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 PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000002148 esters Chemical class 0.000 title abstract description 11
- -1 alkyl phosphonic acid Chemical compound 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 238000001035 drying Methods 0.000 claims abstract description 42
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 33
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims abstract description 12
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001298 alcohols Chemical class 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 159
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 32
- 238000001291 vacuum drying Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 21
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- NYVWRGSKEIZALB-UHFFFAOYSA-N diethoxyphosphoryl ethyl phosphono phosphate Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OP(=O)(O)O NYVWRGSKEIZALB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 abstract description 4
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 44
- 239000008367 deionised water Substances 0.000 description 39
- 229910021641 deionized water Inorganic materials 0.000 description 39
- 238000005406 washing Methods 0.000 description 30
- 238000001914 filtration Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000002638 heterogeneous catalyst Substances 0.000 description 18
- 238000004817 gas chromatography Methods 0.000 description 16
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical group COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 description 12
- 238000010992 reflux Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000002815 homogeneous catalyst Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzenecarbonitrile Natural products N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- BWEKDYGHDCHWEN-UHFFFAOYSA-N 2-methylhex-2-ene Chemical group CCCC=C(C)C BWEKDYGHDCHWEN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- XDRMBCMMABGNMM-UHFFFAOYSA-N ethyl benzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=CC=C1 XDRMBCMMABGNMM-UHFFFAOYSA-N 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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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
- 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
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- Chemical & Material Sciences (AREA)
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- 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)
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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
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:
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:
wherein,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,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)
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.
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