CN101306980A - Method for preparing perchloro cyclopentadiene - Google Patents
Method for preparing perchloro cyclopentadiene Download PDFInfo
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- CN101306980A CN101306980A CNA2008101243842A CN200810124384A CN101306980A CN 101306980 A CN101306980 A CN 101306980A CN A2008101243842 A CNA2008101243842 A CN A2008101243842A CN 200810124384 A CN200810124384 A CN 200810124384A CN 101306980 A CN101306980 A CN 101306980A
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Abstract
The invention discloses a method for making perfluoro cyclopentadiene. The method is as follows: (1) dicyclopentadiene is made into monocyclopentadiene through pyrolysis; (2) the monocyclopentadiene is respectively added in a main chloridizing reactor and a minor chloridizing reactor; (3) chlorine gas is continuously fed in the main chloridizing reactor at a temperature of between 180 and 600 DEG C so as to carry out chlorination reaction, thereby obtaining perfluoro cyclopentadiene crude product; and the minor chloridizing reactor continuously absorbs the tail gas discharged from the main chloridizing reactor at a temperature of between 20 and 150 DEG C so as to carry out chlorination reaction; (4) the perfluoro cyclopentadiene crude product obtained inside the main chloridizing reactor undergoes rectification under reduced pressure and then acidic gas is removed through inert gas bubbling; (5) the original minor chloridizing reactor is converted into a main chloridizing reactor, while the original main chloridizing reactor is filled with monocyclopentadiene and is converted into a minor chloridizing reactor, thereby returning to step (3). The method has fewer steps, simple process, low chlorine gas consumption, low cost, easily realized industrialization and high utilization rate of chlorine gas.
Description
Technical field
The present invention relates to a kind of synthetic method of organic compound, relate in particular to a kind of preparation method of perchlorinated cyclopentadienyl.
Background technology
Perchlorinated cyclopentadienyl is important agricultural chemicals, chemical intermediate, can be used for synthetic pesticide (aldrin, Dieldrin-attapulgite mixture, 5a,6,9,9a-hexahydro-6,9-methano-2,4, Niran, kill mosquito spirit), medicine (antipyrine) and polyamine esters industry fire retardant.
Perchlorinated cyclopentadienyl normal temperature for light yellow or brown yellow transparent liquid, has irritating smell down, and is not flammable.Boiling point be 239 ℃ (68～70 ℃, 1～1.3mmHg), 9.6 ℃ at zero pour, density (d425) 1.7019 * 10
3Kg/m
3, specific refractory power (Nd25) 1.563, no flash-point, water insoluble, dissolve in the organic solvents such as ether, tetracol phenixin.
The method of general synthetic perchlorinated cyclopentadienyl all is with monocycle pentadiene and chlorine reaction in the single reaction still, take an overall view of the proportion of examining reaction solution and determine reaction end, when reaction mass proportion is 1.7, stopped reaction, the product that obtains is a mixture, yield is not high, and the product content of perchlorinated cyclopentadienyl is low.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of elaboration perchlorinated cyclopentadienyl of high yield.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of preparation method of perchlorinated cyclopentadienyl may further comprise the steps:
(1) the dicyclopentadiene Pintsch process is made the monocycle pentadiene;
(2) the monocycle pentadiene is added respectively become owner of chlorination tank and time chlorination tank;
(3) main chlorination tank carries out chlorination reaction at 180～600 ℃ of continuous down feeding chlorine, gets the full-chloro-cyclopentadiene crude product, and tail gas feeds time chlorination tank; Inferior chlorination tank carries out chlorination reaction (mainly utilizing the chlorine in the tail gas) 20～150 ℃ of following continuous absorption master chlorination tank tail gas discharged, finally mainly obtains 1,2,3,4-tetrachloro pentamethylene;
(4) the crude product perchlorinated cyclopentadienyl that obtains in the main chlorination tank is changed over to rectifying tower and carry out rectification under vacuum and get the elaboration perchlorinated cyclopentadienyl, remove sour gas with the rare gas element bubbling again;
(5) original chlorination tank changes main chlorination tank into, adds the monocycle pentadiene in the original main chlorination tank and changes time chlorination tank into, returns step (3).
In the step (1), scission reaction is reacted in still formula or tubular type cracker, and the scission reaction temperature is 150～500 ℃.
In the step (3), preferred 200～500 ℃ of main chlorination tank temperature.
In the step (4), described rectification under vacuum is to carry out under vacuum condition, guarantees that tower top temperature is no more than 200 ℃.Described rare gas element is a nitrogen.
Principle of the present invention is: be raw material with the dicyclopentadiene, become the monocycle pentadiene through Pintsch process, chlorination is 1,2,3 under low temperature (20～150 ℃), 4-tetrachloro pentamethylene, and chlorination is a full-chloro-cyclopentadiene under high temperature (180～600 ℃) again.By the serial operation of primary and secondary chlorination tank, fully improved the utilization ratio of chlorine.Realized serialization production by primary and secondary chlorination tank alternative operator scheme.
The principal reaction equation is as follows:
Beneficial effect: the preparation method of perchlorinated cyclopentadienyl of the present invention, step is few, and technology is simple, and chlorine consumes low, cost is low, is easy to industrialization, the chlorine utilization height, in dicyclopentadiene, total recovery of the present invention reaches more than 93%, and chloro cyclopentadiene product purity is more than 98%.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment:
The present invention is further illustrated below in conjunction with embodiment.Embodiment is the unrestricted the present invention of explanation.Any those of ordinary skill can be understood these embodiments and not limit the present invention in any way in this area, can make suitable modification and without prejudice to essence of the present invention with depart from scope of the present invention.
Embodiment 1:
In the 500L cracking still, add the 100Kg dicyclopentadiene earlier, by the electric heating bag cracking still slowly is warming up to 300～350 ℃, when the top has steam to come out, continuously dicyclopentadiene is added cracking still by under meter with 120 kilograms speed per hour again, steam flows into storage tank and is the monocycle pentadiene behind chilling.In two 500L chlorination tanks, add monocycle pentadiene 200L respectively, two chlorination tanks heat up simultaneously, intensification limit, a chlorination tank limit feeds chlorine, this chlorination tank is main chlorination tank, tail gas feeds the another chlorination tank, this chlorination tank is a time chlorination tank, and main chlorination tank temperature is remained on 200～400 ℃, and inferior chlorination tank temperature remains on 80～120 ℃, unreacted chlorine changes over to again in time chlorination tank and participates in chlorination reaction in the main chlorination tank, chromatogram tracking detects full-chloro-cyclopentadiene content in the main chlorination tank, when full-chloro-cyclopentadiene content greater than 98% the time, main chlorination reaction finishes, change material in the main chlorination tank rectifying of over to rectifying tower still, rectifying obtains the elaboration full-chloro-cyclopentadiene under the reduced pressure, remove acid gas with nitrogen bubble after, obtain 98.5% full-chloro-cyclopentadiene 373Kg, calculate with dicyclopentadiene, yield is 93.6%.
After main chlorination tank material produces, drop into 200L monocycle pentadiene again, heat up, this moment, this chlorination tank became time chlorination tank, and original time chlorination tank becomes main chlorination tank.Feed chlorine continuously in main chlorination tank, and tail gas is fed in time chlorination tank, with the reaction under 200～400 ℃, 80～120 ℃ of primary and secondary chlorination tank holding temperature, cyclical operation successively realizes serialization production respectively.
Embodiment 2:
In the 500L cracking still, add the 100Kg dicyclopentadiene earlier, by the electric heating bag cracking still slowly is warming up to 300～350 ℃, when the top has steam to come out, continuously dicyclopentadiene is added cracking still by under meter with 120 kilograms speed per hour again, steam flows into storage tank and is the monocycle pentadiene behind chilling.In two 500L chlorination tanks, add monocycle pentadiene 210L respectively, two chlorination tanks heat up simultaneously, intensification limit, a chlorination tank limit feeds chlorine, this chlorination tank is main chlorination tank, tail gas feeds the another chlorination tank, this chlorination tank is a time chlorination tank, and main chlorination tank temperature is remained on 210～300 ℃, and inferior chlorination tank temperature remains on 80～150 ℃, unreacted chlorine changes over to again in time chlorination tank and participates in chlorination reaction in the main chlorination tank, chromatogram tracking detects full-chloro-cyclopentadiene content in the main chlorination tank, when full-chloro-cyclopentadiene content greater than 98% the time, main chlorination reaction finishes, change material in the main chlorination tank rectifying of over to rectifying tower still, rectifying obtains the elaboration full-chloro-cyclopentadiene under the reduced pressure, remove acid gas with nitrogen bubble after, obtain 98.8% full-chloro-cyclopentadiene 393Kg, calculate with dicyclopentadiene, yield is 95%.
After main chlorination tank material produces, drop into 200L monocycle pentadiene again, heat up, this moment, this chlorination tank became time chlorination tank, and original time chlorination tank becomes main chlorination tank.Feed chlorine continuously in main chlorination tank, and tail gas is fed in time chlorination tank, with the reaction under 210～300 ℃, 80～150 ℃ of primary and secondary chlorination tank holding temperature, cyclical operation successively realizes serialization production respectively.
Claims (6)
1, a kind of preparation method of perchlorinated cyclopentadienyl is characterized in that this method may further comprise the steps:
(1) the dicyclopentadiene Pintsch process is made the monocycle pentadiene;
(2) the monocycle pentadiene is added respectively become owner of chlorination tank and time chlorination tank;
(3) main chlorination tank carries out chlorination reaction at 180～600 ℃ of continuous down feeding chlorine, gets the full-chloro-cyclopentadiene crude product; Inferior chlorination tank carries out chlorination reaction 20～150 ℃ of following continuous absorption master chlorination tank tail gas discharged;
(4) the crude product perchlorinated cyclopentadienyl that obtains in the main chlorination tank is changed over to rectifying tower and carry out rectification under vacuum and get the elaboration perchlorinated cyclopentadienyl, remove sour gas with the rare gas element bubbling again;
(5) original chlorination tank changes main chlorination tank into, adds the monocycle pentadiene in the original main chlorination tank and changes time chlorination tank into, returns step (3).
2, the preparation method of perchlorinated cyclopentadienyl according to claim 1 is characterized in that in step (1), scission reaction is reacted in still formula or tubular type cracker.
3, the preparation method of perchlorinated cyclopentadienyl according to claim 1 is characterized in that in step (1), the scission reaction temperature is 150～500 ℃.
4, the preparation method of perchlorinated cyclopentadienyl according to claim 1 is characterized in that in step (3), main chlorination tank temperature is controlled at 200～500 ℃.
5, the preparation method of perchlorinated cyclopentadienyl according to claim 1 is characterized in that in step (4), described rectification under vacuum is to carry out under vacuum condition, guarantee that tower top temperature is no more than 200 ℃.
6, the preparation method of perchlorinated cyclopentadienyl according to claim 1 is characterized in that in step (4), described rare gas element is a nitrogen.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008101243842A CN101306980B (en) | 2008-06-30 | 2008-06-30 | Method for preparing perchloro cyclopentadiene |
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| CN2008101243842A CN101306980B (en) | 2008-06-30 | 2008-06-30 | Method for preparing perchloro cyclopentadiene |
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| CN101306980A true CN101306980A (en) | 2008-11-19 |
| CN101306980B CN101306980B (en) | 2011-05-11 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942442A (en) * | 2012-11-27 | 2013-02-27 | 四川大学 | Method for purifying hexachlorocyclopentadiene |
| WO2017181566A1 (en) * | 2016-04-22 | 2017-10-26 | 北京宇极科技发展有限公司 | Manufacturing method of 1,2-dichlorohexafluorocyclopentene |
| CN108164390A (en) * | 2017-12-20 | 2018-06-15 | 大连九信精细化工有限公司 | A kind of industrialized preparing process of perfluoro-cyclopentene |
| CN113072418A (en) * | 2021-03-04 | 2021-07-06 | 老河口华辰化学有限公司 | Production method for double-kettle switching continuous chlorination |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU793976A1 (en) * | 1979-02-22 | 1981-01-07 | Предприятие П/Я В-2287 | Method of preparing hexachlorocyclopentadiene |
| US4246205A (en) * | 1979-09-20 | 1981-01-20 | Velsicol Chemical Corporation | Process for preparing hexachlorocyclopentadiene |
-
2008
- 2008-06-30 CN CN2008101243842A patent/CN101306980B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942442A (en) * | 2012-11-27 | 2013-02-27 | 四川大学 | Method for purifying hexachlorocyclopentadiene |
| WO2017181566A1 (en) * | 2016-04-22 | 2017-10-26 | 北京宇极科技发展有限公司 | Manufacturing method of 1,2-dichlorohexafluorocyclopentene |
| CN109071385A (en) * | 2016-04-22 | 2018-12-21 | 北京宇极科技发展有限公司 | The method for preparing 1,2- dichloro hexafluoro cyclopentene |
| US20190127300A1 (en) * | 2016-04-22 | 2019-05-02 | Beijing Yuji Science & Technology Co., Ltd. | Manufacturing method of 1,2-dichlorohexafluorocyclopentene |
| US10538467B2 (en) | 2016-04-22 | 2020-01-21 | Beijing Yuji Science & Technology Co., Ltd. | Manufacturing method of 1,2-dichlorohexafluorocyclopentene |
| CN109071385B (en) * | 2016-04-22 | 2021-11-05 | 北京宇极科技发展有限公司 | Process for preparing 1, 2-dichlorohexachlorocyclopentene |
| CN108164390A (en) * | 2017-12-20 | 2018-06-15 | 大连九信精细化工有限公司 | A kind of industrialized preparing process of perfluoro-cyclopentene |
| CN108164390B (en) * | 2017-12-20 | 2020-08-25 | 大连九信精细化工有限公司 | Industrial production method of perfluorocyclopentene |
| CN113072418A (en) * | 2021-03-04 | 2021-07-06 | 老河口华辰化学有限公司 | Production method for double-kettle switching continuous chlorination |
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| CN101306980B (en) | 2011-05-11 |
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Address after: 223002 Huaian City, Jiangsu Province Chemical Qingpu District Road No. 30 Patentee after: Andao mai'anbang (Jiangsu) Co., Ltd Address before: 223002 Huaian City, Jiangsu Province Chemical Qingpu District Road No. 30 Patentee before: JIANGSU ANPON ELECTROCHEMICAL Co.,Ltd. |
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