CN1111157C - Prepn. of 2,2,6,6-tetraalkyl-4-piperylhydrazines - Google Patents
Prepn. of 2,2,6,6-tetraalkyl-4-piperylhydrazines Download PDFInfo
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- CN1111157C CN1111157C CN 00121156 CN00121156A CN1111157C CN 1111157 C CN1111157 C CN 1111157C CN 00121156 CN00121156 CN 00121156 CN 00121156 A CN00121156 A CN 00121156A CN 1111157 C CN1111157 C CN 1111157C
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Abstract
The present invention relates to a preparation method of 2, 2, 6, 6-tetraalkyl-4-piperylhydrazines. The method comprises the following steps: in a fixed bed reactor, with the existence of water, C1 to C10 fatty alcohol, or C2 to C6 fatty diol, or a mixture of C1 to C10 fatty alcohol and C2 to C6 fatty diol, palladium or platinum loaded on a porous carrier whose hole diameter is from 10 to 500A is used as a catalytic agent, 2, 2, 6, 6-tetraalkyl-4-piperidine ketone reacts with organic amine, the reaction temperature is from 40 DEG C to 160 DEG C, and the reaction pressure is from 0.1MPa to 10.0MPa. The present invention selects specific reaction conditions, and especially selects the carrier which has the proper hole diameter to lead 2, 2, 6, 6-tetraalkyl-4-piperylhydrazines to be prepared in the fixed bed reactor. High conversion rate and high selectivity can be obtained. The present invention is good for continuous large-scale industrial production.
Description
Technical field
The present invention relates to 2,2,6,6-tetraalkyl-4-piperidinamines preparation.
Background technology:
As everyone knows, 2,2,6,6-tetraalkyl-4-piperidinamines, as N, two (2,2,6, the 6-tetramethyl--4-piperidyl) hexanediamines of N`-can be used as the ultraviolet screener of polymeric material.This compounds is to be that catalyzer is prepared in tank reactor with the precious metal in the prior art.
For example, US 4,104, and 248 have narrated with platinum-carbon and make catalyzer, are reaction medium with methyl alcohol, produce various N in tank reactor, the method for two (2,2,6, the 6-tetramethyl--4-piperidyl) amine of N`-.Similarly also have US 4,326,063, US 4,15,688, US 4,293,466 etc. with it.
CN 86102649A discloses by 2,2,6,6-tetramethyl--4-piperidone and amine prepared in reaction 2,2,6, the method for 6-tetramethyl--4-piperylhydrazine, the catalyzer that uses is selected from platinum, nickel, cobalt, and reaction medium consists of the water of 10-100 weight %, and 0-90 weight % is selected from C
1-C
10Fatty Alcohol(C12-C14 and C12-C18) and C
2-C
6A kind of polar organic compound of aliphatic diol, this reaction also are to carry out in tank reactor.
CN 86104693A has narrated the use palladium carbon catalyst, prepares N in tank reactor, the method for N`-two (2,2,6,6-tetramethyl--4-piperidyl).
EP 0508940A1 has narrated two-step approach and has made N, the process of two (2,2,6, the 6-tetramethyl--4-piperidyl) amine of N`-.
From above-mentioned situation, prior art all adopts still reaction, and in use there is powder phenomenon-tion in catalyzer, reaction mass and catalyst separating difficulty, it is serious to cause noble metal catalyst to run off, and production cost increases, and still reaction is unfavorable for large-scale commercial production.Can adopt continuous processing production though CN 86102649A has mentioned, not specify still formula continuous processing or fixed bed continuous processing, the condition of fixed bed reaction more is not described.
Summary of the invention
The object of the present invention is to provide a kind of employing fixed-bed reactor continuous production 2,2,6, the method for 6-tetraalkyl-4-piperidinamines compound.
2,2,6 of structural formula provided by the invention (I) expression, the preparation method of 6-tetraalkyl-4-piperidinamines comprises: in fixed-bed reactor, at water, C
1-C
10Fatty Alcohol(C12-C14 and C12-C18) or C
2-C
6Under the existence of aliphatic dialcohol or its mixture, be catalyzer, make 2,2,6 of structural formula (II) expression, 6-tetraalkyl-4-piperidone and organic amine reaction with palladium or the platinum that is carried on the porous support that the aperture is 10-500 .
In the formula, R can be C
1-C
18Alkyl, C
5-C
6Cycloalkyl or C
7-C
9Aralkyl; R
1, R
2, R
3And R
4Can be identical or different C
1-C
8Alkyl; A can be a hydrogen, hydroxyl, C
1-C
8Alkoxyl group, C
1-C
8Alkyl, C
2-C
10Alkyl carbonyl or aromatic carbonyl; N is 1,2,3 or 4;
A in the formula, R
1, R
2, R
3And R
4As above-mentioned regulation;
The structure of organic amine is R (NH
2)
n, R and n such as above-mentioned regulation in the formula.Said organic amine is selected from methylamine, butylamine, lauryl amine, octadecylamine, hexahydroaniline, benzene methanamine, triethylenediamine, tetrem support diamines, hexanediamine, pentamethylene diamine, 1,4-butanediamine, 1,12-diamino dodecane, dipropylenetriamine, Diethylenetriaminee (DETA), 1,2,6-triamino hexane and 1, the 4-diamino-cyclohexane.Preferred hexanediamine, pentamethylene diamine and 1, the 4-butanediamine.
Said 4-piperidone is selected from 2,2,6,6-tetramethyl--4-piperidone; 1,2,2,6; 6-pentamethyl--4-piperidone, 1-ethyl-2,2,6; 6-tetramethyl--4-piperidone, 1-n-octyl-2,2,6; 6-tetramethyl--4-piperidone, 2,6-diethyl-2,6 dimethyl-4-piperidine ketone; 2-isobutyl--2,6,6-trimethylammonium-4-piperidone, 1-ethanoyl-2; 2,6,6-tetramethyl--4-piperidone, 1-benzoyl-2; 2,6,6-tetramethyl--4-piperidone, 1-hydroxyl-2; 2,6,6-tetramethyl--4-piperidone, 1-methoxyl group-2; 2,6,6-tetramethyl--4-piperidone and analogue thereof.Preferred 2,2,6,6-tetramethyl--4-piperidone.
In the inventive method, piperidone can be suitably excessive, so that the organic amine complete reaction.
The catalyzer that the inventive method is used, it is the loaded catalyst of precious metals such as palladium, platinum, carrier can be selected the multi-hole type material for use, the aperture of carrier is 10-500 , 50-450 preferably, the carrier that can select for use has aluminum oxide, gac, diatomite or the molecular sieve etc. of different crystal forms, preferred aluminum oxide, diatomite and molecular sieve.
The solvent that reaction is used can be water, C
1-C
10Fatty Alcohol(C12-C14 and C12-C18), C
2-C
6Aliphatic dialcohol or two or more mixture wherein, preferably water, methyl alcohol, ethanol and Virahol, and the mixture of water and methyl alcohol, ethanol or Virahol.The consumption of solvent can determine according to the weight of reaction mixture, and with reactant with product is non-crystallizable separates out to good, the common solvent amount is the 30%-80% of reaction mixture weight.
Temperature of reaction can be 40-160 ℃, preferably 60-130 ℃.
Reaction pressure can be 0.1-10.0MPa, preferably 1.0-6.0MPa.
The charging air speed of reaction can be 0.1-2.0h
-1, 0.5-1.5h preferably
-1
The mol ratio of hydrogen and piperidone can be 2-30: 1, and 4-20 preferably: 1.
Method provided by the invention can be operated according to the following procedure:
With amine and 2,2,6,6-tetraalkyl-4-piperidone is dissolved in the solvent in proportion, sends into reactor by volume pump, and hydrogen enters reactor by relief valve and under meter control pressure and flow together with reaction mixture.Reacted material enters gas-liquid separator through overcooling, and hydrogen can recycle, and liquid phase material is sent into the product separation system and purified.
The by product that generates in the reaction process (as the piperylhydrazine that does not replace fully) can prepare the purpose product by circulating reaction.
The present invention is by selecting specific reaction conditions, and particularly the carrier in suitable aperture makes 2,2,6, and 6-tetraalkyl-4-piperidinamines can prepare in fixed-bed reactor, and reaches high transformation efficiency and selectivity, helps the serialization large-scale commercial production.
Embodiment
Example 1
In the reactor of fixed bed reaction evaluating apparatus, packing into the aluminum oxide is 5% Pd catalyzer of carrier, alumina supporter can several pore diameter ranges at 50-110 , 80 ℃ of temperature of reaction, reaction pressure 2.0MPa, charging air speed 1.0h
-1, 2,2,6, the mol ratio of 6-tetramethyl--4-piperidone and hexanediamine 2.1: 1, Virahol is made solvent, reactant concn 50%, the mol ratio of hydrogen and piperidone 10: 1.Reaction result is listed in table 1.
Comparative example
In the reactor of example 1 said fixed bed reaction evaluating apparatus, packing into the gac is 5% Pd catalyzer of carrier, the aperture of absorbent charcoal carrier＜50 .All the other conditions are with example 1, and reaction result is listed in table 1.Comparative example explanation, the less gac effect in fixed bed reaction in aperture is relatively poor, can not satisfy industrial requirement.
Example 2
In the reactor of fixed bed reaction evaluating apparatus, packing into the aluminum oxide is 3% Pt catalyzer of carrier, alumina supporter can several pore diameter ranges at 100-300 , 98 ℃ of temperature of reaction, reaction pressure 2.0MPa, charging air speed 1.1h
-1, 2,2,6, the mol ratio of 6-tetramethyl--4-piperidone and hexanediamine 2.15: 1,80% aqueous ethanolic solution is made solvent, reactant concn 50%, the mol ratio of hydrogen and piperidone 6: 1.Reaction result is listed in table 1.
Example 3
In the reactor of fixed bed reaction evaluating apparatus, packing into the aluminum oxide is 3% Pd catalyzer of carrier, alumina supporter can several pore diameter ranges at 100-300 , 90 ℃ of temperature of reaction, reaction pressure 3.0MPa, charging air speed 1.2h
-1, 2,2,6, the mol ratio of 6-tetramethyl--4-piperidone and hexanediamine 2.2: 1,80% aqueous ethanolic solution is made solvent, reactant concn 50%, the mol ratio of hydrogen and piperidone 20: 1.Reaction result is listed in table 1.
Example 4
In the reactor of fixed bed reaction evaluating apparatus, packing into the aluminum oxide is 5% Pd catalyzer of carrier, alumina supporter can several pore diameter ranges at 200-600 , 85 ℃ of temperature of reaction, reaction pressure 4.0MPa, charging air speed 1.0h
-1, 2,2,6, the mol ratio of 6-tetramethyl--4-piperidone and hexanediamine 2.15: 1, Virahol is made solvent, reactant concn 50%, the mol ratio of hydrogen and piperidone 12: 1.Reaction result is listed in table 1.
Example 5
In the reactor of fixed bed reaction evaluating apparatus, packing into the aluminum oxide is 3% Pd catalyzer of carrier, alumina supporter can several pore diameter ranges at 300-500 , 90 ℃ of temperature of reaction, reaction pressure 3.0MPa, charging air speed 0.8h
-1, 2,2,6, the mol ratio of 6-tetramethyl--4-piperidone and hexanediamine 2.05: 1, Virahol is made solvent, reactant concn 50%, the mol ratio of hydrogen and piperidone 20: 1.Reaction result is listed in table 1.
Table 1
| Sequence number | Catalyzer | Reaction result (mole) | |||
| TAA transformation efficiency % | Hexanediamine transformation efficiency % | TMPA selectivity % | DTMPA selectivity % | ||
| Comparative example | 5％Pd-C | 75.4 | 100 | 8.3 | 43.2 |
| Example 1 | 5％Pd-Al 2O 3 | 90.2 | 100 | 12.3 | 70.6 |
| Example 2 | 3％Pt-Al 2O 3 | 94.8 | 100 | 9.5 | 85.2 |
| Example 3 | 3％Pd-Al 2O 3 | 95.3 | 100 | 10.2 | 82.3 |
| Example 4 | 5％Pd-Al 2O 3 | 92.7 | 100 | 8.2 | 83.5 |
| Example 5 | 3％Pd-Al 2O 3 | 95.4 | 100 | 9.2 | 85.3 |
Example 6
In the reactor of fixed bed reaction evaluating apparatus, packing into the aluminum oxide is 5% Pd catalyzer of carrier, alumina supporter can several pore diameter ranges at 300-500 , 80 ℃ of temperature of reaction, reaction pressure 2.0MPa, charging air speed 1.5h
-1, keep suitable hydrogen flowing quantity, use the incomplete thick product of reaction to make raw material, the composition of raw material and product is listed in table 2.
Table 2
Annotate: TAA represents 2,2,6, and 6-tetramethyl--4-piperidone TMPA represents that N-(2,2,6,6-tetramethyl--4-piperidyl) hexanediamine DTMPA represents N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexanediamine
| Project | Form (%) | |||
| TAA | TMPA | DTMPA | Impurity | |
| Charging | 27.5 | 2.1 | 45.5 | 24.9 |
| Product | 10.8 | 4.4 | 78.1 | 6.7 |
Claims (9)
1. 2,2,6 of structural formula (I) expression, the preparation method of 6-tetraalkyl-4-piperidinamines comprises: in fixed-bed reactor, at water, C
1-C
10Fatty Alcohol(C12-C14 and C12-C18) or C
2-C
6Under the existence of aliphatic dialcohol or its mixture, with the palladium or the platinum that are carried on the porous support that the aperture is 10-500 is catalyzer, make 2 of structural formula (II) expression, 2,6,6-tetraalkyl-4-piperidone and organic amine reaction, temperature of reaction is 60-130 ℃, reaction pressure is 1.0-6.0MPa, and the charging air speed of reaction is 0.1-2.0h
-1, the mol ratio of hydrogen and piperidone is 2-30: 1,
In the formula, R represents C
1-C
18Alkyl, C
5-C
6Cycloalkyl or C
7-C
9Aralkyl; R
1, R
2, R
3And R
4Represent identical or different C
1-C
8Alkyl; A represents hydrogen, hydroxyl, C
1-C
8Alkoxyl group, C
1-C
8Alkyl, C
2-C
10Alkyl carbonyl or aromatic carbonyl; N is 1,2,3 or 4;
A in the formula, R
1, R
2, R
3And R
4As above-mentioned regulation;
The structure of organic amine is R (NH
2)
n, R and n such as above-mentioned regulation.
2. according to the said preparation method of claim 1, it is characterized in that, said organic amine is selected from methylamine, butylamine, lauryl amine, octadecylamine, hexahydroaniline, benzene methanamine, triethylenediamine, tetrem support diamines, hexanediamine, pentamethylene diamine, 1,4-butanediamine, 1,12-diamino dodecane, dipropylenetriamine, Diethylenetriaminee (DETA), 1,2,6-triamino hexane and 1,4-diamino-cyclohexane.
3. according to the said preparation method of claim 1, it is characterized in that said organic amine select oneself diamines, pentamethylene diamine and 1,4-butanediamine.
4. according to the said preparation method of claim 1, it is characterized in that said piperidone is 2,2,6,6-tetramethyl--4-piperidone.
5. according to the said preparation method of claim 1, it is characterized in that the aperture of said carrier is 50-450 .
6. according to the said preparation method of claim 1, it is characterized in that said carrier is selected from aluminum oxide, diatomite and molecular sieve.
7. according to the said preparation method of claim 1, it is characterized in that said solvent is selected from water, methyl alcohol, ethanol and Virahol, and the mixture of water and methyl alcohol, ethanol or Virahol.
8. according to the said preparation method of claim 1, it is characterized in that the charging air speed is 0.5-1.5h
-1
9. according to the said preparation method of claim 1, it is characterized in that the mol ratio of hydrogen and piperidone is 4-20: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00121156 CN1111157C (en) | 2000-07-28 | 2000-07-28 | Prepn. of 2,2,6,6-tetraalkyl-4-piperylhydrazines |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00121156 CN1111157C (en) | 2000-07-28 | 2000-07-28 | Prepn. of 2,2,6,6-tetraalkyl-4-piperylhydrazines |
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| Publication Number | Publication Date |
|---|---|
| CN1336365A CN1336365A (en) | 2002-02-20 |
| CN1111157C true CN1111157C (en) | 2003-06-11 |
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|---|---|---|---|
| CN 00121156 Expired - Lifetime CN1111157C (en) | 2000-07-28 | 2000-07-28 | Prepn. of 2,2,6,6-tetraalkyl-4-piperylhydrazines |
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| CN106946763B (en) * | 2017-04-26 | 2020-11-24 | 宿迁联盛科技股份有限公司 | Method for preparing hexamethylene diamine piperidine, catalyst and preparation method thereof |
| EP3663284B1 (en) | 2018-12-07 | 2021-02-03 | Evonik Operations GmbH | Improved method for the preparation of triacetonamine |
| CN109836370A (en) * | 2019-03-20 | 2019-06-04 | 萧县新秀新材料有限公司 | The synthetic method of the 2,2,6,6- tetramethyl piperidine amine of specific pH range |
-
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|---|---|
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