CN103880619A - Preparation method of 3,3,5-trimethyl cyclohexanone - Google Patents
Preparation method of 3,3,5-trimethyl cyclohexanone Download PDFInfo
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- CN103880619A CN103880619A CN201410127444.1A CN201410127444A CN103880619A CN 103880619 A CN103880619 A CN 103880619A CN 201410127444 A CN201410127444 A CN 201410127444A CN 103880619 A CN103880619 A CN 103880619A
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- trimethylcyclohexanone
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- isophorone
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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
- C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
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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
- C07C2601/14—The ring being saturated
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 3,3,5-trimethyl cyclohexanone. The preparation method comprises the following steps: 1. adding isophorone and catalysts to a reaction kettle; 2. stirring and heating; 3. filling hydrogen, exerting pressure and maintaining the heating temperature; 4. preparing 3,3,5-trimethyl cyclohexanone via reaction time. The preparation method has the beneficial effects that a solvent and a cocatalyst are not used in the reaction process, so that 3,3,5-trimethyl cyclohexanone is simple to prepare and easy to separate, and meanwhile, the production cost is saved.
Description
Technical field
The present invention relates to a kind of by Hydrogenation the method for compound, relate in particular to a kind of preparation method of 3,3,5-trimethylcyclohexanone.
Background technology
3,3,5-trimethylcyclohexanone is a kind of high boiling organic solvent and medical synthetic intermediate, is mainly used in the field such as medicine, agricultural chemicals.3,3,5-trimethylcyclohexanone derived product is exactly its superoxide, is generally used for the vulcanizing agent of the industries such as rubber, or the outstanding solvent of the multiple system of the polymerization starter of plastic industry and tackiness agent; Also can be used for producing superoxide in the industry such as pigment and coating.
Wu Weize etc. (201210225511.4) report employing: be 20 ℃～100 ℃ in temperature of reaction, be preferably under the condition of 30 ℃～90 ℃, using dehydrated alcohol, supercritical co or methylene dichloride is solvent, also can not use solvent.Preferably use dehydrated alcohol or methylene dichloride as solvent.By loading type Pd or Pt catalyzer and promotor coupling, react and isophorone selective hydrogenation was reduced to 3,3,5-trimethylcyclohexanone in 4 hours.Isophorone transformation efficiency 99.9%, 3,3,5-trimethylcyclohexanone selectivity 98.1%.
From above-mentioned bibliographical information, isophorone transformation efficiency and 3,3, although 5-trimethylcyclohexanone selectivity is high, has used solvent and promotor in reaction process, brought difficulty to separation, has also increased production cost simultaneously.
Summary of the invention
The invention provides the novel method that is different from prior art for the preparation of 3,3,5-trimethylcyclohexanone.
The present invention is that under the condition existing at hydrogen to utilize isophorone itself be exactly the characteristic of high boiling solvent, the in the situation that of solvent-free and promotor, and preparation 3,3,5-trimethylcyclohexanone.
One 3,3 of the present invention, 5-trimethylcyclohexanone preparation method, the steps include:
1, in reactor, add isophorone and catalyzer;
2, stir, heat;
3, pass into hydrogen, pressurization and keep described Heating temperature;
4, reaction 1-1.5 hour, makes 3,3,5-trimethylcyclohexanone.
Preparation feedback of the present invention can carry out in an independent reaction still, also can in two cascade reaction stills, carry out.Preferably independently in reactor, carry out at one.
The catalyzer adopting in step 1 is with γ-Al
2o
3for Pb and the Ni bimetallic catalyst Pd/Ni/Al of carrier
2o
3.The catalyst levels of every 150g isophorone is 0.5～1.5g, preferably 0.8～1.2g.Wherein in catalyzer, weight ratio is: Pd:6～9%, Ni:0.4～1%, γ-Al
2o
3: 90～93.6%.
In step 1, catalyzer is a charging capacity, and catalyzer can be reused repeatedly.
In step 2, be 300-400r/min to the stirring velocity of material, the temperature of reacting by heating is 40～120 ℃, preferably 60～100 ℃.
In step 3, hydrogen pressure is 1.2～2.6Mpa, preferably 1.6～2.0Mpa.
The present invention does not use solvent and promotor in reaction process, makes simply, separates easily, has saved production cost simultaneously.
Embodiment
The present invention is further detailed the present invention by following examples, but the present invention is not limited to this.
Embodiment 1
In 1L autoclave, add 600g isophorone, 6g loaded catalyst (dry weight), rotating speed of agitator 350r/min passes into hydrogen and reaches total pressure 1.6Mpa at 80～100 ℃, and reaction 1.2h, makes 3,3,5-trimethylcyclohexanone.Through gas chromatographic analysis, in product 3,3,5-trimethylcyclohexanone content is 99.2%.
Embodiment 2
Except the hydrogenation reaction total pressure in embodiment 1 is changed into 2.0Mpa, other test conditionss are in the same manner as in Example 1.Gas chromatographic analysis test product, wherein 3,3,5-trimethylcyclohexanone content is 98.6%.
Embodiment 3
Except the hydrogenation reaction total pressure in embodiment 1 is changed into 1.0Mpa, other test conditionss are in the same manner as in Example 1.Gas chromatographic analysis test product, wherein 3,3,5-trimethylcyclohexanone content is 92.3%.
Embodiment 4
Except the hydrogenation reaction temperature in embodiment 1 is changed into 110 ℃, other test conditionss are in the same manner as in Example 1.Gas chromatographic analysis test product, wherein 3,3,5-trimethylcyclohexanone content is 97.4%.
Embodiment 5
Except the hydrogenation reaction temperature in embodiment 1 is changed into 70 ℃, other test conditionss are in the same manner as in Example 1.Gas chromatographic analysis test product, wherein 3,3,5-trimethylcyclohexanone content is 86.8%.
More than test explanation, at solvent-free and auxiliary agent, under the condition of isophorone shortening, the high and high meeting of hydrogenation pressure of temperature of reaction causes 3,3,5-trimethylcyclohexanone selectivity to decline, and speed of reaction is fast, and by product increases; Temperature of reaction is low and hydrogenation pressure is low, and hydrogenation speed is slower, can cause isophorone low conversion rate, and part isophorone is for completing hydrogenation reaction.
Wherein described, the condition of carrying out gas chromatographic analysis in following examples is: import Shimadzu wax chromatographic column, 260 ℃ of injector temperatures, 260 ℃ of detector temperatures, hydrogen, the full-automatic flow control of air, hydrogen flowing quantity: air flow quantity is 1: 10.
In above embodiment, the condition of carrying out gas chromatographic analysis is: import Shimadzu wax chromatographic column, 260 ℃ of injector temperatures, 260 ℃ of detector temperatures, hydrogen, the full-automatic flow control of air, hydrogen flowing quantity: air flow quantity is 1: 10.The condition of carrying out gas chromatographic analysis in embodiment is: import Shimadzu wax chromatographic column, 260 ℃ of injector temperatures, 260 ℃ of detector temperatures, hydrogen, the full-automatic flow control of air, hydrogen flowing quantity: air flow quantity is 1: 10.
Claims (7)
1. one kind 3,3,5-trimethylcyclohexanone preparation method, the steps include:
(1), in reactor, add isophorone and catalyzer;
(2), stir, heat;
(3), pass into hydrogen, pressurization and keep described Heating temperature;
(4), through the reaction times, make 3,3,5-trimethylcyclohexanone.
2. preparation method according to claim 1, its preparation feedback can carry out in an independent reaction still, also can in two cascade reaction stills, carry out; Preferably independently in reactor, carry out at one.
3. preparation method according to claim 1, the catalyzer adopting in step 1 is with Al
2o
3for Pb and the Ni bimetallic catalyst Pd/Ni/ γ-Al of carrier
2o
3; The catalyst levels of every 150g isophorone is 0.5～1.5g, preferably 0.8～1.2g; Wherein in catalyzer, weight ratio is: Pd:6～9%, Ni:0.4～1%, γ-Al
2o
3: 90～93.6%.
4. preparation method according to claim 1, is characterized in that: in step 1, catalyzer is a charging capacity, and catalyzer can be reused repeatedly.
5. preparation method according to claim 1, is characterized in that: in step 2, be 300-400r/min to the stirring velocity of material; The temperature of reacting by heating is 40～120 ℃, preferably 60～100 ℃.
6. preparation method according to claim 1, is characterized in that: in step 3, hydrogen pressure is 1.2～2.6Mpa, preferably 1.6～2.0Mpa.
7. preparation method according to claim 1, is characterized in that: the reaction times of step 4 is 1-1.5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410127444.1A CN103880619B (en) | 2014-04-01 | 2014-04-01 | A kind of preparation method of 3,3,5-trimethylcyclohexanone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410127444.1A CN103880619B (en) | 2014-04-01 | 2014-04-01 | A kind of preparation method of 3,3,5-trimethylcyclohexanone |
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| CN103880619A true CN103880619A (en) | 2014-06-25 |
| CN103880619B CN103880619B (en) | 2016-02-24 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107495A (en) * | 2015-01-31 | 2015-12-02 | 中国石油大学(华东) | Catalyst for preparing TMCH by hydrogenation of isophorone and preparation method thereof |
| CN106496003A (en) * | 2016-09-26 | 2017-03-15 | 中国石油大学(华东) | The method that isophorone selective hydrogenation prepares 3,3,5 trimethylcyclohexanones |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718641A (en) * | 2012-07-03 | 2012-10-10 | 北京化工大学 | Method for preparing 3,3,5-trimethyl-cyclohexanone by selectively hydrogenating isophorone |
-
2014
- 2014-04-01 CN CN201410127444.1A patent/CN103880619B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718641A (en) * | 2012-07-03 | 2012-10-10 | 北京化工大学 | Method for preparing 3,3,5-trimethyl-cyclohexanone by selectively hydrogenating isophorone |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107495A (en) * | 2015-01-31 | 2015-12-02 | 中国石油大学(华东) | Catalyst for preparing TMCH by hydrogenation of isophorone and preparation method thereof |
| CN105107495B (en) * | 2015-01-31 | 2018-02-02 | 中国石油大学(华东) | Isophorone Hydrogenation is for TMCH catalyst and preparation method thereof |
| CN106496003A (en) * | 2016-09-26 | 2017-03-15 | 中国石油大学(华东) | The method that isophorone selective hydrogenation prepares 3,3,5 trimethylcyclohexanones |
| CN106496003B (en) * | 2016-09-26 | 2019-04-23 | 中国石油大学(华东) | The method that isophorone selective hydrogenation prepares 3,3,5- trimethylcyclohexanone |
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| CN103880619B (en) | 2016-02-24 |
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