CN105481634A - Preparing method for chloro-isopentene - Google Patents
Preparing method for chloro-isopentene Download PDFInfo
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- CN105481634A CN105481634A CN201510940280.9A CN201510940280A CN105481634A CN 105481634 A CN105481634 A CN 105481634A CN 201510940280 A CN201510940280 A CN 201510940280A CN 105481634 A CN105481634 A CN 105481634A
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- isoprene
- reaction
- chloroisoamylene
- hydrogenchloride
- isopentene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparing method for chloro-isopentene, and belongs to the technical field of water reducing agent synthesis. According to the preparing method, cyclohexane is used as solvent, isoprene and hydrogen chloride are subjected to an addition reaction to generate chloro-isopentene, the mass ratio of cyclohexane to isoprene is (0.2-0.6):1, the molar ratio of isoprene to hydrogen chloride is 1:(0.8-0.95), the reaction temperature is minus 5 DEG C-10 DEG C, reaction pressure is normal pressure, and the reaction residence time is 2-5 h. Compared with a chloro-isopentene production process in the prior art, the preparing method for chloro-isopentene is simple in process, and generation of bichloro-isopentane in the addition reaction process of hydrogen chloride and isoprene is effectively prevented.
Description
Technical field
The present invention relates to and a kind ofly carry out by isoprene and hydrogenchloride the method that addition reaction prepares chloroisoamylene, is particularly solvent with hexanaphthene, the method stoping dichloro-iso-pentane to generate in the addition reaction process of isoprene and hydrogenchloride.
Background technology
Chloroisoamylene is a kind of very useful fine-chemical intermediate raw material, and it can obtain the mixture of 3-M2BOL (prenol) and 2-M3BOL (methyl butenol) through direct hydrolysis reaction.Prenol is mainly used in and original trimethyl acetate or ethyl ester Reactive Synthesis 3,3-dimethyl-4-pentenoic acid methyl ester or ethyl ester, and it is the important source material preparing pyrethroid key intermediate high-cis dichloro esbiothrin.Methyl butenol is then mainly used as the raw material producing Sulcatone, can be used for synthesis DV-chrysanthemumic acid or chrysanthemum monocarboxylate, different vegetable alcohol, vitamin A, carotenoid, terpenes series fragrance intermediates etc. in addition.
Chloroisoamylene can be obtained by addition reaction by hydrogen chloride gas and isoprene.The addition reaction of hydrogenchloride and isoprene generates 3-methyl-2-butene-1-chlorine (1,3,2-CMB) and 3-methyl-2-butene-2-chlorine (3-chloroisoamylene) simultaneously.
From existing technique, usual addition reaction hydrogen chloride gas is excessive adding, and this addition reaction is thermopositive reaction, when temperature is higher, the chloroisoamylene generated easily and the further addition of hydrogenchloride generate 3-methyl isophthalic acid, 3-dichlorobutane (dichloro-iso-pentane).
Because the existence of this side reaction will affect the yield of chloroisoamylene, therefore take a lot of measure in prior art to suppress its generation.As US Patent No. 4,036,899 propose to adopt metal chlorides to be catalyzer, use water as diluting solvent carries out the addition reaction of hydrogen chloride gas and isoprene to prepare chloroisoamylene, it is said the generation that effectively can control dichloro-iso-pentane under the existence of hydrochloric acid.But, due to the existence of hydrochloric acid, very high to the anticorrosive requirement of equipment.In addition contain water in product, also must be removed by oily water separation in follow-up operation.
Chinese patent CN200510025336 adopts the mode mixed with addition reaction product by isoprene to regulate and control the addition reaction of hydrogenchloride and isoprene, then in conjunction with isomerization reaction and product rectified purified through twice, obtain 1,3,2-CMB purified product.The side reaction generating dichloro-iso-pentane during addition reaction is suppressed.But due to employ excessive hydrogenchloride and be use adduct as thinner, fundamentally cannot stop the generation of addition reaction byproduct in process thing dichloro-iso-pentane.
Based on this, make subject application.
Summary of the invention
The invention provides a kind of preparation method of chloroisoamylene.Technical problem to be solved by this invention is the generation effectively stoping dichloro-iso-pentane in isoprene and hydrogenchloride addition reaction process.
For achieving the above object, the technical scheme taked of the present invention is as follows:
A kind of preparation method of chloroisoamylene, the method take hexanaphthene as solvent, isoprene and hydrogenchloride is made to generate chloroisoamylene through addition reaction, the mass ratio of hexanaphthene and isoprene is (0.2 ~ 0.6): 1, the mol ratio of isoprene and hydrogenchloride is 1:(0.8 ~ 0.95), temperature of reaction is-5 ~ 10 DEG C, and reaction pressure is normal pressure, and reaction time is 2 ~ 5 hours.
Further, as preferably:
Described hexanaphthene and the mass ratio of isoprene are preferably (0.3 ~ 0.5): 1; The mol ratio of isoprene and hydrogenchloride is preferably 1:(0.85 ~ 0.90); Temperature of reaction is preferably 0 ~ 5 DEG C; Reaction time is preferably 3 ~ 4 hours.
Key of the present invention is that a kind of thinner adds in the material system of addition reaction by cyclohexane give, simultaneously strictly the mol ratio of isoprene and hydrogenchloride controlled the level at > 1.After hexanaphthene mixes with isoprene, because in reaction system, the reduction of reactant isoprene concentrations can slow down addition reaction speed, reaction is carried out more stably, avoid the generation causing chloroisoamylene series connection side reaction because of the generation of reaction heat.And the mol ratio of isoprene and hydrogenchloride is being controlled after the level of > 1, because adding of isoprene and hydrogenchloride is Viability far above chloroisoamylene, preferential and isoprene react by hydrogenchloride, simultaneously in excessive isoprene and reaction system, the reduction of chloroisoamylene concentration further suppress again hydrogenchloride and chloroisoamylene addition again, thus effectively prevents the generation of dichloro-iso-pentane in hydrogenchloride and isoprene addition reaction process.
In adduct, unreacted isoprene and solvent hexanaphthene can adopt general rectificating method to reclaim, and as feedstock circulation to addition reactor.
Below by embodiment, details of the present invention is further described.
Embodiment
[embodiment 1 ~ 8]
Addition reaction is carried out in 1000 milliliters of glass there-necked flasks with mechanical stirring and refrigerating unit.Isoprene is added in there-necked flask, start and to stir and that reaction solution is cooled to is temperature required, then at such a temperature Materials Absolute hydrogen chloride gas is passed into reactor by bottom, the reaction times needed for maintenance, make hydrogenchloride and isoprene carry out addition reaction.Because addition reaction is exothermic process, hydrogen chloride gas feed rate be controlled to maintain temperature of reaction.The reaction conditions of each embodiment is in table 1 above, and reaction result is in table 2.
Addition reaction reaction conditions synopsis in table 1 embodiment 1-8
The effect comparison table of table 2 embodiment 1-8 product
In above-described embodiment, be that a kind of thinner adds in the material system of addition reaction by cyclohexane give, simultaneously strictly the mol ratio of isoprene and hydrogenchloride controlled the level at > 1.After hexanaphthene mixes with isoprene, because in reaction system, the reduction of reactant isoprene concentrations can slow down addition reaction speed, reaction is carried out more stably, avoid the generation causing chloroisoamylene series connection side reaction because of the generation of reaction heat.And the mol ratio of isoprene and hydrogenchloride is being controlled after the level of > 1, because adding of isoprene and hydrogenchloride is Viability far above chloroisoamylene, preferential and isoprene react by hydrogenchloride, simultaneously in excessive isoprene and reaction system, the reduction of chloroisoamylene concentration further suppress again hydrogenchloride and chloroisoamylene addition again, therefore, adopt technical solution of the present invention, effectively can prevent the growing amount of dichloro-iso-pentane in hydrogenchloride and isoprene addition reaction process, improve the selectivity of reaction.
And unreacted isoprene and solvent hexanaphthene can adopt general rectificating method to reclaim in adduct, and as feedstock circulation to addition reactor.
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 (5)
1. the preparation method of a chloroisoamylene, it is characterized in that: the method with isoprene and hydrogenchloride for raw material, hexanaphthene is solvent, isoprene and hydrogenchloride is made to generate chloroisoamylene through addition reaction, the mass ratio of hexanaphthene and isoprene is (0.2-0.6): 1, and the mol ratio of isoprene and hydrogenchloride is 1:(0.8-0.95), temperature of reaction is-5-10 DEG C, reaction pressure is normal pressure, and reaction time is 2-5 hour.
2. the preparation method of a kind of chloroisoamylene as claimed in claim 1, it is characterized in that: described hexanaphthene and the mass ratio of chloroisoamylene are (0.2-0.3): 1, and the mol ratio of hydrogenchloride and isoprene is (0.8-0.85): 1.
3. the preparation method of a kind of chloroisoamylene as claimed in claim 1, is characterized in that: described processing temperature of reaction is-5-1 DEG C, and reaction time is 3 hours.
4. the preparation method of a kind of chloroisoamylene as claimed in claim 1, is characterized in that: in adduct, unreacted isoprene and solvent hexanaphthene can adopt rectifying mode to reclaim and be circulated to addition reaction as raw material.
5. the preparation method of a kind of chloroisoamylene as described in any one of claim 1-4, it is characterized in that: with isoprene and hydrogenchloride for raw material, hexanaphthene is solvent, isoprene and hydrogenchloride is made to generate chloroisoamylene through addition reaction, the mass ratio of hexanaphthene and chloroisoamylene is 0.2: 1, the mol ratio of hydrogenchloride and isoprene is 0.8: 1, and processing temperature of reaction is-5 DEG C, and reaction time is 3 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510940280.9A CN105481634A (en) | 2015-12-16 | 2015-12-16 | Preparing method for chloro-isopentene |
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| CN201510940280.9A CN105481634A (en) | 2015-12-16 | 2015-12-16 | Preparing method for chloro-isopentene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721812A (en) * | 2017-09-30 | 2018-02-23 | 绍兴明业化纤有限公司 | A kind of method that chloroisoamylene is prepared by the ether of carbon ten |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102367219A (en) * | 2011-07-19 | 2012-03-07 | 赵明江 | Preparation method of chloroisopentene |
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2015
- 2015-12-16 CN CN201510940280.9A patent/CN105481634A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102367219A (en) * | 2011-07-19 | 2012-03-07 | 赵明江 | Preparation method of chloroisopentene |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721812A (en) * | 2017-09-30 | 2018-02-23 | 绍兴明业化纤有限公司 | A kind of method that chloroisoamylene is prepared by the ether of carbon ten |
| CN107721812B (en) * | 2017-09-30 | 2020-08-04 | 绍兴明业化纤有限公司 | Method for preparing chloroisoamylene from decaether |
| 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 |
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Application publication date: 20160413 |