CN105037128A - Hydrolysis technique of isobutyl cyclopropanecarboxylate by using solid acid catalyst - Google Patents
Hydrolysis technique of isobutyl cyclopropanecarboxylate by using solid acid catalyst Download PDFInfo
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- CN105037128A CN105037128A CN201510306893.7A CN201510306893A CN105037128A CN 105037128 A CN105037128 A CN 105037128A CN 201510306893 A CN201510306893 A CN 201510306893A CN 105037128 A CN105037128 A CN 105037128A
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- cyclopropanecarboxylic acid
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- isopropyl ester
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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Abstract
The invention discloses a hydrolysis technique of isobutyl cyclopropanecarboxylate by using a solid acid catalyst, which comprises the following steps: mixing isopropyl cyclopropanecarboxylate with water and Aciplex-SiO2, heating to reflux, and collecting the 80-82-DEG C fraction; after the fraction outflow weakens, continuously dropwisely adding the isopropyl cyclopropanecarboxylate while keeping the temperature, and continuously the 80-82-DEG C fraction; after no fraction flows out, standing to precipitate the solid catalyst to the bottle bottom, and separating out the supernatant liquid, thereby leaving the liquid and all the catalyst on the bottle bottom; cooling the separated liquid to stratify, weighing the upper water phase, supplementing water, adding into the bottle, and rectifying the lower cyclopropanecarboxylic acid layer to obtain the product; and adding the isobutyl cyclopropanecarboxylate into the bottle, continuing repeating the hydrolysis mode until GC (gas chromatography) detection indicates that the raw material is not completely hydrolyzed, filtering, replacing the same amount of catalyst, and continuing catalytic hydrolysis. The device is odorless in the use spot, thereby ensuring the health of the personnel.
Description
Technical field
The invention belongs to chemical technology field, more specifically, the present invention relates to a kind of hydrolysis process of solid acid catalysis cyclopropanecarboxylic acid isobutyl ester.
Background technology
, in prior art, mainly there is following problem in solid acid catalysis cyclopropanecarboxylic acid isobutyl ester hydrolysis:
(1) in traditional technology for the mainly sodium hydrate solid of the catalyzer of carboxyester hydrolysis and dilute sulphuric acid;
(2) sulfuric acid especially used in traditional technology, not only easily causes equipment corrosion in process of production, and there is hydrolysis not exclusively, is difficultly separated;
(3) if with highly basic as Ester hydrolysis catalyzer, final product exists in a salt form, separate complex, and yield is lower;
(4) no matter with sulfuric acid or highly basic, all can produce a large amount of waste water, produce to environment-protecting clean and bring larger pressure;
(5) reaction yield is lower;
(6) repeating utilization factor of reaction solution is low.
Summary of the invention
The object of this part is some aspects of general introduction embodiments of the invention and briefly introduces some preferred embodiments.May do in the specification digest and denomination of invention of this part and the application a little simplify or omit with avoid making this part, specification digest and denomination of invention object fuzzy, and this simplification or omit and can not be used for limiting the scope of the invention.
In view of Problems existing in the hydrolysis process of above-mentioned and/or existing solid acid catalysis cyclopropanecarboxylic acid isobutyl ester, propose the present invention.
Therefore, an object of the present invention is to provide a kind of hydrolysis process of solid acid catalysis cyclopropanecarboxylic acid isobutyl ester, find one can have better optionally catalyzer to carboxyester hydrolysis.
For solving the problems of the technologies described above, the present invention is to provide following technical scheme: a kind of hydrolysis process of solid acid catalysis cyclopropanecarboxylic acid isobutyl ester, and it comprises, by cyclopropanecarboxylic acid isopropyl ester and water and Aciplex-SiO
2be warming up to backflow after mixing, gather the cut of 80 ~ 82 DEG C; After cut flows out and weakens, insulation continues to drip cyclopropanecarboxylic acid isopropyl ester, and constantly gathers 80 ~ 82 DEG C of cuts, after cut no longer flows out, leaves standstill, and at the bottom of solid catalyst is precipitated to bottle, is separated by supernatant liquid, liquid stay at the bottom of bottle and all catalyzer; The liquid separated, cooling layering, upper water supplies water after weighing mutually, adds in bottle, and lower floor's cyclopropanecarboxylic acid layer rectifying obtains product; Add cyclopropanecarboxylic acid isopropyl ester in bottle, continue to apply mechanically by the hydrolysis of such as upper type, until detect raw material hydrolysis not exclusively by GC, after filtration, the catalyzer changing same amount continues catalytic hydrolysis.
As a kind of preferred version of the hydrolysis process of solid acid catalysis cyclopropanecarboxylic acid isobutyl ester of the present invention, wherein: described by cyclopropanecarboxylic acid isopropyl ester and water and Aciplex-SiO
2mixing, its mixing quality is than being 10:10 ~ 40:1.
As a kind of preferred version of the hydrolysis process of solid acid catalysis cyclopropanecarboxylic acid isobutyl ester of the present invention, wherein: described insulation continues to drip cyclopropanecarboxylic acid isopropyl ester, its quality dripping cyclopropanecarboxylic acid isopropyl ester is 5 ~ 7 times of former addition.
As a kind of preferred version of the hydrolysis process of solid acid catalysis cyclopropanecarboxylic acid isobutyl ester of the present invention, wherein: described upper water supplies water after weighing mutually, the quality of water to former interpolation water is supplied.
As a kind of preferred version of the hydrolysis process of solid acid catalysis cyclopropanecarboxylic acid isobutyl ester of the present invention, wherein: in described bottle, add cyclopropanecarboxylic acid isopropyl ester, its add-on is the quality of former interpolation cyclopropanecarboxylic acid isopropyl ester.
Beneficial effect of the present invention:
(1) the present invention have found one and can have better optionally catalyzer to carboxyester hydrolysis;
(2) this new catalyzer is adopted in technique, lower to the corrodibility of equipment;
(3) use this new catalyzer, be easy to be separated with system;
(4) reduce or no longer produce brine waste;
(5) catalyzer adopted in the present invention can cycling and reutilization.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail below by embodiment.
Set forth a lot of detail in the following description so that fully understand the present invention, but the present invention can also adopt other to be different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar popularization when intension of the present invention, therefore the present invention is by the restriction of following public specific embodiment.
Secondly, alleged herein " embodiment " or " embodiment " refers to special characteristic, structure or the characteristic that can be contained at least one implementation of the present invention.Different local in this manual " in one embodiment " occurred not all refers to same embodiment, neither be independent or optionally mutually exclusive with other embodiments embodiment.
Reaction principle of the present invention:
Embodiment 1
By 128g cyclopropanecarboxylic acid isopropyl ester and 500g water and 12.8gAciplex-SiO
2backflow is warming up to after mixing, the continuous cut gathering 80-82 DEG C, after cut outflow weakens, insulation continues to drip 640g cyclopropanecarboxylic acid isopropyl ester, and constantly gathers 80-82 DEG C of cut, after cut no longer flows out, leave standstill, at the bottom of solid catalyst is precipitated to bottle, supernatant liquid is separated, at the bottom of bottle, stays about 100g liquid and all catalyzer.The liquid separated, cooling layering, upper water supplies 500g water after weighing mutually, adds in bottle, and lower floor's cyclopropanecarboxylic acid layer rectifying obtains product.Add 128g cyclopropanecarboxylic acid isopropyl ester in bottle, continue to apply mechanically by the hydrolysis of such as upper type, until detect raw material hydrolysis not exclusively by GC, after filtration, the catalyzer changing same amount continues catalytic hydrolysis.98% is reached in cyclopropanecarboxylic acid isopropyl ester hydrolysis yield.
Embodiment 2
By 128g cyclopropanecarboxylic acid isopropyl ester and 130g water and 12.8gAciplex-SiO
2backflow is warming up to after mixing, the continuous cut gathering 80-82 DEG C, after cut outflow weakens, insulation continues to drip 640g cyclopropanecarboxylic acid isopropyl ester, and constantly gathers 80-82 DEG C of cut, after cut no longer flows out, leave standstill, at the bottom of solid catalyst is precipitated to bottle, supernatant liquid is separated, at the bottom of bottle, stays about 100g liquid and all catalyzer.The liquid separated, cooling layering, upper water supplies 130g water after weighing mutually, adds in bottle, and lower floor's cyclopropanecarboxylic acid layer rectifying obtains product.Add 128g cyclopropanecarboxylic acid isopropyl ester in bottle, continue to apply mechanically by the hydrolysis of such as upper type, until detect raw material hydrolysis not exclusively by GC, after filtration, the catalyzer changing same amount continues catalytic hydrolysis.97.1% is reached in cyclopropanecarboxylic acid isopropyl ester hydrolysis yield.
Embodiment 3
By 128g cyclopropanecarboxylic acid isopropyl ester and 320g water and 12.8gAciplex-SiO
2backflow is warming up to after mixing, the continuous cut gathering 80-82 DEG C, after cut outflow weakens, insulation continues to drip 640g cyclopropanecarboxylic acid isopropyl ester, and constantly gathers 80-82 DEG C of cut, after cut no longer flows out, leave standstill, at the bottom of solid catalyst is precipitated to bottle, supernatant liquid is separated, at the bottom of bottle, stays about 100g liquid and all catalyzer.The liquid separated, cooling layering, upper water supplies 320g water after weighing mutually, adds in bottle, and lower floor's cyclopropanecarboxylic acid layer rectifying obtains product.Add 128g cyclopropanecarboxylic acid isopropyl ester in bottle, continue to apply mechanically by the hydrolysis of such as upper type, until detect raw material hydrolysis not exclusively by GC, after filtration, the catalyzer changing same amount continues catalytic hydrolysis.97.5% is reached in cyclopropanecarboxylic acid isopropyl ester hydrolysis yield.
As can be seen here, the present invention:
(1) one first will be found can to have better optionally catalyzer to carboxyester hydrolysis;
(2) this new catalyzer, requires the corrodibility of equipment lower;
(3) use this new catalyzer, require to be easy to be separated with system;
(4) reduce or no longer produce brine waste;
(5) catalyzer preferably can cycling and reutilization.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (5)
1. a hydrolysis process for solid acid catalysis cyclopropanecarboxylic acid isobutyl ester, is characterized in that: comprise,
By cyclopropanecarboxylic acid isopropyl ester and water and Aciplex-SiO
2be warming up to backflow after mixing, gather the cut of 80 ~ 82 DEG C;
After cut flows out and weakens, insulation continues to drip cyclopropanecarboxylic acid isopropyl ester, and constantly gathers 80 ~ 82 DEG C of cuts, after cut no longer flows out, leaves standstill, and at the bottom of solid catalyst is precipitated to bottle, is separated by supernatant liquid, liquid stay at the bottom of bottle and all catalyzer;
The liquid separated, cooling layering, upper water supplies water after weighing mutually, adds in bottle, and lower floor's cyclopropanecarboxylic acid layer rectifying obtains product;
Add cyclopropanecarboxylic acid isopropyl ester in bottle, continue to apply mechanically by the hydrolysis of such as upper type, until detect raw material hydrolysis not exclusively by GC, after filtration, the catalyzer changing same amount continues catalytic hydrolysis.
2. the hydrolysis process of solid acid catalysis cyclopropanecarboxylic acid isobutyl ester according to claim 1, is characterized in that: described by cyclopropanecarboxylic acid isopropyl ester and water and Aciplex-SiO
2mixing, its mixing quality is than being 10:10 ~ 40:1.
3. the hydrolysis process of solid acid catalysis cyclopropanecarboxylic acid isobutyl ester according to claim 1 and 2, is characterized in that: described insulation continues to drip cyclopropanecarboxylic acid isopropyl ester, and its quality dripping cyclopropanecarboxylic acid isopropyl ester is 5 ~ 7 times of former addition.
4. the hydrolysis process of solid acid catalysis cyclopropanecarboxylic acid isobutyl ester according to claim 1, is characterized in that: described upper water supplies water after weighing mutually, supplies the quality of water to former interpolation water.
5. the hydrolysis process of solid acid catalysis cyclopropanecarboxylic acid isobutyl ester according to claim 1, is characterized in that: add cyclopropanecarboxylic acid isopropyl ester in described bottle, and its add-on is the quality of former interpolation cyclopropanecarboxylic acid isopropyl ester.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278863A (en) * | 2016-08-04 | 2017-01-04 | 山东省化工研究院 | A kind of preparation method of 2,4 dichlorphenoxyacetic acids |
| CN106278862A (en) * | 2016-08-04 | 2017-01-04 | 山东省化工研究院 | A kind of new technique for synthesizing of 2,4 dichlorphenoxyacetic acids |
| CN109280003A (en) * | 2018-09-29 | 2019-01-29 | 大丰跃龙化学有限公司 | A method of cyclopropanecarboxylic acid is prepared using heteropolyacid catalyst |
| CN110944971A (en) * | 2017-08-02 | 2020-03-31 | 伊士曼化工公司 | Method for producing formic acid using low-boiling formic acid ester |
| CN112479854A (en) * | 2020-12-08 | 2021-03-12 | 苏州扬科新材料科技有限公司 | Green process for producing cyclopropyl formic acid |
| CN114409510A (en) * | 2022-01-11 | 2022-04-29 | 大连普莱瑞迪化学有限公司 | Method for promoting hydrolysis of isooctyl isooctanoate and isooctyl formate |
-
2015
- 2015-06-04 CN CN201510306893.7A patent/CN105037128A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278863A (en) * | 2016-08-04 | 2017-01-04 | 山东省化工研究院 | A kind of preparation method of 2,4 dichlorphenoxyacetic acids |
| CN106278862A (en) * | 2016-08-04 | 2017-01-04 | 山东省化工研究院 | A kind of new technique for synthesizing of 2,4 dichlorphenoxyacetic acids |
| CN106278863B (en) * | 2016-08-04 | 2019-06-21 | 山东省化工研究院 | A kind of preparation method of 2,4 dichlorophenoxyacetic acid |
| CN110944971A (en) * | 2017-08-02 | 2020-03-31 | 伊士曼化工公司 | Method for producing formic acid using low-boiling formic acid ester |
| CN110944971B (en) * | 2017-08-02 | 2023-06-23 | 伊士曼化工公司 | Method for producing formic acid using low boiling point formate |
| CN109280003A (en) * | 2018-09-29 | 2019-01-29 | 大丰跃龙化学有限公司 | A method of cyclopropanecarboxylic acid is prepared using heteropolyacid catalyst |
| CN112479854A (en) * | 2020-12-08 | 2021-03-12 | 苏州扬科新材料科技有限公司 | Green process for producing cyclopropyl formic acid |
| CN112479854B (en) * | 2020-12-08 | 2023-09-08 | 杭州龙晶医药科技有限公司 | Green process for producing cyclopropylformic acid |
| CN114409510A (en) * | 2022-01-11 | 2022-04-29 | 大连普莱瑞迪化学有限公司 | Method for promoting hydrolysis of isooctyl isooctanoate and isooctyl formate |
| CN114409510B (en) * | 2022-01-11 | 2024-01-30 | 大连普莱瑞迪化学有限公司 | Method for promoting hydrolysis of isooctyl isooctanoate and isooctyl formate |
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Application publication date: 20151111 |