N-substituted acrylic amide synthesized through amine oxide cracking elimination method and method

A technology of acrylamide and amine oxide, which is applied in chemical instruments and methods, preparation of carboxylic acid amides, preparation of organic compounds, etc., can solve the problems of high cracking reaction temperature and low utilization rate of equipment.

Inactive Publication Date: 2013-12-04
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Cleavage of β-dialkylamino-N-substituted propionic acid amide (II) by Hofmann has the disadvantages that the cracking reaction temperat

Method used

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  • N-substituted acrylic amide synthesized through amine oxide cracking elimination method and method
  • N-substituted acrylic amide synthesized through amine oxide cracking elimination method and method
  • N-substituted acrylic amide synthesized through amine oxide cracking elimination method and method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0079] The preparation of embodiment 1N-isopropylacrylamide (NIPAM)

[0080]

[0081] 1) Oxidation reaction of 3-dimethylamino-N-isopropylpropionamide (DMAPPA)

[0082] Add 157g of DMAPPA, 0.38g of sodium tungstate and 0.38g of sodium pyrophosphate into a four-necked flask with a reflux condenser, and add 119g of 30% hydrogen peroxide (excess 5% by mole) dropwise within 30 minutes at 70°C. After reacting at 70-75°C for 3h, cool down to 40°C, add 1.0g MnO 2 , at 50°C for 0.5h to remove excess hydrogen peroxide. Filter to remove MnO 2 , that is, the oxidation product 3-(N-isopropylpropionamide)-N,N-dimethyl-N-amine oxide (DMPPOA) aqueous solution (concentration: 65%). The degree of oxidation of DMAPPA was determined by liquid chromatography to be greater than 99%.

[0083] 2) Cleavage elimination reaction

[0084] Add 100g of the above-prepared amine oxide (DMPPOA) aqueous solution, 80g of solvent MPEG400 and 1g of inhibitor phenothiazine into a three-necked flask equipp...

Embodiment 2

[0085] The preparation of embodiment 2N-isopropylacrylamide (NIPAM)

[0086]

[0087] 1) Oxidation reaction of 3-diethylamino-N-isopropylpropionamide (DEAPPA)

[0088] Add 93g of DEAPPA, 0.18g of sodium tungstate and 0.18g of sodium pyrophosphate into a four-necked flask with a reflux condenser, and add 113g of 30% hydrogen peroxide dropwise within 30 minutes at 70°C (molar ratio is 1:2). After reacting at 70-75°C for 5h, add 1.0g MnO after cooling down to 40°C 2 , at 50°C for 0.5h to remove excess hydrogen peroxide. Filter to remove MnO 2 , that is, the oxidation product 3-(N-isopropylpropionamide)-N,N-diethyl-N-amine oxide (DEPPOA) in aqueous solution (concentration: 55%). The degree of oxidation of DEAPPA was determined by liquid chromatography to be greater than 99%.

[0089] 2) Cleavage elimination reaction

[0090] Add 100g of the above-mentioned prepared amine oxide DEPPOA aqueous solution, 60g of xylene and 1g of polymerization inhibitor phenothiazine into a th...

Embodiment 3－13

[0091] Example 3-13 Preparation of N-isopropylacrylamide (NIPAM)

[0092] The oxidation product 3-(N-isopropylpropionamide)-N,N-dimethyl-N-amine oxide (DMPPOA) aqueous solution (concentration: 65%) was prepared by the same method as in Example 1.

[0093] Add 100g of the above-prepared amine oxide (DMPPOA) aqueous solution, 1g of inhibitor phenothiazine, and different amounts of solvents into a three-necked flask equipped with a reflux condenser, and perform cracking and elimination reactions at different vacuum degrees and cracking temperatures. Collect fractions in cold traps, and measure the yield of N-isopropylacrylamide (NIPAM) in the bottom of the still by liquid chromatography after no liquid distills out or cracks for 1 hour.

[0094] The yields of NIPAM under different types of solvents and their amounts, cracking temperature and vacuum are listed in Table 1.

[0095] The influence of table 1 cleavage condition on NIPAM productive rate

[0096] Experiment n...

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Abstract

The invention relates to N-substituted acrylic amide synthesized through an amine oxide cracking elimination method and a method. The method is that the N-substituted acrylic amide is synthesized by beta-dialkyl amine-N-substituted acrylic amide (II) through the amine oxide cracking elimination method. The method includes the steps that (1), in water media, hydrogen peroxide performs oxidation on the beta-dialkyl amine-N-substituted acrylic amide (II), and then an amine oxide (III) solution is prepared; (2), a vacuum cracking elimination reaction is performed on the amide oxide in an aprotic solvent, so that N-mono-substituted acrylic amide or N, N-disubstituted acrylic amide is prepared. Beta-dialkyl amine-N-substituted acrylic amide (II) can be prepared with secondary amine R32NH as a protective agent and acrylic ester and alkylamine HNR1R2 as raw materials. According to the process route, the method has the advantages of being low in racking reaction temperature, high in yield and capable of preparing the mono-substituted acrylic amide and the disubstituted acrylic amide, and product monomers are not prone to self-polymerization.

Description

technical field [0001] The invention belongs to N-monosubstituted acrylamide and N,N-disubstituted acrylamide compounds and their preparation methods. Background technique [0002] N-substituted acrylamide is a kind of functional monomer, its molecular structure formula is: [0003] [0004] According to R 1 , R 2 The group structure, reactivity, and functionality are different, and acrylamide derivatives can be divided into: [0005] (1) N-monohydrocarbyl substituted acrylamide (R 1 = H), [0006] (2) N,N-dihydrocarbyl substituted acrylamide, [0007] (3) Functionally substituted acrylamide derivatives, such as reactive (N-methylolated acrylamide), cationic [0008] Ionic (acrylamidopropyldimethylamine), anionic (2-acrylamido-2-methylpropanesulfonic acid), surface active (acrylamide dodecylsulfonate), etc. [0009] Due to different substituents, N-hydrocarbyl substituted acrylamide compounds can still maintain water solubility, or become hydrophobic monomers, or h...

Claims

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Application Information

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IPC IPC(8): C07C231/12C07C233/09
Inventor 郭睿威张建华杜小燕李亚琼
Owner TIANJIN UNIV
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