, 25(12): 21-25; in slow building, how to fight violence, yield strength, research on the flame retardant PC of hexaphenoxycyclotriphosphazene and the pyrolysis process thereof, Chinese plastics, 2013,27(1): 92-97; xulu, wangyihong, liuyujia, etc. hexaphenoxycyclotriphosphazene/potassium perfluorobutylsulfonate synergistic flame retardant PC. plastic industry, 2014, 42 (4): 101-105; queen, Xulu, Suqian, etc. Hexaphenoxycyclotriphosphazene has fire retarding effect on polycarbonate, modern plastic processing application 2014, 26(4): 25-28%. The hexaphenoxycyclotriphosphazene is mainly prepared by taking phenol and hexachlorocyclotriphosphazene as raw materials through nucleophilic substitution reaction, and a common method is a two-phase transfer catalysis method [ Huangjie, Tang' an bin, Ma Qing Ke, and the like ] synthetic method of fire retardant hexaphenoxycyclotriphosphazene is CN 101985455A, 2011-03-16; preparation method of Hexaphenoxy cyclotriphosphazene under dawn, CN 103319538A, 2013-09-25; carr L J, Nichols GM. Process for preparation of phosphoesters. U.S. Pat. No. 5,153,1986-07-15; liu Shi Jun, Wu Ju, Li Liang, etc. Synthesis of hexaphenoxy cyclotriphosphazene and its flame retardant application, proceedings of Wuhan engineering university, 2013, 35 (4): 48-51; hexaphenoxy cyclotriphosphazene preparation method CN 103539820A, 2014-01-29). The method generally uses chlorobenzene as a solvent and tetrabutylammonium bromide as a phase transfer catalyst. Because of the difficulty of purifying hexachlorocyclotriphosphazene, in order to simplify the process, the method can directly use the synthetic liquid of hexachlorocyclotriphosphazene as raw material to prepare hexaphenoxycyclotriphosphazene, so as to omit the processes of purifying hexachlorocyclotriphosphazene and removing solvent [ Luqingchang, Zhouxiao, Wangshuhua. By adopting the method, besides the hexaphenoxycyclotriphosphazene, a certain amount of octaphenoxycyclotetraphosphazene, decaphenoxycyclopentaphosphazene and the like are generated, and the amount of the byproducts depends on the selectivity of the synthesis of the hexachlorocyclotriphosphazene. Therefore, after the reaction is finished, the product is purified by a proper method, and the method generally comprises the following steps: firstly, removing by-products of potassium chloride or sodium chloride and a phase transfer catalyst by washing or filtering, then removing chlorobenzene to obtain a crude product, and crystallizing the crude product by ethanol to obtain a product. However, this method has the following problems: the purification yield of hexaphenoxycyclotriphosphazene is low, the purification yield is greatly influenced by the content of impurities such as octaphenoxycyclotetraphosphazene, decaphenoxycyclopentaphosphazene and the like in a crude product, the content of the impurities is higher, and the purification yield of hexaphenoxycyclotriphosphazene is lower, even the impurities cannot be separated.
Disclosure of Invention
In order to overcome the problems in the purification process of hexaphenoxycyclotriphosphazene, the inventors of the present invention conducted intensive studies on a method for purifying hexaphenoxycyclotriphosphazene from a synthetic liquid. The inventors have now found that the synthesis solution contains a certain amount of phenol (unreacted starting material) and tributylamine (decomposition product of tetrabutylammonium bromide), the presence of which has a significant effect on the crystallization of hexaphenoxycyclotriphosphazene from ethanol solution, and have therefore proposed an improved purification process for hexaphenoxycyclotriphosphazene from the synthesis solution, i.e. a purification process in which phenol is removed by washing with sodium hydroxide solution, tributylamine is removed by washing with hydrochloric acid solution, chlorobenzene is then removed, and the crude hexaphenoxycyclotriphosphazene product is recrystallized from ethanol.
The technical scheme of the invention is as follows:
a purification method of hexaphenoxycyclotriphosphazene comprises the following process steps:
(1) preparing raw materials: weighing hexaphenoxycyclotriphosphazene synthetic solution, 5-10% of sodium hydroxide solution, 5-10% of hydrochloric acid solution, water and absolute ethyl alcohol; the mass ratio of the hexaphenoxycyclotriphosphazene synthetic solution to the sodium hydroxide solution to the hydrochloric acid solution to the water to the absolute ethyl alcohol is 1.0: 0.2-0.7: 0.3-0.9: 0.5-1.5: 0.4 to 1.2.
(2) Washing of the synthetic solution: adding 5-10% of sodium hydroxide solution into hexaphenoxycyclotriphosphazene synthetic solution, stirring for 10-30 min at room temperature, standing to separate out a water phase, adding 1/2 water, stirring for 10-30 min at room temperature, standing to separate out the water phase, adding 5-10% of hydrochloric acid solution, stirring for 10-30 min at room temperature, standing to separate out the water phase, adding 1/2 water, stirring for 10-30 min at room temperature, and standing to separate out the water phase. Finally, distilling out chlorobenzene in the oil phase to obtain a crude hexaphenoxycyclotriphosphazene product;
(3) and (3) recrystallizing hexaphenoxycyclotriphosphazene: heating and dissolving the hexaphenoxycyclotriphosphazene crude product by using 1/2 anhydrous ethanol, cooling to-10-0 ℃, crystallizing for 4-8 h at the temperature, filtering, washing the filter cake for 2 times by using-10-0 ℃ anhydrous ethanol, washing by using 1/4 ethanol for each time, and drying the filter cake at 90-100 ℃ to constant weight to obtain the hexaphenoxycyclotriphosphazene.
Further, the mass ratio of the hexaphenoxycyclotriphosphazene synthetic solution to the sodium hydroxide solution is preferably 1.0: 0.4 to 0.6;
the mass ratio of the hexaphenoxycyclotriphosphazene synthetic liquid to the hydrochloric acid solution is preferably 1.0: 0.4 to 0.7;
the mass ratio of the hexaphenoxycyclotriphosphazene synthetic liquid to water is preferably 1.0: 0.8 to 1.2;
the mass ratio of the hexaphenoxycyclotriphosphazene synthetic solution to the absolute ethyl alcohol is preferably 1.0: 0.6 to 1.0.
The purification method has the advantage of remarkably improving the purification yield of hexaphenoxycyclotriphosphazene.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
All percentages used in the present invention are mass percentages unless otherwise indicated.
In the examples, the contents of hexaphenoxycyclotriphosphazene and octaphenoxycyclotetraphosphazene were analyzed by high performance liquid chromatography. The liquid chromatographic analysis conditions were, column: HyperODS 2C 18 column (250 mm. times.4.6 mm); mobile phase: v (acetonitrile)/V (water) ═ 90/10; flow rate: 1.0 mL/min; column temperature: room temperature; detection wavelength: 210 nm. The liquid chromatograph used was a Waters 600 high performance liquid chromatograph from Watts corporation, USA.
Example 1
The preparation method of the hexaphenoxycyclotriphosphazene synthetic solution comprises the following process steps:
(1) synthesis of hexachlorocyclotriphosphazene: adding 12.8kg (239.7mol) of ammonium chloride (ground and dried), 1kg of self-made catalyst and 40kg of chlorobenzene into a 250L reaction kettle provided with a stirrer, a thermometer and a reflux condenser tube, heating to micro reflux, and then dropwise adding PCl5In chlorobenzene solution [41.66kg (200mol) PCl5+80kg of chlorobenzene]About 5h, followed by refluxing for 3 h. Cooling to room temperature, adding 50L multiplied by 3 water to wash for 3 times to obtain chlorobenzene solution of hexachlorocyclotriphosphazene.
(2) Preparing hexaphenoxycyclotriphosphazene synthetic solution: 37.65kg (400mol) of phenol, 3.0kg of tetrabutylammonium bromide and 80kg of chlorobenzene are sequentially added into a 500L reaction kettle provided with a stirrer, a thermometer and a reflux condenser pipe, then 16kg of powdery sodium hydroxide (the content of the sodium hydroxide is 96%) is added in batches, the temperature is controlled not to exceed 50 ℃, and the sodium hydroxide is stirred for 0.5h after being added; dripping the chlorobenzene solution of hexachlorocyclotriphosphazene prepared above at 50 ℃ for about 0.5h, and then heating to 110 ℃ for reaction for 24 h. After the reaction is finished, the reaction product is cooled to 20-30 ℃, 100L multiplied by 3 water is used for washing for 3 times, and 241 kg of hexaphenoxycyclotriphosphazene chlorobenzene solution (hexaphenoxycyclotriphosphazene synthetic solution for short) is obtained, wherein 36.79kg of hexaphenoxycyclotriphosphazene (theoretical yield 46.26kg), 5.77kg of octaphenoxycyclotetraphosphazene and 1.78kg of other phenoxyphosphazenes are contained.
Example 2
A purification method of hexaphenoxycyclotriphosphazene comprises the following process steps:
adding 500g of 10% sodium hydroxide solution into 1000g of the hexaphenoxycyclotriphosphazene synthetic solution prepared in example 1, stirring at room temperature for 10-30 min, standing to separate out an aqueous phase, adding 500g of water, stirring at room temperature for 10-30 min, standing to separate out the aqueous phase, adding 500g of 5% hydrochloric acid solution, stirring at room temperature for 10-30 min, standing to separate out the aqueous phase, adding 500g of water, stirring at room temperature for 10-30 min, and standing to separate out the aqueous phase. Evaporating chlorobenzene from the washed oil phase to obtain about 200g of crude hexaphenoxycyclotriphosphazene, adding 500mL of absolute ethyl alcohol, heating to dissolve, cooling to-10-0 ℃, crystallizing at the temperature for 4-8 h, filtering, washing a filter cake for 2 times by using the absolute ethyl alcohol at-10-0 ℃, using 250mL of absolute ethyl alcohol each time, and drying at 90-100 ℃ until the weight is constant to obtain 146.25g of hexaphenoxycyclotriphosphazene (the theoretical yield is 191.95g), the product yield is 76.19%, the melting point is 109-111 ℃ (the literature value is 110-111 ℃), and the product purity is 99.1%.
Example 3
A purification method of hexaphenoxycyclotriphosphazene comprises the following process steps:
adding 700g of 10% sodium hydroxide solution into 1000g of hexaphenoxycyclotriphosphazene synthetic solution prepared in example 1, stirring at room temperature for 10-30 min, standing to separate out an aqueous phase, adding 600g of water, stirring at room temperature for 10-30 min, standing to separate out the aqueous phase, adding 500g of 5% hydrochloric acid solution, stirring at room temperature for 10-30 min, standing to separate out the aqueous phase, adding 500g of water, stirring at room temperature for 10-30 min, and standing to separate out the aqueous phase. Evaporating chlorobenzene from the washed oil phase to obtain about 200g of crude hexaphenoxycyclotriphosphazene, adding 500mL of absolute ethyl alcohol, heating to dissolve, cooling to-10-0 ℃, crystallizing at the temperature for 4-8 h, filtering, washing the filter cake for 2 times with the absolute ethyl alcohol at the temperature of-10-0 ℃, using 250mL of absolute ethyl alcohol each time, and drying the filter cake at the temperature of 90-100 ℃ until the weight is constant to obtain 146.35g of hexaphenoxycyclotriphosphazene (the theoretical yield is 191.95g), the product yield is 76.24%, the melting point is 109-111 ℃ (the literature value is 110-111 ℃), and the product purity is 99.2%.
Example 4
A purification method of hexaphenoxycyclotriphosphazene comprises the following process steps:
adding 500g of 10% sodium hydroxide solution into 1000g of the hexaphenoxycyclotriphosphazene synthetic solution prepared in example 1, stirring at room temperature for 10-30 min, standing to separate out an aqueous phase, adding 500g of water, stirring at room temperature for 10-30 min, standing to separate out the aqueous phase, adding 700g of 5% hydrochloric acid solution, stirring at room temperature for 10-30 min, standing to separate out the aqueous phase, adding 500g of water, stirring at room temperature for 10-30 min, and standing to separate out the aqueous phase. Evaporating chlorobenzene from the washed oil phase to obtain about 200g of crude hexaphenoxycyclotriphosphazene, adding 500mL of absolute ethyl alcohol, heating to dissolve, cooling to-10-0 ℃, crystallizing at the temperature for 4-8 h, filtering, washing a filter cake for 2 times by using the absolute ethyl alcohol at the temperature of-10-0 ℃, using 250mL of absolute ethyl alcohol each time, and drying the filter cake at the temperature of 90-100 ℃ until the weight is constant to obtain 146.20g of hexaphenoxycyclotriphosphazene (the theoretical yield is 191.95g), the product yield is 76.17%, the melting point is 109-111 ℃ (the literature value is 110-111 ℃), and the product purity is 99.0%.
Example 5
A purification method of hexaphenoxycyclotriphosphazene comprises the following process steps:
adding 500g of 10% sodium hydroxide solution into 1000g of the hexaphenoxycyclotriphosphazene synthetic solution prepared in example 1, stirring at room temperature for 10-30 min, standing to separate out an aqueous phase, adding 500g of water, stirring at room temperature for 10-30 min, standing to separate out the aqueous phase, adding 500g of 5% hydrochloric acid solution, stirring at room temperature for 10-30 min, standing to separate out the aqueous phase, adding 500g of water, stirring at room temperature for 10-30 min, and standing to separate out the aqueous phase. Evaporating chlorobenzene from the washed oil phase to obtain about 200g of crude hexaphenoxycyclotriphosphazene, adding 700mL of absolute ethyl alcohol, heating to dissolve, cooling to-10-0 ℃, crystallizing at the temperature for 4-8 h, filtering, washing a filter cake for 2 times with the absolute ethyl alcohol at the temperature of-10-0 ℃, using 250mL of absolute ethyl alcohol each time, and drying the filter cake at the temperature of 90-100 ℃ until the weight is constant to obtain 143.7g of hexaphenoxycyclotriphosphazene (the theoretical yield is 191.95g), the product yield is 74.86%, the melting point is 109-111 ℃ (the literature value is 110-111 ℃), and the product purity is 99.3%.
Comparative example
A purification method of hexaphenoxycyclotriphosphazene comprises the following process steps:
steaming out chlorobenzene in 1000g of hexaphenoxycyclotriphosphazene synthetic liquid prepared in example 1 to obtain about 223g of hexaphenoxycyclotriphosphazene crude product, adding 500mL of absolute ethyl alcohol, heating to dissolve, cooling to-10-0 ℃, crystallizing for 4-8 h at the temperature, filtering, washing a filter cake with-10-0 ℃ absolute ethyl alcohol for 2 times, using 250mL of absolute ethyl alcohol each time, and drying the filter cake at 90-100 ℃ to constant weight to obtain 134.31g of hexaphenoxycyclotriphosphazene (191.95 g of theoretical yield), 69.97% of product yield, 109-111 ℃ (literature value 110-111 ℃) of product purity 99.1%. The product yield of the comparative example was 6.22% lower than that of example 1.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. 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.
Claims (5)
1. A purification method of hexaphenoxycyclotriphosphazene is characterized in that the process flow is as follows: adding 5-10% of sodium hydroxide solution into hexaphenoxycyclotriphosphazene synthetic solution, stirring for 10-30 min at room temperature, standing to separate out a water phase, adding 1/2 water, stirring for 10-30 min at room temperature, standing to separate out the water phase, adding 5-10% of hydrochloric acid solution, stirring for 10-30 min at room temperature, standing to separate out the water phase, adding 1/2 water, stirring for 10-30 min at room temperature, standing to separate out the water phase, and finally evaporating chlorobenzene in the washed oil phase to obtain a crude hexaphenoxycyclotriphosphazene product; heating and dissolving the crude product by using 1/2 anhydrous ethanol, cooling to-10-0 ℃, crystallizing for 4-8 hours at the temperature, filtering, washing a filter cake by using-10-0 ℃ anhydrous ethanol for 2 times, using 1/4 ethanol for each washing, and drying the filter cake at 90-100 ℃ to constant weight to obtain hexaphenoxycyclotriphosphazene.
2. The purification method according to claim 1, wherein the mass ratio of the hexaphenoxycyclotriphosphazene synthetic solution to the 5-10% sodium hydroxide solution is 1.0: 0.2 to 0.7.
3. The purification method according to claim 1, wherein the mass ratio of the hexaphenoxycyclotriphosphazene synthetic solution to the 5-10% hydrochloric acid solution is 1.0: 0.3 to 0.9.
4. The purification method of claim 1, wherein the mass ratio of the hexaphenoxycyclotriphosphazene synthetic solution to water is 1.0: 0.5 to 1.5.
5. The purification method of claim 1, wherein the mass ratio of the hexaphenoxycyclotriphosphazene synthetic fluid to the absolute ethyl alcohol is 1.0: 0.4 to 1.2.
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Citations (5)
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|---|---|---|---|---|
| US4600791A (en) * | 1983-12-12 | 1986-07-15 | Borg-Warner Chemicals, Inc. | Process for preparation of phosphazene esters |
| US6627122B1 (en) * | 1998-08-26 | 2003-09-30 | Otsuka Chemical Co., Ltd. | Powdery flame retardant |
| US20080091050A1 (en) * | 2005-01-21 | 2008-04-17 | Asahi Kasei Chemical Corporation | Process For Producing Phosphonitrilic Acid Ester |
| CN104945438A (en) * | 2015-06-24 | 2015-09-30 | 南通泰通化学科技有限公司 | Hexaphenoxy cyclotriphosphazene production technology |
| CN106336435A (en) * | 2016-08-25 | 2017-01-18 | 威海金威化学工业有限责任公司 | Improved hexaphenoxycyclotriphosphazene preparation method |
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2020
- 2020-07-07 CN CN202010644704.8A patent/CN111793092A/en active Pending
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| US4600791A (en) * | 1983-12-12 | 1986-07-15 | Borg-Warner Chemicals, Inc. | Process for preparation of phosphazene esters |
| US6627122B1 (en) * | 1998-08-26 | 2003-09-30 | Otsuka Chemical Co., Ltd. | Powdery flame retardant |
| US20080091050A1 (en) * | 2005-01-21 | 2008-04-17 | Asahi Kasei Chemical Corporation | Process For Producing Phosphonitrilic Acid Ester |
| CN104945438A (en) * | 2015-06-24 | 2015-09-30 | 南通泰通化学科技有限公司 | Hexaphenoxy cyclotriphosphazene production technology |
| CN106336435A (en) * | 2016-08-25 | 2017-01-18 | 威海金威化学工业有限责任公司 | Improved hexaphenoxycyclotriphosphazene preparation method |
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| 唐安斌等: "六苯氧基环三磷腈的合成及其在层压板中的阻燃应用", 《应用化学》 * |
| 成国亮等: "苯氧基磷腈的组成对其阻燃PC/ABS的影响", 《化工科技》 * |
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