CN115181126B - Method for synthesizing tri (1-chloro-2-propyl) phosphate by continuous flow - Google Patents

Method for synthesizing tri (1-chloro-2-propyl) phosphate by continuous flow Download PDF

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CN115181126B
CN115181126B CN202210825010.3A CN202210825010A CN115181126B CN 115181126 B CN115181126 B CN 115181126B CN 202210825010 A CN202210825010 A CN 202210825010A CN 115181126 B CN115181126 B CN 115181126B
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continuous flow
reactor
catalyst
phosphorus oxychloride
propylene oxide
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CN115181126A (en
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王勇
胡新利
李廉洁
刘斌
刘航
任树勇
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Suqian Shengrui New Material Co ltd
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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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl

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  • Organic Chemistry (AREA)
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Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing tri (1-chloro-2-propyl) phosphate by continuous flow, which takes phosphorus oxychloride as a raw material, and performs esterification reaction with propylene oxide in a continuous flow reactor under the catalysis effect to prepare a flame retardant tri (1-chloro-2-propyl) phosphate; wherein, the yield of the target product reaches more than 98 percent, and the purity reaches more than 99 percent; the invention provides a method for synthesizing tri (1-chloro-2-propyl) phosphate by continuous flow, which is simple and convenient to operate and has good process safety.

Description

Method for synthesizing tri (1-chloro-2-propyl) phosphate by continuous flow
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing tri (1-chloro-2-propyl) phosphate by continuous flow.
Background
The tri (1-chloro-2-propyl) phosphate (TCPP) is a common low molecular weight phosphorus-chlorine flame retardant, the tri (1-chloro-2-propyl) phosphate is colorless to yellowish oily liquid, is dissolved in benzene, alcohol, carbon tetrachloride and other organic solvents, is insoluble in water and aliphatic hydrocarbon, has a relative density of 1.27-1.31, a refractive index of 1.4916 (21.5), a viscosity of 58mm 2/S, a chlorine content of 32.8%, a phosphorus content of 9.5%, and remarkable flame retardant performance, and has the functions of plasticization, moisture resistance, static resistance and the like, and is mainly used for flame retardance of polyvinyl chloride, polystyrene, phenolic resin, propylene resin, rubber and paint.
In the prior art, a method for synthesizing tri (1-chloro-2-propyl) phosphate is reported more, wherein in the traditional process, phosphorus oxychloride and propylene oxide are subjected to esterification reaction at 50-80 ℃ in the presence of a Lewis acid catalyst to obtain a TCPP crude product. And (3) washing the crude product with alkali, separating liquid, washing with water to neutrality, separating liquid, and dehydrating to obtain a TCPP finished product. The method can produce a large amount of wastewater in alkaline washing and water washing treatment, and the product has higher aldehyde compound content and higher smell. (refer to Wang Qiuwei. Lv Yunxing. Wang Fubing. Wang Mimi. Research progress of the flame retardant of the warred and the chlorophosphate [ J ] chemical management 2020 (2): 110) the technology reported by Chinese patent CN 112209964A with Lewis acid as a catalyst has large odor, and odor removal by two-stage distillation is needed, so that a large amount of energy sources are used; the process reported in chinese patent CN110294773a also produces a strong odor, which is removed by using a strong oxidizer.
Disclosure of Invention
In order to solve the problems, the invention discloses a continuous flow method which is simple to operate, green and environment-friendly, and improves the production efficiency.
In order to achieve the above purpose, the present invention provides the following technical solutions:
A method for preparing tri (1-chloro-2-propyl) phosphate, comprising the following steps: uniformly mixing a catalyst and phosphorus oxychloride, preheating to 40-70 ℃, replacing the continuous flow reactor with nitrogen for three times, conveying the phosphorus oxychloride and the catalyst to the continuous flow reactor through a feed pump, and simultaneously conveying propylene oxide to the continuous flow reactor through another feed pump to react to obtain the tri (1-chloro-2-propyl) phosphate. And (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product.
Further, the supported catalyst is Al [ PW 12O40]/Al2O3 ].
Further, the particle size of the supported catalyst is 40-60 microns.
Further, the mass of the catalyst is 1 to 3 percent of the total mass of phosphorus oxychloride and propylene oxide
Further, the molar ratio of phosphorus oxychloride to propylene oxide is 1:1-1.3.
Further, the preheating temperature of the phosphorus oxychloride and the catalyst is 40-70 ℃ and the preheating time is 10-30min.
Further, the temperature of the reaction is 50-80 ℃, and the pressure of the reaction is 0-1.0Mpa.
Further, the material residence time of the reaction is 10-30min.
Compared with the prior art, the invention has the following advantages and beneficial effects:
The preparation method of the tri (1-chloro-2-propyl) phosphate provided by the invention has the advantages that (1) the post-treatment of the reaction solution is simple, and the catalyst can be used for multiple times; the solvent used for the post-treatment can also be used for multiple times. And (2) the reaction speed is greatly improved, and the production efficiency is improved. And (3) the product has low odor, high product yield and good quality.
Drawings
FIG. 1 is a gas chromatograph of the product of example 1.
Detailed Description
The present invention is further illustrated in the following drawings and detailed description, which are to be understood as being merely illustrative of the invention and not limiting the scope of the invention.
The particle size of the catalyst Al [ PW 12O40]/Al2O3 ] used in the following embodiments is 40-60 μm.
Example 1:
Mixing 250g phosphorus oxychloride with 6.9g catalyst (Al [ PW 12O40]/Al2O3 ] to 60 ℃, replacing nitrogen in a continuous flow reactor for three times, maintaining the internal pressure of the reactor at 0.5Mpa, then conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, introducing 104.17g propylene oxide into the other pipeline, reacting at 70 ℃, taking care of maintaining the pressure in the reactor at 0.5Mpa, and keeping the residence time for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in tables 1,3 and FIG. 1.
Example 2:
Mixing 250g phosphorus oxychloride with 10.65g catalyst (Al [ PW 12O40]/Al2O3 ] to 60 ℃, replacing nitrogen in a continuous flow reactor for three times, maintaining the internal pressure of the reactor at 0.5Mpa, then conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, introducing 104.17g propylene oxide into the other pipeline, reacting at 70 ℃, taking care of maintaining the pressure in the reactor at 0.5Mpa, and keeping the residence time for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Example 3:
Mixing 250g phosphorus oxychloride with 3.55g catalyst (Al [ PW 12O40]/Al2O3 ] to 60 ℃, replacing nitrogen in a continuous flow reactor for three times, maintaining the internal pressure of the reactor at 0.5Mpa, then conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, introducing 104.17g propylene oxide into the other pipeline, reacting at 70 ℃, taking care of maintaining the pressure in the reactor at 0.5Mpa, and keeping the residence time for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Example 4:
Mixing 250g phosphorus oxychloride with 6.9g catalyst (Al [ PW 12O40]/Al2O3 ] to 60 ℃, replacing nitrogen in a continuous flow reactor for three times, maintaining the internal pressure of the reactor at 0.5Mpa, then conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, introducing 94.7g propylene oxide into the other pipeline, reacting at 70 ℃, taking care of maintaining the pressure in the reactor at 0.5Mpa, and keeping the residence time for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Example 5:
Mixing 250g phosphorus oxychloride with 6.9g catalyst (Al [ PW 12O40]/Al2O3 ] to 60 ℃, replacing nitrogen in a continuous flow reactor for three times, maintaining the internal pressure of the reactor at 0.5Mpa, then conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, simultaneously introducing 123.11g propylene oxide into another pipeline, reacting at 70 ℃, taking care of maintaining the pressure in the reactor at 0.5Mpa, and keeping the residence time for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Example 6:
Mixing 250g phosphorus oxychloride with 6.9g catalyst (Al [ PW 12O40]/Al2O3 ] to 40 ℃, replacing nitrogen in a continuous flow reactor for three times, maintaining the internal pressure of the reactor at 0.5Mpa, then conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, introducing 104.17g propylene oxide into the other pipeline at the same time, reacting at 50 ℃, taking care of maintaining the pressure in the reactor at 0.5Mpa, and keeping the residence time for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Example 7:
mixing 250g phosphorus oxychloride with 6.9g catalyst (Al [ PW 12O40]/Al2O3 ] to 50 ℃, replacing nitrogen in a continuous flow reactor for three times, maintaining the internal pressure of the reactor at 0.5Mpa, then conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, introducing 104.17g propylene oxide into the other pipeline, reacting at 60 ℃, taking care of maintaining the pressure in the reactor at 0.5Mpa, and keeping the residence time for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Example 8:
Mixing 250g phosphorus oxychloride with 6.9g catalyst (Al [ PW 12O40]/Al2O3 ] to 70 deg.C, displacing nitrogen in continuous flow reactor for three times, maintaining internal pressure of reactor at 0.5Mpa, pumping the mixture of phosphorus oxychloride and catalyst to reactor, introducing 104.17g propylene oxide into another pipeline, reacting at 80 deg.C, keeping pressure in reactor at 0.5Mpa, and keeping for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Example 9:
Mixing 250g phosphorus oxychloride with 6.9g catalyst (Al [ PW 12O40]/Al2O3 ] to 60 ℃, replacing nitrogen in a continuous flow reactor for three times, maintaining the internal pressure of the reactor at 0.5Mpa, then conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, introducing 104.17g propylene oxide into the other pipeline, reacting at 70 ℃, taking care of maintaining the pressure in the reactor at 0.5Mpa, and keeping the residence time for 10min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Example 10:
Mixing 250g phosphorus oxychloride with 6.9g catalyst (Al [ PW 12O40]/Al2O3 ] to 60 ℃, replacing nitrogen in a continuous flow reactor for three times, maintaining the internal pressure of the reactor at 0.5Mpa, then conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, introducing 104.17g propylene oxide into the other pipeline, reacting at 70 ℃, taking care of maintaining the pressure in the reactor at 0.5Mpa, and keeping the residence time for 30min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Example 11:
Mixing 250g phosphorus oxychloride with 6.9g catalyst (Al [ PW 12O40]/Al2O3 ]) and preheating to 60 ℃, displacing nitrogen in the continuous flow reactor for three times, keeping the internal normal pressure of the reactor, then conveying the mixture of phosphorus oxychloride and catalyst to the reactor through a pump, simultaneously introducing 104.17g propylene oxide into another pipeline, reacting at 70 ℃, keeping the internal normal pressure of the reactor, and keeping the residence time for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Example 12:
Mixing 250g phosphorus oxychloride with 6.9g catalyst (Al [ PW 12O40]/Al2O3 ] to 60 ℃, replacing nitrogen in a continuous flow reactor for three times, maintaining the internal pressure of the reactor at 1.0Mpa, then conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, introducing 104.17g propylene oxide into the other pipeline, reacting at 70 ℃, taking care of maintaining the pressure in the reactor at 1.0Mpa, and keeping the residence time for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Comparative example 1:
Mixing 250g of phosphorus oxychloride with 6.9g of catalyst (AlCl 3), preheating to 60 ℃, replacing nitrogen in a continuous flow reactor for three times, keeping the internal pressure of the reactor at 0.5Mpa, conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, introducing 104.17g of propylene oxide into another pipeline, reacting at 70 ℃, and keeping the pressure in the reactor at 0.5Mpa for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Comparative example 2:
Mixing 250g of phosphorus oxychloride with 6.9g of catalyst (AlCl 3/SiO2), preheating to 60 ℃, replacing nitrogen in a continuous flow reactor for three times, keeping the internal pressure of the reactor at 0.5Mpa, conveying the mixture of phosphorus oxychloride and the catalyst to the reactor through a pump, introducing 104.17g of propylene oxide into another pipeline, reacting at 70 ℃, and keeping the pressure in the reactor at 0.5Mpa for 20min; and (3) evaporating excessive propylene oxide after the reaction is finished, and then performing alkali washing, water washing and dehydration to obtain a low-odor product. The results and yields are shown in Table 1.
Table 1: detection result and product yield
And (3) the catalyst is used mechanically:
The catalyst was used 5 times in comparison with example 1, and the results and yields are shown in Table 2.
Table 2: catalyst sleeve
By data comparison, the catalytic effect of the supported catalyst Al [ PW 12O40]/Al2O3 ] is better than that of the catalysts AlCl 3 and AlCl 3/SiO2 commonly used in the prior art, and the process can be industrially amplified, so that the odor can be effectively reduced, the product yield is high, the quality is good, the pressure in the reactor is more than or equal to 0.5Mpa, propylene oxide is in a liquid state, the reaction rate can be accelerated, and the production efficiency is improved; wherein the catalyst can be repeatedly used for 5 times, the product yield of the sixth time is obviously reduced, and the alkali washing and water washing wastewater in the post-treatment can be repeatedly used. Comparative example 1 is the use of AlCl 3 catalyst in the present process and comparative example 2 is the use of AlCl 3/SiO2 catalyst in the present process.
The product of the example 1 is subjected to TCPP gas chromatography, the spectrogram is shown in figure 1, and the data of each product peak of the TCPP gas chromatography of the product of the example 1 is shown in table 3.
Table 3: EXAMPLE 1 product TCPP gas chromatography data for each product peak
It should be noted that the foregoing merely illustrates the technical idea of the present invention and is not intended to limit the scope of the present invention, and that a person skilled in the art may make several improvements and modifications without departing from the principles of the present invention, which fall within the scope of the claims of the present invention.

Claims (2)

1. A method for continuous flow synthesis of tris (1-chloro-2-propyl) phosphate, comprising the steps of: uniformly mixing and preheating a supported catalyst and phosphorus oxychloride, replacing a continuous flow reactor with nitrogen for three times, conveying the phosphorus oxychloride and the catalyst to the continuous flow reactor through a feed pump, and simultaneously conveying propylene oxide to the continuous flow reactor through another feed pump to react to obtain tri (1-chloro-2-propyl) phosphate;
the mass of the catalyst is 1% -3% of the total mass of phosphorus oxychloride and propylene oxide;
the mol ratio of the phosphorus oxychloride to the propylene oxide is 1:1-1.3;
The supported catalyst is Al [ PW 12O40]/Al2O3 ];
the preheating temperature is 40-70 ℃;
The reaction temperature is 50-80 ℃, and the reaction pressure is 0-1.0Mpa;
The reaction time is 10-30min.
2. The method for continuous flow synthesis of tris (1-chloro-2-propyl) phosphate according to claim 1, wherein the supported catalyst has a particle size of 40-60 microns.
CN202210825010.3A 2022-07-14 2022-07-14 Method for synthesizing tri (1-chloro-2-propyl) phosphate by continuous flow Active CN115181126B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1660494A (en) * 2004-12-18 2005-08-31 浙江工业大学 Catalyst of aluminium phosphotungstic acid, preparation method and application
CN101235050A (en) * 2007-02-02 2008-08-06 朗盛德国有限责任公司 Production of propoxylated products containing phosphorous through use of aluminium trichloride
CN111153934A (en) * 2020-01-10 2020-05-15 江苏雅克科技股份有限公司 Method for synthesizing tri- (2-chloroisopropyl) phosphate by solid catalysis
CN112028927A (en) * 2020-09-09 2020-12-04 扬州晨化新材料股份有限公司 Continuous preparation process of phosphate flame retardant based on microchannel reactor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1660494A (en) * 2004-12-18 2005-08-31 浙江工业大学 Catalyst of aluminium phosphotungstic acid, preparation method and application
CN101235050A (en) * 2007-02-02 2008-08-06 朗盛德国有限责任公司 Production of propoxylated products containing phosphorous through use of aluminium trichloride
CN111153934A (en) * 2020-01-10 2020-05-15 江苏雅克科技股份有限公司 Method for synthesizing tri- (2-chloroisopropyl) phosphate by solid catalysis
CN112028927A (en) * 2020-09-09 2020-12-04 扬州晨化新材料股份有限公司 Continuous preparation process of phosphate flame retardant based on microchannel reactor

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