CN109694308B - Method for obtaining cis-1, 3-dichloropropene by in-situ reversion of trans-1, 3-dichloropropene - Google Patents
Method for obtaining cis-1, 3-dichloropropene by in-situ reversion of trans-1, 3-dichloropropene Download PDFInfo
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- CN109694308B CN109694308B CN201810981051.5A CN201810981051A CN109694308B CN 109694308 B CN109694308 B CN 109694308B CN 201810981051 A CN201810981051 A CN 201810981051A CN 109694308 B CN109694308 B CN 109694308B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Abstract
The invention discloses a method for obtaining cis-1, 3-dichloropropene by in-situ reversion of trans-1, 3-dichloropropene, which comprises the following steps: (1) preparing trans-1, 3-dichloropropene as a raw material, adding the trans-1, 3-dichloropropene into an alcohol solvent to prepare an alcohol solution; (2) adding a light promoter into the alcohol solution; (3) and (3) carrying out ultraviolet irradiation on the alcohol solution added with the light promoter, controlling the reaction temperature, and reacting to obtain the cis-1, 3 dichloropropene. The method of the invention converts trans-1, 3 dichloropropene into cis-1, 3 dichloropropene, which has the advantages of low cost and environmental protection and has high commercial value.
Description
Technical Field
The invention relates to a method for obtaining cis-1, 3-dichloropropene by in-situ reversion of trans-1, 3-dichloropropene. Under the irradiation of ultraviolet light, trans-1, 3-dichloropropene dissociates chlorine free radicals and allyl chloride free radicals, and the free radicals are recombined to form cis-trans-1, 3-dichloropropene mixture.
Background
1,3 dichloropropene is a by-product in the production of epichlorohydrin. The 1, 3-dichloropropene on the market exists in the form of a mixture of cis-1, 3-dichloropropene and trans-1, 3-dichloropropene isomers. The boiling point difference of cis-trans isomers is small, and the energy consumption of rectification separation is large. Cis-1, 3-dichloropropene is used for synthesizing propiolic alcohol, and trans-1, 3-dichloropropene cannot synthesize propiolic alcohol. Therefore, if trans-1, 3-dichloropropene which does not participate in the reaction can be converted into cis-1, 3-dichloropropene, the cost for synthesizing the propiolic alcohol can be obviously reduced, the utilization rate of raw materials is increased, the discharge of waste materials and byproducts is reduced, and the method has great significance for the comprehensive utilization of the carbon three raw materials.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the method for converting the trans-1, 3-dichloropropene which does not participate in the reaction into the cis-1, 3-dichloropropene, which can obviously reduce the cost for synthesizing the propiolic alcohol, increase the utilization rate of raw materials, reduce the discharge of waste materials and byproducts, and obtain the cis-1, 3-dichloropropene by in-situ reversion of the trans-1, 3-dichloropropene which is very meaningful for the comprehensive utilization of the carbon three raw materials.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for obtaining cis-1, 3-dichloropropene by in-situ inversion of trans-1, 3-dichloropropene comprises the following steps of (1) converting trans-1, 3-dichloropropene by ultraviolet irradiation to obtain cis-1, 3-dichloropropene; the reaction equation is as follows:
specifically, the method for obtaining cis-1, 3-dichloropropene by in-situ reversion of trans-1, 3-dichloropropene comprises the following preparation steps:
(1) an ultraviolet light pipe is arranged in the quartz glass reactor with a jacket, and cooling water is introduced into the jacket; preparing trans-1, 3-dichloroethylene into an alcohol solution with a certain concentration, adding the alcohol solution into a reactor, and slightly blowing nitrogen into the reaction solution;
(2) adding a light promoter into the reaction solution;
(3) starting ultraviolet illumination, controlling the temperature of the reaction system by the amount of cooling water, and detecting whether the cis-trans isomerism is close to 1:1 by gas phase to finish the reaction.
The glass reactor used in the step (1) of the present invention is made of quartz glass, and has high ultraviolet transmittance, and the quartz glass reactor has the characteristic of high ultraviolet transmittance, and if other reactors are used, the transmittance of ultraviolet rays is greatly influenced, and thus the experiment is influenced.
The alcohol solution prepared from trans-1, 3-dichloroethylene in the step (1) of the invention with a certain concentration is as follows: an alcohol solution at a concentration of 0.5% to 100% by weight; preferably 20% to 50% by weight (i.e. the weight percentage of trans-1, 3-dichloroethylene in the alcohol solution).
The alcohol in the step (1) is mainly small molecular alcohol such as methanol, ethanol, isopropanol and the like; methanol or ethanol is preferred.
The light accelerator in the step (2) is an anthracene or fluorenone compound; the dosage of the light promoter is 0.001-5 percent of the mole number of the trans-1, 3-dichloropropene, and is preferably 0.1-1 percent.
The wavelength of the ultraviolet light in the step (3) is selected to be 250nm-400nm, and the ultraviolet light source is from a high-pressure mercury lamp or an ultraviolet LED lamp, preferably a light source and an LED single-wavelength light source provided by a high-pressure mercury lamp with 365nm as the main wavelength. A large amount of heat is generated in the process of illumination, and the temperature of the reaction liquid is controlled to be lower than the boiling point of the solution by cooling water.
The temperature of the reaction system in the above step (3) of the present invention is 25 to 110 deg.C, preferably 70 deg.C. When ultraviolet light irradiates a solution in equipment, a large amount of heat is generated, the solution is heated continuously, so that the reaction temperature needs to be controlled, the temperature of the solution is below the boiling point of the solution, the reaction efficiency is higher when the temperature is within a range of 25-110 ℃, the reaction speed is fastest at 70 ℃, and the conversion speed is highest.
The illumination time and the concentration of the raw materials are in a direct proportion relation, and the illumination time and the concentration of the raw materials are in an inverse proportion relation with the power of a light source.
The invention has the advantages and beneficial effects that:
1. the invention adopts a method for promoting the in-situ conversion of trans-1, 3-dichloropropene into cis-1, 3-dichloropropene under the condition of ultraviolet illumination for the first time, and the method has the advantages of simple implementation, high efficiency and no pollution.
2. The invention adopts ultraviolet light to realize the reversal of the two, and the reaction mechanism of the reaction is that chlorohydrocarbon decomposes into chlorine free radicals and allyl free radicals under the irradiation of ultraviolet light, and the free radicals are recombined to realize cis-trans isomerism in a certain proportion; the method can convert the trans-1, 3-dichloroethylene which does not participate in the reaction into the cis-1, 3-dichloropropene capable of synthesizing the propiolic alcohol, thereby improving the yield and supply quantity of the cis-1, 3-dichloropropene and reducing the cost for synthesizing the propiolic alcohol; in addition, the invention can realize the effect of 50 percent conversion rate by adopting simple ultraviolet light irradiation reaction, increases the utilization rate of raw materials, reduces the discharge of waste materials and byproducts, and has great significance for the comprehensive utilization of the carbon three raw materials.
Detailed Description
The present invention is further illustrated by the following examples, which should be construed as limiting the scope of the invention.
The trans-1, 3-dichloroethylene serving as a raw material is separated from the market, for example, the trans-form does not participate in the reaction after rectification separation or a mixture is used for reaction, and the trans-form is separated as a byproduct.
Example 1
(1) A250 ml quartz jacketed glass reactor was charged with 100ml of a 5 wt% (weight percent concentration, the same applies to the following examples) methanol solution of trans-1, 3-dichloroethylene, and 0.1% of a light promoter, anthracene N2, was added to the solution to bubble slightly;
(2) adding 0.1% of light accelerator anthracene;
(3) then starting light irradiation: the light of an LED lamp with the wavelength of 40w and 310nm is controlled, the temperature is controlled to be 25 ℃, and the cis-trans isomerism proportion is detected by a gas phase. After illumination for 1.2h, the cis-trans isomerization ratio is 1:2, and the reaction is stopped to obtain a reaction product.
Example 2
(1) A 250ml quartz jacketed glass reaction kettle, 100ml of 5 percent trans-1, 3-dichloroethylene methanol solution is added, and N2 is slightly bubbled;
(2) adding 0.1% of light accelerator anthracene;
(3) then starting light irradiation: the light of 40w and 310nm LED lamps, the temperature is controlled to be 25 ℃, and the cis-trans isomerism proportion is detected by gas phase. After illumination for 0.5h, the cis-trans isomerization ratio is 1:2, and the reaction is stopped to obtain a reaction product.
Example 3
(1) A 250ml quartz jacketed glass reaction kettle is added with 100ml of 5 percent trans-1, 3-dichloroethylene methanol solution, and N2 is slightly bubbled;
(2) adding 0.1% of light accelerator anthracene;
(3) then starting light irradiation: the light of a 40w310nmLED lamp is controlled at 50 ℃, and the cis-trans isomerism proportion is detected by gas phase. After illumination for 1.2h, the cis-trans isomerization ratio is 1:1.5, and the reaction is stopped to obtain a reaction product.
Example 4
(1) A 250ml quartz jacketed glass reaction kettle is added with 100ml of 5 percent trans-1, 3-dichloroethylene methanol solution, and N2 is slightly bubbled;
(2) adding 0.1% of light accelerator anthracene;
(3) then starting light irradiation: the light of 40w and 310nm LED lamps, the temperature is controlled at 50 ℃, and the cis-trans isomerism proportion is detected by gas phase. After illumination for 1.2h, the cis-trans isomerization ratio is 1:1.2, and the reaction is stopped to obtain a reaction product.
Example 5
(1) A 250ml quartz jacketed glass reaction kettle, 100ml of 5 percent trans-1, 3-dichloroethylene methanol solution is added, and N2 is slightly bubbled;
(2) adding 0.1% of light accelerator anthracene;
(3) then starting light irradiation: the light of 40w and 310nm LED lamps, the temperature is controlled at 70 ℃, and the cis-trans isomerism proportion is detected by gas phase. After illumination for 1.2h, the cis-trans isomerization ratio is 1:1, and the reaction is stopped to obtain a reaction product.
Example 6
(1) A 250ml quartz jacketed glass reaction kettle is added with 100ml of methanol solution of 10 percent trans-1, 3-dichloroethylene, and N2 is slightly bubbled;
(2) adding 0.1% of light accelerator anthracene;
(3) then starting light irradiation: the light of 40w and 310nm LED lamps, the temperature is controlled at 70 ℃, and the cis-trans isomerism proportion is detected by gas phase. After 2 hours of illumination, the cis-trans isomerization ratio is 1:1, and the reaction is stopped to obtain a reaction product.
Example 7
(1) A 250ml quartz jacketed glass reaction kettle is added with 100ml of methanol solution of 20 percent trans-1, 3-dichloroethylene, and N2 is slightly bubbled;
(2) adding 0.1% of light accelerator anthracene;
(3) then starting light irradiation: the light of 40w and 310nm LED lamps, the temperature is controlled at 100 ℃, and the cis-trans isomerism proportion is detected by gas phase. After 2.5 hours of illumination, the cis-trans isomerization ratio is 1:1, and the reaction is stopped to obtain a reaction product.
Example 8
(1) A 250ml quartz jacketed glass reaction kettle is added with 100ml of 50 percent trans-1, 3-dichloroethylene methanol solution, and N2 is slightly bubbled;
(2) adding 0.1% of light accelerator anthracene;
(3) then starting light irradiation: 40w and 310nm, LED lamp illumination, temperature control at 70 ℃, and gas phase detection of cis-trans isomer ratio. After 2.5 hours of illumination, the cis-trans isomerization ratio is 1:3, the reaction is stopped, and a reaction product is obtained.
Example 9
(1) A 250ml quartz jacketed glass reaction kettle is added with 100ml of 50 percent trans-1, 3-dichloroethylene methanol solution, and N2 is slightly bubbled;
(2) adding 0.1% of light accelerator anthracene;
(3) then starting light irradiation: irradiating by a 150w high-pressure mercury lamp, controlling the temperature at 70 ℃, and detecting the cis-trans isomerization ratio by a gas phase. After 0.5h of illumination, the cis-trans isomerization ratio is 1:1, and the reaction is stopped to obtain a reaction product.
Example 10
(1) A 250ml quartz jacketed glass reaction kettle is added with 100ml of a 95 percent ethanol solution of 50 percent trans-1, 3-dichloroethylene, and N2 is slightly bubbled;
(2) adding 0.1% of light accelerator anthracene;
(3) then starting light irradiation: irradiating by a 150w high-pressure mercury lamp, controlling the temperature to be 75 ℃, and detecting the cis-trans isomerization ratio by a gas phase. After 0.5h of illumination, the cis-trans isomerization ratio is 1:1, and the reaction is stopped to obtain a reaction product.
Example 11
(1) A 250ml quartz jacketed glass reaction kettle is added with 100ml of 100 percent trans-1, 3-dichloroethylene and slightly bubbled with N2;
(2) adding 0.1% of light accelerator anthracene;
(3) then starting light irradiation: irradiating by a 150w high-pressure mercury lamp, controlling the temperature to be 75 ℃, and detecting the cis-trans isomerization ratio by a gas phase. After 0.5h of illumination, the cis-trans isomerization ratio is 1: 8. After illumination for 1.5h, the cis-trans isomerization ratio is 1:7, and the reaction is stopped to obtain a reaction product.
Example 12
The reaction system of example 8 was used, except that after the illumination reaction of the LED lamp, the lamp was changed from 310nm to 150w high pressure mercury lamp for continuous illumination, and after 0.5h, the cis-trans isomerization ratio was measured in the gas phase, the cis-trans isomerization ratio was 1:1.
Claims (9)
1. A method for obtaining cis-1, 3-dichloropropene by in-situ reversion of trans-1, 3-dichloropropene is characterized by comprising the following steps: the method utilizes ultraviolet irradiation to convert trans-1, 3-dichloropropene and obtain cis-1, 3-dichloropropene; the reaction equation is as follows:
the method comprises the following specific preparation steps:
(1) an ultraviolet light pipe is arranged in a glass reactor with a jacket, and cooling water is introduced into the jacket; preparing trans-1, 3-dichloroethylene into an alcohol solution with a certain concentration, adding the alcohol solution into a reactor, and slightly blowing nitrogen into the reaction solution;
(2) adding a light promoter into the reaction solution;
(3) starting ultraviolet illumination, controlling the temperature of a reaction system by the amount of cooling water, and detecting whether cis-trans isomerism is close to 1:1 reaction completion by a gas phase; the light accelerator in the step (2) is an anthracene or fluorenone compound.
2. The process according to claim 1 for in situ inversion of trans 1, 3-dichloropropene to yield cis 1, 3-dichloropropene, which comprises: the glass reactor used in step (1) is quartz glass.
3. The process according to claim 1 for in situ inversion of trans 1, 3-dichloropropene to yield cis 1, 3-dichloropropene, which comprises: and (2) the mass fraction of the trans-1, 3-dichloroethylene in the step (1) is 0.5-100 wt% of alcohol solution.
4. The process according to claim 3 for in situ reversion of trans 1, 3-dichloropropene to cis 1, 3-dichloropropene, which comprises: and (2) alcohol solution with the mass fraction of the trans-1, 3-dichloroethylene of 20-50 wt% in the step (1).
5. The process according to claim 1 for in situ inversion of trans 1, 3-dichloropropene to yield cis 1, 3-dichloropropene, which comprises: the alcohol in the step (1) is one of methanol, ethanol and isopropanol.
6. The process according to claim 1 for in situ inversion of trans 1, 3-dichloropropene to yield cis 1, 3-dichloropropene, which comprises: in the step (2), the dosage of the photo-promoter is 0.001-5% of the mole number of the trans-1, 3-dichloropropene.
7. The process according to claim 6 for in situ reversion of trans 1, 3-dichloropropene to cis 1, 3-dichloropropene, which comprises: the dosage of the light promoter is 0.1 to 1 percent of the mole number of the trans-1, 3-dichloropropene.
8. The process according to claim 2 for in situ reversion of trans 1, 3-dichloropropene to cis 1, 3-dichloropropene, which comprises: the wavelength of the ultraviolet light in the step (3) is selected to be 250nm-400nm, and an ultraviolet light source is from a high-pressure mercury lamp or an ultraviolet LED lamp.
9. The process according to claim 2 for in situ reversion of trans 1, 3-dichloropropene to cis 1, 3-dichloropropene, which comprises: the temperature of the reaction system in the step (3) is 25-110 ℃.
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| CN111848334A (en) * | 2020-07-30 | 2020-10-30 | 江苏扬农化工集团有限公司 | Method for treating by-products in process of preparing chloropropene by chlorination of propylene |
| CN112898118B (en) * | 2021-03-03 | 2023-03-24 | 江苏扬农化工集团有限公司 | Preparation method of trans-1, 3-dichloropropene |
| CN114560751B (en) * | 2022-02-15 | 2023-04-07 | 江苏瑞恒新材料科技有限公司 | Method for producing cis-or trans-1, 3-dichloropropene |
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| US3914167A (en) * | 1974-08-26 | 1975-10-21 | Dow Chemical Co | Process for making cis-1,3-dichloropropene |
| US5072063A (en) * | 1990-01-09 | 1991-12-10 | Dowelanco | Process for rearranging allylic geminal dihalogen compounds |
| EP0752403A3 (en) * | 1995-07-07 | 1997-05-28 | Dow Chemical Co | Improved catalyst for the rearrangement of allylic geminal dihalogen compounds |
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| CN105152850A (en) * | 2015-07-20 | 2015-12-16 | 山东联创节能新材料股份有限公司 | Method for synthesizing cis/trans-3,3,3-trifluoro-1-chloropropylene |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3914167A (en) * | 1974-08-26 | 1975-10-21 | Dow Chemical Co | Process for making cis-1,3-dichloropropene |
| US5072063A (en) * | 1990-01-09 | 1991-12-10 | Dowelanco | Process for rearranging allylic geminal dihalogen compounds |
| EP0752403A3 (en) * | 1995-07-07 | 1997-05-28 | Dow Chemical Co | Improved catalyst for the rearrangement of allylic geminal dihalogen compounds |
| CN102219637A (en) * | 2011-04-27 | 2011-10-19 | 浙江医药股份有限公司新昌制药厂 | Method for isomerizing 1,4-dichloro-2-butylene from cis-form to trans-form |
| CN105152850A (en) * | 2015-07-20 | 2015-12-16 | 山东联创节能新材料股份有限公司 | Method for synthesizing cis/trans-3,3,3-trifluoro-1-chloropropylene |
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