CN111153799A - Preparation method of methyl 3-methoxyacrylate - Google Patents
Preparation method of methyl 3-methoxyacrylate Download PDFInfo
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- CN111153799A CN111153799A CN202010063179.0A CN202010063179A CN111153799A CN 111153799 A CN111153799 A CN 111153799A CN 202010063179 A CN202010063179 A CN 202010063179A CN 111153799 A CN111153799 A CN 111153799A
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- methyl
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- xylene
- ionic liquid
- methoxyacrylate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- AUTCCPQKLPMHDN-ONEGZZNKSA-N methyl (e)-3-methoxyprop-2-enoate Chemical compound CO\C=C\C(=O)OC AUTCCPQKLPMHDN-ONEGZZNKSA-N 0.000 title claims description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 234
- 238000006243 chemical reaction Methods 0.000 claims abstract description 116
- 239000002608 ionic liquid Substances 0.000 claims abstract description 110
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000003379 elimination reaction Methods 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 30
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
- -1 monocarboxylic acid ester Chemical class 0.000 claims abstract description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 213
- 239000008096 xylene Substances 0.000 claims description 163
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 110
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- 238000010438 heat treatment Methods 0.000 claims description 60
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 59
- 229910052757 nitrogen Inorganic materials 0.000 claims description 55
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 46
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 44
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 44
- 239000000460 chlorine Substances 0.000 claims description 40
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 29
- 230000003472 neutralizing effect Effects 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 25
- 238000004821 distillation Methods 0.000 claims description 18
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 239000012454 non-polar solvent Substances 0.000 claims description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011831 acidic ionic liquid Substances 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 6
- 229940017219 methyl propionate Drugs 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000005882 aldol condensation reaction Methods 0.000 abstract description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract 2
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 72
- 239000000047 product Substances 0.000 description 39
- 239000000203 mixture Substances 0.000 description 32
- 239000011259 mixed solution Substances 0.000 description 31
- 150000001875 compounds Chemical class 0.000 description 26
- 238000009833 condensation Methods 0.000 description 26
- 230000005494 condensation Effects 0.000 description 26
- 238000011084 recovery Methods 0.000 description 25
- 238000001514 detection method Methods 0.000 description 23
- 238000004321 preservation Methods 0.000 description 23
- 238000006359 acetalization reaction Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000004693 imidazolium salts Chemical class 0.000 description 2
- SMCVPMKCDDNUCQ-UHFFFAOYSA-N methyl 3,3-dimethoxypropanoate Chemical compound COC(OC)CC(=O)OC SMCVPMKCDDNUCQ-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000005900 Flonicamid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- RLQJEEJISHYWON-UHFFFAOYSA-N flonicamid Chemical compound FC(F)(F)C1=CC=NC=C1C(=O)NCC#N RLQJEEJISHYWON-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- IYMLUHWAJFXAQP-UHFFFAOYSA-N topramezone Chemical compound CC1=C(C(=O)C2=C(N(C)N=C2)O)C=CC(S(C)(=O)=O)=C1C1=NOCC1 IYMLUHWAJFXAQP-UHFFFAOYSA-N 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 3-methoxy methyl acrylate, which comprises the steps of taking saturated monocarboxylic acid ester as a raw material and taking the saturated carboxylic acid ester as an auxiliary material, introducing formyl by utilizing methyl formate under the action of a catalyst, carrying out aldol condensation reaction with methanol under the condition that ionic liquid is taken as the catalyst to obtain 3, 3-dimethoxy methyl propionate, decompressing and separating the methanol after the reaction is completed, raising the temperature to 80-150 ℃ after the separation is completed, and removing one molecule of methanol on the 3, 3-dimethoxy methyl propionate by elimination reaction to obtain the 3-methoxy methyl acrylate, wherein the methyl formate can be replaced by CO, and the cost of the raw material is lower. The method has the advantages of simple operation, easily obtained raw materials, high conversion rate, safety, environmental protection and low cost, and can realize industrial production.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of 3-methoxy methyl acrylate.
Background
The 3-methoxy methyl acrylate is an important pharmaceutical and chemical intermediate, can be used for synthesizing various organic compounds, such as cefbutan, insecticide flonicamid, herbicide topramezone and the like, has wide application prospect in the fields of medicines, pesticides, high polymer materials and lithium batteries, and has increasingly vigorous market demand.
At present, the synthesis method of the 3-methoxy methyl acrylate mainly comprises the following steps:
1) methyl acrylate and methanol are used as raw materials, and palladium chloride and cuprous chloride are used as catalysts to synthesize the product under high pressure. The catalyst prepared by the method is expensive and not easy to recover, the utilization rate of the catalyst is low, the cost is increased, and the accumulation of heavy metals causes serious environmental pollution and does not meet the requirement of environmental protection.
2) Synthesizing by trichloroacetyl chloride and vinyl ethyl ether to obtain 3, 3-dimethoxy methyl propionate, and then cracking under the catalysis of p-toluenesulfonic acid or similar substances to prepare the product.
3) The methyl 3, 3-dimethoxypropionate is synthesized from carbon tetrachloride and vinyl ethyl ether, and the method needs a large amount of methanol and produces a large amount of methanol and ethanol mixture which is difficult to directly recycle, so that the raw material cost is overhigh and the industrial production is not facilitated.
In summary, the processes using methanol and methyl acrylate as starting materials and carbon tetrachloride and vinyl ethyl ether as starting materials in the prior art are all deficient to some extent, and a synthetic route more suitable for industrial production needs to be developed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of 3-methoxy methyl acrylate, through the designed reaction route, not only can a target product be obtained, but also an ionic liquid catalyst can be well recycled, the regeneration is convenient, the method is safe and environment-friendly, the reaction process is simple to operate, raw materials are easy to obtain, and the cost is reduced.
In order to realize the purpose, the technical scheme adopted by the invention is a preparation method of methyl 3-methoxyacrylate, which comprises the following steps:
step 1, using methyl acetate as a reaction raw material, using methyl formate or CO as a reaction auxiliary material, and reacting in a nonpolar solvent under the condition of existence of alkali metal alkoxide by using inert gas as protection to obtain an addition product suspension;
step 2, cooling the obtained suspension of the addition product, neutralizing the suspension of the addition product with acid under the protection of inert gas until the pH value is acidic, and standing for layering to obtain an addition product solution;
step 3, adding ionic liquid serving as a catalyst into the adduct solution, adding methanol, heating to 20-80 ℃ for reaction, and separating methanol after the reaction is finished to obtain a condensate solution;
and 4, heating the condensate solution to 80-160 ℃, and carrying out elimination reaction under the action of a catalyst to obtain the 3-methoxy methyl acrylate.
By controlling the reaction temperature in the step 3, preferably 60-65 ℃, the reaction temperature is matched with the physical properties of the ionic liquid body fluid, and the temperature condition at the solid critical point of the ionic liquid is very favorable for the acetal reaction, so that the reaction can be well promoted to be carried out, the obtained reaction product is controllable, if the reaction temperature is too high, the side reactions are more, the yield and the content of the obtained product are poor, and if the reaction temperature is too low, the reaction is slow, the reaction is incomplete, the production period is long, and the yield is low. The elimination reaction is to remove one molecule of methanol on the methyl 3, 3-dimethoxypropionate.
In one embodiment of the present invention, in step 1, the molar ratio of the alkali metal alkoxide to the methyl acetate is 1: 0.5-1, wherein the addition amount of the ionic liquid is 20-30% (wt%) of methyl acetate.
In an embodiment of the invention, in step 1 and step 2, the suspension of the adduct is cooled to 0-5 ℃, neutralized with an acid under the protection of an inert gas until the pH value is 2-6, and then kept stand for layering to obtain an adduct solution.
In one embodiment of the invention, in step 3, unreacted methanol is separated off by distillation under reduced pressure at a temperature of 40 to 80 ℃.
In an embodiment of the invention, in step 4, the temperature is raised to 100-120 ℃ for elimination reaction, standing and layering are carried out after the reaction is completed, a lower layer of ionic liquid is separated, and high vacuum distillation is switched after the upper layer of feed liquid is subjected to reduced pressure desolventizing and drying to obtain the methyl 3-methoxyacrylate. The elimination reaction can be carried out by evaporating low-boiling-point substances under normal pressure while keeping the temperature, and the elimination temperature is too high, so that the solvent flows out too fast, which is not beneficial to the reaction.
In an embodiment of the present invention, in step 3, the nonpolar solvent is toluene or xylene, the reaction temperature is 60-80 ℃, and the reaction time is 2-6 h. And a nonpolar solvent is used as a solvent of the reaction system, so that side reactions are few.
In an embodiment of the present invention, the alkali metal alkoxide is sodium methoxide or sodium ethoxide or potassium methoxide or potassium tert-butoxide
In one embodiment of the present invention, the ionic liquid is a Brosted-Lewis double acid ionic liquid. The adopted Brosted-Lewis double-acid ionic liquid has good catalytic effect and strong stability, can be recycled for 200 times, and is easy to separate and regenerate.
In one embodiment of the present invention, the Brosted-Lewis bi-acidic ionic liquid is 1-methyl-3- (propyl-3-sulfonic acid) imidazolium chloride salt, or 1-methyl-3- (propyl-3-sulfonic acid) imidazolium chloride salt.
In an embodiment of the present invention, the preparation method of the ionic liquid comprises: mixing 1, 3-propane sultone and methyl acetate, slowly dripping N-methylimidazole at 60-65 ℃ for reaction, washing and drying by using methyl acetate after the reaction is finished to obtain 1-methyl-3- (propyl 3-sulfonic acid) imidazole salt, dissolving a proper amount of 1-methyl-3- (propyl 3-sulfonic acid) imidazole salt in deionized water, slowly dripping equimolar hydrochloric acid at room temperature, reacting at 85-90 ℃ for 2-2.5h, decompressing, dehydrating and drying to obtain 1-methyl-3- (propyl-3-sulfonic acid) imidazole chloride salt ([ HO (H) chloride3S(CH2)3-mim]Cl); under the protection of nitrogen, [ HO ] is carried out3S(CH2)3-mim]Cl and AlCl3Heating to [ HO3S(CH2)3-mim]Cl in molten state, with AlCl3Reacting until the solid particles are completely dissolved to obtain 1-methyl-3- (propyl-3 sulfonic acid) imidazole aluminum chloride salt ([ HO ] S3S(CH2)3-mim]Cl.AlCl3)。
In an embodiment of the present invention, in step 1, the methyl formate is first mixed with toluene or xylene, and then is simultaneously added dropwise to the toluene or xylene solution of the alkali metal alkoxide together with methyl acetate, respectively, where the molar ratio of methyl formate to methyl acetate is 1: 0.5-1. The unit consumption of methyl formate caused by volatilization is reduced by adopting a mode of dropwise adding after mixing methyl formate and dimethylbenzene or methylbenzene, and the quality of the reaction is ensured. The methyl acetate is added to the reaction system in a dropwise manner.
In an embodiment of the present invention, in step 1, the reaction auxiliary material may be replaced by CO, an inert gas is introduced during the reaction, and CO is introduced for the reaction after the gas replacement is completed. Introducing CO to 0.3-0.8Mpa, reacting for a certain time, and obtaining a condensation compound solution after the heat preservation.
The technical scheme has the following beneficial effects:
methyl acetate is used as a raw material, formyl is introduced by utilizing methyl formate or CO under the action of a catalyst to obtain formyl carboxylic ester sodium salt, then aldol condensation reaction is carried out between the formyl carboxylic ester sodium salt and methanol under the condition that ionic liquid is used as a catalyst to obtain 3, 3-dimethoxy methyl propionate, after the reaction is completed, the methanol is decompressed and separated, after the separation is completed, the temperature is raised to 80-150 ℃, the elimination reaction is carried out to remove one molecule of methanol on the 3, 3-dimethoxy methyl propionate to obtain 3-methoxy methyl acrylate; wherein the condensation reaction and the elimination reaction can be completed in one pot, the operation is simple, and the industrial production process is greatly facilitated. Meanwhile, the prepared double-acid ionic liquid has strong catalytic capability and stability in the using process, can be recycled for 200 times, is convenient to regenerate, and is not polluted by materials.
The method has the advantages of simple operation of the selected process route, safe and controllable reaction process, lower cost of raw materials, higher yield of the target product under proper process conditions, good quality of the obtained 3-methoxy methyl acrylate with the content of more than 99 percent, and better conformity with the environmental protection requirement and the requirement of industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
[HO3S(CH2)3-mim]Cl.AlCl3Preparation of ionic liquids
The preparation method of the ionic liquid comprises the following steps: 1, 3-propane sultone and methyl acetateMixing, slowly dripping N-methylimidazole at 60 ℃ for reaction, washing and drying by methyl acetate after the reaction is finished to obtain 1-methyl-3- (propyl 3-sulfonic acid) imidazolium salt, then dissolving a proper amount of 1-methyl-3- (propyl 3-sulfonic acid) imidazolium salt in deionized water, slowly dripping equimolar hydrochloric acid at room temperature, reacting for 2 hours at 90 ℃, decompressing and dehydrating, drying, and cleaning water by using ethanol to obtain 1-methyl-3- (propyl-3-sulfonic acid) imidazolium chloride ([ HO ] chloride3S(CH2)3-mim]Cl). Methyl acetate is used as a solvent, so that the 1, 3-propane sultone has good solubility and good reaction effect, and the solvent is easy to remove after the reaction is completed and has a low boiling point; 1-methyl-3- (propyl 3-sulfonic acid) imidazole and hydrogen chloride are salified, and if water exists, the obtained chlorine salt is poor in quality, so that the obtained product is high in purity by adopting a method of completely cleaning water by using ethanol.
Then, under the protection of nitrogen, [ HO ] is carried out3S(CH2)3-mim]Cl and AlCl3Heating to [ HO3S (CH2)3-mim]Cl in molten state, with AlCl3Reacting until the solid particles are completely dissolved to obtain 1-methyl-3- (propyl-3 sulfonic acid) imidazole aluminum chloride salt ([ HO ] S3S(CH2)3-mim]Cl.AlCl3). The 1-methyl-3- (propyl-3-sulfonic acid) imidazole chloride reacts with aluminum trichloride in a heating and melting state, and the method has the advantages of fast reaction, full reaction, visual phenomenon and easy process control.
Prepared by3S(CH2)3-mim]Cl.AlCl3The reaction was carried out as a catalyst.
Example 1
27g of sodium methoxide is put into 200g of xylene solution, the temperature is raised to 60 ℃, 0.5mol of methyl acetate is added dropwise while the nitrogen protection is carried out, the mixed solution of 0.58mol of methyl formate and 62g of xylene is added dropwise, the dropwise addition is finished after controlling for 2 hours, and then the temperature is kept for 2 hours, so that xylene mixed solution of the addition product is obtained.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, stirring for 30min, slowly heating to 60 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a xylene condensation compound solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 120 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate, wherein in the embodiment, the molar total yield of the methyl 3-methoxyacrylate is 85%, and the purity of the methyl 3-methoxyacrylate is more than 99% through gas phase detection.
Example 2
27g of sodium methoxide is put into 200g of xylene solution, the temperature is raised to 60 ℃, 0.5mol of methyl acetate is dripped while the nitrogen protection is carried out, the mixed solution of 1mol of methyl formate and 62g of xylene is dripped, the dripping is finished after the control for 2 hours, and then the temperature is kept for 2 hours, thus obtaining the xylene mixed solution of the addition product.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, stirring for 30min, slowly heating to 65 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a xylene condensation compound solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 120 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 86%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 3
54g of sodium methoxide is put into 200g of xylene solution, the temperature is raised to 60 ℃, 0.5mol of methyl acetate is added dropwise while the nitrogen protection is carried out, the mixed solution of 0.58mol of methyl formate and 62g of xylene is added dropwise, the dropwise addition is finished after controlling for 2 hours, and then the temperature is kept for 2 hours, so that the xylene mixed solution of the addition product is obtained.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, stirring for 30min, slowly heating to 60 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a xylene condensation compound solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 120 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 60%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 4
13.5g of sodium methoxide is put into 200g of xylene solution, the temperature is raised to 70 ℃, 0.5mol of methyl acetate is dripped while the nitrogen is used for protection, the mixed solution of 0.58mol of methyl formate and 62g of xylene is dripped, the dripping is finished after controlling for 2 hours, and then the temperature is kept for 2 hours, thus obtaining the xylene mixed solution of the addition product.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, stirring for 30min, slowly heating to 65 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a xylene condensation compound solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 120 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 48%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 5
27g of sodium methoxide is put into 200g of xylene solution, the temperature is raised to 60 ℃, 0.5mol of methyl acetate is dripped while the nitrogen protection is carried out, the mixed solution of 0.5mol of methyl formate and 62g of xylene is dripped, the dripping is finished after controlling for 2 hours, and then the temperature is kept for 2 hours at the temperature, so as to obtain the xylene mixed solution of the addition product.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, stirring for 30min, slowly heating to 65 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a xylene condensation compound solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 120 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 80%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 6
27g of sodium methoxide is put into 200g of xylene solution, the temperature is raised to 80 ℃, 0.5mol of methyl acetate is added dropwise while the nitrogen protection is carried out, the mixed solution of 0.58mol of methyl formate and 62g of xylene is added dropwise, the dropwise addition is finished after controlling for 2 hours, and then the temperature is kept for 2 hours, so that xylene mixed solution of the addition product is obtained.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, stirring for 30min, slowly heating to 25 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a xylene condensation compound solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 120 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 42%, and the purity of methyl 3-methoxyacrylate was greater than 95% by gas phase detection.
Example 7
27g of sodium methoxide is put into 200g of xylene solution, the temperature is raised to 80 ℃, 0.5mol of methyl acetate is added dropwise while the nitrogen protection is carried out, the mixed solution of 0.58mol of methyl formate and 62g of xylene is added dropwise, the dropwise addition is finished after controlling for 2 hours, and then the temperature is kept for 2 hours, so that xylene mixed solution of the addition product is obtained.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, stirring for 30min, slowly heating to 80 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a xylene condensation compound solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 120 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 70%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 8
27g of sodium methoxide is put into 200g of xylene solution, the temperature is raised to 60 ℃, 0.5mol of methyl acetate is added dropwise while the nitrogen protection is carried out, the mixed solution of 0.58mol of methyl formate and 62g of xylene is added dropwise, the dropwise addition is finished after controlling for 2 hours, and then the temperature is kept for 2 hours, so that xylene mixed solution of the addition product is obtained.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, stirring for 30min, slowly heating to 65 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a xylene condensation compound solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 160 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 78%, and the purity of methyl 3-methoxyacrylate was greater than 98% by gas phase detection.
Example 9
27g of sodium methoxide was put in 200g of a toluene solution, the temperature was raised to 60 ℃, a mixed solution of 0.58mol of methyl acetate and 62g of toluene was added dropwise under nitrogen protection, the addition was completed by controlling for 2 hours, and the temperature was maintained at this temperature for 2 hours to obtain a toluene mixed solution of an adduct.
Adding toluene mixture of the adduct into a four-neck flask, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH of 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper toluene solution3S(CH2)3-mim]Cl.AlCl310g, stirring for 30min, slowly heating to 60 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a condensation compound toluene solution.
And (3) continuously heating the obtained condensation compound toluene solution to 100 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure toluene removal on the upper layer toluene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 81%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 10
27g of sodium methoxide is put into 200g of toluene solution, the temperature is raised to 80 ℃, 0.5mol of methyl acetate is added dropwise while the nitrogen protection is carried out, the mixed solution of 0.58mol of methyl formate and 62g of xylene is added dropwise, the dropwise addition is finished after controlling for 2 hours, and then the temperature is kept for 2 hours, so that the xylene mixed solution of the addition product is obtained.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, stirringStirring for 30min, slowly heating to 60 deg.C, keeping the temperature for reaction for 3 hr, and after the aldolization reaction is completed, distilling off unreacted methanol under reduced pressure to obtain xylene condensate solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 120 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 83%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 11
27g of sodium methoxide is put into 200g of xylene solution, the temperature is raised to 60 ℃, 0.5mol of methyl acetate is added dropwise while the nitrogen protection is carried out, the mixed solution of 0.58mol of methyl formate and 62g of xylene is added dropwise, the dropwise addition is finished after controlling for 2 hours, and then the temperature is kept for 2 hours, so that xylene mixed solution of the addition product is obtained.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl35g, stirring for 30min, slowly heating to 70 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a xylene condensation compound solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 120 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 72%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 12
27g of sodium methoxide is put into 200g of xylene solution, the temperature is raised to 60 ℃, 0.5mol of methyl acetate is added dropwise while the nitrogen protection is carried out, the mixed solution of 0.58mol of methyl formate and 62g of xylene is added dropwise, the dropwise addition is finished after controlling for 2 hours, and then the temperature is kept for 2 hours, so that xylene mixed solution of the addition product is obtained.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl315g, stirring for 30min, slowly heating to 55 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a xylene condensation compound solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 110 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 82%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 13
27g of sodium methoxide is put into 200g of xylene solution, the temperature is raised to 60 ℃, 0.5mol of methyl acetate is added dropwise while the nitrogen protection is carried out, the mixed solution of 0.58mol of methyl formate and 62g of xylene is added dropwise, the dropwise addition is finished after controlling for 2 hours, and then the temperature is kept for 2 hours, so that xylene mixed solution of the addition product is obtained.
Adding xylene mixture of the adduct into a four-neck flask, cooling to 0-5 ℃, and neutralizing with 15% hydrochloric acid under the protection of nitrogen until the pH value is 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl320g, stirring for 30min,slowly heating to 65 ℃, preserving the temperature for reaction for 3 hours, and after the acetalization reaction is finished, distilling off unreacted methanol under reduced pressure to obtain a xylene condensation compound solution.
And (3) continuously heating the xylene solution of the obtained condensation compound to 100 ℃ without separating out ionic liquid to carry out elimination reaction, standing for 30min for layering after the reaction is finished, separating out the ionic liquid at the lower layer, and ensuring that the recovery rate of the ionic liquid is more than 99%. And (3) carrying out reduced pressure xylene removal on the upper xylene material liquid at the temperature of 60-80 ℃, and distilling by using a high vacuum oil pump after drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 77%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 14
Adding 27g of sodium methoxide, 200g of dimethylbenzene, 37g of methyl acetate and 1g of methanol into an autoclave, replacing the autoclave by nitrogen, introducing CO for replacement once after replacement is finished, introducing CO to the autoclave to reach the pressure of 0.5Mpa, preserving the temperature at 60 ℃, and obtaining dimethylbenzene mixed liquor of an addition product after the reaction is finished. By adopting CO instead of methyl formate, the raw material cost is lower.
Adding xylene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH 6. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, reacting at 65 ℃ for 6 hours under heat preservation, slowly heating to 70 ℃ after the reaction is finished, distilling unreacted methanol under reduced pressure, continuously heating to 120 ℃ after the distillation is finished, carrying out elimination reaction, standing for layering after the reaction is finished, separating out lower-layer ionic liquid, wherein the recovery rate of the ionic liquid is more than 99%, and distilling the upper-layer xylene material liquid by using a high vacuum oil pump after reduced pressure xylene removal and drying to obtain the methyl 3-methoxyacrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 83%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 15
27g of sodium methoxide, 200g of toluene, 37g of methyl acetate and 1g of methanol are added into an autoclave, nitrogen is used for replacement in the autoclave, after the replacement is finished, CO is introduced for replacement once, then CO is introduced to the autoclave to reach the pressure of 0.5Mpa, the temperature is kept at 80 ℃, and the toluene mixed solution of the addition product is obtained after the reaction is finished. By adopting CO instead of methyl formate, the raw material cost is lower.
Adding toluene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH 6. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper toluene solution3S(CH2)3-mim]Cl.AlCl310g, reacting at 65 ℃ for 6 hours under heat preservation, slowly heating to 70 ℃ after the reaction is finished, distilling unreacted methanol under reduced pressure, continuing heating to 120 ℃ to perform elimination reaction after the distillation is finished, reacting for 3 hours under heat preservation, standing and layering after the reaction is finished, separating out lower-layer ionic liquid, wherein the recovery rate of the ionic liquid is more than 99%, and distilling upper-layer toluene material liquid by using a high vacuum oil pump after reducing pressure and removing toluene and drying to obtain the methyl 3-methoxyacrylate, wherein in the embodiment, the total molar yield of the methyl 3-methoxyacrylate is 81%, and the purity of the methyl 3-methoxyacrylate is more than 98% through gas phase detection.
Example 16
34g of sodium ethoxide, 200g of xylene, 37g of methyl acetate and 1g of methanol are added into an autoclave, nitrogen is used for replacement in the autoclave, CO is introduced for replacement once after the replacement is finished, then CO is introduced to the autoclave to reach the pressure of 0.5Mpa, the temperature is kept at 60 ℃, and the xylene mixed solution of the addition product is obtained after the reaction is finished. By adopting CO instead of methyl formate, the raw material cost is lower.
Adding xylene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH 6. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, reacting at 60 ℃ for 6 hours under heat preservation, slowly heating to 70 ℃ after the reaction is finished, distilling unreacted methanol under reduced pressure, continuing heating to 120 ℃ after the distillation is finished, carrying out elimination reaction, reacting for 3 hours under heat preservation, standing for layering after the reaction is finished, separating out lower-layer ionic liquid, wherein the recovery rate of the ionic liquid is more than or equal to that of the ionic liquid99 percent, after the upper xylene material liquid is decompressed, xylene removed and dried, the 3-methoxy methyl acrylate is obtained by distillation with a high vacuum oil pump, in the embodiment, the total molar yield of the 3-methoxy methyl acrylate is 83 percent, and the purity of the 3-methoxy methyl acrylate is more than 99 percent through gas phase detection.
Example 17
Adding 56g of potassium tert-butoxide, 200g of xylene, 37g of methyl acetate and 1g of methanol into an autoclave, replacing the autoclave by nitrogen, introducing CO for replacement once after the replacement is finished, introducing CO to the pressure of 0.5Mpa, preserving the temperature at 60 ℃, and obtaining xylene mixed liquor of the addition product after the reaction is finished. By adopting CO instead of methyl formate, the raw material cost is lower.
Adding xylene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH 6. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, reacting at 65 ℃ for 6 hours under heat preservation, slowly heating to 70 ℃ after the reaction is finished, distilling unreacted methanol under reduced pressure, continuing heating to 120 ℃ to perform elimination reaction after the distillation is finished, reacting for 3 hours under heat preservation, standing and layering after the reaction is finished, separating out lower-layer ionic liquid, wherein the recovery rate of the ionic liquid is more than 99%, and distilling the upper-layer xylene material liquid by using a high vacuum oil pump after reduced pressure xylene removal and drying to obtain the 3-methoxy methyl acrylate, wherein in the embodiment, the total molar yield of the 3-methoxy methyl acrylate is 75%, and the purity of the 3-methoxy methyl acrylate is more than 98% through gas phase detection.
Example 18
Adding 48g of sodium tert-butoxide, 200g of dimethylbenzene, 37g of methyl acetate and 1g of methanol into an autoclave, replacing the autoclave with nitrogen, introducing CO for replacement once after the replacement is finished, introducing CO to the pressure of 0.5Mpa, preserving the temperature at 60 ℃, and obtaining dimethylbenzene mixed liquor of the addition product after the reaction is finished. By adopting CO instead of methyl formate, the raw material cost is lower.
Adding xylene mixed solution of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, neutralizing with 15% hydrochloric acid under nitrogen protection to pHIs 6. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, reacting at 65 ℃ for 6 hours under heat preservation, slowly heating to 70 ℃ after the reaction is finished, distilling unreacted methanol under reduced pressure, continuing heating to 120 ℃ to perform elimination reaction after the distillation is finished, reacting for 3 hours under heat preservation, standing and layering after the reaction is finished, separating out lower-layer ionic liquid, wherein the recovery rate of the ionic liquid is more than 99%, and distilling the upper-layer xylene material liquid by using a high vacuum oil pump after reduced pressure xylene removal and drying to obtain the 3-methyl methoxyacrylate, wherein in the embodiment, the total molar yield of the 3-methyl methoxyacrylate is 77%, and the purity of the 3-methyl methoxyacrylate is more than 99% through gas phase detection.
Example 19
Adding 40g of sodium methoxide, 200g of dimethylbenzene, 37g of methyl acetate and 1g of methanol into an autoclave, replacing the autoclave by nitrogen, introducing CO for replacement once after replacement is finished, introducing CO to the autoclave to reach the pressure of 0.5Mpa, preserving heat at 70 ℃, and obtaining dimethylbenzene mixed liquor of an addition product after reaction is finished. By adopting CO instead of methyl formate, the raw material cost is lower.
Adding xylene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH 6. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, reacting at 65 ℃ for 6 hours under heat preservation, slowly heating to 70 ℃ after the reaction is finished, distilling unreacted methanol under reduced pressure, continuing heating to 120 ℃ to perform elimination reaction after the distillation is finished, reacting for 3 hours under heat preservation, standing and layering after the reaction is finished, separating out lower-layer ionic liquid, wherein the recovery rate of the ionic liquid is more than 99%, and distilling the upper-layer xylene material liquid by using a high vacuum oil pump after reduced pressure xylene removal and drying to obtain the methyl 3-methoxyacrylate, wherein in the embodiment, the total molar yield of the methyl 3-methoxyacrylate is 80%, and the purity of the methyl 3-methoxyacrylate is more than 99% through gas phase detection.
Example 20
Adding 35g of potassium methoxide, 200g of dimethylbenzene, 37g of methyl acetate and 1g of methanol into an autoclave, replacing the autoclave by nitrogen, introducing CO for replacement once after replacement is finished, introducing CO to 0.8MPa of pressure, preserving heat at 60 ℃, and obtaining dimethylbenzene mixed liquor of an addition product after reaction is finished. By adopting CO instead of methyl formate, the raw material cost is lower.
Adding xylene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH 6. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, reacting at 65 ℃ for 6 hours under heat preservation, slowly heating to 70 ℃ after the reaction is finished, distilling unreacted methanol under reduced pressure, continuing heating to 120 ℃ to perform elimination reaction after the distillation is finished, reacting for 3 hours under heat preservation, standing and layering after the reaction is finished, separating out lower-layer ionic liquid, wherein the recovery rate of the ionic liquid is more than 99%, and distilling upper-layer xylene material liquid by using a high vacuum oil pump after reduced pressure xylene removal and drying to obtain the 3-methoxy methyl acrylate, wherein in the embodiment, the total molar yield of the 3-methoxy methyl acrylate is 81%, and the purity of the 3-methoxy methyl acrylate is more than 99% through gas phase detection.
Example 21
42g of potassium ethoxide, 200g of xylene, 37g of methyl acetate and 1g of methanol are added into an autoclave, nitrogen is used for replacement in the autoclave, CO is introduced for replacement once after the replacement is finished, then CO is introduced to the autoclave to reach the pressure of 0.5Mpa, the temperature is kept at 60 ℃, and the xylene mixed liquor of the addition product is obtained after the reaction is finished. By adopting CO instead of methyl formate, the raw material cost is lower.
Adding xylene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH 6. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, reacting at 65 ℃ for 6 hours in a heat preservation way, slowly heating to 70 ℃ after the reaction is finished, distilling unreacted methanol under reduced pressure, continuously heating to 120 ℃ after the distillation is finished, carrying out elimination reaction, and reacting for 3 hours in a heat preservation wayAnd then standing and layering after the reaction is finished, separating out lower-layer ionic liquid, wherein the recovery rate of the ionic liquid is more than 99%, and distilling the upper-layer xylene material liquid by using a high vacuum oil pump after removing xylene under reduced pressure and drying. In this example, the total molar yield of methyl 3-methoxyacrylate was 80%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
Example 22
Adding 27g of sodium methoxide, 200g of dimethylbenzene, 37g of methyl acetate and 1g of methanol into an autoclave, replacing the autoclave by nitrogen, introducing CO for replacement once after replacement is finished, introducing CO to the autoclave to reach the pressure of 0.3Mpa, preserving the temperature at 60 ℃, and obtaining dimethylbenzene mixed liquor of an addition product after the reaction is finished. By adopting CO instead of methyl formate, the raw material cost is lower.
Adding xylene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH 6. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]Cl.AlCl310g, reacting at 80 ℃ for 6 hours under heat preservation, slowly heating to 70 ℃ after the reaction is finished, distilling unreacted methanol under reduced pressure, continuously heating to 100 ℃ after the distillation is finished, carrying out elimination reaction, standing for layering after the reaction is finished, separating out lower-layer ionic liquid, wherein the recovery rate of the ionic liquid is more than 99%, and distilling the upper-layer xylene material liquid by using a high vacuum oil pump after reduced pressure xylene removal and drying to obtain the 3-methoxy methyl acrylate. In this example, the total molar yield of methyl 3-methoxyacrylate was 65%, and the purity of methyl 3-methoxyacrylate was greater than 99% by gas phase detection.
In the above examples, the gas phase detection conversion rate > 98% is used as the reaction end point in the manner of determining the completion of the reaction in the elimination reaction, the purity of the target product, namely, 3-methoxy methyl acrylate, can substantially reach more than 99%, and the yield of the target product can reach as high as 86% under the specific reaction conditions.
Comparative example 1
Selection of [ HO3S(CH2)3-mim]Cl as catalyst for comparison。
27g of sodium methoxide is added into 200g of dimethylbenzene, the temperature of the system is raised to 60 ℃, 37g of methyl acetate is dropwise added while nitrogen protection is adopted, the mixture of 35g of methyl formate and 62g of dimethylbenzene is dropwise added, the dropwise addition is controlled to be finished for 2 hours, and then the temperature is kept for 2 hours, so that the dimethylbenzene mixture of the addition product is obtained.
Adding xylene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH of 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ HO ] into upper xylene addition solution3S(CH2)3-mim]And (2) Cl 10g, reacting at 65 ℃ for 6 hours with the heat preservation, the conversion rate being less than 90%, slowly heating to 70 ℃, distilling unreacted methanol under reduced pressure, continuing heating to 120 ℃ after the distillation is finished, carrying out elimination reaction, reacting at the heat preservation for 3 hours with the conversion rate being less than 85%, standing and separating to obtain no ionic liquid, and distilling the material liquid by using a high vacuum oil pump after removing dimethylbenzene under reduced pressure and drying to obtain the methyl 3-methoxyacrylate. The ionic liquid is mixed with high boiling water and is difficult to recover. In this example, the total molar yield of methyl 3-methoxyacrylate was 70%.
Comparative example 2
Selection of [ C4mim]Cl was used as a catalyst for comparison.
27g of sodium methoxide is added into 200g of dimethylbenzene, the temperature of the system is raised to 60 ℃, 37g of methyl acetate is dropwise added while nitrogen protection is adopted, the mixture of 35g of methyl formate and 62g of dimethylbenzene is dropwise added, the dropwise addition is controlled to be finished for 2 hours, and then the temperature is kept for 2 hours, so that the dimethylbenzene mixture of the addition product is obtained.
Adding xylene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH of 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ C ] into upper xylene addition solution4mim]Keeping the temperature of 10g of Cl at 65 ℃ for 6 hours for reaction, wherein the conversion rate is less than 80 percent, slowly heating to 70 ℃, distilling unreacted methanol under reduced pressure, continuing heating to 120 ℃ for elimination reaction after the distillation is finished, keeping the temperature for reaction for 3 hours, wherein the conversion rate is less than 60 percent, and the ionic liquid and the product are obtainedMixing and dissolving the materials, removing dimethylbenzene under reduced pressure, removing dryness, and distilling with a high vacuum oil pump to obtain the methyl 3-methoxyacrylate. After completion, 50g of water and 50g of xylene were added. Layering, distilling and dehydrating the ionic liquid and water together, and recovering the ionic liquid with the recovery rate of 70%. In this example, the total molar yield of methyl 3-methoxyacrylate was 55%.
Comparative example 3
Selecting strong acidic ionic liquid [ C ]4mim]BF4The comparison was carried out as a catalyst.
27g of sodium methoxide is added into 200g of dimethylbenzene, the temperature of the system is raised to 60 ℃, 37g of methyl acetate is dropwise added while nitrogen protection is adopted, the mixture of 35g of methyl formate and 62g of dimethylbenzene is dropwise added, the dropwise addition is controlled to be finished for 2 hours, and then the temperature is kept for 2 hours, so that the dimethylbenzene mixture of the addition product is obtained.
Adding xylene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH of 3. Standing for layering, separating lower water layer, adding 60g methanol and ionic liquid [ C ] into upper xylene addition solution4mim]BF410g, reacting at 65 ℃ for 6 hours with the heat preservation, the conversion rate being more than 97 percent, slowly heating to 70 ℃, distilling unreacted methanol under reduced pressure, continuing heating to 120 ℃ after the distillation is finished, carrying out elimination reaction, reacting for 3 hours with the heat preservation, standing and layering with the conversion rate being more than 95 percent, separating lower-layer ionic liquid, and the recovery rate of the ionic liquid being 70 percent. After the xylene material liquid at the upper layer is subjected to reduced pressure xylene removal and drying, the 3-methoxy methyl acrylate is obtained by distillation with a high vacuum oil pump, and in the embodiment, the total molar yield of the 3-methoxy methyl acrylate is 72%.
Comparative example 4
The comparison was carried out using an organic acid as catalyst.
27g of sodium methoxide is added into 200g of dimethylbenzene, the temperature of the system is raised to 60 ℃, 37g of methyl acetate is dropwise added while the nitrogen protection is adopted, a mixed solution of 62g of methyl formate and 62g of dimethylbenzene is dropwise added, the dropwise addition is controlled to be finished for 2 hours, and then the temperature is kept for 2 hours, so that a dimethylbenzene mixed solution of an addition product is obtained.
Adding xylene mixture of the adduct into a four-mouth bottle, cooling to 0-5 deg.C, and neutralizing with 15% hydrochloric acid under nitrogen protection to pH of 3. Standing and layering, separating a lower water layer, adding 60g of methanol and 20g of p-toluenesulfonic acid into an upper xylene addition solution, carrying out heat preservation reaction at 65 ℃ for 6 hours, slowly heating to 70 ℃ after the reaction is finished, carrying out reduced pressure distillation on unreacted methanol, continuously heating to 120 ℃ after the distillation is finished, carrying out elimination reaction, carrying out heat preservation reaction for 3 hours, cooling to 20 ℃ after the reaction is finished, filtering out p-toluenesulfonic acid, carrying out reduced pressure xylene removal on filtrate, and carrying out drying removal on the filtrate, and distilling by using a high vacuum oil pump to obtain the methyl 3-methoxyacrylate.
As can be seen from comparative examples 1-4, when the above substances are used as catalysts, the catalysts can not be or are inconvenient to recover, and the method adopts the bi-acidic ionic liquid as the catalyst, so that the subsequent recovery is easy, a higher yield can be obtained under the optimal conditions, the purity of the target product is high, and the requirement of industrial production is met.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any changes and alterations made without inventive step within the spirit and scope of the claims are intended to fall within the scope of the invention.
Claims (12)
1. A preparation method of methyl 3-methoxyacrylate is characterized by comprising the following steps:
step 1, using methyl acetate as a reaction raw material, using methyl formate or CO as a reaction auxiliary material, and reacting in a nonpolar solvent under the condition of existence of alkali metal alkoxide by using inert gas as protection to obtain an addition product suspension;
step 2, cooling the obtained suspension of the addition product, neutralizing the suspension of the addition product with acid under the protection of inert gas until the pH value is acidic, and standing for layering to obtain an addition product solution;
step 3, adding ionic liquid serving as a catalyst into the adduct solution, adding methanol, heating to 20-80 ℃ for reaction, and separating methanol after the reaction is finished to obtain a condensate solution;
and 4, heating the condensate solution to 80-160 ℃, and carrying out elimination reaction under the action of a catalyst to obtain the 3-methoxy methyl acrylate.
2. The method of claim 1, wherein the molar ratio of the alkali metal alkoxide to the methyl acetate is 1: 0.5-1, wherein the addition amount of the ionic liquid is 20-30% (wt%) of methyl acetate.
3. The method for preparing methyl 3-methoxyacrylate according to claim 1, wherein in step 2, the suspension of the adduct is cooled to 0-5 ℃, neutralized with an acid under the protection of an inert gas to a pH value of 2-6, and allowed to stand for layering to obtain an adduct solution.
4. The process for producing methyl 3-methoxyacrylate according to claim 1, wherein in the step 3, unreacted methanol is separated by distillation under reduced pressure at a temperature of 40 to 80 ℃.
5. The method as claimed in claim 1, wherein the temperature in step 4 is raised to 100-120 ℃ to carry out elimination reaction, the reaction is followed by standing for layering, the lower ionic liquid layer is separated, the upper liquid layer is subjected to reduced pressure desolventization, and high vacuum distillation is switched after drying to obtain the methyl 3-methoxyacrylate.
6. The method of claim 1, wherein the nonpolar solvent is toluene or xylene, the reaction temperature is 60-80 ℃, and the reaction time is 2-6 h.
7. The process for producing methyl 3-methoxyacrylate according to claim 1, wherein the alkali metal alkoxide is sodium methoxide or sodium ethoxide or potassium methoxide or potassium tert-butoxide.
8. The process for preparing methyl 3-methoxyacrylate according to any one of claims 1 to 7, wherein the ionic liquid is a Brosted-Lewis diacidic ionic liquid.
9. The method of claim 8, wherein the Brosted-Lewis double acidic ionic liquid is 1-methyl-3- (propyl-3-sulfonic acid) imidazolium chloride salt, or 1-methyl-3- (propyl-3-sulfonic acid) imidazolium chloride salt.
10. The method for preparing methyl 3-methoxyacrylate according to claim 9, wherein the method for preparing the ionic liquid comprises: mixing 1, 3-propane sultone and methyl acetate, slowly dripping N-methylimidazole at 60-65 ℃ for reaction, washing and drying by using methyl acetate after the reaction is finished to obtain 1-methyl-3- (propyl 3-sulfonic acid) imidazole salt, dissolving a proper amount of 1-methyl-3- (propyl 3-sulfonic acid) imidazole salt in deionized water, slowly dripping equimolar hydrochloric acid at room temperature, reacting at 85-90 ℃, decompressing and dehydrating after the reaction is finished, and dehydrating to obtain 1-methyl-3- (propyl-3-sulfonic acid) imidazole chloride salt ([ HO ] chloride3S(CH2)3-mim]Cl); under the protection of nitrogen, [ HO ] is carried out3S(CH2)3-mim]Cl and AlCl3Heating to [ HO3S(CH2)3-mim]Cl in molten state, with AlCl3Reacting until the solid particles are completely dissolved to obtain 1-methyl-3- (propyl-3 sulfonic acid) imidazole aluminum chloride salt ([ HO ] S3S(CH2)3-mim]Cl.AlCl3)。
11. The process for preparing methyl 3-methoxyacrylate according to claim 8, wherein in step 1, the methyl formate is mixed with toluene or xylene and then added dropwise simultaneously with methyl acetate to a solution of alkali metal alkoxide in toluene or xylene, respectively, in a molar ratio of methyl formate to methyl acetate of 1: 0.5-1.
12. The process according to claim 11, wherein in step 1, an inert gas is introduced during the reaction, and CO is introduced after the gas substitution is completed.
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