CN108997356A - A method of catalysis Ethylenimine synthesizes 2- methyl triethylene diamine with 2- methyl piperazine - Google Patents
A method of catalysis Ethylenimine synthesizes 2- methyl triethylene diamine with 2- methyl piperazine Download PDFInfo
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- CN108997356A CN108997356A CN201810790778.5A CN201810790778A CN108997356A CN 108997356 A CN108997356 A CN 108997356A CN 201810790778 A CN201810790778 A CN 201810790778A CN 108997356 A CN108997356 A CN 108997356A
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- methyl
- ethylenimine
- triethylene diamine
- methyl piperazine
- synthesizes
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- QXKMWFFBWDHDCB-UHFFFAOYSA-N CC1N(CC2)CCN2C1 Chemical compound CC1N(CC2)CCN2C1 QXKMWFFBWDHDCB-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/08—Bridged systems
Abstract
The present invention discloses a kind of method that catalysis Ethylenimine synthesizes 2- methyl triethylene diamine with 2- methyl piperazine, is to solve the problems, such as that existing method synthesis step is more, selectivity of product is low.This method is applied to using Ethylenimine and 2- methyl piperazine as raw material, the use of pentasil zeolite is catalyst, and a step catalyzes and synthesizes in the reaction of 2- methyl triethylene diamine, has the advantage that synthesis step is few, selectivity of product is high.
Description
Technical field
The invention belongs to field of fine chemical, and in particular to a kind of catalysis Ethylenimine synthesizes 2- methyl with 2- methyl piperazine
The method of triethylene diamine.
Background technique
2- methyl triethylene diamine is also known as 2- methyl-1, and 4- diazabicylo [2.2.2] octane, is a kind of new polyurethane
Foam amination catalysis.Compared to traditional catalyst triethylene diamine, 2- methyl triethylene diamine is because it is with higher boiling point
(184~186 DEG C) and lower fusing point (0 DEG C of <), and hygroscopicity is small, production method is simple, and application range is more extensive, has
Hope a kind of perfect substitute for becoming triethylene diamine.
Currently, the synthesis of 2- methyl triethylene diamine is mainly synthesized by reactant of hydroxyethylpiperazine derivative, such as
CN103641836, CN201610761294.9, US4754036 and JP2016199471A are disclosed with 1- ethoxy -3- methyl piperazine
One or both of piperazine, 1- ethoxy -2- methyl piperazine, N- β-hydroxypropylpiperazine and N- Alpha-Methyl-beta-hydroxyethyl piperazine are
Reaction raw materials synthesize 2- methyl triethylene diamine, but cost of material is relatively expensive.
By reaction raw materials of 2- methyl piperazine compared to using hydroxyethylpiperazine derivative as Material synthesis 2- methyl triethylene
Diamines cost is more cheap, has apparent economic advantages.Trejbal etc. first adds hydrogen using ethylenediamine and 1,2- propylene glycol as raw material
2- methyl piperazine is synthesized, then by reacting synthesis 2- methyl triethylene diamine with ethylenediamine or with the ethylenediamine solution of piperazine, but
Selectivity of product is not more than 19.8% (Petroleum&Coal 2012,54 (4), 335-339；
Chem.Eng.Technol.2007,30(11),1506-1511)；Xia Rong is raw material in first using 2- methyl piperazine and ethylene oxide
Hydroxyethyl methyl piperazine is first synthesized in benzene, then in the in the mixed solvent of biphenyl and diphenyl ether, is synthesized by catalyst of phenyl-phosphonic acid
2- methyl triethylene diamine (Southeast China University, master thesis, 2012).However the reaction process introduces ethylene oxide, needs
Slowly carried out under condition of ice bath, and synthesis obtain intermediate hydroxyethyl methyl piperazine after need to exist again after carrying out vacuum distillation purification
2- methyl triethylene diamine is synthesized under the conditions of lower 325 DEG C of organic acid catalysis effect, synthesis step is more, severe reaction conditions；
Yakhontov etc. first generates corresponding chloride with hcl reaction by raw material of 2- methyl piperazine, then reacts with sodium nitrite
Azido compound is obtained, primary amine is obtained after hydrogenated aluminium lithium reduction, then react to obtain bromide with Bromofume, then in palladium carbon
Under catalyst action plus hydrogen obtains 2- methyl triethylene diamine.Although reaction substrate is 2- methyl piperazine, raw material is single, needs
The reaction of five steps can just obtain target product, and synthesis step is more, reaction process complexity (Khimiko-farmatsevticheskii
Zhurnal,1989,23(1),30-35)。
Summary of the invention
The technical problem to be solved by the present invention is to for more than synthesis step in the prior art and problem that selectivity of product is low,
A kind of method that Ethylenimine catalyzes and synthesizes 2- methyl triethylene diamine with one step of 2- methyl piperazine is provided, is shown below:
The method that Ethylenimine provided by the invention and 2- methyl piperazine catalyze and synthesize 2- methyl triethylene diamine, feature
It is that the present invention using Ethylenimine and 2- methyl piperazine as raw material, uses solid acid Hydrogen pentasil zeolite for catalyst, passes through
Ethylenimine ternary azacyclo- open loop, then intermolecular deamination reaction occurs with the 2- methyl piperazine after activation, ultimately produce target
Product 2- methyl triethylene diamine.
Wherein pentasil zeolite also contains at least one divalent, trivalent or tetravalent metal M hetero atom in addition to silicon oxygen skeleton,
Wherein M is one of Mn, Mg, Fe, B, Al, Co, Ni, Mo, La, Sn, Cr, Ga, Ti, Zr and Ge or a variety of, preferably Al, Mn,
One of Fe, Ti, B, Cr, further preferably one of Al, Mn, Fe, and Si/M molar ratio are 100~1000.When M is Al,
Si/Al molar ratio is 80~200；When M is Mn, Si/Mn molar ratio is 120~600；When M is Fe, Si/Fe molar ratio is
100~300.
Pentasil zeolite is the mixed structure of ZSM-5 or ZSM-11 or both in the present invention, while pentasil zeolite
It need to be all or part of Hydrogen, conventional ion-exchange preparation can be used.
The present invention is using continuous operation, wherein Ethylenimine in raw material flow: 2- methyl piperazine: the mass ratio of solvent is 5~
50:10~30:10~80.Solvent is selected from water, ammonium hydroxide, methanol, N-Methyl pyrrolidone, benzene,toluene,xylene, trimethylbenzene, chlorine
It is one of imitative or a variety of.In view of subsequent rectifying purification process, preferably one of water, ammonium hydroxide and methanol, further preferably water.
Reaction temperature of the present invention is 330~420 DEG C, preferably 350~400 DEG C；In reactor absolute pressure be 0.1~
10bar, preferably synthesis under normal pressure；Liquid volume air speed is 0.05~3h-1, preferably 0.2~1h-1。
The present invention carries out gas-solid catalysis using fixed bed or fluidized-bed reactor and synthesizes 2- methyl triethylene diamine,
It is preferred that fixed bed.
Beneficial effects of the present invention:
In the prior art, more using 2- methyl piperazine as the synthetic method step of reaction substrate, usually two steps to five
Step reaction, and target product 2- methyl triethylene diamine is selectively relatively low (≤19.8%), and synthesis step of the present invention is few,
For single step reaction, and 2- methyl triethylene diamine selectively reaches 75.8%, with the obvious advantage.
Specific embodiment
The invention will be further described by the following examples, but the present invention is not limited by the following example.
Embodiment 1
Using fixed bed reactors, reactor size 700mm × Φ 40mm × 6mm.Reaction carries out under normal pressure, with
HZSM-5 (n (Si/Al)=200) be catalyst, loadings 30mL, using the Ethylenimine aqueous solution of 2- methyl piperazine as raw material,
Wherein Ethylenimine: 2- methyl piperazine: the mass ratio of water is 5:20:80, is entered after first passing through constant-flux pump, then the preheating of preheated device
Fixed bed reactors, 370 DEG C of reaction temperature, liquid air speed 1h-1.Sampling analysis after stable reaction 6h, 2- methyl piperazine conversion ratio
51.1%, 2- methyl triethylene diamine are selectively 75.8%.
Embodiment 2
Using fixed bed reactors, reactor size is the same as embodiment 1.Reaction carries out under normal pressure, with HZSM-11 (n (Si/
It Al)=120) is catalyst, loadings 30mL, using the Ethylenimine aqueous solution of 2- methyl piperazine as raw material, wherein Ethylenimine:
2- methyl piperazine: the mass ratio of water is 10:18:70, enters fixed bed reaction after first passing through constant-flux pump, then the preheating of preheated device
Device, 360 DEG C of reaction temperature, liquid air speed 1h-1.Sampling analysis after stable reaction 6h, 2- methyl piperazine conversion ratio 63.7%, 2- first
Base triethylene diamine is selectively 68.6%.
Embodiment 3
Using fixed bed reactors, reactor size is the same as embodiment 1.Reaction carries out under normal pressure, with Mn-ZSM-5 (n
It (Si/Mn)=210) is catalyst, loadings 30mL, using the Ethylenimine aqueous solution of 2- methyl piperazine as raw material, wherein ethylene
Imines: 2- methyl piperazine: the mass ratio of ammonium hydroxide is 8:20:80, enters fixed bed after first passing through constant-flux pump, then the preheating of preheated device
Reactor, 350 DEG C of reaction temperature, liquid air speed 0.8h-1.Sampling analysis after stable reaction 6h, 2- methyl piperazine conversion ratio
47.3%, 2- methyl triethylene diamine are selectively 58.7%.
Embodiment 4
Using fixed bed reactors, reactor size is the same as embodiment 1.Reaction carries out under normal pressure, with HZSM-5 (n (Si/
It Al)=160) is catalyst, loadings 30mL, using the Ethylenimine ammonia spirit of 2- methyl piperazine as raw material, wherein ethylene is sub-
Amine: 2- methyl piperazine: the mass ratio of ammonium hydroxide is 5:30:70, first passes through constant-flux pump, then to enter fixed bed after the preheating of preheated device anti-
Answer device, 370 DEG C of reaction temperature, liquid air speed 0.5h-1.Sampling analysis after stable reaction 6h, 2- methyl piperazine conversion ratio 57.1%,
2- methyl triethylene diamine is selectively 72.5%.
Claims (4)
1. a kind of method that catalysis Ethylenimine synthesizes 2- methyl triethylene diamine with 2- methyl piperazine, it is characterised in that:
It the use of pentasil zeolite is catalyst using Ethylenimine and 2- methyl piperazine as raw material；
In continuous operation, Ethylenimine in raw material flow: 2- methyl piperazine: the mass ratio of solvent be 5~50:10~30:10~
80；
Pentasil zeolite also contains at least one divalent, trivalent or tetravalent metal M hetero atom in addition to silicon oxygen skeleton, and wherein M is
One of Mn, Mg, Fe, B, Al, Co, Ni, Mo, La, Sn, Cr, Ga, Ti, Zr and Ge or a variety of, and Si/M molar ratio is 100
~1000；Pentasil zeolite is the mixed structure of ZSM-11 or ZSM-5 or both, and pentasil zeolite is at least partly with Hydrogen
In the presence of；
Solvent is one of water, ammonium hydroxide, methanol, N-Methyl pyrrolidone, benzene,toluene,xylene, trimethylbenzene, chloroform or more
Kind；
Reaction temperature is 330~420 DEG C；
Absolute pressure is 0.1~10bar in reactor；
Liquid volume air speed is 0.05~3h-1；
Reactor uses fixed bed or fluidized bed.
2. the method that catalysis Ethylenimine according to claim 1 synthesizes 2- methyl triethylene diamine with 2- methyl piperazine,
It is characterized in that M is one of Al, Mn, Fe, Ti, B, Cr.
3. the method that catalysis Ethylenimine according to claim 1 synthesizes 2- methyl triethylene diamine with 2- methyl piperazine,
It is characterized in that M is one of Al, Mn, Fe；When M is Al, Si/Al molar ratio is 80~200；When M is Mn, Si/Mn
Molar ratio is 120~600；When M is Fe, Si/Fe molar ratio is 100~300.
4. the method that catalysis Ethylenimine according to claim 1 synthesizes 2- methyl triethylene diamine with 2- methyl piperazine,
It is characterized in that solvent is one of water, ammonium hydroxide and methanol in raw material flow.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810790778.5A CN108997356B (en) | 2018-07-18 | 2018-07-18 | Method for synthesizing 2-methyl triethylene diamine by catalyzing ethylene imine and 2-methyl piperazine |
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| CN201810790778.5A CN108997356B (en) | 2018-07-18 | 2018-07-18 | Method for synthesizing 2-methyl triethylene diamine by catalyzing ethylene imine and 2-methyl piperazine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108912120A (en) * | 2018-07-18 | 2018-11-30 | 西安近代化学研究所 | A kind of preparation method of triethylene diamine coproduction N- aminoethyl piperazine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0312734B1 (en) * | 1987-10-17 | 1992-01-02 | Hüls Aktiengesellschaft | Process for the preparation of 1,4-diazabicyclo(2.2.2)-octane from piperazine |
| CN103641836A (en) * | 2013-11-21 | 2014-03-19 | 绍兴兴欣化工有限公司 | Preparation method of 2-methyl triethylene diamine |
| CN107163054A (en) * | 2017-05-16 | 2017-09-15 | 绍兴兴欣化工有限公司 | A kind of synthetic method of triethylene diamine |
-
2018
- 2018-07-18 CN CN201810790778.5A patent/CN108997356B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0312734B1 (en) * | 1987-10-17 | 1992-01-02 | Hüls Aktiengesellschaft | Process for the preparation of 1,4-diazabicyclo(2.2.2)-octane from piperazine |
| CN103641836A (en) * | 2013-11-21 | 2014-03-19 | 绍兴兴欣化工有限公司 | Preparation method of 2-methyl triethylene diamine |
| CN107163054A (en) * | 2017-05-16 | 2017-09-15 | 绍兴兴欣化工有限公司 | A kind of synthetic method of triethylene diamine |
Non-Patent Citations (1)
| Title |
|---|
| 杨国忠，等: "三乙烯二胺的合成及应用", 《精细与专用化学品》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108912120A (en) * | 2018-07-18 | 2018-11-30 | 西安近代化学研究所 | A kind of preparation method of triethylene diamine coproduction N- aminoethyl piperazine |
| CN108912120B (en) * | 2018-07-18 | 2021-01-05 | 西安近代化学研究所 | Preparation method for co-production of N-aminoethyl piperazine by triethylene diamine |
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