CN103992294A - Synthesis method of acrylamide type reactive diluent - Google Patents

Synthesis method of acrylamide type reactive diluent Download PDF

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Publication number
CN103992294A
CN103992294A CN201410231383.3A CN201410231383A CN103992294A CN 103992294 A CN103992294 A CN 103992294A CN 201410231383 A CN201410231383 A CN 201410231383A CN 103992294 A CN103992294 A CN 103992294A
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acrylic amide
reactive thinner
synthetic method
amide reactive
amides
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CN201410231383.3A
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CN103992294B (en
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宋国强
罗九艳
曹引梅
张文楠
姚昶旭
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CHANGZHOU XIAOGUO INFORMATION SERVICES Co.,Ltd.
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Changzhou University
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

The invention relates to a synthesis method of an acrylamide type reactive diluent and belongs to the field of organic synthesis. The synthesis method is performed according to the following steps: adding an amide type compound, a formaldehyde solution (or introducing formaldehyde gas) and a catalyst, maintaining the temperature at 80-90 DEG C under stirring conditions and reacting for 15-20h so as to obtain a crude product of the acrylamide type reactive diluent. After the end of reaction, an organic solvent is added for azeotropic dehydration, the catalyst is removed by filtering, a proper amount of polymerization inhibitor is finally added and reduced pressure distillation is performed so as to obtain a product of the acrylamide type reactive diluent. The synthesis method disclosed by the invention can overcome numerous shortcomings of the prior art and realize high yield and simple steps, wherein the yield is about 80% and the purity is more than 98%.

Description

A kind of synthetic method of acrylic amide reactive thinner
 
Technical field
The invention belongs to organic synthesis neighborhood, what relate to is a kind of synthetic method of acrylic amide reactive thinner.
Background technology
Reactive thinner is one of key ingredient of UV solidify material, and consumption is large.Research and practical application show, carbon-carbon double bond in acrylic amide reactive thinner is compared with other esters of acrylic acid reactive thinner, there is good polymerization, reactive behavior is high, be easy to carry out homopolymerization or copolyreaction, in UV solidify material, be with a wide range of applications, as be applied to the fields such as photoresist material, 3D printed material, occulter, finishing material, Drug re-lease materials, scavenging agent and foodstuff additive, can obviously improve photosensitive property and the quality product of this series products.
 
-N (R 1r 2) be all kinds of secondary-amine compounds
Formula 1 acrylic amide reactive thinner chemical structure
According to existing bibliographical information, synthesizing generally under stopper, acid binding agent effect of N-acryloyl morpholine, acrylate chloride and morpholine are that raw material single step reaction makes, then under vacuum condition, reaction solution are carried out to rectifying purifying and obtain N-acryloyl morpholine, and its reaction scheme is as shown in the formula shown in 2:
Traditional synthetic route of formula 2 acryloyl morpholines
Although the product yield that this synthetic method obtains is higher, owing to using acrylate chloride as raw material, the hydrogenchloride that reaction generates is large to the corrodibility of equipment, need to be processed it, product aftertreatment is comparatively complicated, and production cost is also higher, is not suitable for suitability for industrialized production application.
According to existing bibliographical information, N, N-diethyl acrylamide (DEAA) can be obtained by 3-methoxylation compound thermo-cracking: 3-methoxyl group-N, the cracking under vacuum condition of N-diethyl propionic acid amide, split product is methyl alcohol and DEAA.Through second distillation, obtain purer DEAA.Its reaction scheme is as shown in the formula shown in 3:
Formula 3 N, the synthetic route of N-diethyl acrylamide
The total recovery that this synthetic method obtains product is 78% left and right, and the method cracking temperature is up to 400 DEG C, and product purity is low, raw material sources difficulty.
 
Summary of the invention
The object of the present invention is to provide the synthetic novel method of a kind of acrylic amide reactive thinner, can overcome all deficiencies that exist in prior art, its advantage has: adopt second (or third) amides and formaldehyde synthesis of acrylamide class reactive thinner.The method has reaction conditions gentleness, purification refine technique is simple, product stable, the easily separated and difficult advantages such as polymerization that occur, and is applicable to the requirement of suitability for industrialized production.
For completing the object of the invention, adopt following technical scheme:
A synthetic method for acrylic amide reactive thinner, is characterized in that, taking second (or third) amides, formaldehyde as raw material, obtains target product acrylic amide reactive thinner.
Its reaction formula of described method is as shown in the formula shown in 4:
R=H or CH 3,-N (R 1r 2) be all kinds of secondary-amine compounds
R 1,r 2=alkane, ether
Formula 4 acrylic amide reactive thinner new synthesis routes
Formula 5 acryloyl morpholine new synthesis routes
Formula 6 N, N-diethyl acrylamide new synthesis route
Formula 7 methacrylic morpholide new synthesis routes
A synthetic method for acrylic amide reactive thinner, carry out according to following step:
1) add amides, formaldehyde solution (or passing into formaldehyde gas), catalyzer, under agitation condition, 80 ~ 90 DEG C of holding temperatures, react 15 ~ 20 hours, obtain acrylic amide reactive thinner crude product.After reaction finishes, add organic solvent azeotropic dehydration, filter and remove catalyzer, finally add appropriate stopper, underpressure distillation, obtains acrylic amide reactive thinner product.
 
Described amides ( ) in secondary amine structure be specially: , , , deng;
Described R is H or methyl.
Described R 1, R 2for alkane, ether;
Described amides and the mol ratio of formaldehyde are 1.0:1.0 ~ 1.0:4.0;
Described catalyzer is highly basic, comprises sodium hydroxide, sodium methylate, sodium tert-butoxide, potassium hydroxide etc., preferably sodium hydroxide;
Described raw material amides compounds and the mol ratio of highly basic are 1.0:0.2 ~ 1.0:1.0;
Described raw material amides and the temperature of reaction of formaldehyde are 80 DEG C ~ 90 DEG C;
Described organic solvent is dimethylbenzene, benzene, toluene, hexanaphthene, sherwood oil, preferably hexanaphthene;
Described stopper is Resorcinol, benzoquinones, thiodiphenylamine, oil of mirbane, picric acid, MEHQ, butyl-catechol, 4-methoxyphenol, preferably MEHQ;
While stating stopper in the use, generally the mol ratio of stopper and amides is controlled to (0.0025 ~ 0.025): in 1 scope;
The present invention has overcome many deficiencies of prior art, and yield is high, and step is simple, and yield is about 80%, and purity is greater than 98%.The method, compared with prior synthesizing method, comprises following advantage:
1) with the comparison of traditional acrylate chloride method, the acrylic amide reactive thinner that the inventive method obtains does not use acyl chlorides raw material, produces without hydrogen chloride gas, little to the corrodibility of equipment.
2), compared with the high-temperature cracking method of document, have that temperature of reaction is low, product yield is high, the feature of good product quality.
3) the inventive method technical process is brief, and raw material is easy to get, and equipment is simple, and reaction conditions is easy to control.
4) present method reaction conditions gentleness, purification refine technique is simple, and product is stablized easily separated, is difficult for occurring polymerism.
 
Embodiment
Describe the present invention with specific embodiment.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
 
The preparation of embodiment 1 acryloyl morpholine
In 100mL four-hole boiling flask, add acetyl morphine 5.58g(0.043mol), formaldehyde solution 3.50g(0.043mol), catalyst n aOH 0.35g(0.0086mol), maintain the temperature at 85 DEG C ~ 90 DEG C, react 15 ~ 20 hours, obtain acryloyl morpholine crude product.After reaction finishes, add hexanaphthene 30ml azeotropic dehydration, finally add 0.012g MEHQ (0.0001mol) again, underpressure distillation, obtains acryloyl morpholine 4.95g, and yield is 81.2%, purity 98.1%.
 
The preparation of embodiment 2 acryloyl morpholines
In 100mL four-hole boiling flask, add acetyl morphine 4.62g(0.036mol), formaldehyde solution 11.62g(0.140mol), catalyst n aOH 1.44g(0.036mol), maintain the temperature at 85 DEG C ~ 90 DEG C, react 15 ~ 20 hours, obtain acryloyl morpholine crude product.After reaction finishes, add hexanaphthene 30ml azeotropic dehydration, filter and remove NaOH, finally add 0.012g MEHQ (0.0001mol) again, underpressure distillation, obtains acryloyl morpholine 4.32g, and yield is 85.5%, purity 98.3%.
 
Embodiment 3 N, the preparation of N-diethyl acrylamide
In 100mL four-hole boiling flask, add N, N-diethyl acetamide 5.68g(0.049mol), formaldehyde solution 4.00g(0.049mol), catalyst n aOH 0.39g(0.098mol) maintain the temperature at 85 DEG C ~ 90 DEG C, react 15 ~ 20 hours, obtain N, N-diethyl acrylamide crude product.After reaction finishes, add hexanaphthene 30ml azeotropic dehydration, filter and remove NaOH, finally add 0.012g MEHQ (0.0001mol) again, underpressure distillation, obtains N, N-diethyl acrylamide 5.20g, and yield is 82.9%, purity 98.0%.
 
Embodiment 4 N, the preparation of N-diethyl acrylamide
In 100mL four-hole boiling flask, add N, N-diethyl acetamide 4.34g(0.038mol), formaldehyde solution 12.24g(0.15mol), catalyst n aOH 1.52g(0.038mol), maintain the temperature at 85 DEG C ~ 90 DEG C, react 15 ~ 20 hours, obtain N, N-diethyl acrylamide crude product.After reaction finishes, add hexanaphthene 30ml azeotropic dehydration, filter and remove NaOH, finally add 0.012g MEHQ (0.0001mol), underpressure distillation, obtains N again, N-diethyl acrylamide 4.02g, yield is 83.9%, purity > 98.4%.
 
The preparation of embodiment 5 methacrylic morpholides
In 100mL four-hole boiling flask, add propionyl morpholine 5.43g(0.040mol), formaldehyde solution 3.26g(0.040mol), catalyst n aOH 0.32g(0.008mol), maintain the temperature at 85 DEG C ~ 90 DEG C, react 15 ~ 20 hours, obtain methacrylic morpholide crude product.After reaction finishes, add hexanaphthene 30ml azeotropic dehydration, filter and remove NaOH, finally add 0.012g MEHQ (0.0001mol) again, underpressure distillation, obtains methacrylic morpholide 5.25g, and yield is 84.2%, purity 98.5%.
 
The preparation of embodiment 6 methacrylic morpholides
In 100mL four-hole boiling flask, add propionyl morpholine 5.43g(0.040mol), formaldehyde solution 12.97g(0.16mol), catalyst n aOH 1.6g(0.040mol), maintain the temperature at 85 DEG C ~ 90 DEG C, react 15 ~ 20 hours, obtain methacrylic morpholide crude product.After reaction finishes, add hexanaphthene 30ml azeotropic dehydration, filter and remove NaOH, finally add 0.012g MEHQ (0.0001mol) again, underpressure distillation, obtains methacrylic morpholide 5.36g, and yield is 85.9%, purity 98.4%.

Claims (8)

1. a synthetic method for acrylic amide reactive thinner, is characterized in that carrying out according to following step:
Add amides, formaldehyde solution (or passing into formaldehyde gas), catalyzer, under agitation condition, 80 ~ 90 DEG C of holding temperatures, react 15 ~ 20 hours, obtain acrylic amide reactive thinner crude product; After reaction finishes, add organic solvent azeotropic dehydration, filter and remove catalyzer, finally add appropriate stopper, underpressure distillation, obtains acrylic amide reactive thinner product.
2. the synthetic method of a kind of acrylic amide reactive thinner according to claim 1, is characterized in that described amides in secondary amine structure be specially: , , ,
deng; Described R is H or methyl.
3. the synthetic method of a kind of acrylic amide reactive thinner according to claim 1, is characterized in that described amides and the mol ratio of formaldehyde are 1.0:1.0 ~ 1.0:4.0.
4. the synthetic method of a kind of acrylic amide reactive thinner according to claim 1, is characterized in that described catalyzer is sodium hydroxide, sodium methylate, sodium tert-butoxide, potassium hydroxide etc., preferably sodium hydroxide.
5. the synthetic method of a kind of acrylic amide reactive thinner according to claim 1, is characterized in that described raw material amides compounds and the mol ratio of highly basic are 1.0:0.2 ~ 1.0:1.0; Described raw material amides and the temperature of reaction of formaldehyde are 80 DEG C ~ 90 DEG C.
6. the synthetic method of a kind of acrylic amide reactive thinner according to claim 1, is characterized in that described organic solvent is dimethylbenzene, benzene, toluene, hexanaphthene, sherwood oil, preferably hexanaphthene.
7. the synthetic method of a kind of acrylic amide reactive thinner according to claim 1, it is characterized in that described stopper is Resorcinol, benzoquinones, thiodiphenylamine, oil of mirbane, picric acid, MEHQ, butyl-catechol, 4-methoxyphenol, preferably MEHQ.
8. the synthetic method of a kind of acrylic amide reactive thinner according to claim 1, is characterized in that the mol ratio of stopper and amides is controlled at (0.0025 ~ 0.025): in 1 scope.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017181A (en) * 2015-07-02 2015-11-04 南京师范大学 Carfilzomib key intermediate and preparation method of its derivative
WO2018210274A1 (en) 2017-05-18 2018-11-22 深圳市有为化学技术有限公司 Preparation method for co-producing acrylamide and formamide compounds
JP2018203694A (en) * 2017-06-08 2018-12-27 昭和電工株式会社 METHOD FOR PRODUCING N, N-DISUBSTITUTED α, β-UNSATURATED CARBOXYLIC ACID AMIDE
JP2020026435A (en) * 2018-08-10 2020-02-20 学校法人神奈川大学 PRODUCTION METHOD OF N,N-DISUBSTITUTED α,β-UNSATURATED CARBOXYLIC ACID AMIDE AND CATALYST FOR PRODUCTION OF N,N-DISUBSTITUTED α,β-UNSATURATED CARBOXYLIC ACID AMIDE

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017181A (en) * 2015-07-02 2015-11-04 南京师范大学 Carfilzomib key intermediate and preparation method of its derivative
CN105017181B (en) * 2015-07-02 2017-10-10 南京师范大学 The preparation method of Carfilzomib key intermediate and its derivative
WO2018210274A1 (en) 2017-05-18 2018-11-22 深圳市有为化学技术有限公司 Preparation method for co-producing acrylamide and formamide compounds
JP2018203694A (en) * 2017-06-08 2018-12-27 昭和電工株式会社 METHOD FOR PRODUCING N, N-DISUBSTITUTED α, β-UNSATURATED CARBOXYLIC ACID AMIDE
JP2020026435A (en) * 2018-08-10 2020-02-20 学校法人神奈川大学 PRODUCTION METHOD OF N,N-DISUBSTITUTED α,β-UNSATURATED CARBOXYLIC ACID AMIDE AND CATALYST FOR PRODUCTION OF N,N-DISUBSTITUTED α,β-UNSATURATED CARBOXYLIC ACID AMIDE
JP7345754B2 (en) 2018-08-10 2023-09-19 学校法人神奈川大学 Method for producing N,N-disubstituted α,β-unsaturated carboxylic acid amide and catalyst for producing N,N-disubstituted α,β-unsaturated carboxylic acid amide

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