CN115364896A - Catalyst for synthesizing alkyl phosphonic acid dialkyl ester and preparation method and application thereof - Google Patents

Catalyst for synthesizing alkyl phosphonic acid dialkyl ester and preparation method and application thereof Download PDF

Info

Publication number
CN115364896A
CN115364896A CN202110545465.5A CN202110545465A CN115364896A CN 115364896 A CN115364896 A CN 115364896A CN 202110545465 A CN202110545465 A CN 202110545465A CN 115364896 A CN115364896 A CN 115364896A
Authority
CN
China
Prior art keywords
catalyst
drying
reaction
product
polystyrene resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110545465.5A
Other languages
Chinese (zh)
Other versions
CN115364896B (en
Inventor
李骏
刘国亮
何文军
戈军伟
王小飞
张道明
薛浩亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN202110545465.5A priority Critical patent/CN115364896B/en
Publication of CN115364896A publication Critical patent/CN115364896A/en
Application granted granted Critical
Publication of CN115364896B publication Critical patent/CN115364896B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalyst for synthesizing alkyl phosphonic acid dialkyl ester, a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: under the condition of the existence of an alkaline catalyst, 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, good selectivity of products and good stability in the reaction of catalyzing trialkyl phosphonite to isomerize into dialkyl alkylphosphonate. And the problem that the catalyst is difficult to separate from the product when methyl iodide or methyl p-toluenesulfonate is used as a liquid phase catalyst in the prior art is solved.

Description

Catalyst for synthesizing alkyl phosphonic acid dialkyl ester and preparation method and application thereof
Technical Field
The invention relates to a catalyst for synthesizing alkyl phosphonic acid dialkyl ester, a preparation method thereof and application of phosphonous acid trialkyl ester in synthesis of alkyl phosphonic acid dialkyl ester through isomerization reaction.
Background
Alkyl phosphonic acid dialkyl ester is an additive organic phosphorus flame retardant, has the advantages of high phosphorus content, excellent flame retardant performance, low price, small addition amount and the like, is 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 is widely researched as a lithium battery electrolyte flame retardant additive in recent years. Compared with the traditional halogen flame retardant and inorganic flame retardant, the alkyl dialkyl phosphonate has advantages in the aspects of environmental protection, self-extinguishing property, plasticity, low temperature resistance, ultraviolet resistance, antistatic property and the like, is particularly suitable for transparent or light and beautiful color products and spraying, and is considered as a new generation of efficient flame retardant.
At present, the process route of homogeneous catalyst is mainly adopted for the production of alkyl phosphonic acid dialkyl ester by trialkyl phosphite isomerization reaction, and the reaction route is as follows:
Figure BDA0003073458340000011
in the early stage of research, iodine (CN 103102369A) or methyl iodide (CN 101624402A) is used as a catalyst to react at normal pressure, and the conversion rate is higher, but the iodine or methyl iodide has certain toxicity, low boiling point, instability, incapability of recycling and higher cost, so the industrial application of the iodine or methyl iodide is greatly limited. CN103073581A uses benzonitrile compound as catalyst, and the reaction is carried out under alkaline condition, but the reaction pressure is higher than 1.2MPa, and the yield is lower. CN102702256A discloses a method for producing dimethyl methylphosphonate by catalyzing trimethyl phosphonite with methyl p-toluenesulfonate as an environment-friendly catalyst, but the catalyst has the problems of 7-10% of mass fraction, 180-200 ℃ of reaction temperature, 9-13 hours of reaction time, harsh reaction conditions, low production efficiency and the like.
At present, homogeneous catalysts are adopted for synthesizing alkyl dialkyl phosphonate, and products and the catalysts are mixed and difficult to separate. 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 alkylphosphonate product and a catalyst are difficult to separate in the prior art, and provides the catalyst for synthesizing the dialkyl alkylphosphonate, a preparation method thereof and application of the catalyst in synthesizing the dialkyl alkylphosphonate by a trialkyl phosphonite isomerization reaction. 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 invention provides a catalyst for synthesizing alkyl dialkyl phosphonate, which has the following structural general formula:
Figure BDA0003073458340000021
wherein the content of the first and second substances,
Figure BDA0003073458340000022
the resin is a polystyrene resin, and R is an alkyl group, preferably selected from a methyl group or an ethyl group, and more preferably a methyl group.
In the technical scheme, in the catalyst,
Figure BDA0003073458340000023
the content of (B) is 0.6 to 1.8mmol/g catalyst, preferably 1.2 to 1.8mmol/g catalyst.
The second aspect of the present invention provides a method for preparing a catalyst for synthesizing dialkyl alkylphosphonate, comprising:
under the condition of the existence of a basic catalyst, sulfonyl chloride polystyrene resin is contacted with alcohol for reaction, and the obtained product is subjected to first drying to obtain the catalyst.
In the above technical solution, the basic 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 is 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 a benzene ring is 1.5-2.0mmol/g resin. The polystyrene resin can be prepared by a conventional method, for example, preparing a polystyrene resin and then bonding a sulfonyl chloride group to the polystyrene resin. The polystyrene resin is polymerized by styrene monomer.
In the above technical scheme, in the reaction system, the raw materials include 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. 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 is preferably vacuum drying, and the conditions are as follows: the drying temperature is 90-130 ℃, and the drying time is 1-3h. Wherein the vacuum degree can be between-0.1 MPa and-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 to obtain the catalyst, wherein the heat treatment conditions of the mixed solution of water and methanol are as follows: the mass ratio of the first dried substance 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 is preferably vacuum drying, and the conditions are as follows: the drying temperature is 90-130 deg.C, and the drying time is 4-5h. Wherein the vacuum degree can be between-0.1 MPa and-0.08 MPa.
In the above-described embodiment, 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 washed by deionized water for 2-5 times and methanol for 2-5 times, and the second washing can be washed by absolute ethyl alcohol for 2-5 times.
In the above technical solution, the preparation method of the catalyst preferably can adopt the following specific processes, including: dissolving an alkaline catalyst in water, adding sulfonyl chloride polystyrene resin, adding anhydrous alcohol (such as anhydrous methanol and/or anhydrous ethanol), reacting at the temperature of 30-50 ℃ for 10-14h, performing first washing and first filtering after the reaction is finished, performing 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, performing second filtering, and performing second drying to obtain the catalyst. Wherein the first washing can be sequentially and respectively washed by deionized water and methanol, and the second washing can be washed by absolute ethyl alcohol. The first filtration and the second filtration may be performed by a conventional filtration method such as suction filtration.
In a third aspect, the present invention provides a method for synthesizing dialkyl alkylphosphonate, comprising: and taking trialkyl phosphonite as a raw material, and contacting with the catalyst to react to obtain dialkyl alkylphosphonate.
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 is performed in a batch mode, and the reaction conditions include: the reaction temperature is 130-180 ℃, preferably 150-180 ℃, the dosage of the catalyst accounts for 1-5 percent, preferably 3-5 percent of the mass of the raw materials, and the reaction time is 6-20 hours, preferably 8-12 hours.
In the technical scheme, the reaction product can be simply filtered to obtain the product alkyl dialkyl phosphonate, and the catalyst obtained after filtering can be repeatedly used.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalyst is a novel heterogeneous catalyst, solves the problem that the product 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 being used for the trialkyl phosphonite isomerization reaction to synthesize alkyl phosphonic acid dialkyl ester.
2. The preparation method of the catalyst provided by the invention has the advantages that sulfonyl chloride active groups on the sulfonyl chloride polystyrene resin are utilized to react with methanol, and the obtained catalyst not only has a methyl benzenesulfonate structure, but also can be matched with a polystyrene resin body, so that the improvement of the activity and the selectivity of the catalyst is promoted. In particular, the catalyst after heat treatment of the mixed solution of water and methanol can further improve the activity of the catalyst.
3. When the catalyst is used for synthesizing alkyl phosphonic acid dialkyl ester by phosphonous 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 recovered catalyst are kept good after 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 reaction product obtained by using the catalyst of example 1; wherein DMMP is dimethyl methylphosphonate;
FIG. 4 is a gas chromatography-mass spectrometry chromatogram of a product after reaction using the catalyst obtained in 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 present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the invention, the infrared absorption spectrogram adopts a Bruker VERTEX70 instrument, and the wave number range is as follows: 1000cm -1 -4000cm -1 。
In the present invention, the thermogravimetric analysis chart uses a relaxation-resistant STA2500 as an instrument, the test condition is a nitrogen atmosphere, and the temperature programming condition is that the temperature is raised from 30 ℃ to 600 ℃ at the rate of 20 ℃ per minute.
In the invention, the gas chromatogram of the product is obtained by using SP6890 of Shandong Lunan Rainbow chemical engineering instrument, inc., nitrogen as carrier gas, FID detector, programmed temperature rising condition of 50 ℃ and rising rate of 20 ℃ per minute to 250 ℃ and keeping for 3min.
In the present invention, the apparatus used in the GC-320MS is a 450GC-320MS from Varian.
[ example 1 ]
Adding 1.5g of anhydrous potassium carbonate into 4mL of deionized water for dissolution, then adding 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 with 100-200 meshes), reacting for 12h at 30 ℃, then washing three times by using the deionized water and the anhydrous methanol respectively, drying for 1h in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa), taking the dried modified resin, heating and refluxing for 4h in 4mL of deionized water and 7mL of methanol solution at 75 ℃, then washing three times by using the anhydrous ethanol, and drying in the 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 5h to obtain the novel heterogeneous catalyst. The content of methyl benzenesulfonate in the catalyst was about 1.5mmol/g catalyst.
0.4g of the catalyst was taken in a sealed tube containing 8mL of trimethyl phosphite and reacted in an oil bath at 160 ℃ for 14 hours. And (3) filtering and separating the product from the catalyst, wherein the molar conversion rate of the raw material is 100% and the molar selectivity of the dimethyl methylphosphonate product is 96.43% through gas chromatography detection.
The IR spectrum (upper curve) of sulfonyl chloride polystyrene resin as a starting material and the IR spectrum (lower curve) of the catalyst obtained in example 1 are shown in FIG. 1, wherein the IR spectrum is at 1090cm -1 An infrared absorption peak is formed, and the infrared absorption peak is a C-O stretching vibration absorption peak.
The thermogravimetric analysis of the catalyst obtained in example 1 is shown in FIG. 2, and it can be seen from FIG. 2 that it has good thermal stability below 180 ℃.
The chromatogram of the product after the reaction is shown in FIG. 3. And (3) carrying out quantitative analysis by adopting an internal standard method, taking ethylbenzene as an internal standard substance and methanol as a solvent, and detecting trimethyl phosphite which is not completely reacted, the internal standard substance and a substance to be detected 1:1, detecting 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 product gas chromatography chromatogram obtained after the reaction is shown in FIG. 4. As can be seen from FIG. 4, trimethyl phosphite can be converted into dimethyl methylphosphonate with high selectivity by using the catalyst of the present invention.
[ example 2 ]
Adding 1.5g of anhydrous potassium carbonate into 3mL of deionized water for dissolution, then adding 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 with 100-200 meshes), reacting for 12h at 30 ℃, then washing three times by using the deionized water and the anhydrous methanol respectively, drying for 1h in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa), taking the dried modified resin, heating and refluxing for 4h in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then washing three times by using the anhydrous ethanol, and drying in the 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 5h to obtain the novel heterogeneous catalyst. The catalyst contained methyl benzenesulfonate in an amount of about 1.5mmol/g catalyst.
0.3g of the catalyst was charged into a sealed tube containing 8mL of trimethyl phosphite and reacted in an oil bath at 160 ℃ for 14 hours. And (3) filtering and separating the product from the catalyst, and detecting by gas chromatography, wherein the molar conversion rate of the raw material is 100%, and the molar selectivity of the product dimethyl methylphosphonate is 98.23%.
[ example 3 ]
Adding 1.5g of anhydrous potassium carbonate into 3mL of deionized water for dissolution, then adding 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 with 100-200 meshes), reacting for 12h at 30 ℃, then washing three times by using the deionized water and the anhydrous methanol respectively, drying for 1h in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa), taking the dried modified resin, heating and refluxing for 4h in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then washing three times by using the anhydrous ethanol, and drying in the 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 5h to obtain the novel heterogeneous catalyst. The content of methyl benzenesulfonate in the catalyst was about 1.5mmol/g catalyst.
0.3g of the catalyst was charged into a sealed tube containing 8mL of trimethyl phosphite and reacted in an oil bath at 130 ℃ for 14 hours. And (3) filtering and separating the product from the catalyst, wherein the molar conversion rate of the raw material is 90.39% and the molar selectivity of the product dimethyl methylphosphonate is 95.98% by gas chromatography detection.
[ example 4 ] A method for producing a polycarbonate
Adding 1.5g of anhydrous potassium carbonate into 3mL of deionized water for dissolution, then adding 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 with 100-200 meshes), reacting for 12h at 30 ℃, then washing three times by using the deionized water and the anhydrous methanol respectively, drying for 1h in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa), taking the dried modified resin, heating and refluxing for 4h in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then washing three times by using the anhydrous ethanol, and drying in the 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 5h to obtain the novel heterogeneous catalyst. The content of methyl benzenesulfonate in the catalyst was about 1.5mmol/g catalyst.
0.3g of the catalyst was charged into a sealed tube containing 8mL of trimethyl phosphite and reacted in an oil bath at 130 ℃ for 18 hours. And (3) filtering and separating the product from the catalyst, wherein the molar conversion rate of the raw material is 95.08% and the molar selectivity of the dimethyl methylphosphonate product is 95.85% through gas chromatography detection.
[ example 5 ]
Adding 1.5g of anhydrous potassium carbonate into 3mL of deionized water for dissolution, then adding 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 with 100-200 meshes), reacting for 12h at 30 ℃, then washing three times by using the deionized water and the anhydrous methanol respectively, drying for 1h in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa), taking the dried modified resin, heating and refluxing for 4h in 3mL of deionized water and 7mL of methanol solution at 75 ℃, then washing three times by using the anhydrous ethanol, and drying in the 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 5h to obtain the novel heterogeneous catalyst. The content of methyl benzenesulfonate in the catalyst was about 1.5mmol/g catalyst.
0.3g of this catalyst was taken in a sealed tube containing 8mL of trimethyl phosphite and reacted in an oil bath at 150 ℃ for 12h. And (3) filtering and separating the product from the catalyst, and detecting by gas chromatography, wherein the molar conversion rate of the raw material is 99.74%, and the molar selectivity of the dimethyl methylphosphonate product is 97.86%.
[ example 6 ]
Adding 1.2g of anhydrous potassium carbonate into 3mL of deionized water for dissolving, then adding 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein the granularity is 100-200 meshes, and the content of sulfonyl chloride groups is about 1.8mmol/g of resin), reacting for 12h at 30 ℃, then washing with deionized water and anhydrous methanol three times respectively, drying in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 1h, taking the dried modified resin, heating and refluxing for 4h in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then washing with anhydrous ethanol three times, and drying in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 5h to obtain the novel heterogeneous catalyst. The catalyst contained methyl benzenesulfonate in an amount of about 1.5mmol/g catalyst.
0.24g of the catalyst was taken and charged into a sealed tube containing 8mL of trimethyl phosphite and reacted in an oil bath at 150 ℃ for 8 hours. And (3) filtering and separating the product from the catalyst, and detecting by gas chromatography, wherein the molar conversion rate of the raw material is 100%, and the molar selectivity of the product dimethyl methylphosphonate is 97.42%.
[ example 7 ]
Adding 1.4g of anhydrous potassium carbonate into 3mL of deionized water for dissolution, then adding 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 with 100-200 meshes), reacting for 12h at 30 ℃, then washing three times by using the deionized water and the anhydrous methanol respectively, drying for 1h in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa), taking the dried modified resin, heating and refluxing for 4h in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then washing three times by using the anhydrous ethanol, and drying in the 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 5h to obtain the novel heterogeneous catalyst. The content of methyl benzenesulfonate in the catalyst was about 1.5mmol/g catalyst.
0.16g of this catalyst was taken in a sealed tube containing 8mL of trimethyl phosphite and reacted in a 160 ℃ oil bath for 8h. And (3) filtering and separating the product from the catalyst, and detecting by gas chromatography, wherein the molar conversion rate of the raw material is 98.65%, and the molar selectivity of the product dimethyl methylphosphonate is 98.29%.
[ example 8 ]
Adding 1.5g of anhydrous potassium carbonate into 3mL of deionized water for dissolution, then adding 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 with 100-200 meshes), reacting for 12h at 30 ℃, then washing three times by using the deionized water and the anhydrous methanol respectively, drying for 1h in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa), taking the dried modified resin, heating and refluxing for 4h in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then washing three times by using the anhydrous ethanol, and drying in the 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 5h to obtain the novel heterogeneous catalyst. The content of methyl benzenesulfonate in the catalyst was about 1.5mmol/g catalyst.
0.1g of the catalyst was charged into a sealed tube containing 10mL of trimethyl phosphite and reacted in a 160 ℃ oil bath for 8 hours. And (3) filtering and separating the product from the catalyst, wherein the molar conversion rate of the raw material is 95.45% and the molar selectivity of the dimethyl methylphosphonate is 94.80% by gas chromatography detection.
[ example 9 ]
Adding 1.5g of anhydrous potassium carbonate into 3mL of deionized water for dissolution, then adding 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 with 100-200 meshes), reacting for 12h at 30 ℃, then washing three times by using the deionized water and the anhydrous methanol respectively, drying for 1h in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa), taking the dried modified resin, heating and refluxing for 4h in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then washing three times by using the anhydrous ethanol, and drying in the 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 5h to obtain the novel heterogeneous catalyst. The content of methyl benzenesulfonate in the catalyst was about 1.5mmol/g catalyst.
0.3g of the catalyst was charged into a sealed tube containing 10mL of trimethyl phosphite and reacted in a 160 ℃ oil bath for 6 hours. And (3) filtering and separating the product from the catalyst, wherein the molar conversion rate of the raw material is 99.23% and the molar selectivity of the dimethyl methylphosphonate product is 96.70% through gas chromatography detection.
[ example 10 ]
Adding 1.5g of anhydrous potassium carbonate into 3mL of deionized water for dissolving, then adding 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (wherein the granularity is 100-200 meshes, and the sulfonyl chloride group content is about 1.6mol/g of resin), reacting for 12h at 30 ℃, then washing with deionized water and anhydrous methanol three times respectively, drying in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 1h, taking the dried modified resin, heating and refluxing for 4h in 3mL of deionized water and 6mL of methanol solution at 75 ℃, then washing with anhydrous ethanol three times, and drying in a 110 ℃ vacuum drying oven (the vacuum degree is about-0.1 MPa) for 5h to obtain the novel heterogeneous catalyst. The content of methyl benzenesulfonate in the catalyst was about 1.4mmol/g catalyst.
0.3g of the catalyst was charged into a sealed tube containing 8mL of trimethyl phosphite and reacted at 160 ℃ in an oil bath for 12 hours. And (3) filtering and separating the product from the catalyst, and detecting by gas chromatography, wherein the molar conversion rate of the raw material is 100%, and the molar selectivity of the product dimethyl methylphosphonate is 96.26%.
[ example 11 ]
The catalyst after the reaction was collected [ example 10 ] and recovered by filtration, then washed three times with absolute ethanol, and dried in a vacuum oven at 110 ℃ (vacuum degree of about-0.1 MPa) for 5 hours to obtain 0.27g of heterogeneous catalyst, which was recycled for the second catalytic cycle.
0.24g of the catalyst was charged into a sealed tube containing 6.4mL of trimethyl phosphite and reacted in a 160 ℃ oil bath for 12 hours. And (3) filtering and separating the product from the catalyst, and detecting by gas chromatography, wherein the molar conversion rate of the raw material is 100% and the molar selectivity of the product dimethyl methylphosphonate is 95.84%.
[ example 12 ]
The catalyst after the reaction is filtered and recovered, then washed three times by absolute ethyl alcohol, and dried in a vacuum drying oven at 110 ℃ (the vacuum degree is about-0.1 MPa) for 5 hours to obtain 0.20g of heterogeneous catalyst, and the heterogeneous catalyst is recycled for the third catalysis.
0.18g of this catalyst was charged into a sealed tube containing 4.8mL of trimethyl phosphite and reacted in a 160 ℃ oil bath for 12 hours. And (3) filtering and separating the product from the catalyst, wherein the molar conversion rate of the raw material is 100% and the molar selectivity of the dimethyl methylphosphonate product is 96.22% through gas chromatography detection.
[ COMPARATIVE EXAMPLE 1 ]
Referring to the method disclosed in CN102702256a, a homogeneous catalyst methyl p-toluenesulfonate is used, and the specific process is as follows:
treating a three-neck flask and trimethyl phosphite at low temperature of 0 ℃, then adding 50g of trimethyl phosphite into the three-neck flask under the protection of nitrogen atmosphere, wherein the catalyst is 6g of methyl p-toluenesulfonate, and the mass ratio of the two is 100:12. the three-necked flask was put in an oil bath, a condenser tube was installed, and the reaction was carried out under nitrogen atmosphere. The temperature is raised to 200 ℃ under the condition of stirring, the reaction lasts for 13h, and the reaction yield is 83.4%.
[ example 13 ]
Adding 1.5g of potassium hydroxide into 9mL of anhydrous methanol, then adding 1g of sulfonyl chloride polystyrene resin (same as example 2), reacting for 12h at 30 ℃, then washing three times by using deionized water and the anhydrous methanol respectively, heating and refluxing the dried modified resin in 3mL of deionized water and 6mL of methanol solution at 75 ℃ for 4h in a vacuum drying oven (the vacuum degree is about-0.1 MPa) at 110 ℃ for 1h, then washing three times by using the anhydrous ethanol, and drying in the vacuum drying oven at 110 ℃ for 5h (the vacuum degree is about-0.1 MPa) to obtain the novel heterogeneous catalyst. In the catalyst, the content of the benzene sulfonic acid methyl ester is 0.6mmol/g catalyst.
0.4g of the catalyst was taken in a sealed tube containing 8mL of trimethyl phosphite and reacted in an oil bath at 160 ℃ for 14 hours. The product and the catalyst are filtered and separated, and the gas chromatography detection shows that 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.
[ example 14 ] A method for producing a polycarbonate
1.5g of anhydrous potassium carbonate is added into 3mL of deionized water to be dissolved, then 6mL of anhydrous ethanol and 1g of sulfonyl chloride polystyrene resin (same as example 2) are added to react for 12h at 30 ℃, then the mixture is washed three times by using the deionized water and the anhydrous ethanol respectively, and the mixture is dried for 5h in a vacuum drying oven (the vacuum degree is about-0.1 MPa) at 110 ℃ to obtain the novel heterogeneous catalyst. In the catalyst, the content of the ethyl benzene sulfonate is 0.8mmol/g of the catalyst.
0.2g of this catalyst was taken in a sealed tube containing 5mL of trimethyl phosphite and reacted in an oil bath at 180 ℃ for 14h. The product and the catalyst are filtered and separated, and the gas chromatography detection shows that 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.
[ example 15 ]
1.5g of anhydrous potassium carbonate is added into 3mL of deionized water to be dissolved, then 6mL of anhydrous methanol and 1g of sulfonyl chloride polystyrene resin (same as example 2) are added to react for 12h at 30 ℃, then the mixture is washed three times by using the deionized water and the anhydrous methanol respectively, and a vacuum drying oven (the vacuum degree is about-0.1 MPa) at 110 ℃ is used for 5h to obtain the novel heterogeneous catalyst.
0.3g of the catalyst was charged into a sealed tube containing 8mL of trimethyl phosphite and reacted in an oil bath at 160 ℃ for 14 hours. And (3) filtering and separating the product from the catalyst, wherein the molar conversion rate of the raw material is 96.04% and the molar selectivity of the dimethyl methylphosphonate is 96.73% by gas chromatography detection.
The specific embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (13)

1. A catalyst for synthesizing alkyl dialkyl phosphonate has the following structural general formula:
Figure FDA0003073458330000011
wherein the content of the first and second substances,
Figure FDA0003073458330000012
is a polystyrene resin, R is an alkyl group, preferably selected from methyl or ethyl.
2. The catalyst according to claim 1, wherein in the catalyst,
Figure FDA0003073458330000013
the content of (B) is from 0.6 to 1.8mmol/g of catalyst, preferably from 1.2 to 1.8mmol/g of catalyst.
3. A method of preparing a catalyst for the synthesis of dialkyl alkylphosphonates comprising:
under the condition of the existence of a basic catalyst, sulfonyl chloride polystyrene resin is contacted with alcohol for reaction, and the obtained product is subjected to first drying to obtain the catalyst.
4. The process according to claim 3, wherein the basic catalyst is at least one selected from potassium carbonate and potassium hydroxide, preferably potassium carbonate.
5. The method according to claim 3, wherein the alcohol is at least one of methanol and ethanol.
6. The production method according to claim 3, wherein the sulfochloride polystyrene resin has a particle size of 100 to 200 mesh and a content of sulfochloride group bonded to a benzene ring of 1.5 to 2.0mmol/g resin.
7. The preparation method according to claim 3, wherein in the reaction system, the raw materials 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.
8. The method of claim 3, wherein the reaction conditions are as follows: the reaction temperature is 30-50 ℃ and the reaction time is 10-14h.
9. The method according to claim 3, wherein the first drying is vacuum drying under the following conditions: the drying temperature is 90-130 deg.C, and the drying time is 1-3h.
10. The method according to claim 3, wherein the catalyst is obtained by subjecting the obtained first dried product to a heat treatment with a mixed solution of water and methanol under the following conditions, and then subjecting the first dried product to a second drying: the mass ratio of the first dried substance 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, the second drying is vacuum drying, and the conditions are as follows: the drying temperature is 90-130 deg.C, and the drying time is 4-5h.
11. A method of synthesizing a dialkyl alkylphosphonate comprising: the trialkyl phosphonite is used as a starting material and is contacted with the catalyst of any one of claims 1 to 2 or the catalyst prepared by the method of any one of claims 3 to 10 to react to obtain the dialkyl alkylphosphonate.
12. A process as recited in claim 11 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.
13. The process of claim 11, wherein the reaction is carried out in a batch mode and the reaction conditions comprise: the reaction temperature is 130-180 ℃, preferably 150-180 ℃, the dosage of the catalyst accounts for 1-5 percent, preferably 3-5 percent of the mass of the raw materials, and the reaction time is 6-20 hours, preferably 8-12 hours.
CN202110545465.5A 2021-05-19 2021-05-19 Catalyst for synthesizing dialkyl alkylphosphonate, and preparation method and application thereof Active CN115364896B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110545465.5A CN115364896B (en) 2021-05-19 2021-05-19 Catalyst for synthesizing dialkyl alkylphosphonate, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110545465.5A CN115364896B (en) 2021-05-19 2021-05-19 Catalyst for synthesizing dialkyl alkylphosphonate, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115364896A true CN115364896A (en) 2022-11-22
CN115364896B CN115364896B (en) 2024-03-26

Family

ID=84059603

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110545465.5A Active CN115364896B (en) 2021-05-19 2021-05-19 Catalyst for synthesizing dialkyl alkylphosphonate, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115364896B (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0232006A2 (en) * 1986-01-22 1987-08-12 Imperial Chemical Industries Plc Compositions for surface treatment, polymers therefor, and method of surface treatment
EP0429215A2 (en) * 1989-11-20 1991-05-29 Imperial Chemical Industries Plc Production of polymer system for water-erodible coatings
JPH09100331A (en) * 1995-06-06 1997-04-15 Dow Chem Co:The Production of polyphenol from ketone or aldehyde and phenol
CN1613885A (en) * 2003-10-31 2005-05-11 三星Sdi株式会社 Preparation of sulfonated polystyrene as polymer electrolyte for fuel cell
CN1631909A (en) * 2004-11-25 2005-06-29 南开大学 Polystyrene sulfinate resin and its preparing method
JP2006169400A (en) * 2004-12-16 2006-06-29 Chiba Univ Method for producing polymer sulfonic acid ester
CN102702256A (en) * 2012-05-25 2012-10-03 武汉理工大学 Preparation method of halogen-free retardant dimethyl methylphosphonate
CN105833904A (en) * 2016-04-12 2016-08-10 沈阳化工大学 A modifying method of a sulfonic acid resin catalyst for polyoxymethylene dimethyl ethers
JP2017061422A (en) * 2015-09-24 2017-03-30 東ソー有機化学株式会社 High-purity para-styrene sulfonic acid ester, and method for producing thereof
CN111377967A (en) * 2020-02-26 2020-07-07 青岛长荣化工科技有限公司 Preparation method of cyclic phosphonate flame retardant
CN111925697A (en) * 2019-05-13 2020-11-13 中国科学院化学研究所 Graphene/water-soluble polymer composite material and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0232006A2 (en) * 1986-01-22 1987-08-12 Imperial Chemical Industries Plc Compositions for surface treatment, polymers therefor, and method of surface treatment
EP0429215A2 (en) * 1989-11-20 1991-05-29 Imperial Chemical Industries Plc Production of polymer system for water-erodible coatings
JPH09100331A (en) * 1995-06-06 1997-04-15 Dow Chem Co:The Production of polyphenol from ketone or aldehyde and phenol
CN1613885A (en) * 2003-10-31 2005-05-11 三星Sdi株式会社 Preparation of sulfonated polystyrene as polymer electrolyte for fuel cell
CN1631909A (en) * 2004-11-25 2005-06-29 南开大学 Polystyrene sulfinate resin and its preparing method
JP2006169400A (en) * 2004-12-16 2006-06-29 Chiba Univ Method for producing polymer sulfonic acid ester
CN102702256A (en) * 2012-05-25 2012-10-03 武汉理工大学 Preparation method of halogen-free retardant dimethyl methylphosphonate
JP2017061422A (en) * 2015-09-24 2017-03-30 東ソー有機化学株式会社 High-purity para-styrene sulfonic acid ester, and method for producing thereof
CN105833904A (en) * 2016-04-12 2016-08-10 沈阳化工大学 A modifying method of a sulfonic acid resin catalyst for polyoxymethylene dimethyl ethers
CN111925697A (en) * 2019-05-13 2020-11-13 中国科学院化学研究所 Graphene/water-soluble polymer composite material and preparation method thereof
CN111377967A (en) * 2020-02-26 2020-07-07 青岛长荣化工科技有限公司 Preparation method of cyclic phosphonate flame retardant

Also Published As

Publication number Publication date
CN115364896B (en) 2024-03-26

Similar Documents

Publication Publication Date Title
CN103495437A (en) Supported ionic liquid catalyst, as well as preparation and application thereof
CN104437645A (en) Metal-organic framework supported heteropoly acid catalyst for synthesizing glutaraldehyde and production method of metal-organic framework supported heteropoly acid catalyst
CN109364993B (en) For catalytic conversion of CO at normal pressure2Polyion liquid catalyst and preparation method thereof
CN102698799A (en) Polymer supported quaternary ammonium salt ion catalyst as well as preparation method and application thereof
CN107698699A (en) For being catalyzed the α diimine nickels containing contraposition benzhydryl substitution of ethene and 2 hexene oligomerizations（Ⅱ）Complex
CN110479374A (en) A kind of phosphorus heteropoly tungstic acid salt catalyst and preparation method thereof for synthesizing epoxy chloropropane
CN112169836A (en) Porous ionic polymer heterogeneous catalyst and method for catalytically synthesizing N-formamide by using same
CN112316978A (en) Organic catalyst for synthesizing cyclic carbonate, preparation method and catalytic reaction method thereof
CN108722479B (en) Ionic liquid catalyst, preparation method and application thereof
CN109692709B (en) Catalyst for olefin metathesis reaction and preparation and application methods thereof
CN111468191A (en) Synthetic method of ruthenium carbene catalyst
CN114733566A (en) Chiral super-strong carbonic acid catalyst based on BINOL skeleton and preparation method and application thereof
CN107602369B (en) Preparation method of acrylic acid or acrylic ester
CN115364896B (en) Catalyst for synthesizing dialkyl alkylphosphonate, and preparation method and application thereof
CN110732347A (en) binuclear ionic liquid type heteropoly acid salt solid acid catalyst for synthesizing chalcone derivatives, preparation method and application
CN106220464B (en) A kind of method for being catalyzed australene dimerization reaction
CN104892801A (en) Organic porous material after-supported single cyclopentadienyl chromium catalyst and application thereof
CN114671910A (en) Green synthesis method of cidofovir
CN114797978A (en) Carboxylated triazine polyion liquid catalyst and preparation method and application thereof
CN103709010A (en) Method for synthesizing cyclohexanol by reacting cyclohexene, carboxylic acid and water
CN111018899B (en) Method for preparing 1, 1-boron alkyne compound by metal catalysis of terminal olefin
CN114315553A (en) Method for preparing levulinic acid by catalyzing glucose in hydrophilic DES (data encryption Standard) by solid acid
CN103739624B (en) The synthetic method of aluminum diethylphosphinate
CN113416147A (en) Schiff base-metal organic complex and preparation method and application thereof
CN113004248A (en) Method for synthesizing carbazole compound by catalyzing hydrocarbon amination reaction with cobalt

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant