CN112457238B - Method for co-producing triacetonamine and isophorone - Google Patents
Method for co-producing triacetonamine and isophorone Download PDFInfo
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- CN112457238B CN112457238B CN202011329996.2A CN202011329996A CN112457238B CN 112457238 B CN112457238 B CN 112457238B CN 202011329996 A CN202011329996 A CN 202011329996A CN 112457238 B CN112457238 B CN 112457238B
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- isophorone
- triacetonamine
- acetone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D211/74—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The application discloses a method for co-producing triacetonamine and isophorone, and relates to the technical field of compound synthesis. The synthesis method comprises the following steps: adding raw materials of acetone, ammonia gas and an alkaline catalyst into a reaction kettle, stirring and reacting for 4-10 hours at the reaction temperature of 50-100 ℃ to obtain a reaction solution containing triacetonamine and isophorone, carrying out reduced pressure rectification, continuously applying the front cut, and separating to obtain the triacetonamine and isophorone. According to the application, an alkaline catalyst is adopted to catalyze the dehydration condensation of acetone to generate mesityl oxide, and further catalyze the mesityl oxide and the acetone to generate the phorone and the isophorone, so that the efficient co-production of triacetonamine and isophorone is realized; the post-treatment is simple, the catalyst can be recycled, and no solid waste salt is generated; the proportion of the reaction raw materials is adjustable, and the selectivity of the triacetonamine and the isophorone is easy to control.
Description
Technical Field
The application relates to the technical field of compound synthesis, in particular to a method for co-producing triacetonamine and isophorone.
Background
Triacetonamine, chemical name 2, 6-tetramethylpiperidone, is the only precursor for the synthesis of Hindered Amine Light Stabilizers (HALS), is the most important intermediate for the production of HALS, the base stock for the derivatives 2, 6-tetramethylpiperidinol, 2, 6-tetramethylpiperidinamine and HALS most commonly used in the current market. With the increasing demand of the light stabilizer market, the synthesis of triacetonamine has been widely focused by scientists, and related synthesis researches report endlessly.
The synthesis routes of triacetonamine reported in the current literature are mainly divided into the following two types:
1) The one-step method comprises the following steps: the method takes acetone and ammonia as raw materials, adopts an acid catalyst for catalytic synthesis, and the common catalysts are mainly ammonium nitrate (US 4275211), caY molecular sieve (US 6646127) and strong acid macroporous resin (US 4275211). At present, the industrial production adopts ammonium nitrate as a catalyst, but the ammonium nitrate is unstable and has hidden explosion hazards, meanwhile, the catalyst needs to be quenched in the post-treatment process, a large amount of solid hazardous waste is generated, and the problem of environmental pollution exists; the catalyst of CaY molecular sieve is adopted, and the reaction time is too long; the use of sulfonic acid resin for catalysis is difficult to limit the maximum industrialization of the resin because of the swelling and poor mechanical strength of the resin and short service life.
2) The two-step method comprises the following steps: acetone is used as a raw material, and then acetonin (US 3960875), phorone (US 3943139) and diacetone alcohol (US 4252958) are synthesized, and then reacted with acetone and ammonia gas continuously to generate triacetonamine. The two-step method has long reaction period, difficult separation of intermediates and high industrialization cost.
Isophorone, chemical name 3, 5-trimethyl-2-cyclohexane-1-one, has higher boiling point and low hygroscopicity, has good dissolving capacity, dispersibility and leveling property, is a good solvent for high polymer materials, and can dissolve nitrocellulose, acrylic ester, alkyd resin, polyester, epoxy resin and the like. Because of the unsaturated ketone structure, the double bond can further react to generate important products such as alcohol, acid, amine, ester, isocyanate and the like, and the double bond has wide application in industries such as plastics, pesticides, medicines, coatings and the like. With the rising level of industries such as domestic paint, the domestic isophorone market is in a rapid development stage, and the market demand will continue to increase, and the market demand is mainly dependent on import at present.
The current synthesis method for co-production of triacetonamine and isophorone has few reports, the used catalyst can not be recycled, a large amount of solid waste salt is generated, and the selectivity of the triacetonamine and isophorone is not easy to control.
Disclosure of Invention
The application provides a method for co-producing triacetonamine and isophorone, which aims at the defects of the prior art.
The application solves the technical problems by the following technical means:
the application relates to a synthetic method for co-producing triacetonamine and isophorone, which has the following reaction mechanism: the method comprises the steps of dehydrating and condensing raw material acetone under the catalysis of an alkaline catalyst to generate mesityl oxide, and generating isophorone and isophorone by mesityl oxide and acetone; further carrying out Michael addition reaction on the phorone and ammonia gas to synthesize the triacetonamine.
The synthesis method comprises the following steps: adding raw materials of acetone, ammonia gas and an alkaline catalyst into a reaction kettle, stirring and reacting for 4-10 hours at the reaction temperature of 50-100 ℃ to obtain a reaction solution containing triacetonamine and isophorone, carrying out reduced pressure rectification, continuously applying the front cut, and separating to obtain the triacetonamine and isophorone; wherein the molar ratio of the acetone to the ammonia in the raw materials is 3:1-9:1, and the addition amount of the alkaline catalyst is 5-30% of the total mass of the acetone and the ammonia.
Optionally, the alkaline catalyst is one or a mixture of several of sodium hydroxide, potassium hydroxide, tetrabutylammonium hydroxide and hexadecyl trimethyl ammonium hydroxide.
Optionally, the addition amount of the alkaline catalyst is 10-20% of the total mass of the acetone and the ammonia gas.
Alternatively, the reaction temperature is 60-70 ℃. The reaction temperature is too low, the reaction rate is slow, and the efficiency is low; the reaction temperature is high, the side reaction is aggravated, the reaction pressure is high, and the requirement on equipment is high.
Optionally, the raw materials comprise acetone: the molar ratio of ammonia is 4:1-6:1. The reaction molar ratio is low, and the formation amount of triacetonamine is small; excessive side reactions are exacerbated.
Alternatively, the reaction time is 6-8 hours.
Compared with the prior art, the application has at least one of the following beneficial effects:
(1) The method comprises the steps of catalyzing dehydration condensation of acetone by an alkaline catalyst to generate mesityl oxide, and further catalyzing mesityl oxide and acetone to generate phorone and isophorone, so that high-efficiency co-production of triacetonamine and isophorone is realized;
(2) The post-treatment is simple, the catalyst can be recycled, and no solid waste salt is generated;
(3) The proportion of the reaction raw materials is adjustable, and the selectivity of the triacetonamine and the isophorone is easy to control.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application are clearly and completely described, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
232g of acetone is added into a reaction kettle, 17g of ammonia gas is introduced, 20g of solid sodium hydroxide is added, the temperature is raised to 60 ℃, and after reaction is carried out for 6 hours, sampling analysis is carried out. In the gas-phase diagram, the conversion rate of acetone is 60%, the selectivity of triacetonamine is 35%, and the selectivity of isophorone is 40%.
Comparative example 1
232g of acetone is added into a reaction kettle, 17g of ammonia gas is introduced, 20g of ammonium nitrate is added, the temperature is raised to 60 ℃, and after reaction is carried out for 6 hours, sampling analysis is carried out. In the gas-phase diagram, the conversion of acetone was 50%, the selectivity of triacetonamine was 55%, and the selectivity of isophorone was 2%.
From comparison of the results of comparative example 1 and example 1, it is known that the basic catalyst can catalyze ammonia gas and acetone to form triacetonamine; meanwhile, the alkaline catalyst can also improve the selectivity of isophorone, so that the conversion efficiency of acetone is generally improved, and the application amount is reduced.
Example 2
The preparation process was exactly the same as in example 1, except that the reaction temperature was 80℃and the conversion of acetone was 66% by gas chromatography analysis, the selectivity for triacetonamine was 33% and the selectivity for isophorone was 46%.
Example 3
The preparation process was exactly the same as in example 1, except that the catalyst was tetrabutylammonium hydroxide, the conversion of acetone was 51% by gas chromatography analysis of the reaction solution, the selectivity for triacetonamine was 40%, and the selectivity for isophorone was 34%.
Example 4
The preparation process was exactly the same as in example 1, except that the molar ratio of the reaction was 9:1, the conversion of acetone was 58%, the selectivity of triacetonamine was 25% and the selectivity of isophorone was 50% by gas chromatography analysis of the reaction solution.
It is noted that relational terms such as first and second, and the like, if any, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above embodiments are only for illustrating the technical solution of the present application, and are not limiting; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present application.
Claims (3)
1. The synthesis method for co-producing the triacetonamine and the isophorone is characterized by comprising the following steps of: adding raw materials of acetone, ammonia gas and an alkaline catalyst into a reaction kettle, stirring and reacting for 6 hours at the reaction temperature of 60 ℃ or 80 ℃ to obtain a reaction solution containing triacetonamine and isophorone, carrying out reduced pressure rectification, continuously applying the front cut, and separating to obtain the triacetonamine and isophorone; wherein the molar ratio of the acetone to the ammonia in the raw materials is 3:1-9:1, and the addition amount of the alkaline catalyst is 5% -30% of the total mass of the acetone and the ammonia; the alkaline catalyst is sodium hydroxide or tetrabutylammonium hydroxide.
2. The synthetic method for co-producing triacetonamine and isophorone according to claim 1, wherein the addition amount of the alkaline catalyst is 10% -20% of the total mass of acetone and ammonia.
3. The method for synthesizing the co-production of the triacetonamine and the isophorone according to claim 1, wherein the raw materials comprise acetone: the molar ratio of ammonia is 4:1-6:1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011329996.2A CN112457238B (en) | 2020-11-24 | 2020-11-24 | Method for co-producing triacetonamine and isophorone |
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| CN202011329996.2A CN112457238B (en) | 2020-11-24 | 2020-11-24 | Method for co-producing triacetonamine and isophorone |
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| CN112457238A CN112457238A (en) | 2021-03-09 |
| CN112457238B true CN112457238B (en) | 2023-09-26 |
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Citations (7)
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|---|---|---|---|---|
| CN103467263A (en) * | 2013-09-13 | 2013-12-25 | 江苏焕鑫高新材料科技有限公司 | Preparation method of isophorone |
| CN103664745A (en) * | 2012-09-07 | 2014-03-26 | 赢创工业集团股份有限公司 | Method for preparing and treating triacetonamine-containing reaction mixture |
| CN103664560A (en) * | 2013-11-30 | 2014-03-26 | 兰州大学 | Method for preparing alpha-isophorone |
| CN107033066A (en) * | 2017-05-05 | 2017-08-11 | 衡水凯亚化工有限公司 | The method and special equipment of a kind of heterogeneous catalysis synthesis triacetonamine |
| CN108484482A (en) * | 2018-05-01 | 2018-09-04 | 衡水凯亚化工有限公司 | A method of preparing triacetonamine using synthesis triacetonamine process byproduct |
| CN110407738A (en) * | 2019-08-13 | 2019-11-05 | 宿迁市振兴化工有限公司 | A kind of preparation method of triacetonamine |
| US20200181088A1 (en) * | 2018-12-07 | 2020-06-11 | Evonik Operations Gmbh | Method for preparing triacetone amine |
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2020
- 2020-11-24 CN CN202011329996.2A patent/CN112457238B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664745A (en) * | 2012-09-07 | 2014-03-26 | 赢创工业集团股份有限公司 | Method for preparing and treating triacetonamine-containing reaction mixture |
| CN103467263A (en) * | 2013-09-13 | 2013-12-25 | 江苏焕鑫高新材料科技有限公司 | Preparation method of isophorone |
| CN103664560A (en) * | 2013-11-30 | 2014-03-26 | 兰州大学 | Method for preparing alpha-isophorone |
| CN107033066A (en) * | 2017-05-05 | 2017-08-11 | 衡水凯亚化工有限公司 | The method and special equipment of a kind of heterogeneous catalysis synthesis triacetonamine |
| CN108484482A (en) * | 2018-05-01 | 2018-09-04 | 衡水凯亚化工有限公司 | A method of preparing triacetonamine using synthesis triacetonamine process byproduct |
| US20200181088A1 (en) * | 2018-12-07 | 2020-06-11 | Evonik Operations Gmbh | Method for preparing triacetone amine |
| CN110407738A (en) * | 2019-08-13 | 2019-11-05 | 宿迁市振兴化工有限公司 | A kind of preparation method of triacetonamine |
Non-Patent Citations (2)
| Title |
|---|
| Towards amoresustainableproductionoftriacetoneaminewith heterogeneous catalysis;Gherardo Gliozzi et al.;《Journal ofMolecularCatalysisA:Chemical》;第325-332页 * |
| 丙酮缩合制异佛尔酮研究进展;李云龙等;《化工进展》;第35卷(第4期);第1190-1196页 * |
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