CN106632143B - The cycle the preparation method of N-methylmorpholine - Google Patents
The cycle the preparation method of N-methylmorpholine Download PDFInfo
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- CN106632143B CN106632143B CN201611073210.9A CN201611073210A CN106632143B CN 106632143 B CN106632143 B CN 106632143B CN 201611073210 A CN201611073210 A CN 201611073210A CN 106632143 B CN106632143 B CN 106632143B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of cycle the preparation methods of N methyl morpholines, include the following steps：1) it, synthesizes：N methyl diethanolamines are reacted with sulfuric acid, are then cooled to room temperature, and synthesis reaction solution is obtained；2), ammonium salt shifts：N methyl diethanolamines are added in synthesis reaction solution obtained by step 1) and ammonium salt transfer agent is added and carry out ammonium salt transfer exchange reaction；3) it, distills：Ammonium salt transfer reaction liquid obtained by step 2) is evaporated under reduced pressure, fraction and kettle liquid are respectively obtained, fraction is N methyl morpholines；4), circular response：Kettle liquid obtained by step 3) is subjected to synthetic reaction, then cools to room temperature, obtains circular response kettle liquid；With circular response kettle liquid alternative steps 2) in synthesis reaction solution and ammonium salt transfer agent, then successively carry out step 2) described in ammonium salt transfer and step 3) described in distillation.
Description
Technical field
The present invention relates to a kind of cycle preparation methods of organic compound, i.e. the cycle preparation method of N-methylmorpholine.
Background technology
N-methylmorpholine is a kind of heterocyclic tertiary amines, and the property with ether and amine is widely used in insecticide, fungicide, plant
The synthesis of the agricultural chemical compounds such as object growth regulator is also used for surfactant, lubrication oil coolant, metal antirusting agent, fiber
The synthesis of the fine chemical products such as inorganic agent, structural formula is as shown in S-1.
Comprehensive literature reports that the preparation of N-methylmorpholine at present mainly uses following methods：
1), morpholine method (DE2205597,1973)：It is that raw material is manufactured through methylating using morpholine.Process is in the reaction with stirring
It is intermittently carried out in kettle, raw material proportioning is morpholine：Formaldehyde：Formic acid=1：1~2：1~2, reaction temperature 5O~110 DEG C, normal pressure is received
Rate nearly 90%.This law technology is more ripe, and condition is milder, and yield is higher, but raw material morpholine is expensive, production cost compared with
It is high.
2), dichloroether method (US3155656,1964)：Dichloroether reacts in the presence of 110 DEG C and alkali with methylamine,
N-methylmorpholine, yield 50%, while by-product dimethyl ether can be made.Dichloroether may be from the pair of chlorohydrination production ethylene oxide
Product, it is inexpensive, but resource is limited.This method yield is relatively low, and raw and auxiliary material consumption is larger, and the waste that process generates is more.
3), diglycol process (DE333337182,1986)：Diethylene glycol (DEG), methylamine, hydrogen are at 150~250 DEG C and 1 × 105~5 ×
105N-methylmorpholine is catalyzed and synthesized under the pressure of Pa.Its shortcoming is to react to carry out at high temperature under high pressure, and raw materials used first
Amine and hydrogen are inflammable and explosive, and the big toxicity of methylamine smell is big, and effect on environment is big so that produce of high cost with safety guarantee.
4), diethanolamine method (SU7939787,1981)：Diethanol amine and dimethyl suflfate react at 105~200 DEG C,
With active oxidation Calcium treatment, decomposition of methyl product and neutralisation of sulphuric acid radical ion obtain N-methylmorpholine, yield 81~95.This
Method reaction process should be alkylated reaction, while carry out ring-closure reaction again.High, selecting response is technically required in this way
Property is relatively low.
5), N methyldiethanol amine method (PL85092,1977)：Using N methyldiethanol amine as raw material, hydrochloric acid is catalysis
Agent needs to make the N-methylmorpholine hydrochloride of generation parse with inorganic base, generates a large amount of sodium chloride, and consumption is big, and discharge is big, is not inconsistent
Close green chemistry principles.
Invention content
The technical problem to be solved in the present invention is to provide a kind of cycle the preparation methods of environmentally protective N-methylmorpholine.
In order to solve the above technical problem, the present invention provides a kind of cycle the preparation methods of N-methylmorpholine, including following step
Suddenly：
1) it, synthesizes：
N methyldiethanol amine is added in container (being, for example, four-hole boiling flask), is added with stirring sulfuric acid, N- methyl diethyls
Hydramine：The molar ratio of sulfuric acid is 1：1.1~1.5 (preferably 1:1.1~1.2), reaction temperature is 150~180 DEG C, to steam
The water generated is reacted, the reaction time is 6~8 hours；It then cools to room temperature, obtains synthesis reaction solution；
Remarks explanation：In this step, sulfuric acid is added in a manner of dropwise addition, and control temperature is no more than 60 during being added dropwise
℃；
2), ammonium salt shifts：
(dropwise addition) N methyldiethanol amine is added in synthesis reaction solution obtained by step 1) and ammonium salt transfer agent is added
Carry out ammonium salt transfer exchange reaction (purpose is to obtain free state N-methylmorpholine)；
The molar ratio of the N methyldiethanol amine and the N methyldiethanol amine in step 1) is 1：1, ammonium salt transfer agent
Mass ratio with the N methyldiethanol amine in step 1) is 1%~2%；
It is 60~70 DEG C that ammonium salt, which shifts exchange reaction temperature, and the time is 30 ± 5 minutes；
Remarks explanation：In this step, N methyldiethanol amine is added in a manner of being added dropwise, and time for adding is controlled 25~30
Minute；
3) it, distills：
Ammonium salt transfer reaction liquid obtained by step 2) is evaporated under reduced pressure, fraction and kettle liquid, fraction N- are respectively obtained
Methyl morpholine；
4), circular response：
Kettle liquid obtained by step 3) is reacted 6~8 hours at a temperature of 150~180 DEG C, steams the water that reaction generates；
It then cools to room temperature, obtains circular response kettle liquid；
With circular response kettle liquid alternative steps 2) in synthesis reaction solution and ammonium salt transfer agent, then carry out successively
The distillation described in ammonium salt transfer and step 3) described in step 2).
Remarks explanation：Kettle liquid obtained by step 3) is the mixed liquor containing N methyldiethanol amine, sulfuric acid and ammonium salt transfer agent；
The operation of one cycle reaction is above are only, later each circular response operates in this manner.It is anti-in cycle
It answers in corresponding " ammonium salt transfer " step, the dosage and reaction temperature of N methyldiethanol amine and time are the same as original step
2)。
The improvement of the cycle the preparation method of N-methylmorpholine as the present invention：
In the circular response of the step 4), with circular response kettle liquid alternative steps 2) in synthesis reaction solution and
Ammonium salt transfer agent, and addition ammonium salt transfer agent is supplemented, the ammonium salt transfer agent for supplementing addition accounts for the ammonium salt transfer agent being added for the first time
The 0.6%~3% of weight.
Described in remarks：Because of the loss of preceding primary first-order equation, it is therefore desirable to add ammonium salt transfer agent in right amount.
The cycle the preparation method of N-methylmorpholine as the present invention is further improved：
The ammonium salt transfer agent is polyether substance, and polyether substance is polyethers or polyamine ether；Polyethers is polyethylene glycol
(PEG), for example, polyethylene glycol is PEG-8000, PEG-6000；Polyamine ether is, for example, T-5000, D-4000, M-2070.
The cycle the preparation method of N-methylmorpholine as the present invention is further improved：
Sulfuric acid in step 1) is the concentrated sulfuric acid of mass concentration >=98%.
In the present invention, step 1) is to make N methyldiethanol amine react under the catalytic action of sulfuric acid to generate N- methyl
Quinoline sulfate.
T-5000, D-4000, M-2070 are purchased from JEFFAMINE companies of the U.S..Its structural formula is as follows：
The present invention is using N methyldiethanol amine as raw material, the reaction generation N-methylmorpholine under the catalytic action of the concentrated sulfuric acid
Sulfate carries out ammonium by the way that raw material N methyldiethanol amine is added into reaction solution and is used as the polyether substance of ammonium salt transfer agent
Transfer exchange reaction obtains free state N-methylmorpholine, is evaporated under reduced pressure, to steam all N-methylmorpholines；Kettle liquid continues anti-
It answers；That is, after distillation, ammonium salt transfer agent need not be handled, and can be recycled.Then heating carries out next secondary response, is formed
One technique for recycling sulphuric acid catalysis synthesis N-methylmorpholine.In the present invention, the number of cycle can be example many times
Such as it is at least 5 times.
The reaction process of the present invention is made of following catalyst etherifying and ammonium salt transfer process：
The present invention has following technical advantage：
Using raw material and ammonium salt transfer agent by N-methylmorpholine sulfate conversion at free state N-methylmorpholine and N- methyl
Diethanol amine sulfate does not need the inorganic bases division object sulfate such as sodium hydroxide, and can follow compared with existing conventional method
Ring utilizes the concentrated sulfuric acid.Present invention process, which has, saves sour material, does not use inorganic base material, does not generate sodium sulphate, by-product is
The advantages that water.Therefore there is Important Economic meaning and the value of environmental protection.
Specific implementation mode
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Embodiment 1, a kind of cycle the preparation method of N-methylmorpholine, using N methyldiethanol amine as raw material, the concentrated sulfuric acid (concentration
98%) it is catalyst, follows the steps below successively：
1) it, synthesizes：
In the four-hole boiling flask of 500ml, the 110g concentrated sulfuric acids (1.1mol, 98%) are slowly added dropwise and (control temperature to be no more than
Completion of dropwise addition in 60 DEG C, about 30 minutes) it returns in the N methyldiethanol amine (1mol) of 119.16g, being warming up to 160~170 DEG C
Stream reaction 7 hours, has water to steam in reaction process.After reaction, it is cooled to room temperature, obtains synthesis reaction solution.
2), ammonium salt shifts：
Under the conditions of being stirred at room temperature, by 119.16gN- methyl diethanolamines (1mol) instillation, (time for adding is about 30 points
Clock) in synthesis reaction solution, the PEG-8000 (about the 1% of N methyldiethanol amine quality) of 1.19g is then added, is then risen
Temperature to 60~70 DEG C stir 30 minutes.
3) it, distills：
Ammonium salt transfer reaction liquid obtained by step 2) is evaporated under reduced pressure, 55~60 DEG C are collected under -0.95MPa pressure
Under fraction, obtain N-methylmorpholine 98.72g.Product purity is 99.9%；On the basis of the N methyldiethanol amine of consumption,
Yield is 97.5%.
Embodiment 1-1, first time circular response：
(that is, kettle liquid, the kettle liquid is containing N methyldiethanol amine, sulfuric acid for reaction solution after 1 step 3) of embodiment is distilled
With the polyether substance as ammonium salt transfer agent) be warming up to 160~170 DEG C react 7 hours, then cool to room temperature, must recycle
Reaction kettle liquid；
With synthesis reaction solution and polyether substance (PEG- of this circular response in 1 step 2) of kettle liquid alternate embodiment
8000), and it is appropriate supplement addition 0.015g PEG-8000, that is, supplemented PEG-8000 accounts for the PEG-8000 being added for the first time
The 1.26% of weight.60~70 DEG C are then heated to, is stirred 30 minutes；The dosage and feed postition of N methyldiethanol amine are the same as real
Apply the step 2) of example 1.
Finally repeat the step 3) of above-described embodiment 1.
Remarks explanation：Due to consideration that ammonium salt transfer agent has moderate loss in experiment every time, it is therefore desirable to carry out suitable
Addition.
Embodiment 1-2, second of circular response：
Kettle liquid after embodiment 1-1 distillations is subjected to second of circular response according to embodiment 1-1 the methods, is mended
Fill the Change Weight To 0.02g of the PEG-8000 of addition.
And so on ,~the five cycle is recycled to obtain the third time corresponding to embodiment 1-3~embodiment 1-5,
Acquired results are described in table 1 below.
Table 1
Embodiment 2, a kind of cycle the preparation method of N-methylmorpholine, using N methyldiethanol amine as raw material, the concentrated sulfuric acid (concentration
98%) it is catalyst, follows the steps below successively：
1) it, synthesizes：
In 500ml four-hole boiling flasks, the 120g concentrated sulfuric acids (1.2mol, 98%) are slowly added dropwise and (controls temperature and is no more than 60
DEG C, completion of dropwise addition in about 30 minutes) in 119.16gN- methyl diethanolamines (1mol), being warming up to, 160~170 DEG C of reflux are anti-
It answers 7 hours, there is water to steam in reaction process.After reaction, it is cooled to room temperature, obtains synthesis reaction solution.
2), ammonium salt shifts：
Under the conditions of being stirred at room temperature, by 119.16gN- methyl diethanolamines (1mol) instillation, (time for adding is about 30 points
Clock) in synthesis reaction solution, the T-5000 (about the 2% of N methyldiethanol amine quality) of 2.38g is then added, is then heated up
It is stirred 30 minutes to 60~70 DEG C.
3) it, distills：
Ammonium salt transfer reaction liquid obtained by step 2) is evaporated under reduced pressure, 55~60 DEG C are collected under -0.95MPa pressure
Under fraction, obtain N-methylmorpholine 99.63g.Product purity is 99.9%；On the basis of the N methyldiethanol amine of consumption,
Yield is 98.4%.
Embodiment 2-1, first time circular response：
Reaction solution (that is, kettle liquid) after 2 step 3) of embodiment is distilled is warming up to 160~170 DEG C and reacts 7 hours,
It then cools to room temperature, obtains circular response kettle liquid；
With synthesis reaction solution and polyether substance (T- of this circular response in 2 step 2) of kettle liquid alternate embodiment
5000), and it is appropriate supplement addition 0.015g T-5000, that is, supplemented T-5000 accounts for the T-5000 weight being added for the first time
0.63%.60~70 DEG C are then heated to, is stirred 30 minutes；The dosage and feed postition of N methyldiethanol amine are the same as embodiment 2
Step 2).
Finally repeat the step 3) of above-described embodiment 2.
Embodiment 2-2, second of circular response：
Kettle liquid after embodiment 2-1 distillations is subjected to second of circular response according to embodiment 2-1 the methods, is mended
Fill the Change Weight To 0.03g of the T-5000 of addition.
And so on ,~the five cycle is recycled to obtain the third time corresponding to embodiment 2-3~embodiment 2-5,
Acquired results are described in table 2 below.
Table 2
Embodiment 3~6 changes reaction condition in embodiment 1, that is, when reaction temperature in changing the step 1) and reaction
Between, remaining is equal to embodiment 1, and to obtain embodiment 3~6, gained total recovery is shown in Table 3.
Table 3
| Embodiment | 3 | 4 | 5 | 6 |
| Reaction temperature/DEG C | 150~159 | 171~180 | 160~170 | 160~170 |
| Reaction time/h | 7 | 7 | 6 | 8 |
| Yield/% | 96.8 | 97.1 | 96.9 | 97.1 |
| Product purity/% | 99.9 | 99.8 | 99.9 | 99.8 |
Embodiment 7~10, the type and dosage for changing ammonium salt transfer agent in embodiment 1, remaining process conditions is equal to
Embodiment 1, to obtain embodiment 7~10, gained total recovery is shown in Table 4.
Table 4
| Embodiment | 7 | 8 | 9 | 10 |
| Ammonium salt transfer agent model | PEG-6000 | T-5000 | D-4000 | M-2070 |
| Molecular weight | 5500~7000 | 5000 | 4000 | 2000 |
| Dosage/g | 1.19 | 1.19 | 2.38 | 2.38 |
| Mass fraction % | 1% | 1% | 2% | 2% |
| Yield/% | 97.2 | 97.1 | 97.5 | 97.5 |
| Product purity/% | 99.9 | 99.8 | 99.8 | 99.9 |
Comparative example 1, the use for cancelling ammonium salt transfer agent in embodiment 1, the i.e. dosage of PEG-8000 make 0g by 1.19g.
Remaining condition is equal to embodiment 1.Test acquired results：Product purity is 99.0%, yield 85.7%.
Reaction condition in comparative example 2~3, change embodiment 1, that is, reaction temperature, reaction time in changing the step 1),
Remaining is equal to embodiment 1, and to obtain comparative example 2~3, acquired results are shown in Table 5.
Table 5
| Comparative example | 2 | 3 |
| Reaction temperature/DEG C | 130~140 | 190~200 |
| Reaction time | 7 | 7 |
| Product purity/% | 99.3 | 99.1 |
| Yield/% | 84.9 | 85.1 |
Catalyst type (mole is constant, is still 1.1mol) in comparative example 4, change embodiment 1, i.e., will be in step 1)
The concentrated sulfuric acid make concentrated hydrochloric acid into, remaining process is equal to embodiment 1, to obtain corresponding comparative example 4.
Comparative example 4-1, the kettle liquid after the distillation of comparative example 4 is followed according to recycling mode of the present invention
Ring reacts, to obtain comparative example 4-1.
Catalyst type (mole is constant, is still 1.1mol) in comparative example 5, change embodiment 1, i.e., will be in step 1)
The concentrated sulfuric acid make concentrated phosphoric acid into, remaining process is equal to embodiment 1, to obtain corresponding comparative example 5.
Comparative example 5-1, the kettle liquid after the distillation of comparative example 5 is followed according to recycling mode of the present invention
Ring reacts, to obtain comparative example 5-1.
Acquired results are shown in Table 6.
Table 6
| Comparative example | 6 | 6-1 | 7 | 7-1 |
| Catalyst type | Concentrated hydrochloric acid | Concentrated hydrochloric acid | Concentrated phosphoric acid | Concentrated phosphoric acid |
| Catalyst circulation access times | 0 | 1 | 0 | 1 |
| Ammonium salt transfer agent additive amount/g | 1.19 | 0.015 | 1.19 | 0.015 |
| Product purity/% | 99.2 | 99.0 | 99.2 | 99.0 |
| Yield/% | 87.5 | 83.1 | 86.4 | 81.9 |
Remarks explanation：The hydrochloric acid is the concentrated hydrochloric acid of mass concentration >=37%；The phosphoric acid is mass concentration >=85%
Concentrated phosphoric acid.
Finally, it should also be noted that exemplified as above is only several specific embodiments of the present invention.Obviously, the present invention is not
It is limited to above example, also very many deformations.Those skilled in the art can directly lead from present disclosure
All deformations for going out or associating, are considered as protection scope of the present invention.
Claims (4)
- The cycle the preparation method of 1.N- methyl morpholines, it is characterized in that including the following steps：1) it, synthesizes：N methyldiethanol amine is added in a reservoir, is added with stirring sulfuric acid, N methyldiethanol amine：The molar ratio of sulfuric acid is 1： 1.1~1.5, reaction temperature is 150~180 DEG C, and to steam the water that reaction generates, the reaction time is 6~8 hours；Then cold But to room temperature, synthesis reaction solution is obtained；2), ammonium salt shifts：N methyldiethanol amine is added in synthesis reaction solution obtained by step 1) and ammonium salt transfer agent is added and carries out ammonium salt turn Move exchange reaction；The molar ratio of the N methyldiethanol amine and the N methyldiethanol amine in step 1) is 1：1, ammonium salt transfer agent with step It is rapid 1) in N methyldiethanol amine mass ratio be 1%~2%；It is 60~70 DEG C that ammonium salt, which shifts exchange reaction temperature, and the time is 30 ± 5 minutes；3) it, distills：Ammonium salt transfer reaction liquid obtained by step 2) is evaporated under reduced pressure, fraction and kettle liquid are respectively obtained, fraction is N- methyl Morpholine；4), circular response：Kettle liquid obtained by step 3) is reacted 6~8 hours at a temperature of 150~180 DEG C, steams the water that reaction generates；Then It is cooled to room temperature, obtains circular response kettle liquid；With circular response kettle liquid alternative steps 2) in synthesis reaction solution and ammonium salt transfer agent, then carry out step successively 2) distillation described in ammonium salt transfer and step 3) described in；The ammonium salt transfer agent is polyethylene glycol, T-5000, D-4000 or M-2070.
- 2. the cycle the preparation method of N-methylmorpholine according to claim 1, it is characterized in that：In the circular response of the step 4), with circular response kettle liquid alternative steps 2) in synthesis reaction solution and ammonium salt Transfer agent, and addition ammonium salt transfer agent is supplemented, the ammonium salt transfer agent for supplementing addition accounts for the ammonium salt transfer agent weight being added for the first time 0.6%~3%.
- 3. the cycle the preparation method of N-methylmorpholine according to claim 1 or 2, it is characterized in that：Polyethylene glycol is PEG-8000, PEG-6000.
- 4. the cycle the preparation method of N-methylmorpholine according to claim 3, it is characterized in that：Sulfuric acid in step 1) is the concentrated sulfuric acid of mass concentration >=98%.
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| US3155656A (en) * | 1960-04-14 | 1964-11-03 | Pennsalt Chemicals Corp | Novel process for nu-alkylmorpholines |
| CN100494186C (en) * | 2007-02-07 | 2009-06-03 | 浙江理工大学 | Process for preparing N-methyl morpholine |
| CN101638397A (en) * | 2009-06-22 | 2010-02-03 | 曲阜市圣泉催化应用科技有限公司 | Method for synthesizing N-methylmorpholine with granular solid superacid as catalyst |
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