CN107032952B - Preparation process of 2-methallyl alcohol - Google Patents
Preparation process of 2-methallyl alcohol Download PDFInfo
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- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000000047 product Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 16
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- -1 methyl propenyl carboxylic ester Chemical class 0.000 claims abstract description 11
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 9
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 6
- 238000006199 crossed Cannizzaro oxidation reduction reaction Methods 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 9
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000011949 solid catalyst Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000010931 ester hydrolysis Methods 0.000 claims description 4
- MCVVUJPXSBQTRZ-UHFFFAOYSA-N methyl but-2-enoate Chemical compound COC(=O)C=CC MCVVUJPXSBQTRZ-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 25
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005882 aldol condensation reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 239000008346 aqueous phase Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 239000004280 Sodium formate Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 8
- 235000019254 sodium formate Nutrition 0.000 description 8
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 7
- 238000004891 communication Methods 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XMHDLKFMJMNOAX-UHFFFAOYSA-N 2-methyl-3-(2-methylprop-2-enoxy)prop-1-ene Chemical compound CC(=C)COCC(C)=C XMHDLKFMJMNOAX-UHFFFAOYSA-N 0.000 description 1
- IVKYUXHYUAMPMT-UHFFFAOYSA-N 2-methylprop-2-enyl acetate Chemical compound CC(=C)COC(C)=O IVKYUXHYUAMPMT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SJRDNQOIQZOVQD-UHFFFAOYSA-M sodium;2,2-dimethylpropanoate Chemical compound [Na+].CC(C)(C)C([O-])=O SJRDNQOIQZOVQD-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a new process for preparing 2-methallyl alcohol, which is to use 2-methylacrolein and methanol
Description
Technical Field
The invention relates to a new process for preparing 2-methallyl alcohol, belonging to the field of chemical synthesis and the technical field of fine chemical engineering.
Background
2-methallyl alcohol is soluble in water and organic solvents, can generate self-polymerization and copolymerization reaction, is an important organic intermediate, is widely applied to a plurality of fields such as medicines, pesticides, spices, resins, polycarboxylic acid water reducing agents and the like, is particularly used for synthesizing polycarboxylic acid water reducing agents, and has been greatly developed in recent years. Because of their performance similarity to allyl alcohol and their much lower toxicity than allyl alcohol, a number of fields have replaced allyl alcohol. Therefore, the market prospect of the 2-methallyl alcohol is very wide.
At present, the preparation processes of 2-methallyl alcohol which are publicly reported mainly comprise the following processes: (1) direct hydrolysis of methallyl chloride. U.S. Pat. No. 5,410,2015 uses methylallyl chloride plus sodium hydroxide or sodium carbonate for direct hydrolysis to obtain 2-methylallyl alcohol. The method has weak activity of the methallyl chloride, needs to add strong base and organic solvent under high temperature and high pressure during hydrolysis to react, and has the problems of harsh reaction conditions, large generation amount of byproduct ether, low product yield, difficult recovery of the organic solvent and the like. On the basis, the Chinese patent CN101759528A adopts polyethylene glycol as a phase transfer catalyst for improvement, but the effect is general, and the problems of difficult product purification and the like are increased. JP2009107949 uses DMF to promote hydrolysis, but introduces a DMF solvent which is difficult to treat, and causes certain pollution to the environment. (2) Indirect hydrolysis of methallyl chloride. Chinese patent CN103242139A uses methallyl chloride as the starting material, and adopts an esterification hydrolysis two-step method to produce 2-methallyl alcohol, in the method, under the action of a phase transfer catalyst, carboxylate, water and methallyl chloride are added into an autoclave to perform esterification reaction, oil and water are layered to obtain methallyl acetate, the obtained ester is added with alkali to perform hydrolysis, and oil and water are layered to obtain 2-methallyl alcohol. Although the method is the most widely applied industrial method at present, the added sodium acetate is easy to crystallize and block pipelines, the equipment in the esterification process is seriously corroded, and a large amount of waste brine is generated; because esterification is incomplete, residual methallyl chloride in the hydrolysis process generates methallyl ether with higher content, thereby influencing the purity of the product. (3) 2-methacrolein reduction method. CN102167657B, US2767221, JP-B56-36176 and the like adopt 2-methylacrolein hydrogenation catalytic reduction to prepare 2-methylallyl alcohol, but have the defects of high reduction temperature, high hydrogenation pressure, poor catalyst hydrogenation selectivity, high saturated alcohol content and the like. (4) An oxidation process of isobutene. CN103755523A adopts isobutene as raw material, firstly carries out catalytic oxidation to obtain 2-methylacrolein, and then carries out catalytic hydrogenation reduction to obtain 2-methylallyl alcohol. The oxidation and the reduction of the method are carried out at high temperature and high pressure, the requirement of strictly controlling the content of raw materials to be lower than the explosion limit is met, the process difficulty is higher, the double bond of isobutene is easier to be oxidized to generate aldehyde, the double bond of intermediate product olefine aldehyde is easier to be hydrogenated to generate saturated alcohol, the hydrogenation selectivity of the catalyst is low, and the product yield is low. In conclusion, the existing reaction processes have many disadvantages, and generally have the disadvantages of production process of generating waste water containing a large amount of halogenated salts, serious equipment corrosion, low product yield, high content of by-product ether and saturated alcohol, difficult solvent recovery, harsh process conditions, high energy consumption, large pollution and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a green process for preparing 2-methallyl alcohol, which has the advantages of high yield, less byproducts, high atom economy, mild reaction conditions and clean process.
The process for preparing 2-methallyl alcohol of the invention is to use 2-methylacrolein and methanol
The aldehyde is used as a raw material, cross Cannizzaro disproportionation reaction is carried out under the catalytic action to generate methyl propenyl carboxylic ester, then the methyl propenyl carboxylic ester is hydrolyzed in an alkali metal hydroxide solution to generate a target product 2-methyl allyl alcohol, and sodium carboxylate is co-produced. The specific preparation process comprises the following steps:
1. cross Cannizzaro disproportionation
2-methylacrolein, solid catalyst, or
After mixing, reacting for 2-10 h under the pressure of 0.1-3 MPa and the temperature of 50-80 ℃; cooling to room temperature after the reaction is finished, and recovering excessive substances
And (3) filtering the aldehyde to remove the solid catalyst, wherein the filtrate is the methyl propenyl carboxylate.
Is free of
The aldehyde of (a) is formaldehyde or an aldehyde of the structure:
wherein R is1，R2，R3Is an alkyl group having 1 to 4 carbon atoms. Formaldehyde and pivalaldehyde are preferred.
2-methylacrolein and
the molar ratio of the aldehyde (b) is 1:1.1 to 1: 1.3.
The solid catalyst is one or a mixture of more of sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide and strontium hydroxide; the amount of the catalyst is 2-20% of the mass of the 2-methylacrolein.
2. Ester hydrolysis reaction
Adding an alkali metal hydroxide aqueous solution into methyl propenyl carboxylate, heating to 60-90 ℃, and reacting for 1-5 h under the condition of heat preservation; after the reaction is finished, adding formic acid for neutralization, cooling to room temperature, separating out an organic phase and a water phase, rectifying the organic phase to obtain a 2-methallyl alcohol product with the purity of more than or equal to 99.8 percent, and distilling the water phase to obtain a carboxylate product with higher purity; the distilled water is recycled by the system.
The mass concentration of the alkali metal hydroxide aqueous solution is 15-50%; the molar ratio of the alkali metal hydroxide to the methacrylic carboxylate is 1.05:1 to 1.5: 1.
Through gas chromatography detection and analysis according to GB/T693-; the yield is 81-98%; the purity of the carboxylate product is more than or equal to 98 percent.
Compared with the prior art, the invention has the following beneficial effects:
1. all aldehyde starting molecules used are free of
The method conforms to a crossed Cannizzaro disproportionation reaction mechanism, almost no aldol condensation reaction occurs between molecules, few byproducts are generated, and the generated product has high conversion rate and good selectivity;
2. the hydrolysis reaction is carried out completely in an alkaline environment, the yield of the 2-methallyl alcohol product is high, the 2-methallyl alcohol product is easy to separate and purify, meanwhile, the carboxylate product is co-produced, and water in the hydrolysis reaction stage is completely recycled;
3. the cross Cannizzaro disproportionation reaction and hydrolysis reaction conditions are mild, the energy consumption is low, and the atom economy is high;
4. the 2-methallyl alcohol product is obtained by two steps in one pot, the process is simple, the cost is low, and the method is green and environment-friendly.
Detailed Description
The process for preparing 2-methylallyl alcohol according to the invention is further illustrated by the following specific examples.
Example 1
Into a 500mL pressure resistant vessel with a stirrer were charged 70.0g of 2-methacrolein and 2.6g of barium hydroxide (Ba (OH))2·8H2And O), screwing the pressure-resistant kettle and checking the air tightness. Replacing air in the pressure-resistant kettle with nitrogen, introducing formaldehyde gas under stirring, increasing the pressure in the kettle to 0.5MPa, continuously supplementing formaldehyde gas when the pressure in the kettle is reduced quickly in the initial stage, reducing slowly in the later stage, starting to raise the temperature when the pressure is basically stable, controlling the reaction temperature to be 60 ℃, and reacting for 7 hours. When the pressure in the kettle is unchanged, communicating a second pressure-resistant kettle filled with raw materials, stirring and absorbing redundant formaldehyde in the first reaction kettle, when the pressure is unchanged, cutting off a communication pipeline, cooling to room temperature, opening the pressure-resistant kettle, filtering the reaction liquid, adding the filtrate into a three-neck flask, and slowly adding 98g of the filtrateSodium hydroxide aqueous solution with the quantitative concentration of 45 percent), and continuously carrying out hydrolysis reaction for 3 hours at 70 ℃ under mechanical stirring; and 4.6g of formic acid is added for neutralization after complete hydrolysis, then the mixture is cooled to room temperature and stands, the aqueous phase is separated by liquid separation, and the organic phase is rectified to obtain the 2-methallyl alcohol product, wherein the total yield reaches 97.6 percent. The aqueous phase was crystallized by distillation to give sodium formate, which after drying had a mass of 71.8g and the water separated was used for the hydrolysis of water. The above reaction equation is as follows:
the hydrogen spectrum data of 2-methallyl alcohol are as follows:
1HNMR (400 MHz，CDCl3)，:1.75(s,3H,-CH3);1.85(s,1H,-OH);4.03(s,2H,-CH2-)；4.86(s,1H);4.96(s,1H)。
adopting 7890A type gas chromatograph for analysis, wherein a chromatographic column is 19091N-213 strong polarity; the carrier gas is N2The flow rate is 5 mL/min; the vaporizer was 240 ℃ and the detector was 280 ℃ (hydrogen flame detector). The initial temperature is 80 ℃, the temperature is kept for 2 min, the heating rate is 10 ℃/min, the temperature is kept for 5 min when the temperature reaches 140 ℃, and the product purity is 99.9 percent.
The sodium formate product is subjected to titration analysis according to GB/T693-.
Example 2
Into a pressure resistant vessel having a capacity of 500mL and equipped with a stirrer were charged 70.0g of 2-methacrolein and 4.4g of barium hydroxide (Ba (OH)2·8H2And O), screwing the pressure-resistant kettle and checking the air tightness. Replacing air in the pressure-resistant kettle with nitrogen, introducing formaldehyde gas under stirring, increasing the pressure in the kettle to 0.5MPa, continuously supplementing formaldehyde gas when the pressure in the kettle is reduced quickly in the initial stage, reducing slowly in the later stage, starting to raise the temperature when the pressure is basically stable, controlling the reaction temperature to be 60 ℃, and reacting for 7 hours. When the pressure in the kettle is unchanged, communicating a second pressure-resistant kettle filled with raw materials, stirring and absorbing redundant formaldehyde in the first reaction kettle, when the pressure is unchanged, disconnecting the communication pipeline, cooling to room temperature, opening the pressure-resistant kettle, filtering the reaction liquid, adding the filtrate into a three-neck flask, and slowly adding the filtrate into the three-neck flaskAdding 98g of 45 mass percent sodium hydroxide aqueous solution, continuously heating and reacting at 70 ℃ for 3h under mechanical stirring, adding 4.6g of formic acid for neutralization after complete hydrolysis, cooling to room temperature, standing, separating aqueous phase by liquid separation, rectifying the organic phase to obtain 2-methallyl alcohol product, wherein the total yield is 98.8 percent, the product purity is 99.9 percent, sodium formate is obtained by distilling and crystallizing the aqueous phase, the mass is 70.5g after drying, and the separated water is used for hydrolyzing water.
The characterization method and results of the 2-methallyl alcohol product are the same as in example 1.
Example 3
A500 mL pressure resistant vessel with a stirrer was charged with 70.0g of 2-methacrolein and 3.5g of calcium hydroxide, and the pressure resistant vessel was tightened to check airtightness. Replacing air in the pressure-resistant kettle with nitrogen, introducing formaldehyde gas under stirring, increasing the pressure in the kettle to 0.5MPa, continuously supplementing formaldehyde gas when the pressure in the kettle is reduced quickly in the initial stage, reducing slowly in the later stage, starting to raise the temperature when the pressure is basically stable, controlling the reaction temperature to be 60 ℃, and reacting for 7 hours. When the pressure in the kettle is unchanged, a second pressure-resistant kettle filled with raw materials is communicated, the second pressure-resistant kettle is stirred to absorb redundant formaldehyde in the first reaction kettle, when the pressure is unchanged, a communication pipeline is cut off, the temperature is reduced to room temperature, the pressure-resistant kettle is opened, reaction liquid is filtered, filtrate is added into a three-neck flask, then 98g of sodium hydroxide aqueous solution with the mass concentration of 45% is slowly added, the heating reaction is continuously carried out for 3 hours at 70 ℃ under mechanical stirring, 4.6g of formic acid is added for neutralization after the hydrolysis is completed, then the reaction liquid is cooled to room temperature and stands, the aqueous phase is separated through liquid separation, the organic phase is rectified to obtain a 2-methallyl alcohol product, the total yield reaches 96.8%, the product purity is 99.8%, the aqueous phase is distilled and crystallized to obtain sodium formate, the mass is 67.7g after the drying.
The characterization method and results of the 2-methallyl alcohol product are the same as in example 1.
Example 4
Into a pressure resistant vessel having a capacity of 500mL and equipped with a stirrer were charged 70.0g of 2-methacrolein and 13.2g of barium hydroxide (Ba (OH))2·8H2And O), screwing the pressure-resistant kettle and checking the air tightness. Replacing air in the pressure-resistant kettle with nitrogen, and introducing formaldehyde while stirringAnd (3) gas, wherein the pressure in the kettle rises to 0.5MPa, the pressure in the kettle at the initial stage drops fast, the formaldehyde gas is required to be supplemented continuously, the pressure drops slowly at the later stage, and the temperature begins to rise when the pressure is basically stable. The reaction temperature is controlled at 60 ℃, and the reaction time is controlled at 7 h. When the pressure in the kettle is unchanged, a second pressure-resistant kettle filled with raw materials is communicated, the second pressure-resistant kettle is stirred to absorb redundant formaldehyde in the first reaction kettle, when the pressure is unchanged, a communication pipeline is cut off, the temperature is reduced to room temperature, the pressure-resistant kettle is opened, reaction liquid is filtered, filtrate is added into a three-neck flask, then 98g of sodium hydroxide aqueous solution with the mass concentration of 45% is slowly added, the heating reaction is continuously carried out for 3 hours at 70 ℃ under mechanical stirring, 4.6g of formic acid is added for neutralization after the hydrolysis is completed, then the reaction liquid is cooled to room temperature and stands, the aqueous phase is separated through liquid separation, the organic phase is rectified to obtain a 2-methallyl alcohol product, the total yield reaches 95.4%, the product purity is 99.8%, the aqueous phase is distilled and crystallized to obtain sodium formate, the mass is 70.4g after the drying.
The characterization method and results of the 2-methallyl alcohol product are the same as in example 1.
Example 5
Into a 500mL pressure resistant vessel equipped with a stirrer were charged 70.0g of 2-methacrolein and 4.4g of barium hydroxide (Ba (OH)2·8H2And O), screwing the pressure-resistant kettle and checking the air tightness. Replacing air in the pressure-resistant kettle with nitrogen, introducing formaldehyde gas under stirring, increasing the pressure in the kettle to 0.5MPa, continuously replenishing the formaldehyde gas when the pressure in the kettle is reduced quickly in the initial stage, and starting to increase the temperature when the pressure is basically stable in the later stage. The reaction temperature is controlled at 70 ℃, and the reaction time is controlled at 7 h. When the pressure in the kettle is not changed, communicating a second pressure-resistant kettle filled with raw materials, stirring and absorbing redundant formaldehyde in the first reaction kettle, when the pressure is not changed, cutting off a communication pipeline, cooling to room temperature, opening the pressure-resistant kettle, filtering reaction liquid, adding filtrate into a three-neck flask, then slowly adding 98g of sodium hydroxide aqueous solution with the mass concentration of 45%, continuously heating and reacting for 3 hours at 70 ℃ under mechanical stirring, adding 4.6g of formic acid for neutralization after complete hydrolysis, then cooling to room temperature, standing, separating aqueous phase through liquid separation, rectifying an organic phase to obtain a 2-methallyl alcohol product, wherein the total yield is 90.9%, and the product purity is 99.8%,the aqueous phase was crystallized by distillation to give sodium formate, which after drying had a mass of 72.6g and the water separated was used for the hydrolysis of water.
The product 2-methallyl alcohol is characterized as in example 1.
Example 6
Into a pressure resistant vessel having a capacity of 500mL with stirring were charged 70.0g of 2-methacrolein and 4.4g of barium hydroxide (Ba (OH)2·8H2And O), screwing the pressure-resistant kettle and checking the air tightness. Replacing air in the pressure-resistant kettle with nitrogen, introducing formaldehyde gas under stirring, increasing the pressure in the kettle to 1.0MPa, continuously replenishing the formaldehyde gas when the pressure in the kettle is reduced rapidly at the initial stage, reducing slowly at the later stage, and starting to increase the temperature when the pressure is basically stable. The reaction temperature is controlled at 60 ℃, and the reaction time is controlled at 7 h. When the pressure in the kettle is unchanged, a second pressure-resistant kettle filled with raw materials is communicated, the second pressure-resistant kettle is stirred to absorb redundant formaldehyde in the first reaction kettle, when the pressure is unchanged, a communication pipeline is cut off, the temperature is reduced to room temperature, the pressure-resistant kettle is opened, reaction liquid is filtered, filtrate is added into a three-neck flask, then 98g of sodium hydroxide aqueous solution with the mass concentration of 45% is slowly added, the heating reaction is continuously carried out for 3 hours at 70 ℃ under mechanical stirring, 4.6g of formic acid is added for neutralization after the hydrolysis is completed, then the reaction liquid is cooled to room temperature and stands, the aqueous phase is separated through liquid separation, the organic phase is rectified to obtain a 2-methallyl alcohol product, the total yield reaches 99.0%, the product purity is 99.9%, the aqueous phase is distilled and crystallized to obtain sodium formate, the mass is 72.6g after the drying.
The product 2-methallyl alcohol is characterized as in example 1.
Example 7
Into a pressure resistant vessel having a capacity of 500mL with stirring were charged 70.0g of 2-methacrolein and 4.4g of barium hydroxide (Ba (OH)2·8H2And O), screwing the pressure-resistant kettle and checking the air tightness. Replacing air in the pressure-resistant kettle with nitrogen, introducing formaldehyde gas under stirring, increasing the pressure in the kettle to 2.0MPa, continuously replenishing the formaldehyde gas when the pressure in the kettle is reduced rapidly at the initial stage, reducing slowly at the later stage, and starting to increase the temperature when the pressure is basically stable. The reaction temperature is controlled at 60 ℃, and the reaction time is controlled at 7 h. When the pressure in the kettle is not changed, the second pressure-resistant kettle which is communicated with the raw materials is stirredStirring and absorbing redundant formaldehyde in the first reaction kettle, cutting off a communication pipeline when the pressure is unchanged, cooling to room temperature, opening a pressure-resistant kettle, filtering the reaction liquid, adding the filtrate into a three-neck flask, slowly adding 98g of sodium hydroxide aqueous solution with the mass concentration of 45%, continuously heating and reacting at 70 ℃ for 3 hours under mechanical stirring, adding 4.6g of formic acid for neutralization after complete hydrolysis, cooling to room temperature for standing, separating a water phase by liquid separation, rectifying the organic phase to obtain a 2-methallyl alcohol product, wherein the total yield is 99.1%, the product purity is 99.9%, the water phase is distilled and crystallized to obtain sodium formate, the mass is 72.8g after drying, and the separated water is used for hydrolyzing water.
The product 2-methallyl alcohol is characterized as in example 1.
Example 8
Into a 500mL pressure resistant vessel equipped with a stirrer were charged 70.0g of 2-methacrolein and 4.4g of barium hydroxide (Ba (OH))2·8H2O) and 87g of pivalaldehyde were charged into a pressure vessel, and the airtightness was checked. Replacing air in the pressure-resistant kettle with nitrogen, stirring, raising the temperature, controlling the reaction temperature at 60 ℃, and reacting for 7 hours, wherein the pressure in the kettle is raised to 0.12 MPa. Cooling to room temperature, opening the pressure-resistant kettle, filtering the reaction liquid, adding the filtrate into a three-neck flask, slowly adding 98g of sodium hydroxide aqueous solution with the mass concentration of 45%, continuously heating at 70 ℃ under mechanical stirring for reaction for 3 hours, adding 10.0g of pivalic acid for neutralization after complete hydrolysis, cooling to room temperature and standing, separating a water phase through liquid separation, rectifying an organic phase to obtain a 2-methallyl alcohol product, wherein the total yield reaches 81.6%, the product purity is 99.8%, distilling and crystallizing the water phase to obtain sodium pivalate, drying to obtain 95.3g of water, and using the separated water for hydrolysis.
The product 2-methallyl alcohol is characterized as in example 1.
Claims (5)
1. A preparation process of 2-methallyl alcohol comprises the steps of firstly, taking 2-methacrolein and aldehyde without alpha-H as raw materials, carrying out cross Cannizzaro disproportionation reaction under the catalytic action to generate methyl propenyl carboxylic ester, then hydrolyzing the methyl propenyl carboxylic ester in an alkali metal hydroxide solution to generate a target product 2-methallyl alcohol, and simultaneously co-producing sodium carboxylate;
the crossed Cannizzaro disproportionation reaction process comprises the following steps: mixing 2-methylacrolein, a solid catalyst and alpha-H-free aldehyde, and reacting for 2-10H under the pressure of 0.1-3 MPa and at the temperature of 50-80 ℃; cooling to room temperature after the reaction is finished, recovering excessive alpha-H-free aldehyde, and filtering to remove the solid catalyst, wherein the filtrate is the methyl propenyl carboxylate; wherein the alpha-H free aldehyde is formaldehyde or an aldehyde of the structure:
wherein R is1，R2，R3An alkyl group having 1 to 4 carbon atoms;
the solid catalyst is one or a mixture of more of sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide and strontium hydroxide;
the ester hydrolysis reaction process comprises the following steps: adding an alkali metal hydroxide aqueous solution into methyl propenyl carboxylate, heating to 60-90 ℃, and reacting for 1-5 h under the condition of heat preservation; after the reaction is finished, adding formic acid for neutralization, cooling to room temperature, separating out an organic phase and a water phase, rectifying the organic phase to obtain a 2-methallyl alcohol product, and distilling the water phase to obtain a carboxylate product; the distilled water is recycled by the system.
2. The process according to claim 1 for the preparation of 2-methallyl alcohol wherein: in the crossed Cannizzaro disproportionation reaction process, the amount of the solid catalyst is 2-20% of the mass of the 2-methylacrolein.
3. The process according to claim 1 for the preparation of 2-methallyl alcohol wherein: in the crossed Cannizzaro disproportionation reaction process, the molar ratio of 2-methylacrolein to alpha-H-free aldehyde is 1: 1.1-1: 1.3.
4. The process according to claim 1 for the preparation of 2-methallyl alcohol wherein: in the ester hydrolysis reaction, the molar ratio of the alkali metal hydroxide to the methacrylic carboxylate is 1.05: 1-1.5: 1.
5. The process according to claim 1 for the preparation of 2-methallyl alcohol wherein: in the ester hydrolysis reaction, the mass concentration of the alkali metal hydroxide aqueous solution is 15-50%.
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| TW503232B (en) * | 1997-08-07 | 2002-09-21 | Mitsubishi Gas Chemical Co | Process for producing polyhydric alcohol |
| 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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