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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- China
- Prior art keywords
- chlorination tank
- main
- chloridizing
- reactor
- perchlorinated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 238000000034 method Methods 0.000 title claims abstract description 11
- VUNCWTMEJYMOOR-UHFFFAOYSA-N hexachlorocyclopentadiene Chemical compound ClC1=C(Cl)C(Cl)(Cl)C(Cl)=C1Cl VUNCWTMEJYMOOR-UHFFFAOYSA-N 0.000 title 1
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 81
- 239000007789 gas Substances 0.000 claims abstract description 16
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 230000005587 bubbling Effects 0.000 claims abstract description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 19
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010504 bond cleavage reaction Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000007017 scission Effects 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- BDTKCOREDQRWGK-UHFFFAOYSA-N 1,2,3,4,5,5-hexafluorocyclopenta-1,3-diene Chemical compound FC1=C(F)C(F)(F)C(F)=C1F BDTKCOREDQRWGK-UHFFFAOYSA-N 0.000 abstract 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 3
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000005336 cracking Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- -1 1,2,3,4-tetrachloro pentamethylene Chemical group 0.000 description 1
- GWHRPSOIZQENQQ-UHFFFAOYSA-N 5-chlorocyclopenta-1,3-diene Chemical compound ClC1C=CC=C1 GWHRPSOIZQENQQ-UHFFFAOYSA-N 0.000 description 1
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N Aminoantipyrine Natural products CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229960005222 phenazone Drugs 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101243842A CN101306980B (en) | 2008-06-30 | 2008-06-30 | Method for preparing perchloro cyclopentadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101243842A CN101306980B (en) | 2008-06-30 | 2008-06-30 | Method for preparing perchloro cyclopentadiene |
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| Publication Number | Publication Date |
|---|---|
| CN101306980A true CN101306980A (en) | 2008-11-19 |
| CN101306980B CN101306980B (en) | 2011-05-11 |
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|---|---|---|---|
| CN2008101243842A Active CN101306980B (en) | 2008-06-30 | 2008-06-30 | Method for preparing perchloro cyclopentadiene |
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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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Publication date |
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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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