CN113943221B - Method for preparing formic acid-2-methyl allyl ester from paraformaldehyde and methacrolein - Google Patents
Method for preparing formic acid-2-methyl allyl ester from paraformaldehyde and methacrolein Download PDFInfo
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- CN113943221B CN113943221B CN202111410850.5A CN202111410850A CN113943221B CN 113943221 B CN113943221 B CN 113943221B CN 202111410850 A CN202111410850 A CN 202111410850A CN 113943221 B CN113943221 B CN 113943221B
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- methacrolein
- paraformaldehyde
- formic acid
- methylallyl
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- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229930040373 Paraformaldehyde Natural products 0.000 title claims abstract description 27
- 229920002866 paraformaldehyde Polymers 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- -1 2-methylallyl formate Chemical compound 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 5
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical group [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000006199 crossed Cannizzaro oxidation reduction reaction Methods 0.000 claims 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000005394 methallyl group Chemical group 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 2-methylallyl formate from paraformaldehyde and methacrolein. The method takes paraformaldehyde and methacrolein as raw materials, adds a polymerization inhibitor, and generates cross Cannizzaro disproportionation reaction under the catalysis of anhydrous alkali to generate formic acid-2-methyl allyl ester. The method uses paraformaldehyde to replace formaldehyde, and the methacrolein is not only a reaction raw material but also a solvent, and has the characteristics of low cost, less environmental pollution, easy transportation and storage of raw materials, high atomic economy and the like; and the cross Cannizzaro disproportionation reaction condition of the paraformaldehyde and the methacrolein is mild, easy to control, low in energy consumption, less in byproducts and high in product yield, and a green, environment-friendly and easy-to-realize way is provided for synthesizing the formic acid-2-methylallyl ester.
Description
Technical Field
The invention belongs to the technical fields of organic synthesis and fine chemical engineering, and particularly relates to the field of a method for preparing 2-methyl allyl formate.
Background
The formic acid-2-methyl allyl ester (Formic acid methallyl ester) is an important organic chemical intermediate, and can be used for producing 2-methyl allyl alcohol by hydrolysis in industry, so that preparation is provided for subsequent synthesis of the polycarboxylic acid high-performance concrete water reducer.
In industrial production, the common synthetic method of the ester is high-temperature catalytic dehydration of strong acid, and the method has the advantages of higher energy consumption, more byproducts, more wastewater generation and serious environmental pollution; the other is the esterification of carboxylate salts with halogenated hydrocarbons, which process is severely corrosive to equipment and produces large amounts of spent brine with by-products of ethers.
Disclosure of Invention
The invention aims to provide a method for preparing 2-methyl allyl formate from paraformaldehyde and methacrolein, which has the advantages of simple process, high yield, low cost, less environmental pollution and easy transportation and storage of raw materials.
The invention relates to a method for preparing formic acid-2-methyl allyl ester from paraformaldehyde and methacrolein, which takes paraformaldehyde and methacrolein as raw materials, adds a polymerization inhibitor, and generates cross Cannizzaro disproportionation reaction under the catalysis of a base catalyst to generate the formic acid-2-methyl allyl ester. The preparation process comprises the following steps:
after the paraformaldehyde, the alkali catalyst, the polymerization inhibitor and the methacrolein are mixed, stirring and heating are carried out to the temperature of 20-60 ℃ (preferably 40-55 ℃) for 2-10 hours (preferably 5-8 hours). Cooling to room temperature after the reaction is completed, and removing the alkali catalyst to obtain the formic acid-2-methyl allyl ester. The reaction formula is as follows:
the molar ratio of paraformaldehyde to methacrolein is 1:1.1-1:1.8, preferably 1:1.2-1:1.5.
The alkali catalyst adopts one or a mixture of several of sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, barium hydroxide and calcium hydroxide; the amount of the catalyst is 2% -20% of the mass of the methacrolein.
The polymerization inhibitor is one or a mixture of more of hydroquinone, p-benzoquinone, p-tert-butyl catechol, p-hydroxyanisole, cuprous chloride and ferric trichloride; the consumption of the polymerization inhibitor is 0.05-1% of the mass of the methacrolein.
Through gas chromatography detection analysis, the purity of the 2-methallyl alcohol product prepared by the method can reach 99.8%; the yield reaches 87%.
Compared with the prior art, the invention has the following beneficial effects:
1. adopts paraformaldehyde easy to transport and store as a starting material to synthesize the formic acid-2-methyl allyl ester. Provides a simple, environment-friendly, easy to realize and valuable way for synthesizing the 2-methyl allyl formate;
2. the cross Cannizzaro disproportionation reaction condition of paraformaldehyde and methacrolein is mild, easy to control, low in energy consumption, less in byproducts and high in product yield;
3. the methacrolein is not only a reaction raw material, but also a solvent, and the methacrolein has the characteristics of low separation cost, small environmental pollution, high atom economy and the like without adding additional solvent.
Detailed Description
The process of the present invention for preparing 2-methylallyl formate is further illustrated by the following specific examples.
Example 1
Into a three-necked flask having a volume of 1000mL and magnetic stirring, 94.5g of methacrolein, 30.0g of paraformaldehyde and 4.7g of barium hydroxide (Ba (OH) were charged at one time 2 ·8H 2 O) and 0.5g of hydroquinone, heating is started under magnetic stirring, the reaction temperature is controlled to be 50 ℃, and the reaction time is 8 hours. The reaction solution was cooled to room temperature, solid impurities were removed by filtration, washed with saturated brine, and the organic phase was distilled to obtain 2-methallyl formate (purity 99.8% by GC) in a yield of 87.6%.
Example 2
Into a three-necked flask having a volume of 1000mL and magnetic stirring, 94.5g of methacrolein, 30.0g of paraformaldehyde and 4.7g of barium hydroxide (Ba (OH) were charged at one time 2 ·8H 2 O) and 0.5g of hydroquinone, heating is started under magnetic stirring, the reaction temperature is controlled to be 60 ℃, and the reaction time is 8 hours. Cooling the reaction solution to room temperature, filtering to remove solid impurities, washing with saturated saline water, and rectifying the organic phase to obtain formic acid-2-methyl alkenePropyl ester (purity 99.4% by GC) was obtained in 82.3% yield.
Example 3
In a three-neck flask with a volume of 1000mL and magnetic stirring, 94.5g of methacrolein, 30.0g of paraformaldehyde, 2.0g of sodium hydroxide and 0.5g of hydroquinone are added at a time, wherein the paraformaldehyde is rapidly decomposed under the action of sodium hydroxide, and the sodium hydroxide is required to be slowly added. Heating is started under magnetic stirring, the reaction temperature is controlled to be 50 ℃, and the reaction time is 8 hours. The reaction solution was cooled to room temperature, washed with saturated brine, and the organic phase was distilled to obtain 2-methallyl formate (purity 99.0% by GC) in a yield of 72.8%.
Example 4
In a three-necked flask with a volume of 1000mL and magnetic stirring, 94.5g of methacrolein, 30.0g of paraformaldehyde, 3.7g of calcium hydroxide and 0.5g of hydroquinone were added at a time, and the temperature was raised under magnetic stirring, and the reaction temperature was controlled at 50℃for 8 hours. The reaction solution was cooled to room temperature, washed with saturated brine, and the organic phase was distilled to obtain 2-methylallyl formate (purity 99.2% by GC) in a yield of 76.2%.
Example 5
In a three-necked flask with a volume of 1000mL and magnetic stirring, 94.5g of methacrolein, 30.0g of paraformaldehyde, 3.4g of sodium ethoxide and 0.5g of hydroquinone were added at a time, and the temperature was raised under magnetic stirring, and the reaction temperature was controlled at 50℃for 8 hours. The reaction solution was cooled to room temperature, washed with saturated brine, and the organic phase was distilled to obtain 2-methylallyl formate (purity 99.0% by GC) in a yield of 56.2%.
Claims (5)
1. A method for preparing formic acid-2-methyl allyl ester from paraformaldehyde and methacrolein takes paraformaldehyde and methacrolein as raw materials, and under the existence of a polymerization inhibitor, cross Cannizzaro disproportionation reaction is carried out under the catalysis of a base catalyst to generate formic acid-2-methyl allyl ester; the alkali catalyst is barium hydroxide; the polymerization inhibitor is hydroquinone.
2. A process for preparing 2-methylallyl formate from paraformaldehyde and methacrolein as claimed in claim 1, wherein: the crossed Cannizzaro disproportionation reaction process comprises the following steps: mixing paraformaldehyde, an alkali catalyst, a polymerization inhibitor and methacrolein, heating to 20-60 ℃ for reaction for 2-10 hours, cooling to room temperature after the reaction is completed, and removing the alkali catalyst to obtain the formic acid-2-methylallyl ester.
3. A process for preparing 2-methylallyl formate from paraformaldehyde and methacrolein as claimed in claim 1 or 2, wherein: the molar ratio of the paraformaldehyde to the methacrolein is 1:1.1-1:1.8.
4. A process for preparing 2-methylallyl formate from paraformaldehyde and methacrolein as claimed in claim 1 or 2, wherein: the dosage of the base catalyst is 2-20% of the mass of the methacrolein.
5. A process for preparing 2-methylallyl formate from paraformaldehyde and methacrolein as claimed in claim 1 or 2, wherein: the consumption of the polymerization inhibitor is 0.05-1% of the mass of the methacrolein.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111410850.5A CN113943221B (en) | 2021-11-25 | 2021-11-25 | Method for preparing formic acid-2-methyl allyl ester from paraformaldehyde and methacrolein |
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| CN202111410850.5A CN113943221B (en) | 2021-11-25 | 2021-11-25 | Method for preparing formic acid-2-methyl allyl ester from paraformaldehyde and methacrolein |
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| CN113943221A CN113943221A (en) | 2022-01-18 |
| CN113943221B true CN113943221B (en) | 2023-12-22 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242139A (en) * | 2013-05-22 | 2013-08-14 | 南京工业大学 | Method for preparing 2-methyl allyl alcohol by two-step esterification and hydrolysis |
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2021
- 2021-11-25 CN CN202111410850.5A patent/CN113943221B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242139A (en) * | 2013-05-22 | 2013-08-14 | 南京工业大学 | Method for preparing 2-methyl allyl alcohol by two-step esterification and hydrolysis |
Non-Patent Citations (3)
| Title |
|---|
| Savitskii, Yu. V. et al..Production of methyl formate from formaldehyde.《Vestnik L'vovskogo Politekhnicheskogo Instituta》.1980,第139卷第61-64页. * |
| 汪多仁.《绿色医药化学品》.科学技术文献出版社,2008,(第1版第1次),第1-9页. * |
| 钱庆安.甲基丙烯醛在储存过程中一种主要副产物的生成探索.《化工管理》.2017,第30页. * |
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