CN115838385A - Preparation method of chlorocyclophosphazene - Google Patents
Preparation method of chlorocyclophosphazene Download PDFInfo
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- CN115838385A CN115838385A CN202211537592.1A CN202211537592A CN115838385A CN 115838385 A CN115838385 A CN 115838385A CN 202211537592 A CN202211537592 A CN 202211537592A CN 115838385 A CN115838385 A CN 115838385A
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- chlorocyclophosphazene
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- hexachlorocyclotriphosphazene
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Abstract
The invention provides a preparation method of chlorocyclophosphazene, which comprises the following steps: mixing and reacting lithium nitride and phosphorus pentachloride, and then carrying out post-treatment to obtain chlorocyclophosphazene; the chlorocyclophosphazene comprises hexachlorocyclotriphosphazene and/or octachlorocyclotetraphosphazene. The preparation method provided by the invention can be used for efficiently and simply preparing the chlorocyclophosphazene, does not generate harmful gases such as hydrogen chloride and the like, is environment-friendly, mild in reaction condition, short in reaction time and low in energy consumption, byproducts generated in the reaction can be directly recovered and sold in the market, the loss of raw materials is less, reactants such as other raw materials and catalysts are not required to be added, the requirements on chemical varieties are reduced, and the cost is reduced.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of chlorocyclophosphazene, in particular to a preparation method of chlorocyclophosphazene which is environment-friendly.
Background
The cyclic phosphazene compound is a high-efficiency flame retardant and is widely applied to various flame-retardant scenes. The hexachlorocyclotriphosphazene is an important one of the cyclic phosphazene compounds, and the existing synthetic method of hexachlorocyclotriphosphazene usually adopts phosphorus pentachloride and ammonium chloride to react (such as KR 101749188A), but the method can generate four equivalents of hydrogen chloride gas, seriously pollutes the environment, and the reaction needs to be carried out at high temperature, so that the energy consumption is large; in addition, the method also needs column chromatography for purifying the product, so that the method is not suitable for industrial production.
CN103896985B discloses a synthetic method and a synthetic device of hexachlorocyclotriphosphazene and a preparation method of terphenyl cyclotriphosphazene, wherein the synthetic method of hexachlorocyclotriphosphazene comprises the following steps: a1, adding powdery ammonium chloride and phosphorus pentachloride into a ceramic reaction kettle, wherein the weight ratio of the powdery ammonium chloride to the powdery phosphorus pentachloride is 900-1500; a2, adding zinc chloride, heating and stirring for reaction, and continuously dropping an acid-binding agent in the stirring process; wherein, the weight ratio of zinc chloride to phosphorus pentachloride is 20 to 35, the weight ratio of acid binding agent to phosphorus pentachloride is 30 to 50, the reaction temperature is 65 to 150 ℃, and the reaction time is 1.5 to 2.5 hours; and A3, conveying the hexachlorocyclotriphosphazene to sublimation purification equipment by adopting a closed screw, heating to 125-135 ℃, and sublimating to obtain the hexachlorocyclotriphosphazene. However, this process also involves the use of ammonium chloride, which also causes environmental pollution.
The existing synthesis and preparation process of hexachlorocyclotriphosphazene has a series of problems. Therefore, how to provide a preparation method of hexachlorocyclotriphosphazene which is environment-friendly, mild in reaction condition and simple in post-treatment becomes a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of chlorocyclophosphazene, in particular to an environment-friendly preparation method of chlorocyclophosphazene. The preparation method provided by the invention can be used for efficiently and simply preparing the chlorocyclophosphazene, cannot generate harmful gases such as hydrogen chloride and the like, is environment-friendly, mild in reaction condition, short in reaction time and low in energy consumption, byproducts generated in the reaction can be directly recovered and sold in the market, the loss of raw materials is less, reactants such as other raw materials and catalysts are not required to be added, the requirements on chemical varieties are reduced, and the cost is reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of chlorocyclophosphazene, which comprises the following steps:
mixing and reacting lithium nitride and phosphorus pentachloride, and then carrying out post-treatment to obtain chlorocyclophosphazene.
The chlorocyclophosphazene comprises hexachlorocyclotriphosphazene and/or octachlorocyclotetraphosphazene.
According to the method, lithium nitride directly reacts with phosphorus pentachloride, and chlorocyclophosphazene can be directly obtained through post-treatment, so that harmful gases such as hydrogen chloride are avoided, the method is environment-friendly, byproducts generated in the reaction can be directly recovered and sold in the market, and the loss of raw materials is less; reactants such as other raw materials, catalysts and the like are not required to be added, the requirements on chemical varieties are reduced, and the cost is reduced; and can prepare hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene simultaneously, and realize the production of various chemical products simultaneously.
Preferably, the reaction is carried out in an inert gas environment, and the inert gas comprises any one of nitrogen, argon or helium.
Preferably, the molar ratio of the lithium nitride to the phosphorus pentachloride is (0.98-1.05): 1.
Preferably, the temperature of the reaction is-30 to 5 ℃.
Preferably, the reaction time is 1-4h.
Wherein, the molar ratio of lithium nitride to phosphorus pentachloride can be 0.98, 0.99
-10, -5, -0 or 5 ℃ and the like, and the reaction time may be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours or 4 hours, but is not limited to the above-listed values, and other values not listed within the above-mentioned range of values are also applicable.
The chloro-cyclophosphazene can be effectively synthesized under the specific reaction conditions, and meanwhile, the method is mild in reaction conditions, short in reaction time and low in energy consumption.
Preferably, the reaction is carried out in a solvent.
Preferably, the solvent includes any one or a combination of at least two of tetrahydrofuran, n-hexane, or cyclohexane, such as tetrahydrofuran and n-hexane, a combination of n-hexane and cyclohexane, or a combination of tetrahydrofuran and cyclohexane, etc., but is not limited to the above-listed combinations, and other combinations not listed within the above-listed combinations are also applicable, preferably a combination of tetrahydrofuran and n-hexane.
The specific solvent can effectively improve the conversion rate of the phosphorus pentachloride, and meanwhile, the specific solvent combination can further improve the conversion rate of the phosphorus pentachloride.
Preferably, the post-treatment comprises the steps of: and filtering and desolventizing the reactant, and heating and sublimating the obtained mixture under negative pressure to obtain the chlorocyclophosphazene.
Preferably, the negative pressure is 0.3-0.5mm Hg, such as 0.3mm Hg, 0.35mm Hg, 0.4mm Hg, 0.45mm Hg or 0.5mm Hg, but not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the chlorocyclophosphazene sublimated at 68-72 ℃ is hexachlorocyclotriphosphazene, which may be, for example, 68 ℃, 69 ℃, 70 ℃, 71 ℃ or 72 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the chlorocyclophosphazene sublimed at 98-102 ℃ is octachlorocyclotetraphosphazene, for example 98 ℃, 99 ℃, 100 ℃, 101 ℃ or 102 ℃, but not limited to the above-listed values, and other values not listed within the above range are equally applicable.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of chlorocyclophosphazene, which is characterized in that lithium nitride directly reacts with phosphorus pentachloride, and then chlorocyclophosphazene can be directly obtained through post-treatment, so that harmful gases such as hydrogen chloride are avoided, the preparation method is environment-friendly, byproducts generated in the reaction can be directly recovered and sold in the market, and the loss of raw materials is less; reactants such as other raw materials, catalysts and the like are not required to be added, the demand on chemical varieties is reduced, and the cost is reduced; and can prepare hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene simultaneously, and realize the production of various chemical products at the same time; the chloro-cyclophosphazene can be effectively synthesized under specific reaction conditions, and meanwhile, the method is mild in reaction conditions, short in reaction time and low in energy consumption; the specific solvent can effectively improve the conversion rate of the phosphorus pentachloride, and meanwhile, the specific solvent combination can further improve the conversion rate of the phosphorus pentachloride.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
In the following examples, the yield of hexachlorocyclotriphosphazene was calculated as the mass of hexachlorocyclotriphosphazene/the mass of theoretical conversion of all phosphorus pentachloride into hexachlorocyclotriphosphazene x 100%, the yield of octachlorocyclotetraphosphazene was calculated as the mass of octachlorocyclotetraphosphazene/the mass of theoretical conversion of all phosphorus pentachloride into octachlorocyclotetraphosphazene x 100%, and the conversion of phosphorus pentachloride was calculated as the mass of phosphorus pentachloride actually converted into a mixture of hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene and other pentamers and higher polychlorocyclophosphazenes/the mass of phosphorus pentachloride as the starting material x 100%.
Example 1
The embodiment provides a preparation method of chlorocyclophosphazene, which comprises the following specific steps:
step S1: under the protection of nitrogen, 400mL of tetrahydrofuran and 208g of phosphorus pentachloride (1 mol) are sequentially added into a reaction device, 34.79g of lithium nitride (1 mol) are slowly added in batches within the range of 0-5 ℃, and the reaction liquid is changed from light green turbid liquid into light yellow turbid liquid; reacting at 0 ℃ for 2h, filtering out a by-product lithium chloride (with the purity of 99 percent, and can be directly dried and recycled for market sale) after the reaction is finished, and distilling the filtrate at normal pressure to recycle tetrahydrofuran to obtain a mixture of hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, pentamer and higher polychlorocyclophosphazene; the recovered tetrahydrofuran is dried and recycled by using anhydrous magnesium sulfate.
Step S2: the resulting polychlorocyclotriphosphazene mixture of hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, pentamer or higher is subjected to sublimation under negative pressure (0.4 mmHg): 99.56g of white crystal hexachlorocyclotriphosphazene is obtained at the temperature of 70 ℃, and the yield is 86.01%; sublimating at 100 ℃ to obtain 13.90g of white crystal octachlorocyclotetraphosphazene with the yield of 11.6 percent; still residue pentamer and higher poly (vinyl chloride)Cyclophosphazene mixture 2.08g, yield: 1.8 percent; the phosphorus pentachloride conversion was 99.41%. Phosphonitrilic chloride trimer PNMR (CDCl) 3 ): 19.99,3P; octachlorocyclotetraphosphazene PNMR (CDCl) 3 )：-6.45，4P。
Example 2
The embodiment provides a preparation method of chlorocyclophosphazene, which comprises the following specific steps:
step S1: under the protection of nitrogen, 400mL of normal hexane and 208g of phosphorus pentachloride (1 mol) are sequentially added into a reaction device, 34.09g of lithium nitride (0.98 mol) tetrahydrofuran solution (400 mL) is slowly added in batches at the temperature of 0-5 ℃, and the reaction liquid is changed from light green turbid liquid to light yellow turbid liquid; reacting at the temperature of minus 30 ℃ for 4 hours, filtering a by-product lithium chloride (with the purity of 99 percent and capable of being directly dried and recovered for market sale) after the reaction is finished, and distilling the filtrate at normal pressure to recover tetrahydrofuran to obtain a hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, pentamer and higher polychlorocyclophosphazene mixture; the recovered tetrahydrofuran is dried and recycled by using anhydrous magnesium sulfate.
Step S2: the resulting polychlorocyclotriphosphazene mixture of hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, pentamer or higher is subjected to sublimation under negative pressure (0.4 mmHg): 102.55g white crystal hexachlorocyclotriphosphazene is obtained at 70 ℃, the yield is 88.6%; sublimating at 100 ℃ to obtain 10.45g of white crystal octachlorocyclotetraphosphazene with the yield of 9 percent; 1.85g of the mixture of still residue pentamer and higher polychlorocyclophosphazene, yield: 1.6 percent; the phosphorus pentachloride conversion was 99.2%.
Example 3
The embodiment provides a preparation method of chlorocyclophosphazene, which comprises the following specific steps:
step S1: under the protection of nitrogen, 400mL of tetrahydrofuran and 208g of phosphorus pentachloride (1 mol) are sequentially added into a reaction device, 36.53g of lithium nitride (1.05 mol) tetrahydrofuran solution (400 mL) is slowly added in batches at the temperature of 0-5 ℃, and the reaction liquid is changed from light green turbid liquid to light yellow turbid liquid; reacting at 5 ℃ for 1h, filtering after the reaction is finished, and distilling the filtrate at normal pressure to recover tetrahydrofuran to obtain a mixture of hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, pentamer and higher polychlorocyclophosphazene; the recovered tetrahydrofuran is dried and recycled by using anhydrous magnesium sulfate.
Step S2: the resulting polychlorocyclotriphosphazene mixture of hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, pentamer or higher is subjected to sublimation under negative pressure (0.4 mmHg): 97.01g white crystal hexachlorocyclotriphosphazene is obtained under the temperature of 70 ℃, and the yield is 83.81%; sublimating at 100 ℃ to obtain 9.47g of white crystal octachlorocyclotetraphosphazene with the yield of 8.18 percent; 7.98g of a mixture of still residue pentamer and higher polychlorocyclophosphazene, yield: 7.78 percent; the phosphorus pentachloride conversion was 99.77%.
Example 4
This example provides a method for preparing chlorocyclophosphazene, which is the same as in example 1 except that tetrahydrofuran is replaced with n-hexane of the same volume.
96.71g of white crystal hexachlorocyclotriphosphazene is finally obtained, and the yield is 83.55 percent; 10.45g of white crystalline octachlorocyclotetraphosphazene, yield 9.03%; 7.98g of a mixture of still residue pentamer and higher polychlorocyclophosphazene, yield: 6.91 percent; the phosphorus pentachloride conversion was 99.49%.
Example 5
This example provides a method for preparing chlorocyclophosphazene, which is the same as example 1 except that tetrahydrofuran is replaced with equal volume of cyclohexane.
97.39g white crystal hexachlorocyclotriphosphazene is finally obtained, the yield is 84.14%;9.80g of white crystalline octachlorocyclotetraphosphazene, yield 8.47%; still residue pentamer and higher polychlorocyclophosphazene mixture 7.66g, yield: 6.62 percent; the phosphorus pentachloride conversion was 99.23%.
Example 6
This example provides a method for preparing chlorocyclophosphazene, which is the same as example 1 except that tetrahydrofuran is replaced by a mixed solution of tetrahydrofuran and cyclohexane (the volume ratio is 1:1) with the same volume.
104.2g of white crystal hexachlorocyclotriphosphazene is finally obtained, and the yield is 90.02%;9.39g of white crystalline octachlorocyclotetraphosphazene, yield 8.11%; 1.83g of a mixture of still residue pentamer and higher polychlorocyclophosphazene, yield: 1.58 percent; the phosphorus pentachloride conversion was 99.71%.
Example 7
The embodiment provides a preparation method of chlorocyclophosphazene, which comprises the following specific steps:
step S1: under the protection of nitrogen, 400mL of tetrahydrofuran, 400mL of n-hexane and 208g of phosphorus pentachloride (1 mol) are sequentially added into a reaction device, 38.27g of lithium nitride (1.1 mol) are slowly added in batches within the range of 0-5 ℃, and the reaction liquid is converted into light yellow turbid liquid from light green turbid liquid; reacting at 0 ℃ for 2h, filtering a by-product lithium chloride (with the purity of 99 percent and capable of being directly dried and recovered for market sale) after the reaction is finished, and distilling the filtrate at normal pressure to recover tetrahydrofuran to obtain a hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, pentamer and higher polychlorocyclophosphazene mixture; the recovered tetrahydrofuran is dried and recycled by using anhydrous magnesium sulfate.
Step S2: the resulting polychlorocyclotriphosphazene mixture of hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, pentamer and higher is sublimed at negative pressure (0.4 mmHg): 74.12g white crystal hexachlorocyclotriphosphazene is obtained under the temperature of 70 ℃, and the yield is 64.03%; sublimating at 100 ℃ to obtain 5.91g of white crystal octachlorocyclotetraphosphazene with the yield of 5.11 percent; kettle residue pentamer and higher polychlorocyclophosphazene mixture 35.34g, yield: 30.53 percent; the phosphorus pentachloride conversion was 99.67%.
Comparative example 1
The comparative example provides a preparation method of chlorocyclophosphazene (refer to US2018/155376A 1), which comprises the following specific steps:
40L of monochlorobenzene, 790g of ammonium chloride and 2.5g of zinc chloride were placed in a 100L flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel to obtain a mixture dispersion. A solution of 2.9kg of phosphorus pentachloride in 10L of chlorobenzene was added dropwise over a period of 20 hours. After addition of phosphorus pentachloride, the mixture was heated at reflux for 20 hours. Subsequently, unreacted ammonium chloride was removed by suction filtration, and chlorobenzene was evaporated from the filtrate under a reduced pressure of 13.3 to 40hPa at 30 to 40 ℃ to give 1460g of chlorocyclophosphane (hexachlorocyclotriphosphazene: 70%, octachlorocyclotetraphosphazene: 19%, pentamer and higher chlorocyclophosphazene: 11%) (yield 90%).
According to the content, the preparation method provided by the invention can be used for efficiently and cleanly synthesizing and preparing chlorocyclophosphazene; comparing example 1 with examples 4-6, it can be seen that the present invention can further improve the conversion of phosphorus pentachloride by selecting a specific combination of solvents; comparing examples 1 and 7, the invention can obviously improve the yield of target products of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene by strictly controlling the proportion of the raw materials; comparing example 1 with comparative example 1, it can be found that the preparation method provided by the invention avoids the generation of harmful gases such as hydrogen chloride and the like, is environment-friendly, and meanwhile, the by-products generated by the reaction can be directly recovered and sold on the market, the loss of raw materials is less, and reactants such as other raw materials and catalysts do not need to be added, thereby reducing the requirements for chemical varieties and reducing the cost, and the preparation method has the advantages of mild reaction conditions, short reaction time and low energy consumption.
The applicant states that the present invention is illustrated by the above examples of the preparation of chlorocyclophosphazene according to the invention, but the present invention is not limited to the above examples, i.e. it is not intended that the invention must be carried out by means of the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. A preparation method of chlorocyclophosphazene is characterized by comprising the following steps:
mixing and reacting lithium nitride and phosphorus pentachloride, and then carrying out post-treatment to obtain chlorocyclophosphazene;
the chlorocyclophosphazene comprises hexachlorocyclotriphosphazene and/or octachlorocyclotetraphosphazene.
2. The preparation method according to claim 1, wherein the molar ratio of the lithium nitride to the phosphorus pentachloride is (0.98-1.05): 1.
3. The method according to claim 1 or 2, wherein the reaction temperature is-30 to 5 ℃.
4. The method according to any one of claims 1 to 3, wherein the reaction time is 1 to 4 hours.
5. The production method according to any one of claims 1 to 4, wherein the reaction is carried out in a solvent.
6. The method according to claim 5, wherein the solvent comprises one or a combination of at least two of tetrahydrofuran, n-hexane, and cyclohexane, preferably a combination of tetrahydrofuran and n-hexane.
7. Preparation method according to any one of claims 1 to 6, characterized in that the post-treatment comprises the following steps: and filtering and desolventizing the reactant, and heating and subliming the obtained mixture under negative pressure to obtain the chlorocyclophosphazene.
8. The method of claim 7, wherein the negative pressure is in the range of 0.3 to 0.5mm Hg.
9. The method according to claim 7 or 8, wherein the chlorocyclophosphazene obtained by sublimation is hexachlorocyclotriphosphazene when heated to 68-72 ℃.
10. The method of any one of claims 7-9, wherein the chlorocyclophosphazene sublimed when heated to 98-102 ℃ is octachlorocyclotetraphosphazene.
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