CN102381940A - Production method of C5 enol - Google Patents
Production method of C5 enol Download PDFInfo
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- CN102381940A CN102381940A CN2011102023856A CN201110202385A CN102381940A CN 102381940 A CN102381940 A CN 102381940A CN 2011102023856 A CN2011102023856 A CN 2011102023856A CN 201110202385 A CN201110202385 A CN 201110202385A CN 102381940 A CN102381940 A CN 102381940A
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Abstract
The invention relates to a production method of a C5 enol. The production method uses isoprene and hydrogen chloride as raw materials and comprises the following steps: 1) performing addition reaction on isoprene and hydrogen chloride to generate a mixture of 1-chloro-isopentene and 3-chloro-isopentene; and 2) performing a hydrolysis reaction on the product of the addition reaction, adding one or more of toluene, ethylbenzene, n-hexane, cyclohexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane and heptane as the solvent in the hydrolysis process, separating out the oil phase product after the hydrolysis, and rectifying to obtain products, namely methylbutenol and 3-methyl-2-buten-1-ol. Compared with the C5 enol production process of the prior art, the side reaction, in which dichloro-isopentane is generated, in the addition reaction process is effectively inhibited; after the solvent is added in the hydrolysis reaction, the yield of the hydrolysis reaction can be increased and the purification of the product can be facilitated; the yields of the addition reaction and the hydrolysis reaction are both more than 98% and are obviously increased as compared with the prior art; and the production cost is greatly reduced.
Description
Technical field
The present invention relates to a kind of working method of C 5 enol, particularly earlier isoprene and hydrogenchloride addition reaction are prepared chloroisoamylene, chloroisoamylene direct hydrolysis is again produced prenol and the pure method of methyl butene.
Background technology
3-methyl-2-butene-1-alcohol (prenol) and 2-methyl-3-butene-2-alcohol (methyl butene alcohol) is two kinds of important fine-chemical intermediates, and two kinds of alcohol only need less theoretical tray just can realize separating in rectifying tower because boiling point differs bigger.Prenol is mainly used in and original trimethyl acetate or synthetic 3,3-dimethyl-4-pentenoic acid methyl ester of ethyl ester reaction or ethyl ester, and it is the important source material of preparation pyrethroid key intermediate high-cis dichloro esbiothrin (DV-chrysanthemumic acid or chrysanthemum monocarboxylate); Methyl butene alcohol then is to produce Sulcatone, and then produces the basic material of phantol, and it still is the midbody of other multiple spices and the major ingredient of control injurious forest-insect sexual attractant in addition.
At present the main technique route of synthetic prenol has iso-butylene and formaldehyde condensation technology and chloroisoamylene through esterification two kinds of hydrolysis processs again.First kind of technology is present most important operational path, and iso-butylene becomes intermediate product 3-methyl-3-butene-1-alcohol with formaldehyde condensation, and isomery becomes prenol under catalyst action again; Second kind of technology then is main raw material with the isoprene; Earlier make chloroisoamylene by isoprene and the addition of anhydrous hydrogen chloride selectivity; Again with sodium acetate, anhydrous under the effect of phase-transfer catalyst Tetrabutyl amonium bromide; Change into acetic acid isopentene ester and stoichiometric sub product sodium-chlor, last acetic acid isopentene ester is hydrolyzed into prenol under alkaline condition.The production technique of methyl butene alcohol has two kinds equally, the one, adopts traditional by acetylene and condensation of acetone repeated hydrogenation explained hereafter, the 2nd, be catalyzer with the protonic acid, the prenol isomery becomes the pure technology of methyl butene.
USP 4028424 has proposed a kind of technology by iso-butylene and formaldehyde condensation repeated hydrogenation explained hereafter prenol.Condensation is carried out in autoclave, and catalyzer is a Sodium phosphate, dibasic, is solvent with the trimethyl carbinol, when temperature of reaction is 150～250 ℃, obtains 3-methyl-3-butene-1-alcohol.3-methyl-3-butylene-v alcohol is at Pd-Se-Ce/SiO
2Under the catalyst action, in fixed-bed reactor, when temperature is 60～100 ℃ and when facing hydrogen, reaction conversion ratio reaches 45%, and the selectivity of prenol has reached 93%～94%.Cui Ru equality people (Guangdong chemical industry, 6:22-23,1986) prepares prenol technology to chloroisoamylene esterification, hydrolysis and studies.Esterification and the hydrolysis reaction condition optimized have been obtained, yield average out to 80.56% (in chloroisoamylene).In esterification; Reasonably chloroisoamylene/sodium acetate, anhydrous/Tetrabutyl amonium bromide is 1: 1.2: 0.01～0.02 (mol ratio); Temperature is 130 ℃, and the time is 120 minutes, and wherein Tetrabutyl amonium bromide is an esterifying catalyst; Sodium acetate, anhydrous needs in the preceding dehydration that feeds intake, otherwise will reduce the prenol selectivity.When the hydrolysis of isopentene acetic ester, the mol ratio of chloroisoamylene/liquid caustic soda is 1: 1.02～1.1, and reflux temperature is 100 ℃, and the time is 60 minutes.
USP 6180839 has been introduced a kind of method of being produced methyl butene alcohol by prenol through isomerization reaction.Adopt reaction rectification technique; Make the prenol that is dissolved in the water under the protonic acid effect; Change into methyl butene alcohol through isomerization reaction; The azeotrope boiling point that utilizes methyl butene alcohol and water to generate again is lower than the characteristics of prenol, continues methyl butene alcohol is told, thereby balance is moved to title product.
USP 4645863 has proposed a kind of method of being produced C 5 enol by isoprene.In tank reactor, add the aprotic organic solvent/isoprene/water of preparation, under the effect of macropore strong acid cation exchange resin catalyst, be converted into C 5 enol.When reaction; In reactor drum, add 50 gram catalyzer earlier; Add 56 gram isoprene and organic sulfoxide volume(tric)fractions again and be 65% 1000 ml water solution, stirring is warming up to 40 ℃, reacts after 4 hours; The isoprene transformation efficiency is 40%, and the pure and mild prenol selectivity of methyl butene is respectively 73% and 10%.Though this technology can be produced 2-methyl-3-butene-2-pure and mild 3-methyl-2-butene-1-alcohol product simultaneously, because water alkene is than too high, reaction efficiency is relatively poor, and required equipment is bulky, and the reaction times is long, makes technology realize that industrialized possibility is lower.
In above-described prenol technical scheme, be raw material with iso-butylene and formaldehyde, through condensation again isomery to produce prenol technology be one of stronger technology of competitive power.Then need an additional cover isomerizing production equipment but produce methyl butene alcohol, operational path is longer again, and investment cost is bigger.Other technical scheme production cost is higher.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of new prenol and the working method of methyl butene alcohol to be provided.
Below be the concrete technical scheme of the present invention:
A kind of working method of C 5 enol, this method is a raw material with isoprene and hydrogenchloride, may further comprise the steps:
1) isoprene and hydrogenchloride carry out the mixture (chloroisoamylene) that addition reaction generates 1-chloroisoamylene and 3-chloroisoamylene; The mol ratio of hydrogenchloride and isoprene is (0.5～1.1): 1; Temperature of reaction is-15～20 ℃, and reaction pressure is a normal pressure, and reaction time is 2～10hr.
2) the addition reaction product reaction that is hydrolyzed makes chloroisoamylene be converted into the pure and mild prenol of methyl butene.In hydrolysis, add solvent, solvent can be: toluene, ethylbenzene, normal hexane, hexanaphthene, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane etc. a kind of, or two or more mixture.The mass ratio of solvent and chloroisoamylene is (0.2～10): 1; The mol ratio of sodium hydroxide and chloroisoamylene is (1.0～1.5): 1, and concentration sodium hydroxide is 5%～50%, temperature of reaction is 40～80 ℃; Reaction pressure is a normal pressure, and reaction time is 10～150 minutes.
3) hydrolysate is told water, and oil phase carries out rectifying, obtains the pure and mild prenol product of methyl butene, and unreacted isoprene is circulated to addition reaction as raw material, and recovered solvent is circulated to hydrolysis reaction.
When methyl butene alcohol was refining, tower top temperature was 70～72 ℃, and tower still temperature is controlled to be 80～90 ℃, and absolute pressure of top of the tower is controlled to be 260～270mmHg, and control of reflux ratio is 1～10.When prenol was refining, tower top temperature was 75～77 ℃, and tower still temperature is controlled to be 85～95 ℃, and absolute pressure of top of the tower is controlled to be 60～75mmHg, and control of reflux ratio is 1～10.
The mol ratio of above-mentioned steps 1 described hydrogenchloride and isoprene is preferably (0.7～0.80): 1; Temperature of reaction is preferably-5～0 ℃; Reaction time is preferably 3～4hr.
Above-mentioned steps 2 described solvents are preferably selected toluene for use; The mass ratio of toluene and chloroisoamylene is preferably (0.3～0.6): 1; The mol ratio of sodium hydroxide and chloroisoamylene is preferably (1.01～1.05): 1, and concentration sodium hydroxide is preferably 10%～20%, and temperature of reaction is preferably 55～60 ℃; Reaction pressure is a normal pressure, and reaction time is preferably 60～120 minutes.
One of key of the present invention is when isoprene and hydrogenchloride addition reaction, strict mol ratio with isoprene and hydrogenchloride is controlled at＞and 1 level.Because the addition activity of isoprene and hydrogenchloride is far above chloroisoamylene; Hydrogenchloride is with preferential and isoprene reaction; The reduction of chloroisoamylene concentration has further suppressed the addition once more of hydrogenchloride and chloroisoamylene again in simultaneously excessive isoprene and the reaction system, thereby has stoped the generation of dichloro-iso-pentane in hydrogenchloride and the isoprene addition reaction process effectively.Make that the content of dichloro-iso-pentane is reduced to below 0.01% in the addition reaction product.And, make the addition reaction yield significantly improve owing to omitted the isomerization process of the refining and 3-chloroisoamylene of 1-chloroisoamylene.
Second crucial part of the present invention is to increase a kind of solvent, adds in the material system of hydrolysis reaction, finds that above-mentioned all kinds of SOLVENTS has triple role: the one, improved the yield of hydrolysis reaction.When the chloroisoamylene hydrolysis; The water that contains sodium hydroxide is a C 5 enol ether with the main by product that the oil phase that contains chloroisoamylene reacts, and it is generated at water by the methyl butene alcohol of a molecule or the chloroisoamylene of a prenol and a molecule.The adding of solvent can be extracted into oil phase with the organism of aqueous phase on the one hand, simultaneously the water drive in the oil phase is pursued water, reduces the generation of by product C 5 enol ether through mass transfer and the reduction concentration of reactants that influences reaction system; The 2nd, the introducing of solvent can reduce the organic content of water, and the water behind the hydrolysis reaction only needs simple stripping just can make its chemical oxygen demand reduce to 500～700 mg/litre; The 3rd, utilize solvent and water to form the azeotropic characteristics moisture contained in the reaction mass is gone out, obtain highly purified methyl butene alcohol product.
Can find out that according to above description compared with prior art there is the advantage of following several respects in the present invention:
1, the side reaction that generates the dichloro-iso-pentane in the addition reaction process receives effective inhibition;
2, addition reaction need not carry out any processing, has simplified technology, has improved the addition reaction yield;
3, in hydrolysis reaction, behind the adding solvent, not only improve the hydrolysis reaction yield, reduced the chemical oxygen demand of waste liquid, and favourable to the purification of product.
4,, and significantly reduced its production cost because the yield of addition reaction and hydrolysis reaction all above 98%, makes the existing technology of total reaction yield be significantly increased.
Come details of the present invention is done further to describe through embodiment below.
Embodiment
[embodiment 1～8]
Addition reaction is carried out in 1000 milliliters of glass there-necked flasks that have mechanical stirring and a refrigerating unit.Isoprene is added in the there-necked flask; Start stirring and reaction solution be cooled to temperature required; Under this temperature, the raw material anhydrous hydrogen chloride gas is fed reactor drum by the bottom then, keep the required reaction times, make hydrogenchloride and isoprene carry out addition reaction.Because addition reaction is an exothermic process, control hydrogen chloride gas air inlet speed to keep temperature of reaction.More than the reaction conditions of each embodiment see table 1, reaction result is seen table 2.
[embodiment 9～16]
Hydrolysis reaction carries out in 1000 milliliters of glass there-necked flasks that have mechanical stirring and a heating unit.Chloroisoamylene, toluene and aqueous sodium hydroxide solution are added in the there-necked flask, start and stir and that reaction solution is heated to is temperature required, keep the required reaction times.More than the reaction conditions of each embodiment see table 3, reaction result is seen table 4.
When methyl butene alcohol was refining, tower top temperature was 70～72 ℃, and tower still temperature is controlled to be 80～90 ℃, and absolute pressure of top of the tower is controlled to be 260～270mmHg, and control of reflux ratio is 1～3.When prenol was refining, tower top temperature was 75～77 ℃, and tower still temperature is 85～95 ℃, and absolute pressure of top of the tower is controlled to be 60～75mmHg, and control of reflux ratio is 1～3.The pure and mild prenol purity of purified methyl butene is seen table 4.
[embodiment 17～23]
Hydrolysis reaction carries out in 1000 milliliters of glass there-necked flasks that have mechanical stirring and a heating unit.Chloroisoamylene, solvent and aqueous sodium hydroxide solution are added in the there-necked flask, start and stir and that reaction solution is heated to is temperature required, keep the required reaction times.More than the reaction conditions of each embodiment see the following form:
Table 1.
Table 2.
Table 3.
Table 4.
Table 5:
Table 6:
Claims (9)
1. the working method of a C 5 enol, this method is a raw material with isoprene and hydrogenchloride, may further comprise the steps:
1) isoprene and hydrogenchloride carry out the mixture (chloroisoamylene) that addition reaction generates 1-chloroisoamylene and 3-chloroisoamylene; The mol ratio of hydrogenchloride and isoprene is (0.5～1.0): 1; Temperature of reaction is-15～20 ℃, and reaction pressure is a normal pressure, and reaction time is 2～10hr.
2) the addition reaction product reaction that is hydrolyzed makes chloroisoamylene be converted into the pure and mild prenol of methyl butene.In hydrolysis, add toluene, ethylbenzene, normal hexane, hexanaphthene, 2-methylpentane, 3-methylpentane, 2; 2-dimethylbutane, 2; 3-dimethylbutane, heptane etc. are solvent, and solvent can be above-mentioned a kind of, also can be above-mentioned two or more mixtures.The mass ratio of solvent and chloroisoamylene is (0.2～10): 1; The mol ratio of sodium hydroxide and chloroisoamylene is (1.0～1.5): 1, and concentration sodium hydroxide is 5%～50%, temperature of reaction is 40～80 ℃; Reaction pressure is a normal pressure, and reaction time is 10～150 minutes.
3) hydrolysate is told water, and oil phase carries out rectifying, obtains the pure and mild prenol product of methyl butene, and unreacted isoprene is circulated to addition reaction as raw material, and the hexanaphthene of recovery is circulated to hydrolysis reaction.
2. the working method of the working method of a kind of C 5 enol according to claim 1 is characterized in that the mol ratio of described hydrogenchloride of step 1 and isoprene is (0.5～1.0): 1.
3. the working method of a kind of C 5 enol according to claim 1 is characterized in that the described temperature of reaction of step 1 is-15～20 ℃.
4. the working method of a kind of C 5 enol according to claim 1 is characterized in that the described reaction time of step 1 is 2～10hr.
5. the working method of a kind of C 5 enol according to claim 1 is characterized in that the mass ratio of described solvent of step 2 and chloroisoamylene is (0.2～10): 1.
6. the working method of a kind of C 5 enol according to claim 1 is characterized in that the mol ratio of described sodium hydroxide of step 2 and chloroisoamylene is (1.0～1.5): 1.
7. the working method of a kind of C 5 enol according to claim 1 is characterized in that the described concentration sodium hydroxide of step 2 is 5%～50%.
8. the working method of a kind of C 5 enol according to claim 1 is characterized in that the described temperature of reaction of step 2 is 40～80 ℃.
9. the working method of a kind of C 5 enol according to claim 1 is characterized in that the described reaction time of step 2 is 10～150 minutes.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341255A (en) * | 2014-09-19 | 2015-02-11 | 江苏省建筑科学研究院有限公司 | Preparation method of unsaturated alcohol |
| CN104788287A (en) * | 2015-03-20 | 2015-07-22 | 安徽海德石油化工有限公司 | Method for producing 3-methyl-2-buten-1-ol by isobutene |
| CN105130751A (en) * | 2015-07-16 | 2015-12-09 | 山东联创节能新材料股份有限公司 | Synthetic method of 3-methyl-3-butene-1-ol |
| CN105523882A (en) * | 2015-12-16 | 2016-04-27 | 绍兴明业化纤有限公司 | Method for inhibiting explosive polymerization of chloroisopentene and device thereof |
| CN105541547A (en) * | 2015-12-16 | 2016-05-04 | 绍兴明业化纤有限公司 | C5 enol production method |
| CN105541544A (en) * | 2015-12-16 | 2016-05-04 | 绍兴明业化纤有限公司 | 3-methyl-3-buten-1-ol production method |
| CN107082740A (en) * | 2016-02-16 | 2017-08-22 | 浙江医药股份有限公司新昌制药厂 | It is a kind of to improve the method that chloro method prepares prenol yield |
| CN109180450A (en) * | 2018-10-09 | 2019-01-11 | 南通天泽化工有限公司 | A kind of preparation method of methyl heptenone |
| CN110818525A (en) * | 2019-11-26 | 2020-02-21 | 江西盛伟科技股份有限公司 | Synthetic method of perfume green grass aldehyde |
| CN111187146A (en) * | 2020-01-17 | 2020-05-22 | 浙江大学宁波理工学院 | Method for producing 2-methyl-3-buten-2-ol |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104341255A (en) * | 2014-09-19 | 2015-02-11 | 江苏省建筑科学研究院有限公司 | Preparation method of unsaturated alcohol |
| CN104788287A (en) * | 2015-03-20 | 2015-07-22 | 安徽海德石油化工有限公司 | Method for producing 3-methyl-2-buten-1-ol by isobutene |
| CN105130751A (en) * | 2015-07-16 | 2015-12-09 | 山东联创节能新材料股份有限公司 | Synthetic method of 3-methyl-3-butene-1-ol |
| CN105523882A (en) * | 2015-12-16 | 2016-04-27 | 绍兴明业化纤有限公司 | Method for inhibiting explosive polymerization of chloroisopentene and device thereof |
| CN105541547A (en) * | 2015-12-16 | 2016-05-04 | 绍兴明业化纤有限公司 | C5 enol production method |
| CN105541544A (en) * | 2015-12-16 | 2016-05-04 | 绍兴明业化纤有限公司 | 3-methyl-3-buten-1-ol production method |
| CN107082740A (en) * | 2016-02-16 | 2017-08-22 | 浙江医药股份有限公司新昌制药厂 | It is a kind of to improve the method that chloro method prepares prenol yield |
| CN107082740B (en) * | 2016-02-16 | 2020-10-02 | 浙江医药股份有限公司新昌制药厂 | Method for improving yield of prenol prepared by chlorination process |
| CN109180450A (en) * | 2018-10-09 | 2019-01-11 | 南通天泽化工有限公司 | A kind of preparation method of methyl heptenone |
| CN109180450B (en) * | 2018-10-09 | 2021-12-28 | 南通天泽化工有限公司 | Preparation method of methyl heptenone |
| CN110818525A (en) * | 2019-11-26 | 2020-02-21 | 江西盛伟科技股份有限公司 | Synthetic method of perfume green grass aldehyde |
| CN111187146A (en) * | 2020-01-17 | 2020-05-22 | 浙江大学宁波理工学院 | Method for producing 2-methyl-3-buten-2-ol |
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Inventor after: Zhao Mingjiang Inventor after: Zhao Mingjun Inventor after: Shang Zhicai Inventor before: Zhao Mingjiang Inventor before: Zhao Mingjun Inventor before: Meng Qinbiao Inventor before: Shang Zhicai |
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Application publication date: 20120321 |