CN115364896B - Catalyst for synthesizing dialkyl alkylphosphonate, and preparation method and application thereof - Google Patents

Catalyst for synthesizing dialkyl alkylphosphonate, and preparation method and application thereof Download PDF

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CN115364896B
CN115364896B CN202110545465.5A CN202110545465A CN115364896B CN 115364896 B CN115364896 B CN 115364896B CN 202110545465 A CN202110545465 A CN 202110545465A CN 115364896 B CN115364896 B CN 115364896B
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catalyst
reaction
sulfonyl chloride
hours
drying
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CN115364896A (en
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李骏
刘国亮
何文军
戈军伟
王小飞
张道明
薛浩亮
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a catalyst for synthesizing dialkyl alkylphosphonate, a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: in the presence of an alkaline catalyst, the sulfonyl chloride polystyrene resin is contacted with alcohols for reaction, and the obtained product is subjected to first drying to obtain the catalyst. The catalyst is simple to prepare, and has high conversion rate of reactants and good selectivity of products and better stability in the reaction of catalyzing the isomerization of trialkyl phosphonite into dialkyl alkylphosphonite. But also solves the problem that the catalyst is difficult to separate from the product when methyl iodide or methyl paratoluenesulfonate is used as a liquid phase catalyst in the prior art.

Description

Catalyst for synthesizing dialkyl alkylphosphonate, and preparation method and application thereof
Technical Field
The invention relates to a catalyst for synthesizing dialkyl alkylphosphonate, a preparation method thereof and application of the catalyst in synthesizing dialkyl alkylphosphonate by isomerization reaction of trialkyl phosphonite.
Background
Dialkyl alkylphosphonate is an additive type organic phosphorus flame retardant, has the advantages of high phosphorus content, excellent flame retardant property, low price, small addition amount and the like, has been widely used as a flame retardant additive in high polymer materials such as epoxy resin, polyurethane foam plastic, unsaturated polyester resin and the like, and has been widely studied in recent years as a flame retardant additive for lithium battery electrolyte. Compared with the traditional halogen flame retardant and inorganic flame retardant, the dialkyl alkyl phosphonate has the advantages of environmental protection, self-extinguishing property, plasticity, low temperature resistance, ultraviolet resistance, antistatic property and the like, is especially suitable for transparent or light and graceful color products and spray coating, and is considered to be a new generation of high-efficiency flame retardant.
At present, the process route of a homogeneous catalyst is mainly adopted for producing alkyl phosphonic acid dialkyl ester by the isomerization reaction of trialkyl phosphite, and the reaction route is as follows:
in early research, iodine (CN 103102369A) or methyl iodide (CN 101624402A) is used as a catalyst for reaction at normal pressure, the conversion rate is high, but the iodine or methyl iodide has certain toxicity, low boiling point, instability, incapability of recycling and high cost, so that the industrial application of the iodine or methyl iodide is greatly limited. CN103073581A adopts benzonitrile compound as catalyst to make reaction under alkaline condition, but the reaction pressure is higher than 1.2MPa, and the yield is lower. CN102702256a discloses an environment-friendly catalyst methyl p-toluenesulfonate to catalyze trimethyl phosphonite to produce dimethyl methylphosphonate, but the catalyst has the problems of harsh reaction conditions, low production efficiency and the like when used in the mass fraction of 7% -10%, the reaction temperature of 180-200 ℃ and the reaction time of 9-13 hours.
At present, a homogeneous catalyst is adopted for synthesizing dialkyl alkylphosphonate, and the product and the catalyst are difficult to separate by blending. Therefore, the development of the novel heterogeneous catalyst can effectively reduce the separation difficulty of the product and the catalyst, improve the production efficiency and reduce the production cost.
Disclosure of Invention
The invention aims to solve the technical problem that a dialkyl alkyl phosphonate product and a catalyst are difficult to separate in the synthesis of the dialkyl alkyl phosphonate in the prior art, and provides a catalyst for synthesizing dialkyl alkyl phosphonate, a preparation method thereof and application thereof in synthesizing dialkyl alkyl phosphonate by isomerization reaction of trialkyl phosphonite. The catalyst not only can solve the problem that the product and the catalyst are difficult to separate caused by the existing homogeneous catalyst, but also has the characteristics of good activity and selectivity.
The first aspect of the invention provides a catalyst for synthesizing dialkyl alkylphosphonate, which has the following structural general formula:
wherein,the polystyrene resin is a polystyrene resin, and R is an alkyl group, preferably selected from methyl or ethyl, and more preferably methyl.
In the technical scheme, in the catalyst,the content of (C) is 0.6-1.8mmol/g catalyst, preferably 1.2-1.8mmol/g catalyst.
In a second aspect, the present invention provides a method for preparing a catalyst for synthesizing a dialkyl alkylphosphonate, comprising:
in the presence of an alkaline catalyst, the sulfonyl chloride polystyrene resin is contacted with alcohols for reaction, and the obtained product is subjected to first drying to obtain the catalyst.
In the above technical scheme, the alkaline catalyst is at least one selected from potassium carbonate or potassium hydroxide, preferably potassium carbonate.
In the above technical solution, the alcohol is preferably at least one of methanol and ethanol, and preferably methanol.
In the technical scheme, the particle size of the sulfonyl chloride polystyrene resin is 100-200 meshes, and the content of sulfonyl chloride groups bonded on the benzene ring is 1.5-2.0mmol/g of resin. The sulfonyl chloride polystyrene resin may be prepared by conventional methods, such as preparing a polystyrene resin and then bonding sulfonyl chloride groups to the polystyrene resin. The polystyrene resin is polymerized by styrene monomer.
In the technical scheme, in the reaction system, raw materials comprise sulfonyl chloride polystyrene resin, water and alcohols, wherein the mass ratio of the sulfonyl chloride polystyrene resin to the alkaline catalyst to the water to the alcohols is 1:1.2-1.8:3-5:4-7. The reaction conditions were as follows: the reaction temperature is 30-50 ℃ and the reaction time is 10-14h. The water is preferably deionized water, and the methanol is preferably anhydrous methanol.
In the above technical solution, the first drying preferably adopts vacuum drying under the following conditions: the drying temperature is 90-130 ℃ and the drying time is 1-3h. Wherein, the vacuum degree can be-0.1 MPa to-0.08 MPa.
In the above technical solution, preferably, the obtained first dried product is subjected to heat treatment by a mixed solution of water and methanol, and then is subjected to second drying, so as to obtain the catalyst, wherein the conditions of the heat treatment by the mixed solution of water and methanol are as follows: the mass ratio of the first dry matter to the water to the methanol is 1:3-5:4-10, the treatment temperature is 70-80 ℃ and the treatment time is 4-5h. Preferably, a reflow heat treatment is employed.
In the above technical solution, the second drying preferably adopts vacuum drying under the following conditions: the drying temperature is 90-130 ℃, and the drying time is 4-5h. Wherein, the vacuum degree can be-0.1 MPa to-0.08 MPa.
In the above-described embodiments, the first washing is preferably performed before the first drying, and the second washing is preferably performed before the second drying. The first washing can be sequentially and respectively carried out for 2-5 times by adopting deionized water and 2-5 times by adopting methanol, and the second washing can be carried out for 2-5 times by adopting absolute ethyl alcohol.
In the above technical scheme, the preparation method of the catalyst preferably adopts the following specific processes: dissolving an alkaline catalyst in water, adding sulfonyl chloride polystyrene resin, adding absolute alcohol (such as absolute methanol and/or absolute ethanol), reacting for 10-14h at 30-50 ℃, performing first washing, first filtering, first drying to obtain a first dried substance, performing heat treatment on the first dried substance by using a mixed solution of water and methanol, performing second washing, second filtering and second drying to obtain the catalyst. The first washing can be sequentially and respectively performed by deionized water and methanol, and the second washing can be performed by absolute ethyl alcohol. The first and second filtration may be performed using conventional filtration methods, such as suction filtration.
In a third aspect, the present invention provides a method of synthesizing a dialkyl alkylphosphonate comprising: the trialkyl phosphonite is used as a raw material, and is contacted with the catalyst to react to obtain dialkyl alkylphosphonite.
In the above technical solution, preferably, the trialkyl phosphite includes at least one of trimethyl phosphite and triethyl triphosphate, and the product dialkyl alkylphosphonate includes at least one of dimethyl methylphosphonate and diethyl ethylphosphonate.
In the above technical scheme, the reaction adopts batch operation, and the reaction conditions include: the reaction temperature is 130-180 ℃, preferably 150-180 ℃, the catalyst dosage is 1-5% of the mass of the raw materials, preferably 3-5%, and the reaction time is 6-20 hours, preferably 8-12 hours.
In the technical scheme, the reaction product is filtered simply to obtain the product alkyl phosphonic acid dialkyl ester, and the catalyst obtained after the filtering can be reused.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalyst is a novel heterogeneous catalyst, solves the problem that products and the catalyst are difficult to separate caused by the homogeneous catalyst in the prior art, and has the characteristics of good activity and selectivity when the catalyst is used for synthesizing dialkyl alkylphosphonate through trialkyl phosphonite isomerization reaction.
2. The preparation method of the catalyst of the invention utilizes sulfonyl chloride active groups on sulfonyl chloride polystyrene resin to react with methanol, and the obtained catalyst not only has a methyl benzenesulfonate structure, but also can be matched with polystyrene resin body, thereby promoting the improvement of the activity and selectivity of the catalyst. In particular to a catalyst after heat treatment of water and methanol mixed solution, which can further improve the activity of the catalyst.
3. When the catalyst is used for synthesizing alkyl phosphonic acid dialkyl ester through the phosphonic acid trialkyl ester isomerization reaction, the conversion rate of reactants is high, the selectivity of products is good, the stability of the catalyst is good, the activity and the selectivity of the catalyst are kept good after the recovered catalyst is subjected to three catalytic cycles, the process flow is simplified, and the production efficiency is improved.
Drawings
FIG. 1 is an infrared spectrum (upper curve) of a sulfonyl chloride polystyrene resin raw material used in example 1 and an infrared spectrum (lower curve) of the obtained catalyst;
FIG. 2 is a thermogravimetric analysis of the catalyst obtained in example 1;
FIG. 3 is a gas chromatogram of the product after reaction using the catalyst of example 1; wherein DMMP is dimethyl methylphosphonate;
FIG. 4 is a gas chromatograph of a product of a reaction using the catalyst of example 1; wherein each substance is described as follows: a represents methyl chloride; b represents dimethyl pentene; c represents dimethyl phosphite; d represents dimethyl methylphosphonate; e represents trimethyl phosphate.
Detailed Description
The invention will now be further illustrated by the following examples, without limiting the scope of the invention.
In the invention, the instrument used in the infrared absorption spectrum is VERTEX70 of Bruker, and the wave number range is: 1000cm -1 -4000cm -1 。
In the invention, the instrument used in the thermogravimetric analysis is a relaxation-resistant STA2500, the test condition is that under the nitrogen atmosphere, the temperature programming condition is that the temperature is increased from 30 ℃ to 600 ℃ at the temperature increasing rate of 20 ℃ per minute.
In the invention, an instrument used for a product gas chromatogram is SP6890 of Shandong Runan Rainbow chemical industry instruments, carrier gas is nitrogen, a FID detector is adopted, the temperature programming condition is 50 ℃, the temperature is raised to 250 ℃ at the temperature raising rate of 20 ℃ per minute, and the temperature is kept for 3min.
In the invention, an instrument used for the gas chromatography is 450GC-320MS of Varian company.
[ example 1 ]
1.5g of anhydrous potassium carbonate is added into 4mL of deionized water for dissolution, 7mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein, the content of sulfonyl chloride groups is about 1.8mmol/g of resin) are added, the mixture is reacted for 12 hours at 30 ℃, then the mixture is washed three times by using deionized water and anhydrous methanol respectively, and dried for 1 hour in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa), the dried modified resin is taken and heated and refluxed for 4 hours in 4mL of deionized water and 7mL of methanol solution at 75 ℃, then the mixture is washed three times by using absolute ethyl alcohol, and the mixture is dried in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 5 hours, so that the novel heterogeneous catalyst is obtained. The catalyst contained about 1.5mmol/g methyl benzenesulfonate.
0.4g of the catalyst was taken and added to a sealed tube containing 8mL of trimethyl phosphite, and reacted in an oil bath at 160℃for 14 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 100% and the molar selectivity of the product methyl dimethyl phosphonate is 96.43% through gas chromatography detection.
The infrared spectrum of the sulfonyl chloride polystyrene resin raw material (upper curve) and the infrared spectrum of the catalyst obtained in example 1 (lower curve) are shown in FIG. 1, wherein, at 1090cm -1 There is an infrared absorption peak, which is a C-O stretching vibration absorption peak.
The thermogravimetric analysis of the catalyst obtained in example 1 is shown in figure 2, and it can be seen from figure 2 that it has good thermal stability below 180 ℃.
The chromatogram of the product after the reaction is shown in FIG. 3. Quantitative analysis is carried out by adopting an internal standard method, ethylbenzene is used as an internal standard substance, methanol is used as a solvent, and the single-point method is used for detecting unreacted and complete trimethyl phosphite, and the internal standard substance and an object to be detected 1:1, detecting the dimethyl methylphosphonate by an internal standard curve method. The retention time is 1.44min for methanol, 3.16min for ethylbenzene, 3.49min for byproduct dimethyl phosphite, 4.16min for main product dimethyl methylphosphonate, and 4.63min for byproduct trimethyl phosphate.
The gas chromatography-mass spectrometry chromatogram of the product after the reaction is shown in figure 4. As can be seen from FIG. 4, trimethyl phosphite can be converted into dimethyl methylphosphonate as a target product with high selectivity by using the catalyst of the invention.
[ example 2 ]
1.5g of anhydrous potassium carbonate is added into 3mL of deionized water for dissolution, then 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein, the content of sulfonyl chloride groups is about 1.8mmol/g of resin) are added, the mixture is reacted for 12 hours at 30 ℃, then the mixture is washed three times by using deionized water and anhydrous methanol respectively, and dried for 1 hour in a vacuum drying oven (the vacuum degree is about-0.1 MPa) at 110 ℃, the dried modified resin is taken and heated and refluxed for 4 hours in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then the mixture is washed three times by using absolute ethyl alcohol, and the mixture is dried in a vacuum drying oven at 110 ℃ for 5 hours (the vacuum degree is about-0.1 MPa), thus obtaining the novel heterogeneous catalyst. The catalyst contained about 1.5mmol/g methyl benzenesulfonate.
0.3g of the catalyst was taken and added to a sealed tube containing 8mL of trimethyl phosphite, and reacted in an oil bath at 160℃for 14 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 100% and the molar selectivity of the product dimethyl methylphosphonate is 98.23% through gas chromatography detection.
[ example 3 ]
1.5g of anhydrous potassium carbonate is added into 3mL of deionized water for dissolution, then 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein, the content of sulfonyl chloride groups is about 1.8mmol/g of resin) are added, the mixture is reacted for 12 hours at 30 ℃, then the mixture is washed three times by using deionized water and anhydrous methanol respectively, and dried for 1 hour in a vacuum drying oven (the vacuum degree is about-0.1 MPa) at 110 ℃, the dried modified resin is taken and heated and refluxed for 4 hours in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then the mixture is washed three times by using absolute ethyl alcohol, and the mixture is dried in a vacuum drying oven at 110 ℃ for 5 hours (the vacuum degree is about-0.1 MPa), thus obtaining the novel heterogeneous catalyst. The catalyst contained about 1.5mmol/g methyl benzenesulfonate.
0.3g of the catalyst was taken and added to a sealed tube containing 8mL of trimethyl phosphite, and reacted in an oil bath at 130℃for 14 hours. The product was separated from the catalyst by filtration, and the molar conversion of the starting material was 90.39% as measured by gas chromatography, and the molar selectivity of the product dimethyl methylphosphonate was 95.98%.
[ example 4 ]
1.5g of anhydrous potassium carbonate is added into 3mL of deionized water for dissolution, 7mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein, the content of sulfonyl chloride groups is about 1.8mmol/g of resin) are added, the mixture is reacted for 12 hours at 30 ℃, then the mixture is washed three times by using deionized water and anhydrous methanol respectively, and dried for 1 hour in a vacuum drying oven (the vacuum degree is about-0.1 MPa) at 110 ℃, the dried modified resin is taken and heated and refluxed for 4 hours in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then the mixture is washed three times by using absolute ethyl alcohol, and the mixture is dried in a vacuum drying oven at 110 ℃ for 5 hours (the vacuum degree is about-0.1 MPa), thus obtaining the novel heterogeneous catalyst. The catalyst contained about 1.5mmol/g methyl benzenesulfonate.
0.3g of the catalyst was taken and added to a sealed tube containing 8mL of trimethyl phosphite, and reacted in an oil bath at 130℃for 18 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 95.08 percent and the molar selectivity of the product methyl dimethyl phosphonate is 95.85 percent through gas chromatography detection.
[ example 5 ]
1.5g of anhydrous potassium carbonate is added into 3mL of deionized water for dissolution, then 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein, the content of sulfonyl chloride groups is about 1.8mmol/g of resin) are added, the mixture is reacted for 12 hours at 30 ℃, then the mixture is washed three times by using deionized water and anhydrous methanol respectively, and dried for 1 hour in a vacuum drying oven (the vacuum degree is about-0.1 MPa) at 110 ℃, the dried modified resin is taken and heated and refluxed for 4 hours in 3mL of deionized water and 7mL of methanol solution at 75 ℃, then the mixture is washed three times by using absolute ethyl alcohol, and the mixture is dried in a vacuum drying oven at 110 ℃ for 5 hours (the vacuum degree is about-0.1 MPa), thus obtaining the novel heterogeneous catalyst. The catalyst contained about 1.5mmol/g methyl benzenesulfonate.
0.3g of the catalyst was taken and added to a sealed tube containing 8mL of trimethyl phosphite, and reacted in an oil bath at 150℃for 12 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 99.74 percent and the molar selectivity of the product dimethyl methylphosphonate is 97.86 percent through gas chromatography detection.
[ example 6 ]
1.2g of anhydrous potassium carbonate is added into 3mL of deionized water for dissolution, then 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein, the content of sulfonyl chloride groups is about 1.8mmol/g of resin) are added, the mixture is reacted for 12 hours at 30 ℃, then the mixture is washed three times by using deionized water and anhydrous methanol respectively, and dried for 1 hour in a vacuum drying oven (the vacuum degree is about-0.1 MPa) at 110 ℃, the dried modified resin is taken and heated and refluxed for 4 hours in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then the mixture is washed three times by using absolute ethyl alcohol, and the mixture is dried in a vacuum drying oven at 110 ℃ for 5 hours (the vacuum degree is about-0.1 MPa), thus obtaining the novel heterogeneous catalyst. The catalyst contained about 1.5mmol/g methyl benzenesulfonate.
0.24g of the catalyst was taken and added to a sealed tube containing 8mL of trimethyl phosphite, and reacted in an oil bath at 150℃for 8 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 100% and the molar selectivity of the product dimethyl methylphosphonate is 97.42% through gas chromatography detection.
[ example 7 ]
1.4g of anhydrous potassium carbonate is added into 3mL of deionized water for dissolution, then 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein, the content of sulfonyl chloride groups is about 1.8mmol/g of resin) are added, the mixture is reacted for 12 hours at 30 ℃, then the mixture is washed three times by using deionized water and anhydrous methanol respectively, and dried for 1 hour in a vacuum drying oven (the vacuum degree is about-0.1 MPa) at 110 ℃, the dried modified resin is taken and heated and refluxed for 4 hours in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then the mixture is washed three times by using absolute ethyl alcohol, and the mixture is dried in a vacuum drying oven at 110 ℃ for 5 hours (the vacuum degree is about-0.1 MPa), thus obtaining the novel heterogeneous catalyst. The catalyst contained about 1.5mmol/g methyl benzenesulfonate.
0.16g of the catalyst was taken and added to a sealed tube containing 8mL of trimethyl phosphite, and reacted in an oil bath at 160℃for 8 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 98.65 percent and the molar selectivity of the product dimethyl methylphosphonate is 98.29 percent through gas chromatography detection.
[ example 8 ]
1.5g of anhydrous potassium carbonate is added into 3mL of deionized water for dissolution, then 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein, the content of sulfonyl chloride groups is about 1.8mmol/g of resin) are added, the mixture is reacted for 12 hours at 30 ℃, then the mixture is washed three times by using deionized water and anhydrous methanol respectively, and dried for 1 hour in a vacuum drying oven (the vacuum degree is about-0.1 MPa) at 110 ℃, the dried modified resin is taken and heated and refluxed for 4 hours in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then the mixture is washed three times by using absolute ethyl alcohol, and the mixture is dried in a vacuum drying oven at 110 ℃ for 5 hours (the vacuum degree is about-0.1 MPa), thus obtaining the novel heterogeneous catalyst. The catalyst contained about 1.5mmol/g methyl benzenesulfonate.
0.1g of the catalyst was taken and added to a sealed tube containing 10mL of trimethyl phosphite, and reacted in an oil bath at 160℃for 8 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 95.45 percent and the molar selectivity of the product dimethyl methylphosphonate is 94.80 percent through gas chromatography detection.
[ example 9 ]
1.5g of anhydrous potassium carbonate is added into 3mL of deionized water for dissolution, then 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein, the content of sulfonyl chloride groups is about 1.8mmol/g of resin) are added, the mixture is reacted for 12 hours at 30 ℃, then the mixture is washed three times by using deionized water and anhydrous methanol respectively, and dried for 1 hour in a vacuum drying oven (the vacuum degree is about-0.1 MPa) at 110 ℃, the dried modified resin is taken and heated and refluxed for 4 hours in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then the mixture is washed three times by using absolute ethyl alcohol, and the mixture is dried in a vacuum drying oven at 110 ℃ for 5 hours (the vacuum degree is about-0.1 MPa), thus obtaining the novel heterogeneous catalyst. The catalyst contained about 1.5mmol/g methyl benzenesulfonate.
0.3g of the catalyst was taken and added to a sealed tube containing 10mL of trimethyl phosphite, and reacted in an oil bath at 160℃for 6 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 99.23% and the molar selectivity of the product dimethyl methylphosphonate is 96.70% through gas chromatography detection.
[ example 10 ]
1.5g of anhydrous potassium carbonate is added into 3mL of deionized water for dissolution, then 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein, the content of sulfonyl chloride groups is about 1.6mol/g of resin) are added, the reaction is carried out for 12 hours at 30 ℃, deionized water and anhydrous methanol are respectively utilized for washing for three times, the drying is carried out for 1 hour in a vacuum drying box (the vacuum degree is about-0.1 MPa) at 110 ℃, the dried modified resin is taken and heated and refluxed for 4 hours in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then the washing is carried out for three times by utilizing the anhydrous ethanol, and the drying is carried out in a vacuum drying box (the vacuum degree is about-0.1 MPa) at 110 ℃ for 5 hours, thus obtaining the novel heterogeneous catalyst. The catalyst contained about 1.4mmol/g methyl benzenesulfonate.
0.3g of the catalyst was taken and added to a sealed tube containing 8mL of trimethyl phosphite, and reacted in an oil bath at 160℃for 12 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 100% and the molar selectivity of the product dimethyl methylphosphonate is 96.26% through gas chromatography detection.
[ example 11 ]
The catalyst was recovered by filtration after the reaction [ example 10 ], and then washed three times with absolute ethyl alcohol, dried in a vacuum oven at 110℃for 5 hours (vacuum degree about-0.1 MPa) to give 0.27g of heterogeneous catalyst, which was recycled for the second catalytic cycle.
0.24g of the catalyst was taken and added to a sealed tube containing 6.4mL of trimethyl phosphite, and reacted in an oil bath at 160℃for 12 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 100% and the molar selectivity of the product dimethyl methylphosphonate is 95.84% through gas chromatography detection.
[ example 12 ]
The catalyst was recovered by filtration after the reaction [ example 11 ], washed three times with absolute ethanol, dried in a vacuum oven at 110℃for 5 hours (vacuum degree about-0.1 MPa) to give 0.20g heterogeneous catalyst, and subjected to a third catalytic cycle.
0.18g of the catalyst was taken and added to a sealed tube containing 4.8mL of trimethyl phosphite, and reacted in an oil bath at 160℃for 12 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 100% and the molar selectivity of the product methyl dimethyl phosphonate is 96.22% through gas chromatography detection.
[ comparative example 1 ]
Referring to the method disclosed in CN102702256A, a homogeneous catalyst, namely methyl p-toluenesulfonate, is adopted, and the specific process is as follows:
the three-necked flask and trimethyl phosphite are treated at a low temperature of 0 ℃, 50g of trimethyl phosphite is added into the three-necked flask under the protection of nitrogen atmosphere, 6g of methyl p-toluenesulfonate is used as a catalyst, and the mass ratio of the two is 100:12. the three-necked flask was placed in an oil bath, a condenser was fitted, and the whole reaction was carried out under nitrogen atmosphere with stirring. Under the condition of stirring, the temperature is raised to 200 ℃, the reaction is carried out for 13 hours, and the reaction yield is 83.4%.
[ example 13 ]
1.5g of potassium hydroxide was added to 9mL of anhydrous methanol, then 1g of sulfonyl chloride polystyrene resin (same as in example 2) was added, reacted at 30℃for 12 hours, then washed three times with deionized water and anhydrous methanol, dried in a vacuum oven (vacuum degree: about-0.1 MPa) at 110℃for 1 hour, dried modified resin was taken and heated under reflux in 3mL of deionized water and 6mL of methanol solution at 75℃for 4 hours, then washed three times with anhydrous ethanol, and dried in a vacuum oven at 110℃for 5 hours (vacuum degree: about-0.1 MPa), to obtain a novel heterogeneous catalyst. In the catalyst, the content of methyl benzenesulfonate is 0.6mmol/g catalyst.
0.4g of the catalyst was taken and added to a sealed tube containing 8mL of trimethyl phosphite, and reacted in an oil bath at 160℃for 14 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 82.89 percent and the molar selectivity of the product dimethyl methylphosphonate is 90.53 percent through gas chromatography detection.
[ example 14 ]
1.5g of anhydrous potassium carbonate was added to 3mL of deionized water for dissolution, then 6mL of anhydrous ethanol and 1g of sulfonyl chloride polystyrene resin (same as in example 2) were added, reacted at 30℃for 12 hours, then washed three times with deionized water and anhydrous ethanol, respectively, and dried in a vacuum oven (vacuum degree: about-0.1 MPa) at 110℃for 5 hours to obtain a novel heterogeneous catalyst. In the catalyst, the content of ethyl benzenesulfonate is 0.8mmol/g catalyst.
0.2g of the catalyst was taken and added to a sealed tube containing 5mL of trimethyl phosphite, and reacted in an oil bath at 180℃for 14 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 67.14 percent and the molar selectivity of the product dimethyl methylphosphonate is 92.35 percent through gas chromatography detection.
[ example 15 ]
1.5g of anhydrous potassium carbonate was added to 3mL of deionized water for dissolution, then 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (same as in example 2) were added, reacted at 30℃for 12 hours, and then washed three times with deionized water and anhydrous methanol, respectively, and dried in a vacuum oven (vacuum degree: about-0.1 MPa) at 110℃for 5 hours to obtain a novel heterogeneous catalyst.
0.3g of the catalyst was taken and added to a sealed tube containing 8mL of trimethyl phosphite, and reacted in an oil bath at 160℃for 14 hours. The product is filtered and separated from the catalyst, and the molar conversion rate of the raw material is 96.04% and the molar selectivity of the product dimethyl methylphosphonate is 96.73% through gas chromatography detection.
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (14)

1. A method of synthesizing a dialkyl alkylphosphonate comprising: taking trialkyl phosphonite as a raw material, and contacting with a catalyst to react to obtain dialkyl alkylphosphonite; the reaction is operated in batch mode, and the reaction conditions include: the reaction temperature is 130-180 ℃, the catalyst consumption is 1-5% of the raw material mass, and the reaction time is 6-20 hours; the catalyst has the structural general formula as follows:
wherein,is polystyrene resin, R is methyl or ethyl;
in the case of the catalyst, the catalyst may be,the content of (C) is 0.6-1.8mmol/g catalyst.
2. A process according to claim 1, wherein, in the catalyst,the content of (C) is 1.2-1.8mmol/g catalyst.
3. The method of claim 1, wherein the catalyst is prepared by a process comprising:
in the presence of an alkaline catalyst, the sulfonyl chloride polystyrene resin is contacted with alcohols for reaction, and the obtained product is subjected to first drying to obtain the catalyst.
4. A method according to claim 3, wherein the basic catalyst is at least one selected from potassium carbonate and potassium hydroxide.
5. The method according to claim 4, wherein the basic catalyst is potassium carbonate.
6. The method according to claim 3, wherein the alcohol is at least one of methanol and ethanol in the preparation method of the catalyst.
7. The method according to claim 3, wherein in the preparation of the catalyst, the particle size of the sulfonyl chloride polystyrene resin is 100 to 200 mesh, and the content of sulfonyl chloride groups bonded to the benzene ring is 1.5 to 2.0mmol/g resin.
8. The method according to claim 3, wherein in the preparation method of the catalyst, raw materials in a reaction system comprise sulfonyl chloride polystyrene resin, water and alcohols, wherein the mass ratio of the sulfonyl chloride polystyrene resin to the basic catalyst to the water to the alcohols is 1:1.2-1.8:3-5:4-7.
9. A process according to claim 3, wherein in the preparation of the catalyst, the reaction conditions are as follows: the reaction temperature is 30-50 ℃ and the reaction time is 10-14h.
10. A method according to claim 3, wherein in the preparation of the catalyst, the first drying is performed by vacuum drying under the following conditions: the drying temperature is 90-130 ℃ and the drying time is 1-3h.
11. A catalyst according to claim 3, wherein the catalyst is prepared by subjecting the first dried product to a mixed liquid heat treatment of water and methanol under the following conditions: the mass ratio of the first dry matter to the water to the methanol is 1:3-5:4-10, the treatment temperature is 70-80 ℃ and the treatment time is 4-5h.
12. The method of claim 11, wherein the second drying is performed by vacuum drying under the following conditions: the drying temperature is 90-130 ℃, and the drying time is 4-5h.
13. The method of claim 1, wherein the trialkyl phosphite comprises at least one of trimethyl phosphite and triethyl triphosphate, and the product dialkyl alkylphosphonate comprises at least one of dimethyl methylphosphonate and diethyl ethylphosphonate.
14. The method of claim 13, wherein the reaction is operated batchwise, and the reaction conditions include: the reaction temperature is 150-160 ℃, the catalyst consumption is 3-5% of the raw material mass, and the reaction time is 8-12 hours.
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