CN105037097A - Synthetic method of 2-methallyl alcohol - Google Patents
Synthetic method of 2-methallyl alcohol Download PDFInfo
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- CN105037097A CN105037097A CN201510346280.6A CN201510346280A CN105037097A CN 105037097 A CN105037097 A CN 105037097A CN 201510346280 A CN201510346280 A CN 201510346280A CN 105037097 A CN105037097 A CN 105037097A
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The invention relates to a synthetic method of 2-methallyl alcohol. The synthetic method comprises the step of carrying out esterification reaction, refinement and separation and hydrolysis reaction on 2-methallyl chloride and sodium carboxylate to prepare 2-methallyl alcohol, wherein the formulas of the esterification reaction and the hydrolysis reaction are respectively formula (1) and formula (2) both referring to the description; the R is CH3 or CH3CH2, namely, methyl or ethyl. According to the invention, the synthetic method is reasonable in technology and easy to operate; the product is high selectivity and relatively high in quality; carboxylic sodium in the esterification reaction stage and water in the hydrolysis reaction stage are recycled and need no external supplement, so that cyclic utilization is achieved, and the product yield is improved.
Description
Technical field
The present invention relates to a kind of synthetic method of 2-methallyl alcohol, belong to field of chemical technology.
Background technology
2-methallyl alcohol has another name called methallyl alcohol, 3-hydroxy-2-methyl propylene, isobutene alcohol, molecular formula CH
2c (CH
3) CH
2oH, molecular weight 72.11, boiling point 113-115 DEG C.Methallyl alcohol is a kind of important fine chemical material, can be used for multiple fields such as medicine, agricultural chemicals, spices, resin, poly carboxylic acid series water reducer, its water soluble and organic solvent, performance is similar to vinyl carbinol, but toxicity is much lower compared with vinyl carbinol, can be used as the substitute of vinyl carbinol in a lot of fields.
Chinese patent CN103588622A, CN101759528A adopt methallyl chloride to add alkali direct hydrolysis method, and main drawback is that etherificate by product is many, and alkaline concentration is low and produce the shortcomings such as wastewater flow rate is large.
Chinese patent CN102167657B, CN103755523A are adopt methacrylic aldehyde or are first that methallyl aldehyde back end hydrogenation reduces and prepares methallyl alcohol with isobutylene oxidation, but have that hydrogenation pressure is high, oxidizing temperature is high, the shortcoming such as catalyst hydrogenation poor selectivity and methacrylic aldehyde are easily polymerized.
Chinese patent CN103242139A discloses the method that esterification catalysis two-step approach prepares 2-methacrylic alcohol.The method is under phase-transfer catalyst effect, carboxylate salt, water and 2-methallyl chloride add in autoclave and carry out esterification, by reaction soln cooling, standing, layering after esterification completes, obtain organic phase and aqueous phase, the mixture that organic phase is is primary product with 2-methacrylic carboxylicesters, an aqueous phase part is used for hydrolysis reaction configuration alkaline solution, and all the other are cycled to used in esterification.Organic addition alkali that the esterification stage obtains is hydrolyzed reaction, be hydrolyzed obtain mixed solution cooling, leave standstill, layering, obtain organic phase and aqueous phase, organic phase is target product 2-methacrylic alcohol.But the method adds water in step of esterification, because reaction need be carried out in encloses container, under higher temperature conditions, the aqueous chloride solution generated easily produces corrosion to general device, especially more can accelerate the corrosion to equipment in temperature compared with relative superiority or inferiority, therefore its appointed condition to suitability for industrialized production requires higher.Meanwhile, the organic phase after esterification is directly hydrolyzed reaction, because it still causes generating the slightly high methallyl ether of relative content in hydrolysis reaction containing a certain amount of methallyl chloride, thus affects the quality of product.
Summary of the invention
For the above-mentioned technical problem of prior art, the object of this invention is to provide a kind of rational technology, simple to operate, selectivity of product is high, have the synthetic method of the 2-methallyl alcohol of higher quality.
For achieving the above object, the present invention is achieved by the following technical solutions:
A synthetic method for 2-methallyl alcohol, to comprise with 2-methallyl chloride and carboxylic acid sodium through esterification, refining spearation and hydrolysis reaction to prepare the method for 2-methallyl alcohol;
The equation of described esterification and hydrolysis reaction is respectively formula (1) and formula (2):
Wherein, R is CH
3, CH
3cH
2, i.e. methyl or ethyl.
Described esterification comprises the following steps: 2-methallyl chloride, carboxylic acid sodium and phase-transfer catalyst are dropped into reactor and carries out esterification, still kettle is proceeded to after esterification, carry out underpressure distillation, overhead product is methacrylic carboxylicesters is main mixture, and in still kettle, residual solids is sodium-chlor.
Described refining spearation comprises the following steps: be that main mixture carries out rectification under vacuum by described methacrylic carboxylicesters, obtain methacrylic carboxylicesters fine work and unreacted methallyl chloride.
Described hydrolysis reaction comprises the following steps: methacrylic carboxylicesters fine work is added aqueous sodium hydroxide solution and to be hydrolyzed reaction, the complete carboxylic acid neutralization of hydrolysis reaction, and be hydrolyzed the mixed solution stratification obtained, upper strata is organic phase, and lower floor is aqueous phase; Described upper organic phase obtains 2-methallyl alcohol finished product through rectifying, described lower floor's aqueous phase is the carboxylic acid sodium aqueous solution, obtain carboxylic acid sodium solid through distillation, described carboxylic acid sodium recycles in the esterification reaction, and the aqueous fraction distilled out prepares sodium hydroxide solution for hydrolysis reaction.
In described esterification, described 2-methallyl chloride and the mol ratio of carboxylic acid sodium are 1.0 ~ 1.5:1, and described carboxylic acid sodium is sodium acetate or Sodium Propionate; Described phase-transfer catalyst is tetrabutylammonium chloride, tri-n-octyl methyl ammonium chloride or palmityl trimethyl ammonium chloride, and phase-transfer catalyst consumption is 1.0 ~ 2.0% of carboxylic acid sodium mass ratio.
Described esterification reaction temperature is 100 ~ 140 DEG C, and react for confined reaction, pressure changes with the change of reaction mass component, and reaction time of esterification is 10 ~ 20h; The temperature of described underpressure distillation is 100 ~ 120 DEG C, and underpressure distillation vacuum tightness is-0.085MPa ~-0.095MPa, and the underpressure distillation time is 4 ~ 9h.
In described rectification under vacuum process, top vacuum degree is :-0.040MPa ~-0.055MPa, and tower top temperature is 60 ~ 75 DEG C, and the unreacted methallyl chloride that described rectifying is collected recycles in the esterification reaction.
In described hydrolysis reaction, the mol ratio of described sodium hydroxide and methacrylic carboxylicesters is 1.1 ~ 1.5:1; Add after described sodium hydroxide water dissolution, the mass concentration of sodium hydroxide alkaline solution is 20 ~ 40%.
Described hydrolysising reacting temperature is 30 ~ 60 DEG C, and the reaction times is 6 ~ 15h; Described carboxylic acid is acetic acid or propionic acid, and the mol ratio of described carboxylic acid and methacrylic carboxylicesters is 0.1 ~ 0.5:1.
Described carboxylic acid sodium aqueous solution distillation temperature is 100 ~ 120 DEG C, and distillation vacuum tightness is-0.085MPa ~-0.095MPa, and distillation time is 5 ~ 10h.
The present invention is for raw material with 2-methallyl chloride and carboxylic acid sodium, obtain 2-methallyl alcohol with phase-transfer catalyst tetrabutylammonium chloride, tri-n-octyl methyl ammonium chloride or palmityl trimethyl ammonium chloride catalytic esterification, refining spearation and hydrolysis reaction, the inventive method has following outstanding advantages and positively effect:
1, esterification stage 2-methallyl chloride and carboxylic acid sodium proportioning are that 2-methallyl chloride is excessive, carboxylic acid sodium complete reaction can be made like this to generate sodium-chlor, and the product of generation comprises methacrylic carboxylicesters, sodium-chlor and excessive 2-methallyl chloride.By underpressure distillation, overhead product is the mixture of methacrylic carboxylicesters and 2-methallyl chloride, and in still kettle, residual solids is sodium-chlor, more than sodium-chlor purity >=97.0%, and moisture≤0.5%.The overhead product of methacrylic carboxylicesters and 2-methallyl chloride obtains methacrylic carboxylicesters fine work through rectifying separation, its methacrylic cl content≤0.1%.
2, in the proportioning of methacrylic carboxylicesters fine work that hydrolysis reaction stage sodium hydroxide and rectifying obtain, sodium hydroxide is excessive, methacrylic carboxyester hydrolysis can be made so complete, content≤0.05% of the organic phase methacrylic carboxylicesters after hydrolysis, simultaneously due to methacrylic cl content≤0.1% in methacrylic carboxylicesters fine work, thus making methacrylic ether content≤0.1% that produces in hydrolysis reaction, after its hydrolysis, organic phase main ingredient is 2-methallyl alcohol.Be hydrolyzed the neutralization of complete carboxylic acid, make excessive sodium hydroxide be converted into carboxylic acid sodium, the carboxylic acid sodium purity obtained after lower floor's aqueous phase distillation is higher, and can be used for next esterification by direct circulation, the aqueous fraction distilled out may be used for preparing sodium hydroxide solution.2-methallyl alcohol content >=99.7% that rectifying is collected, methallyl ether≤0.1%.
3, esterification is reaction under high pressure, generally uses Stainless steel pressure vessels.Do not add water in esterification reaction process, avoid the corrosion of sodium chloride aqueous solution to stainless steel equipment, extend the work-ing life of equipment, thus reduce the conditional request to industrial equipment.
4,2-methallyl alcohol good product selectivity, the carboxylic acid sodium in esterification stage and the water in hydrolysis reaction stage all repeat to apply mechanically, and additionally do not supplement, achieve recycle, improve product yield.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
The experimental technique used in the embodiment of the present invention if no special instructions, is ordinary method.
Material used in the embodiment of the present invention, reagent etc., if no special instructions, all can obtain from commercial channels.
In embodiment, carboxylic acid sodium used is anhydrous carboxylic acid's sodium
Reaction product organic phase adopts Agilent chromatographic, fid detector, HP-5 post, injector temperature: 230 DEG C
Detector temperature: 230 DEG C, column temperature: initial temperature is 40 DEG C, keeps 5min, is warming up to 130 DEG C with 10 DEG C/min, keeps 5min.
The synthetic method of 2-methallyl alcohol of the present invention, to comprise with 2-methallyl chloride and carboxylic acid sodium through esterification, refining spearation and hydrolysis reaction to prepare the method for 2-methallyl alcohol;
The equation of esterification and hydrolysis reaction is respectively formula (1) and formula (2):
Wherein, R is CH
3, CH
3cH
2, i.e. methyl or ethyl.
embodiment 1
Esterification: in autoclave, drop into 588g2-methallyl chloride, 532.8g anhydrous sodium acetate (mol ratio of 2-methallyl chloride and anhydrous sodium acetate is 1.0:1.0) and 10.6g tetrabutylammonium chloride, good seal reactor, open stirring and be warmed up to 100 DEG C, along with the rising of temperature, the highest 0.3MPa of pressure, insulation reaction 20h.React complete, material is transferred to still kettle, distills out organic phase 739.6g, through gas chromatographic analysis, methylallyl alcohol acetate content is 96.2%, 2-methacrylic cl content is 3.8%.In still kettle, solid is mainly sodium-chlor 391.8g, wherein sodium chloride content 97.2%, moisture 0.4%.By organic phase tower top be-0.040MPa, tower top temperature be 70 DEG C of conditions under rectifying, obtain the methallyl yl acetate fine work 669.7g that methacrylic cl content is 0.03%.
Hydrolysis reaction: pour 669.7g methallyl yl acetate fine work into four-hole boiling flask, add the sodium hydroxide solution (mol ratio of sodium hydroxide and methallyl yl acetate is 1.1:1.0) that 1292.3g massfraction is 20%, be warmed up to 30 DEG C, hydrolysis 15h, the neutralization of 35.2g acetic acid is added after hydrolysis completely, then stratification, upper organic phase is 520.8g, and lower floor's aqueous phase is 1476.4g.Aqueous phase is transferred to still kettle, is 100 DEG C in temperature, and vacuum is-0.085MPa, and underpressure distillation 10h, obtains aqueous fraction 943.9g, sodium acetate solid 532.5g, sodium acetate content 99.5%.Through gas chromatographic analysis, in organic phase, 2-methallyl alcohol content is 99.8%, and methacrylic ether content is 0.02%.The yield of 2-methallyl alcohol is 99.7%.
embodiment 2
Esterification: in autoclave, drop into 588g2-methallyl chloride, 410g anhydrous sodium acetate (mol ratio of 2-methallyl chloride and anhydrous sodium acetate is 1.3:1) and 6.1g tetrabutylammonium chloride, good seal reactor, open stirring and be warmed up to 120 DEG C, along with the rising of temperature, the highest 0.4MPa of pressure, insulation reaction 15h.React complete, material is transferred to still kettle, distills out organic phase 706.0g, through gas chromatographic analysis, methylallyl alcohol acetate content is 80.2%, 2-methacrylic cl content is 19.8%.In still kettle, solid is for being mainly sodium-chlor 298.1g, wherein sodium chloride content 98.2%, moisture 0.3%.By organic phase tower top be-0.040MPa, tower top temperature be 70 DEG C of conditions under rectifying, obtain the methallyl yl acetate fine work 541.8g that methacrylic cl content is 0.05%.
Hydrolysis reaction: pour 541.8g methallyl yl acetate fine work into four-hole boiling flask, add the sodium hydroxide solution (mol ratio of sodium hydroxide and methallyl yl acetate is 1.1:1.0) that 697.0g massfraction is 30%, be warmed up to 50 DEG C, hydrolysis 12h, the neutralization of 28.5g acetic acid is added after hydrolysis completely, then stratification, upper organic phase is 348.5g, and lower floor's aqueous phase is 918.8g.Aqueous phase is transferred to still kettle, is 110 DEG C in temperature, and vacuum is-0.090MPa, and underpressure distillation 7.5h, obtains aqueous fraction 527.1g, sodium acetate solid 391.7g, sodium acetate content 99.5%.Through gas chromatographic analysis, in organic phase, 2-methallyl alcohol content is 99.7%, and methacrylic ether content is 0.03%.The yield of 2-methallyl alcohol is 99.6%.
embodiment 3
Esterification: in autoclave, drop into 588g2-methallyl chloride, 355.2g anhydrous sodium acetate (mol ratio of 2-methallyl chloride and anhydrous sodium acetate is 1.5:1) and 3.6g tetrabutylammonium chloride, good seal reactor, open stirring and be warmed up to 140 DEG C, along with the rising of temperature, the highest 0.5MPa of pressure, insulation reaction 10h.React complete, material is transferred to still kettle, distills out organic phase 689.5g, through gas chromatographic analysis, methylallyl alcohol acetate content is 71.6%, 2-methacrylic cl content is 28.4%.In still kettle, solid is for being mainly sodium-chlor 257.3g, wherein sodium chloride content 98.5%, moisture 0.3%.By organic phase tower top be-0.040MPa, tower top temperature be 70 DEG C of conditions under rectifying, obtain the methallyl yl acetate fine work 469.2g that methacrylic cl content is 0.04%.
Hydrolysis reaction: pour 469.2g methallyl yl acetate fine work into four-hole boiling flask, add the sodium hydroxide solution (mol ratio of sodium hydroxide and methallyl yl acetate is 1.1:1.0) that 452.7g massfraction is 40%, be warmed up to 60 DEG C, hydrolysis 9h, the neutralization of 24.7g acetic acid is added after hydrolysis completely, then stratification, upper organic phase is 241.4g, and lower floor's aqueous phase is 705.2g.Aqueous phase is transferred to still kettle, is 120 DEG C in temperature, and vacuum is-0.095MPa, and underpressure distillation 5.0h, obtains aqueous fraction 332.2g, sodium acetate solid 373.0g, sodium acetate content 99.5%.Through gas chromatographic analysis, in organic phase, 2-methallyl alcohol content is 99.7%, and methacrylic ether content is 0.03%.The yield of 2-methallyl alcohol is 99.7%.
embodiment 4
Esterification: in autoclave, drop into 588g2-methallyl chloride, the anhydrous Sodium Propionate of 623.7g (mol ratio of 2-methallyl chloride and anhydrous Sodium Propionate is 1.0:1) and 12.5g tri-n-octyl methyl ammonium chloride, good seal reactor, open stirring and be warmed up to 100 DEG C, along with the rising of temperature, the highest 0.3MPa of pressure, insulation reaction 18h.React complete, material is transferred to still kettle, distills out organic phase 832.4g, through gas chromatographic analysis, methylallyl alcohol propionic ester content is 97.5%, 2-methacrylic cl content is 2.5%.In still kettle, solid is mainly sodium-chlor 391.8g, wherein sodium chloride content 97.1%, moisture 0.2%.By organic phase tower top be-0.050MPa, tower top temperature be 65 DEG C of conditions under rectifying, obtain the methacrylic propionic ester fine work 771.0g that methacrylic cl content is 0.03%.
Hydrolysis reaction: pour 771.0g methacrylic propionic ester fine work into four-hole boiling flask, add the sodium hydroxide solution (mol ratio of sodium hydroxide and methacrylic propionic ester is 1.3:1.0) that 1566.1g massfraction is 20%, be warmed up to 30 DEG C, hydrolysis 12h, the neutralization of 133.7g propionic acid is added after hydrolysis completely, then stratification, upper organic phase is 674.5g, and lower floor's aqueous phase is 1796.3g.Aqueous phase is transferred to still kettle, is 100 DEG C in temperature, and vacuum is-0.085MPa, and underpressure distillation 10h, obtains aqueous fraction 1041.6g, Sodium Propionate solid 754.7g, Sodium Propionate content 99.6%.Through gas chromatographic analysis, in organic phase, 2-methallyl alcohol content is 99.8%, and methacrylic ether content is 0.02%.The yield of 2-methallyl alcohol is 99.7%.
embodiment 5
Esterification: in autoclave, drop into 588g2-methallyl chloride, the anhydrous Sodium Propionate of 479.8g (mol ratio of 2-methallyl chloride and anhydrous Sodium Propionate is 1.3:1.0) and 7.2g tri-n-octyl methyl ammonium chloride, good seal reactor, open stirring and be warmed up to 120 DEG C, along with the rising of temperature, the highest 0.4MPa of pressure, insulation reaction 13h.React complete, material is transferred to still kettle, distills out organic phase 777.6g, through gas chromatographic analysis, methylallyl alcohol propionic ester content is 81.3%, 2-methacrylic cl content is 19.7%.In still kettle, solid is for being mainly sodium-chlor 297.4g, wherein sodium chloride content 98.1%, moisture 0.2%.By organic phase tower top be-0.050MPa, tower top temperature be 65 DEG C of conditions under rectifying, obtain the methacrylic propionic ester fine work 594.3g that methacrylic cl content is 0.04%.
Hydrolysis reaction: pour 594.3g methacrylic propionic ester fine work into four-hole boiling flask, add the sodium hydroxide solution (mol ratio of sodium hydroxide and methacrylic propionic ester is 1.3:1.0) that 804.5g massfraction is 30%, be warmed up to 50 DEG C, hydrolysis 9h, the neutralization of 102.9g propionic acid is added after hydrolysis completely, then stratification, upper organic phase is 402.4g, and lower floor's aqueous phase is 1099.3g.Aqueous phase is transferred to still kettle, is 110 DEG C in temperature, and vacuum is-0.090MPa, and underpressure distillation 8.0h, obtains aqueous fraction 517.7g, Sodium Propionate solid 581.6g, sodium acetate content 99.6%.Through gas chromatographic analysis, in organic phase, 2-methallyl alcohol content is 99.8%, and methacrylic ether content is 0.03%.The yield of 2-methallyl alcohol is 99.7%.
embodiment 6
Esterification: in autoclave, drop into 588g2-methallyl chloride, the anhydrous Sodium Propionate of 415.8g (mol ratio of 2-methallyl chloride and anhydrous Sodium Propionate is 1.5:1) and 4.2g tri-n-octyl methyl ammonium chloride, good seal reactor, open stirring and be warmed up to 140 DEG C, along with the rising of temperature, the highest 0.5MPa of pressure, insulation reaction 11h.React complete, material is transferred to still kettle, distills out organic phase 750.5g, through gas chromatographic analysis, methylallyl alcohol propionic ester content is 70.5%, 2-methacrylic cl content is 29.5%.In still kettle, solid is for being mainly sodium-chlor 257.5g, wherein sodium chloride content 98.4%, moisture 0.3%.By organic phase tower top be-0.050MPa, tower top temperature be 65 DEG C of conditions under rectifying, obtain the methacrylic propionic ester fine work 497.4g that methacrylic cl content is 0.03%.
Hydrolysis reaction: pour 497.4g methacrylic propionic ester fine work into four-hole boiling flask, add the sodium hydroxide solution (mol ratio of sodium hydroxide and methacrylic propionic ester is 1.3:1.0) that 505.2g massfraction is 40%, be warmed up to 60 DEG C, hydrolysis 7h, the neutralization of 86.3g propionic acid is added after hydrolysis completely, then stratification, upper organic phase is 281.0g, and lower floor's aqueous phase is 807.9g.Aqueous phase is transferred to still kettle, is 120 DEG C in temperature, and vacuum is-0.095MPa, and underpressure distillation 5.0h, obtains aqueous fraction 320.4g, Sodium Propionate solid 487.5g, Sodium Propionate content 99.5%.Through gas chromatographic analysis, in organic phase, 2-methallyl alcohol content is 99.8%, and methacrylic ether content is 0.02%.The yield of 2-methallyl alcohol is 99.8%.
embodiment 7
Esterification: in autoclave, drop into 588g2-methallyl chloride, the anhydrous Sodium Propionate of 623.7g (mol ratio of 2-methallyl chloride and anhydrous Sodium Propionate is 1.0:1) and 12.5g palmityl trimethyl ammonium chloride, good seal reactor, open stirring and be warmed up to 100 DEG C, along with the rising of temperature, the highest 0.3MPa of pressure, insulation reaction 18h.React complete, material is transferred to still kettle, distills out organic phase 832.4g, through gas chromatographic analysis, methylallyl alcohol propionic ester content is 97.5%, 2-methacrylic cl content is 2.5%.In still kettle, solid is mainly sodium-chlor 391.8g, wherein sodium chloride content 97.1%, moisture 0.2%.By organic phase tower top be-0.055MPa, tower top temperature be 60 DEG C of conditions under rectifying, obtain the methacrylic propionic ester fine work 771.0g that methacrylic cl content is 0.02%.
Hydrolysis reaction: pour 771.0g methacrylic propionic ester fine work into four-hole boiling flask, add the sodium hydroxide solution (mol ratio of sodium hydroxide and methacrylic propionic ester is 1.5:1.0) that 1807.0g massfraction is 20%, be warmed up to 30 DEG C, hydrolysis 10h, the neutralization of 222.8g propionic acid is added after hydrolysis completely, then stratification, upper organic phase is 759.0g, and lower floor's aqueous phase is 2041.8g.Aqueous phase is transferred to still kettle, is 120 DEG C in temperature, and vacuum is-0.090MPa, and underpressure distillation 8h, obtains aqueous fraction 1041.6g, Sodium Propionate solid 869.9g, Sodium Propionate content 99.7%.Through gas chromatographic analysis, in organic phase, 2-methallyl alcohol content is 99.8%, and methacrylic ether content is 0.02%.The yield of 2-methallyl alcohol is 99.8%.
embodiment 8
Esterification: in autoclave, drop into 588g2-methallyl chloride, 410g anhydrous sodium acetate (mol ratio of 2-methallyl chloride and anhydrous sodium acetate is 1.3:1) and 6.1g palmityl trimethyl ammonium chloride, good seal reactor, open stirring and be warmed up to 120 DEG C, along with the rising of temperature, the highest 0.4MPa of pressure, insulation reaction 15h.React complete, material is transferred to still kettle, distills out organic phase 706.0g, through gas chromatographic analysis, methylallyl alcohol acetate content is 80.2%, 2-methacrylic cl content is 19.8%.In still kettle, solid is for being mainly sodium-chlor 298.1g, wherein sodium chloride content 98.2%, moisture 0.3%.By organic phase tower top be-0.055MPa, tower top temperature be 60 DEG C of conditions under rectifying, obtain the methallyl yl acetate fine work 541.8g that methacrylic cl content is 0.04%.
Hydrolysis reaction: pour 541.8g methallyl yl acetate fine work into four-hole boiling flask, add the sodium hydroxide solution (mol ratio of sodium hydroxide and methallyl yl acetate is 1.5:1.0) that 950.5g massfraction is 30%, be warmed up to 50 DEG C, hydrolysis 8h, the neutralization of 142.5g acetic acid is added after hydrolysis completely, then stratification, upper organic phase is 449.5g, and lower floor's aqueous phase is 1185.3g.Aqueous phase is transferred to still kettle, is 120 DEG C in temperature, and vacuum is-0.090MPa, and underpressure distillation 6.0h, obtains aqueous fraction 597.8g, sodium acetate solid 587.5g, sodium acetate content 99.5%.Through gas chromatographic analysis, in organic phase, 2-methallyl alcohol content is 99.7%, and methacrylic ether content is 0.05%.The yield of 2-methallyl alcohol is 99.6%.
embodiment 9
Esterification: in autoclave, drop into 588g2-methallyl chloride, the anhydrous Sodium Propionate of 415.8g (mol ratio of 2-methallyl chloride and anhydrous Sodium Propionate is 1.5:1) and 4.2g palmityl trimethyl ammonium chloride, good seal reactor, open stirring and be warmed up to 140 DEG C, along with the rising of temperature, the highest 0.5MPa of pressure, insulation reaction 11h.React complete, material is transferred to still kettle, distills out organic phase 750.5g, through gas chromatographic analysis, methylallyl alcohol propionic ester content is 70.5%, 2-methacrylic cl content is 29.5%.In still kettle, solid is for being mainly sodium-chlor 257.5g, wherein sodium chloride content 98.4%, moisture 0.3%.By organic phase tower top be-0.055MPa, tower top temperature be 60 DEG C of conditions under rectifying, obtain the methacrylic propionic ester fine work 497.4g that methacrylic cl content is 0.05%.
Hydrolysis reaction: pour 497.4g methacrylic propionic ester fine work into four-hole boiling flask, add the sodium hydroxide solution (mol ratio of sodium hydroxide and methacrylic propionic ester is 1.5:1.0) that 582.9g massfraction is 40%, be warmed up to 60 DEG C, hydrolysis 6h, the neutralization of 143.8g propionic acid is added after hydrolysis completely, then stratification, upper organic phase is 313.4g, and lower floor's aqueous phase is 910.7g.Aqueous phase is transferred to still kettle, is 120 DEG C in temperature, and vacuum is-0.095MPa, and underpressure distillation 5.0h, obtains aqueous fraction 348.3g, Sodium Propionate solid 562.4g, Sodium Propionate content 99.5%.Through gas chromatographic analysis, in organic phase, 2-methallyl alcohol content is 99.8%, and methacrylic ether content is 0.04%.The yield of 2-methallyl alcohol is 99.7%.
Above content is the further description done provided technical scheme in conjunction with the preferred embodiment of the present invention; can not assert that the present invention specifically implements to be confined to these explanations above-mentioned; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. a synthetic method for 2-methallyl alcohol, is characterized in that: to comprise with 2-methallyl chloride and carboxylic acid sodium through esterification, refining spearation and hydrolysis reaction to prepare the method for 2-methallyl alcohol;
The equation of described esterification and hydrolysis reaction is respectively formula (1) and formula (2):
Wherein, R is CH
3, CH
3cH
2, i.e. methyl or ethyl.
2. the synthetic method of 2-methallyl alcohol as claimed in claim 1, it is characterized in that described esterification comprises the following steps: 2-methallyl chloride, carboxylic acid sodium and phase-transfer catalyst are dropped into reactor and carries out esterification, still kettle is proceeded to after esterification, carry out underpressure distillation, overhead product is methacrylic carboxylicesters is main mixture, and in still kettle, residual solids is sodium-chlor.
3. the synthetic method of 2-methallyl alcohol as claimed in claim 1, it is characterized in that described refining spearation comprises the following steps: be that main mixture carries out rectification under vacuum by described methacrylic carboxylicesters, obtain methacrylic carboxylicesters fine work and unreacted methallyl chloride.
4. the synthetic method of 2-methallyl alcohol as claimed in claim 1, it is characterized in that described hydrolysis reaction comprises the following steps: methacrylic carboxylicesters fine work is added aqueous sodium hydroxide solution and to be hydrolyzed reaction, the complete carboxylic acid of hydrolysis reaction neutralizes, be hydrolyzed the mixed solution stratification obtained, upper strata is organic phase, and lower floor is aqueous phase; Described upper organic phase obtains 2-methallyl alcohol finished product through rectifying, described lower floor's aqueous phase is the carboxylic acid sodium aqueous solution, obtain carboxylic acid sodium solid through distillation, described carboxylic acid sodium recycles in the esterification reaction, and the aqueous fraction distilled out prepares sodium hydroxide solution for hydrolysis reaction.
5. the synthetic method of 2-methallyl alcohol as claimed in claim 2, it is characterized in that: in described esterification, described 2-methallyl chloride and the mol ratio of carboxylic acid sodium are 1.0 ~ 1.5:1, and described carboxylic acid sodium is sodium acetate or Sodium Propionate; Described phase-transfer catalyst is tetrabutylammonium chloride, tri-n-octyl methyl ammonium chloride or palmityl trimethyl ammonium chloride, and phase-transfer catalyst consumption is 1.0 ~ 2.0% of carboxylic acid sodium mass ratio.
6. the synthetic method of 2-methallyl alcohol as claimed in claim 2, it is characterized in that: described esterification reaction temperature is 100 ~ 140 DEG C, react for confined reaction, pressure changes with the change of reaction mass component, and reaction time of esterification is 10 ~ 20h; The temperature of described underpressure distillation is 100 ~ 120 DEG C, and underpressure distillation vacuum tightness is-0.085MPa ~-0.095MPa, and the underpressure distillation time is 4 ~ 9h.
7. the synthetic method of 2-methallyl alcohol as claimed in claim 3, it is characterized in that: in described rectification under vacuum process, top vacuum degree is :-0.040MPa ~-0.055MPa, tower top temperature is 60 ~ 75 DEG C, and the unreacted methallyl chloride that described rectifying is collected recycles in the esterification reaction.
8. the synthetic method of 2-methallyl alcohol as claimed in claim 4, it is characterized in that: in described hydrolysis reaction, the mol ratio of described sodium hydroxide and methacrylic carboxylicesters is 1.1 ~ 1.5:1; Add after described sodium hydroxide water dissolution, the mass concentration of sodium hydroxide alkaline solution is 20 ~ 40%.
9. the synthetic method of 2-methallyl alcohol as claimed in claim 4, it is characterized in that: described hydrolysising reacting temperature is 30 ~ 60 DEG C, the reaction times is 6 ~ 15h; Described carboxylic acid is acetic acid or propionic acid, and the mol ratio of carboxylic acid and methacrylic carboxylicesters is 0.1 ~ 0.5:1.
10. the synthetic method of 2-methallyl alcohol as claimed in claim 4, is characterized in that: described carboxylic acid sodium aqueous solution distillation temperature is 100 ~ 120 DEG C, and distillation vacuum tightness is-0.085MPa ~-0.095MPa, and distillation time is 5 ~ 10h.
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