CN110606834A - Preparation method of acryloyl morpholine - Google Patents
Preparation method of acryloyl morpholine Download PDFInfo
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- CN110606834A CN110606834A CN201910956759.XA CN201910956759A CN110606834A CN 110606834 A CN110606834 A CN 110606834A CN 201910956759 A CN201910956759 A CN 201910956759A CN 110606834 A CN110606834 A CN 110606834A
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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
- C07D295/16—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 acylated on ring nitrogen atoms
- C07D295/18—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 acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
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Abstract
The invention provides a preparation method of acryloyl morpholine, which comprises the following steps: to a device equipped with a condensing reflux, the raw materials were added with stirring: morpholine, acrylic anhydride, a polymerization inhibitor and a catalyst are stirred for 2 hours to obtain a mixture A; step two: and (3) filtering the mixture A obtained in the step one to obtain a filtrate, and distilling and collecting fractions at the temperature of 65-85 ℃ and under 8-12 kPa to obtain the acryloyl morpholine. The yield of the acryloyl morpholine prepared by the method is extremely high and is more than 90 percent; and the purity of the product is higher than 98.0 percent as measured by gas chromatography, thus breaking through the technical problems of lower yield and more byproducts in the prior art. In addition, the preparation method disclosed by the invention is simple and convenient in process, mild in preparation temperature, and hardly generates three wastes, so that the preparation method is an efficient and environment-friendly synthesis method, and is suitable for large-scale popularization and application.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of acryloyl morpholine.
Background
N-acryloyl morpholine is a disubstituted acrylamide derivative, and is a synthetic resin modifier and an active diluent with excellent performance. Due to the double bond and morpholine group, the compound is active in chemical property, and is commonly used for polymer carriers of gel chromatography, semi-permeable membrane preparation of plasma separation, capillary electrophoresis, drug delivery application, synthesis of cross-linked networks of gel-phase peptides and the like. Poly-acryloyl morpholine obtained by polymerization of acryloyl morpholine as a monomer contains hydrophilic morpholine groups and hydrophobic carbon chain structures in molecules, so that the poly-acryloyl morpholine can be dissolved in water and most of organic solvents, and has good biocompatibility. In addition, N-acryloyl morpholine is nontoxic, and is the best choice for replacing toxic acrylamide monomers and polymerization products thereof in certain water treatment fields.
At present, the synthesis method of N-acryloyl morpholine in the prior art mainly comprises two methods. One method is to cleave 3-substituted propionyl morpholine to prepare: JP111000375 synthesizes N-acryloyl morpholine by carrying out vacuum thermal cracking on 3-morpholinyl propionyl morpholine, but the highest yield is only 29%; the patent CN201410028087.3 is improved on the basis, 3-morpholino is changed into diethylamino, so that the problem that 3-morpholinopropionyl morpholine is not easy to separate from a product acryloyl morpholine is solved, but a large amount of byproducts still exist in the product, and the product is not easy to purify again; patent CN201711372683.3 uses dioctadecylamine as raw material to react with acrylate, wherein a vacuum cracking process is required, which is complicated and the yield can only reach 70%. Another method is an acryloyl chloride method: patents US2683703A and CN1345302A all use acrylic acid to prepare acryloyl chloride, and the obtained acryloyl chloride reacts with morpholine to produce acryloyl morpholine, which has the advantages of simple process flow, and disadvantages of the method including many by-products, low yield, high corrosivity, and difficult separation.
Therefore, it is urgently needed to develop a preparation method of N-acryloyl morpholine with simple process, high yield and high purity.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of acryloyl morpholine, which comprises the following steps:
the method comprises the following steps: to a device equipped with a condensing reflux, the raw materials were added with stirring: morpholine, acrylic anhydride, a polymerization inhibitor and a catalyst are stirred for 2 hours to obtain a mixture A;
step two: and (3) filtering the mixture A obtained in the step one to obtain a filtrate, and distilling and collecting fractions at the temperature of 65-85 ℃ and under 8-12 kPa to obtain the acryloyl morpholine.
As a preferable technical scheme, the preparation method of the acryloyl morpholine comprises the following steps:
the method comprises the following steps: to a device equipped with a condensing reflux, at room temperature, the starting materials were added with stirring: stirring morpholine, acrylic anhydride, a polymerization inhibitor, a catalyst and a solvent for 1-3 hours to obtain a mixture A;
step two: and (3) filtering the mixture A obtained in the step one to obtain a filtrate, carrying out desolventizing treatment, and distilling and collecting fractions at the temperature of 65-85 ℃ and under 8-12 kPa to obtain the acryloyl morpholine.
As a preferred technical scheme, the equivalent ratio of morpholine to acrylic anhydride is 1: (1-2).
As a preferable technical scheme, the polymerization inhibitor is selected from one or more of methoxyphenol, phenothiazine, 4-tert-butyl catechol, p-hydroxyanisole, hydroquinone, benzoquinone, nitrobenzene, picric acid and cuprous chloride.
As a preferred technical scheme, the mass ratio of morpholine to polymerization inhibitor is 1: (0.001-0.1).
As a preferred technical scheme, the catalyst is an acid catalyst and/or a basic catalyst.
As a preferred technical scheme, the acid catalyst is selected from one or more of concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid and acetic anhydride; the alkaline catalyst is selected from one or more of 4-dimethylamino pyridine, potassium tert-butoxide, sodium bicarbonate, sodium carbonate, sodium methoxide, sodium hydroxide, potassium hydroxide and calcium hydroxide.
As a preferred technical scheme, the mass ratio of morpholine to catalyst is 1: (0.005-0.2).
As a preferable technical scheme, the solvent is selected from one or more of acetone, butanone, methyl isobutyl ketone, dichloromethane, trichloromethane, carbon tetrachloride, chloroform, chlorobenzene, n-hexane, neohexane, cyclohexane, 2-methylpentane, 3-methylpentane and 2, 3-dimethylbutane.
As a preferable technical scheme, the mass ratio of the solvent to the morpholine is (0-5): except for 1 and 0.
Has the advantages that: the preparation method of acryloyl morpholine takes morpholine and acrylic anhydride as raw materials, and adds polymerization inhibitor, a small amount of catalyst and the like to prepare the acryloyl morpholine. The yield of the acryloyl morpholine prepared by the method is extremely high and is more than 90 percent; the purity of the product measured by gas chromatography is higher, more than 98.0 percent, and the technical problems of lower yield and more byproducts in the prior art are solved. In addition, the preparation method disclosed by the invention is simple and convenient in process, mild in preparation temperature, and hardly generates three wastes (waste water, waste gas and solid waste), is an efficient and environment-friendly synthesis method, and is suitable for large-scale popularization and application.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the technical problem, the invention provides a preparation method of acryloyl morpholine, which comprises the following steps:
the method comprises the following steps: to a device equipped with a condensing reflux, the raw materials were added with stirring: stirring morpholine, acrylic anhydride, a polymerization inhibitor and a catalyst for 1-3 hours to obtain a mixture A;
step two: and (3) filtering the mixture A obtained in the step one to obtain a filtrate, and distilling and collecting fractions at the temperature of 65-85 ℃ and under 8-12 kPa to obtain the acryloyl morpholine.
The reaction equation of the method is shown as follows:
< morpholine >
Morpholine, the english name morpholine, also known as morphine, CAS number: 110-91-8, is colorless oily liquid at normal temperature. It is mainly used for preparing rubber vulcanization accelerator, and also used for synthesizing surfactant, textile printing and dyeing auxiliary, medicine and pesticide. Morpholine is also used as a metal corrosion inhibitor and rust inhibitor, and is also a solvent for dyes, resins, waxes, shellac, casein and the like.
The morpholine was purchased from Nanjing blue whitening chemical Co.
< acrylic anhydride >
Acrylic anhydride, english name Acrylic anhydride, CAS number: 2051-76-5 is an important fine organic chemical intermediate, and can be widely applied to the fields of medicines, pesticides, chemical industry and the like.
In a preferred embodiment, the equivalent ratio of morpholine to acrylic anhydride is 1: (1-2).
In a more preferred embodiment, the equivalent ratio of morpholine to acrylic anhydride is 1: 1.1.
the acrylic anhydride was purchased from Shanghai Vast chemical Co.
In the present invention, the equivalent ratio of morpholine to acrylic anhydride, i.e., the molar ratio of morpholine to acrylic anhydride, refers to the ratio of the amount of morpholine to the amount of acrylic anhydride used in the reaction.
< polymerization inhibitor >
The polymerization inhibitor is an industrial aid, and is generally used to prevent the progress of polymerization. The inhibitor molecules react with the chain radicals to form non-radical species or low reactive radicals that cannot initiate, thereby terminating the polymerization.
In a preferred embodiment, the polymerization inhibitor is selected from one or more of methoxyphenol, phenothiazine, 4-tert-butylcatechol, p-hydroxyanisole, hydroquinone, benzoquinone, nitrobenzene, picric acid and cuprous chloride.
In a more preferred embodiment, the polymerization inhibitor is phenothiazine.
(phenothiazine)
Phenothiazine, english name Phenothiazine, CAS number: 92-84-2, yellow to green gray powder or flaky crystal. It is readily soluble in benzene, soluble in ether and hot acetic acid, slightly soluble in alcohol and mineral oil, and practically insoluble in petroleum ether; chloroform and water.
In a preferred embodiment, the mass ratio of morpholine to polymerization inhibitor is 1: (0.001-0.1).
In a more preferred embodiment, the mass ratio of morpholine to polymerization inhibitor is 1: 0.006.
the phenothiazine was purchased from Ningbos Mike pharmaceuticals, Inc.
< catalyst >
In a preferred embodiment, the mass ratio of morpholine to catalyst is 1: (0.005-0.2).
In a more preferred embodiment, the mass ratio of morpholine to catalyst is 1: 0.005.
in a preferred embodiment, the catalyst is an acidic catalyst and/or a basic catalyst.
(acid catalyst)
In a preferred embodiment, the acidic catalyst is selected from one or more of concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid, and acetic anhydride.
In a more preferred embodiment, the acidic catalyst is concentrated sulfuric acid.
Concentrated sulfuric acid
In a further preferred embodiment, the concentrated sulfuric acid is a 98% concentrated sulfuric acid by mass concentration.
In a more preferred embodiment, the order of addition of the starting materials is: morpholine, phenothiazine, concentrated sulfuric acid and acrylic anhydride are added in sequence; the adding temperature of the morpholine, the phenothiazine and the concentrated sulfuric acid is room temperature; the adding temperature of the acrylic anhydride is 40-50 ℃; the addition mode of the acrylic anhydride is dropwise addition; the dropping time of the acrylic anhydride is 0.5-1 h.
In a further preferred embodiment, the addition temperature of the acrylic anhydride is 45 ℃; the dropping time of the acrylic anhydride is 0.5 h.
(basic catalyst)
In a preferred embodiment, the basic catalyst is selected from one or more of 4-dimethylaminopyridine, potassium tert-butoxide, sodium bicarbonate, sodium carbonate, sodium methoxide, sodium hydroxide, potassium hydroxide and calcium hydroxide.
In a more preferred embodiment, the basic catalyst is 4-dimethylaminopyridine and/or potassium tert-butoxide.
The invention also provides another preparation method of acryloyl morpholine, which comprises the following steps:
the method comprises the following steps: to a device equipped with a condensing reflux, at room temperature, the starting materials were added with stirring: stirring morpholine, acrylic anhydride, a polymerization inhibitor, a catalyst and a solvent for 1-3 hours to obtain a mixture A;
step two: and (3) filtering the mixture A obtained in the step one to obtain a filtrate, carrying out desolventizing treatment, and distilling and collecting fractions at the temperature of 65-85 ℃ and under 8-12 kPa to obtain the acryloyl morpholine.
In a preferred embodiment, the mass ratio of the solvent to morpholine is (0-5): except for 1 and 0.
In a more preferred embodiment, the mass ratio of the solvent to morpholine is 2.5: 1.
in a preferred embodiment, the solvent is selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, methylene chloride, chloroform, carbon tetrachloride, chloroform, chlorobenzene, n-hexane, neohexane, cyclohexane, 2-methylpentane, 3-methylpentane, 2, 3-dimethylbutane, and combinations thereof.
The desolventizing treatment according to the present invention is not particularly limited, and any treatment method known to those skilled in the art for removing the solvent from the filtrate may be used.
4-dimethylaminopyridine
4-dimethylaminopyridine, english name 4-diamminepolypyridine (dmap), CAS number: 1122-58-3, which is a white crystalline powder.
In a further preferred embodiment, the catalyst is 4-dimethylaminopyridine; the solvent is dichloromethane.
In a more preferred embodiment, the order of addition of the starting materials is: adding acrylic anhydride, phenothiazine, 4-dimethylaminopyridine, dichloromethane and morpholine in sequence; the addition interval of the morpholine and the dichloromethane is 0.5-1 h.
In a further preferred embodiment, the morpholine and dichloromethane are added at an interval of 0.5 h.
The 4-dimethylaminopyridine was purchased from Ningbo Salon chemical Co.
Potassium tert-butoxide
Potassium tert-butoxide, english name Potassium t-butoxide (ktb), CAS number: 865-47-4, is an important organic base.
In a further preferred embodiment, the catalyst is potassium tert-butoxide; the solvent is acetone.
In a more preferred embodiment, the order of addition of the starting materials is: morpholine, phenothiazine, potassium tert-butoxide, acetone and acrylic anhydride are added in sequence; the addition interval of the acrylic anhydride and the acetone is 0.5-1 h.
In a further preferred embodiment, the addition of acrylic anhydride and acetone is separated by 0.5 h.
The potassium tert-butoxide was purchased from Zhonghua (Hangzhou) science and technology Co.
The synthesis method of N-acryloyl morpholine in the prior art mainly comprises a preparation method of cracking 3-substituent propionyl morpholine and an acryloyl chloride method. Both methods have the defects of low yield, more byproducts, complex preparation method, low yield, high corrosivity, difficult separation and the like.
The inventor creatively takes morpholine and acrylic anhydride as raw materials, adds a small amount of auxiliary agent, and improves the purity and yield of the prepared acryloyl morpholine to a certain extent. And the inventors found that when morpholine to acrylic anhydride equivalent ratio used is 1: (1-2), particularly 1: 1.1, the purity of the obtained acryloyl morpholine is further improved. The inventor speculates that the reason may be that nucleophilic nitrogen atom with stronger activity in morpholine is combined with one end of unsaturated chemical bond with partial positive charge in acrylic anhydride under the action of catalyst, so that one end of acrylic anhydride with negative charge is separated to form acryloyl morpholine; meanwhile, because the unsaturated chemical bond in the acrylic anhydride has a delocalized chemical bond at one end with partial positive charge, the steric effect of the delocalized chemical bond also limits the attack of nucleophilic nitrogen atoms in morpholine on carbon atoms in the acrylic anhydride, and prevents the formation of byproducts. However, how to determine the proportional relationship between the reactants and the auxiliary agents, the types of the auxiliary agents, the preparation method, the process parameters and the like is a great problem to be solved by the inventor.
The inventor finds that when the mass ratio of morpholine to polymerization inhibitor is 1: (0.001-0.1), wherein the mass ratio of morpholine to catalyst is 1: (0.005-0.2), the purity of the obtained product is further improved. The inventor believes that under the action of an auxiliary agent such as a catalyst, acryloyl morpholine monomer is easy to polymerize to form polyacrylyl morpholine, the purity of the product is affected, and the difficulty of purification is increased; when the amount of the added polymerization inhibitor is small and the amount of the added catalyst is large, a polymer obtained by polymerizing a part of acryloyl morpholine monomers still exists in the obtained product, and the excessive amount of the catalyst can increase the attack probability of nucleophilic nitrogen atoms in morpholine on carbon atoms in acrylic anhydride, so that the number of byproducts is increased; when the added polymerization inhibitor is more and the catalyst is less, the yield of the acryloyl morpholine in the obtained product is too low, and excessive polymerization inhibitor and other byproducts are introduced, so that the difficulty of post-treatment is increased, and the purity of the finally obtained product is influenced.
By controlling the mass ratio of the reactants and the auxiliary agent, although the purity of the product is improved to a certain extent, a small amount of by-products still exist to influence the purity of the product. The inventor unexpectedly finds that when the distillation pressure is selected to be 10kPa, and the distillation temperature range is selected to be 70-80 ℃, the yield and the purity of the obtained product are remarkably improved. The inventor believes that morpholine, acrylic anhydride and polymerization inhibitor used in the preparation process may be affected by the catalyst, and a certain amount of byproducts which are difficult to separate are generated; meanwhile, when the distillation temperature is too high, the prepared acryloyl morpholine is more prone to generate polymers to influence the purity of the product, and the product obtained by distillation at too low temperature contains less acryloyl morpholine and too many byproducts; when distillation is adopted to collect the fraction of 70-80 ℃ under 10kPa, the high-purity acryloyl morpholine fraction is collected, a small amount of by-products are left in the filtrate, and the yield and the purity of the obtained product are ensured.
The preparation method of the acryloyl morpholine provided by the invention is a high-efficiency and environment-friendly synthesis method, wherein morpholine and acrylic anhydride are used as raw materials, a small amount of auxiliary agent is added, and the high-purity acryloyl morpholine is prepared.
The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.
Examples
Example 1
Embodiment 1 of the present invention provides a method for preparing acryloyl morpholine, comprising the following steps:
the method comprises the following steps: to a device equipped with a condensing reflux, the raw materials were added with stirring: morpholine, acrylic anhydride, a polymerization inhibitor and a catalyst are stirred for 2 hours to obtain a mixture A;
step two: and (3) filtering the mixture A obtained in the step one to obtain a filtrate, and distilling and collecting fractions at the temperature of 70-80 ℃ and under 10kPa to obtain the acryloyl morpholine.
The amount of morpholine is 0.23 mol; the amount of the substance of acrylic anhydride was 0.25 mol.
The polymerization inhibitor is phenothiazine; the mass of the phenothiazine is 0.12 g.
The catalyst is an acidic catalyst; the acid catalyst is concentrated sulfuric acid; the concentrated sulfuric acid is 98% concentrated sulfuric acid by mass concentration; the mass of the concentrated sulfuric acid is 0.1 g.
The adding sequence of the raw materials is as follows: morpholine, phenothiazine, concentrated sulfuric acid and acrylic anhydride are added in sequence; the adding temperature of the morpholine, the phenothiazine and the concentrated sulfuric acid is room temperature; the adding temperature of the acrylic anhydride is 45 ℃; the addition mode of the acrylic anhydride is dropwise addition; the dropping time of the acrylic anhydride is 0.5 h.
Example 2
The embodiment 2 of the invention provides a preparation method of acryloyl morpholine, which comprises the following steps:
the method comprises the following steps: to a device equipped with a condensing reflux, at room temperature, the starting materials were added with stirring: morpholine, acrylic anhydride, a polymerization inhibitor, a catalyst and a solvent are stirred for 2 hours to obtain a mixture A;
step two: and (3) filtering the mixture A obtained in the step one to obtain a filtrate, carrying out desolventizing treatment, and distilling and collecting fractions at the temperature of 70-80 ℃ and under 10kPa to obtain the acryloyl morpholine.
The amount of morpholine is 0.23 mol; the amount of the substance of acrylic anhydride was 0.25 mol.
The polymerization inhibitor is phenothiazine; the mass of the phenothiazine is 0.12 g.
The catalyst is a basic catalyst; the alkaline catalyst is 4-dimethylaminopyridine; the mass of the 4-dimethylaminopyridine was 0.1 g.
The solvent is dichloromethane; the mass of the solvent was 50 g.
The adding sequence of the raw materials is as follows: adding acrylic anhydride, phenothiazine, 4-dimethylaminopyridine, dichloromethane and morpholine in sequence; the addition interval of morpholine and dichloromethane was 0.5 h.
Example 3
Embodiment 3 of the present invention provides a method for preparing acryloyl morpholine, comprising the following steps:
the method comprises the following steps: to a device equipped with a condensing reflux, at room temperature, the starting materials were added with stirring: morpholine, acrylic anhydride, a polymerization inhibitor, a catalyst and a solvent are stirred for 2 hours to obtain a mixture A;
step two: and (3) filtering the mixture A obtained in the step one to obtain a filtrate, carrying out desolventizing treatment, and distilling and collecting fractions at the temperature of 70-80 ℃ and under 10kPa to obtain the acryloyl morpholine.
The amount of morpholine is 0.23 mol; the amount of the substance of acrylic anhydride was 0.25 mol.
The polymerization inhibitor is phenothiazine; the mass of the phenothiazine is 0.12 g.
The catalyst is a basic catalyst; the alkaline catalyst is potassium tert-butoxide; the mass of the potassium tert-butoxide is 0.1 g.
The solvent is acetone; the mass of the solvent was 50 g.
The adding sequence of the raw materials is as follows: morpholine, phenothiazine, potassium tert-butoxide, acetone and acrylic anhydride are added in sequence; the addition interval of the acrylic anhydride and the acetone is 0.5 h.
Comparative example 1
Comparative example 1 of the present invention provides a preparation method of acryloyl morpholine, which is similar to example 1, except that the mass of acrylic anhydride is replaced by 0.6mol from 0.25 mol.
Comparative example 2
Comparative example 2 of the present invention provides a production method of acryloyl morpholine, which is similar to example 1, except that the mass of phenothiazine was changed from 0.12g to 0.3 g.
Comparative example 3
Comparative example 3 of the present invention provides a method for producing acryloyl morpholine, which is similar to example 1, except that the mass of the concentrated sulfuric acid is changed from 0.1g to 5 g.
Comparative example 4
Comparative example 4 of the present invention provides a preparation method of acryloyl morpholine, which is similar to example 1, except that the temperature range of the fraction collected in the second step is changed from 70-80 ℃ to 55-65 ℃.
Comparative example 5
Comparative example 5 of the present invention provides a preparation method of acryloyl morpholine, which is similar to example 1, except that the temperature range of the fraction collected in the second step is changed from 70-80 ℃ to 85-95 ℃.
Comparative example 6
Comparative example 6 of the present invention provides a preparation method of acryloyl morpholine, which is similar to example 1, except that the pressure of the fraction collected in step two is changed from 10kpa to 5 kpa.
Comparative example 7
Comparative example 7 of the present invention provides a preparation method of acryloyl morpholine, which is similar to example 1, except that the pressure of the fraction collected in step two is changed from 10kpa to 15 kpa.
Comparative example 8
Comparative example 8 of the present invention provides a preparation method of acryloyl morpholine, which is similar to example 2, except that the mass of acrylic anhydride is replaced by 0.6mol from 0.25 mol.
Comparative example 9
Comparative example 9 of the present invention provides a production method of acryloyl morpholine, which is similar to example 2, except that the mass of phenothiazine was changed from 0.12g to 0.3 g.
Comparative example 10
Comparative example 10 of the present invention provides a preparation method of acryloyl morpholine, which is similar to example 2, except that the mass of 4-dimethylaminopyridine was replaced with 5g from 0.1 g.
Evaluation of Performance
1. Yield: the acryloyl morpholine obtained in the examples 1-3 and the comparative examples 1-10 is subjected to the following formula: (actual yield/theoretical yield of product). times.100%, the yield of acryloyl morpholine obtained was calculated and the results are shown in Table 1.
2. Purity: the acryloyl morpholines obtained in examples 1-3 and comparative examples 1-10 were tested for purity by GC (gas chromatography), and the results are shown in Table 1.
TABLE 1 test results
| Examples | Yield/%) | Purity/%) |
| Example 1 | 93.12 | 99.30 |
| Example 2 | 91.89 | 98.80 |
| Example 3 | 90.35 | 99.00 |
| Comparative example 1 | 85.43 | 97.65 |
| Comparative example 2 | 88.65 | 98.32 |
| Comparative example 3 | 80.53 | 96.25 |
| Comparative example 4 | 55.52 | 63.45 |
| Comparative example 5 | 69.63 | 71.12 |
| Comparative example 6 | 71.26 | 73.50 |
| Comparative example 7 | 68.35 | 67.10 |
| Comparative example 8 | 84.13 | 95.83 |
| Comparative example 9 | 86.77 | 96.97 |
| Comparative example 10 | 77.32 | 94.65 |
The combination of the above experimental results shows that: the preparation method of acryloyl morpholine provided by the invention takes morpholine and acrylic anhydride as raw materials, and adds a small amount of auxiliary agent to prepare the acryloyl morpholine. The acryloyl morpholine prepared by the method has high yield which is more than 90%; and the product purity is higher, more than 98.0 percent, measured by GC (gas chromatography). In addition, the preparation method disclosed by the invention is simple and convenient in process, mild in preparation temperature, and hardly generates three wastes (waste water, waste gas and solid waste), is an efficient and environment-friendly synthesis method, and is suitable for large-scale popularization and application.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. The invention is not limited to the embodiments described above, but rather, many modifications and variations may be made by one skilled in the art without departing from the scope of the invention.
Claims (10)
1. The preparation method of acryloyl morpholine is characterized by comprising the following steps:
the method comprises the following steps: to a device equipped with a condensing reflux, the raw materials were added with stirring: stirring morpholine, acrylic anhydride, a polymerization inhibitor and a catalyst for 1-3 hours to obtain a mixture A;
step two: and (3) filtering the mixture A obtained in the step one to obtain a filtrate, and distilling and collecting fractions at the temperature of 65-85 ℃ and under 8-12 kPa to obtain the acryloyl morpholine.
2. The process for the preparation of acryloyl morpholine according to claim 1, comprising the steps of:
the method comprises the following steps: to a device equipped with a condensing reflux, at room temperature, the starting materials were added with stirring: stirring morpholine, acrylic anhydride, a polymerization inhibitor, a catalyst and a solvent for 1-3 hours to obtain a mixture A;
step two: and (3) filtering the mixture A obtained in the step one to obtain a filtrate, carrying out desolventizing treatment, and distilling and collecting fractions at the temperature of 65-85 ℃ and under 8-12 kPa to obtain the acryloyl morpholine.
3. The process for the preparation of acryloyl morpholine according to claim 1 or 2, wherein the equivalent ratio of morpholine to acrylic anhydride is 1: (1-2).
4. The method of claim 1 or 2, wherein the polymerization inhibitor is one or more selected from methoxyphenol, phenothiazine, 4-tert-butylcatechol, p-hydroxyanisole, hydroquinone, benzoquinone, nitrobenzene, picric acid, and cuprous chloride.
5. The method for producing acryloylmorpholine according to claim 1 or 2, wherein the mass ratio of morpholine to polymerization inhibitor is 1: (0.001-0.1).
6. The process for producing acryloylmorpholine according to claim 1 or 2, wherein the catalyst is an acidic catalyst and/or a basic catalyst.
7. The method for preparing acryloyl morpholine according to claim 6, wherein the acidic catalyst is selected from one or more of concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid, acetic anhydride; the alkaline catalyst is selected from one or more of 4-dimethylamino pyridine, potassium tert-butoxide, sodium bicarbonate, sodium carbonate, sodium methoxide, sodium hydroxide, potassium hydroxide and calcium hydroxide.
8. The method for producing acryloylmorpholine according to claim 1 or 2, wherein the mass ratio of morpholine to catalyst is 1: (0.005-0.2).
9. The method for preparing acryloyl morpholine according to claim 2, wherein the solvent is selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, methylene chloride, chloroform, carbon tetrachloride, chloroform, chlorobenzene, n-hexane, neohexane, cyclohexane, 2-methylpentane, 3-methylpentane, 2, 3-dimethylbutane, and combinations thereof.
10. The method for preparing acryloyl morpholine according to claim 2 or 9, wherein the mass ratio of the solvent to morpholine is (0-5): except for 1 and 0.
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| CN201910956759.XA CN110606834A (en) | 2019-10-10 | 2019-10-10 | Preparation method of acryloyl morpholine |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159490A (en) * | 2020-10-16 | 2021-01-01 | 中国医学科学院药用植物研究所 | Polymer containing 2-morpholinyl ethyl methacrylate monomer unit and application |
| CN112557582A (en) * | 2020-12-17 | 2021-03-26 | 南通恒华粘合材料科技有限公司 | Method for measuring hydroxyl value of polyester polyol |
| CN114989114A (en) * | 2022-06-02 | 2022-09-02 | 杭州福斯特电子材料有限公司 | Synthesis method of N-acryloyl morpholine and photocuring composition |
| CN115925652A (en) * | 2022-12-08 | 2023-04-07 | 南通沃兰化工有限公司 | Preparation method of acryloyl morpholine |
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2019
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159490A (en) * | 2020-10-16 | 2021-01-01 | 中国医学科学院药用植物研究所 | Polymer containing 2-morpholinyl ethyl methacrylate monomer unit and application |
| CN112159490B (en) * | 2020-10-16 | 2022-03-11 | 中国医学科学院药用植物研究所 | Polymer containing 2-morpholinyl ethyl methacrylate monomer unit and application |
| CN112557582A (en) * | 2020-12-17 | 2021-03-26 | 南通恒华粘合材料科技有限公司 | Method for measuring hydroxyl value of polyester polyol |
| CN114989114A (en) * | 2022-06-02 | 2022-09-02 | 杭州福斯特电子材料有限公司 | Synthesis method of N-acryloyl morpholine and photocuring composition |
| CN115925652A (en) * | 2022-12-08 | 2023-04-07 | 南通沃兰化工有限公司 | Preparation method of acryloyl morpholine |
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