CN109810011B - Preparation method of N-isobornyl acrylamide - Google Patents
Preparation method of N-isobornyl acrylamide Download PDFInfo
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- CN109810011B CN109810011B CN201910253327.2A CN201910253327A CN109810011B CN 109810011 B CN109810011 B CN 109810011B CN 201910253327 A CN201910253327 A CN 201910253327A CN 109810011 B CN109810011 B CN 109810011B
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- camphene
- acrylonitrile
- isobornyl
- isobornyl acrylamide
- acrylamide
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Abstract
The invention discloses a preparation method of N-isobornyl acrylamide, which takes natural renewable resources alpha-pinene and isomeric product camphene of beta-pinene as raw materials and FeCl3As a catalyst, camphene is subjected to isomerization, coupling and hydration reaction with acrylonitrile and water to obtain N-isobornyl acrylamide. The preparation process of the N-isobornyl acrylamide is simple, no additional solvent is needed, the used catalyst is low in price, the reaction selectivity is good, and the product yield is high.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and relates to a preparation method of N-isobornyl acrylamide.
Background
N-isobornyl acrylamide, an England name N-isobornyl acrylamide, is a white solid, and can be used as a monomer for high-molecular polymerization due to the carbon-carbon double bond. The unique bridge ring structure makes it possess excellent water resistance, high heat stability, high glass transition temperature, high compatibility with resin, solvent and pigment and filler, and is one excellent functional monomer.
The catalysts used for synthesizing N-isobornyl acrylamide at present mainly comprise the following types: (I) strong mineral acids such as sulfuric acid; (II) organic acids such as p-toluenesulfonic acid, methanesulfonic acid; (III) halogens such as iodine; (IV) heteropolyacids such as phosphotungstic acid, phosphomolybdic acid. Inorganic acid and organic acid catalysts have the defects of more side reactions, low product yield, serious corrosion to equipment, large post-treatment wastewater amount and the like, and heteropoly acid and iodine catalysts have the defects of high cost, complex post-treatment and the like. How to overcome the disadvantages is one of the research directions for preparing high-purity N-isobornyl acrylamide by selecting a cheap catalyst system and an ideal process route.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the existing book, the invention aims to provide a preparation method of N-isobornyl acrylamide, aims to provide a catalyst system and a post-treatment process which are low in cost, simple in post-treatment and high in catalytic activity and reaction selectivity for preparing the N-isobornyl acrylamide, and overcomes the defects of the existing process.
The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a preparation method of N-isobornyl acrylamide takes Lewis acid as a catalyst and camphene as a raw material, and the Lewis acid, the camphene and acrylonitrile and water are subjected to isomerization, coupling and hydration reaction under the condition of no solvent to obtain the N-isobornyl acrylamide; the reaction formula is as follows:
the preparation method of the N-isobornyl acrylamide comprises the steps of enabling the molar ratio of camphene to acrylonitrile to be 1: 1-1: 3 and enabling the molar ratio of camphene to water to be 1: 1.
The Lewis acid catalyst used in the preparation method of the N-isobornyl acrylamide is selected from AlCl3、ZnCl2、SnCl4、Fe2(SO4)3、FeSO4、FeCl2、FeCl3、CuCl2、Ce(SO4)2. Preferably FeCl3And the using amount is 8-10% of the total reaction mass.
The preparation method of the N-isobornyl acrylamide has the reaction temperature of 90-120 ℃.
The preparation method of the N-isobornyl acrylamide has the reaction time of 6-18 h.
In the preparation method of the N-isobornyl acrylamide, the camphene is obtained by isomerizing alpha-pinene and beta-pinene.
According to the method for synthesizing the N-isobornyl acrylamide, the molar ratio of camphene to acrylonitrile is 1: 1-1: 3, and the molar ratio of camphene to water is 1: 1; FeCl3Being catalysts, FeCl3The amount of the catalyst is 8-10% of the total mass of the reactants; reacting with acrylonitrile and water at 90-120 ℃ for 6-18 h; after the reaction liquid is decompressed and distilled to recover acrylonitrile, the distillation residue is dissolved in ethyl acetate, and is washed to be neutral by saturated saline solution, and the ethyl acetate is removed by decompressing and distilling to obtain the N-isobornyl acrylamide product.
Has the advantages that: compared with the prior art, the invention has the advantages that: using FeCl3The N-isobornyl acrylamide is prepared for the catalyst, and the reaction is carried out under the solvent-free condition. The catalyst has high activity, good catalytic effect, product yield up to 90 percent and reaction selectivity of 97.8 percent. In addition, the catalyst is cheap and easy to remove after reaction, and the defects of high price of the catalyst, complex post-treatment, large environmental pollution and the like in the existing production process are overcome.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
100.00g of camphene (purity 88%, 0.646mol), 126.8mL of acrylonitrile (1.938mol) and 11.63g H2O was premixed and charged into a 500mL four-necked flask equipped with a thermometer, condenser and mechanical stirrer, followed by 15.26g FeCl3The materials react for 12 hours at 100 ℃ and are tracked and detected by gas chromatography. Distilling the reaction liquid under reduced pressure to recover acrylonitrile, dissolving the residual solid in ethyl acetate, washing with saturated saline solution to neutrality, distilling under reduced pressure to remove ethyl acetate to obtain N-isobornyl acrylamideThe rate was 73.5% and the reaction selectivity was 82.3%. The prepared product N-isobornyl acrylamide is characterized, and the specific results are as follows:1H NMR(400MHz,Chloroform-d)δ：6.21(dd,J＝17.0,1.6Hz,1H),6.07(dd,J＝17.0,10.2Hz,1H),5.59(dt,J＝10.1,3.0Hz,2H),3.97(td,J＝9.0,5.1Hz,1H),1.85(dd,J＝13.3,9.1Hz,1H),1.72(d,J＝4.5Hz,1H),1.68(dq,J＝11.8,3.9Hz,1H),1.62-1.57(m,1H),1.56-1.50(m,1H),1.28(ddd,J＝12.4,9.1,3.3Hz,1H),1.14(ddd,J＝11.9,9.4,4.3Hz,1H),0.90(s,3H),0.82(d,J＝5.2Hz,6H)。13C NMR(100MHz,CDCl3)δ：164.87,131.32,125.90,77.37,77.05,76.73,56.76,48.71,47.10,44.88,39.04,35.94,26.98,20.29,20.25,11.69。
example 2
100.00g of camphene (purity 88%, 0.646mol), 126.8mL of acrylonitrile (1.938mol) and 11.63g H2O was premixed and charged into a 500mL four-necked flask equipped with a thermometer, condenser and mechanical stirrer, followed by 19.07g FeCl3The materials react for 12 hours at 120 ℃ and are tracked and detected by gas chromatography. And distilling the reaction liquid under reduced pressure to recover acrylonitrile, dissolving the residual solid in ethyl acetate, washing the mixture for a plurality of times by using saturated saline solution, and removing the solvent by reduced pressure distillation to obtain the N-isobornyl acrylamide, wherein the yield is 90 percent, and the reaction selectivity is 97.8 percent.
Example 3
100.00g of camphene (purity 88%, 0.646mol), 84.5mL of acrylonitrile (1.292mol) and 11.63g H2O was premixed and charged into a 500mL four-necked flask equipped with a thermometer, condenser and mechanical stirrer, followed by 15.65g FeCl3The materials react for 12 hours at 120 ℃ and are tracked and detected by gas chromatography. And distilling the reaction liquid under reduced pressure to recover acrylonitrile, dissolving the residual solid in ethyl acetate, washing with saturated saline solution for several times, and distilling under reduced pressure to remove the solvent to obtain the N-isobornyl acrylamide, wherein the yield is 67.8 percent and the reaction selectivity is 80.0 percent.
Example 4
100.00g of camphene (purity 88%, 0.646mol), 126.8mL of acrylonitrile (1.938mol) and 11.63g H2O is premixed and then introduced into a mixer equipped with a thermometer, a condenser and a mechanical stirrer500mL four-necked flask, followed by 17.16g FeCl3The materials are reacted for 18 hours at 110 ℃ and are detected by gas chromatography tracking. And distilling the reaction liquid under reduced pressure to recover acrylonitrile, dissolving the residual solid in ethyl acetate, washing with saturated saline solution for several times, and distilling under reduced pressure to remove the solvent to obtain the N-isobornyl acrylamide, wherein the yield is 77.78 percent and the reaction selectivity is 84.5 percent.
Example 5
100.00g of camphene (purity 88%, 0.646mol), 126.8mL of acrylonitrile (1.938mol) and 11.63g H2O was premixed and charged into a 500mL four-necked flask equipped with a thermometer, condenser and mechanical stirrer, followed by 15..26g FeCl3The materials react for 12 hours at 90 ℃ and are tracked and detected by gas chromatography. And distilling the reaction liquid under reduced pressure to recover acrylonitrile, dissolving the residual solid in ethyl acetate, washing with saturated saline solution for several times, and distilling under reduced pressure to remove the solvent to obtain the N-isobornyl acrylamide, wherein the yield is 63.4 percent and the reaction selectivity is 83.9 percent.
Comparative example 1
100.00g of camphene (purity 88%, 0.646mol), 126.8mL of acrylonitrile (1.938mol) and 11.63g H2O was premixed and charged into a 500mL four-necked flask equipped with a thermometer, condenser and mechanical stirrer, followed by 19.07g of phosphotungstic acid, and the material was reacted at 120 ℃ for 12 hours with gas chromatography follow-up detection. And distilling the reaction liquid under reduced pressure to recover acrylonitrile, dissolving the residual solid in ethyl acetate, washing the mixture for a plurality of times by using saturated saline solution, and removing the solvent by reduced pressure distillation to obtain the N-isobornyl acrylamide, wherein the yield is 59.8 percent, and the reaction selectivity is 80.6 percent.
Comparative example 2
100.00g of camphene (purity 88%, 0.646mol), 126.8mL of acrylonitrile (1.938mol) and 11.63g H2O was premixed and charged into a 500mL four-necked flask equipped with a thermometer, condenser and mechanical stirrer, followed by 19.07g of iodine, and the contents were reacted at 120 ℃ for 12 hours with a follow-up gas chromatography. Distilling the reaction solution under reduced pressure to recover acrylonitrile, dissolving the rest solid in ethyl acetate, washing with saturated saline solution for several times, and distilling under reduced pressure to remove solvent to obtain N-isobornyl acryloylThe yield of amine is 66.9 percent, and the reaction selectivity is 73.5 percent.
Comparative example 3
100.00g of camphene (purity 88%, 0.646mol), 126.8mL of acrylonitrile (1.938mol) and 11.63g H2O is premixed and added into a 500mL four-neck flask provided with a thermometer, a condenser and a mechanical stirrer, then 10..4mL concentrated sulfuric acid is slowly dropped into the flask by a constant pressure funnel, and the materials react for 12h at 40 ℃ and are detected by gas chromatography tracking. And distilling the reaction liquid under reduced pressure to recover acrylonitrile, dissolving the residual solid in ethyl acetate, washing with saturated saline solution for several times, and distilling under reduced pressure to remove the solvent to obtain the N-isobornyl acrylamide, wherein the yield is 40.8 percent, and the reaction selectivity is 73.5 percent.
Claims (7)
1. A preparation method of N-isobornyl acrylamide is characterized in that Lewis acid is used as a catalyst, camphene is used as a raw material, and the Lewis acid and acrylonitrile and water are subjected to isomerization, coupling and hydration reaction under the condition of no solvent to obtain the N-isobornyl acrylamide; the Lewis acid catalyst is FeCl3(ii) a The reaction formula is as follows:
2. the method of claim 1, wherein the molar ratio of camphene to acrylonitrile is 1:1 to 1:3, and the molar ratio of camphene to water is 1: 1.
3. The process for producing N-isobornyl acrylamide according to claim 1, wherein FeCl is used3The amount of the catalyst is 8-10% of the total mass of the reactants.
4. The process for producing N-isobornyl acrylamide according to claim 1, wherein the reaction temperature is 90 to 120 ℃.
5. The method for synthesizing N-isobornyl acrylamide according to claim 1, wherein the reaction time is 6 to 18 hours.
6. The method of synthesizing N-isobornyl acrylamide as set forth in claim 1, wherein camphene is obtained by isomerization of α -pinene and β -pinene.
7. The method for synthesizing N-isobornyl acrylamide according to claim 1, wherein the molar ratio of camphene to acrylonitrile is 1:1 to 1:3, and the molar ratio of camphene to water is 1: 1; FeCl3Being catalysts, FeCl3The amount of the catalyst is 8-10% of the total mass of the reactants; reacting with acrylonitrile and water at 90-120 ℃ for 6-18 h; after the reaction liquid is decompressed and distilled to recover acrylonitrile, the distillation residue is dissolved in ethyl acetate, and is washed to be neutral by saturated saline solution, and the ethyl acetate is removed by decompressing and distilling to obtain the N-isobornyl acrylamide product.
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Citations (5)
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| RU2024494C1 (en) * | 1991-07-08 | 1994-12-15 | Данов Сергей Михайлович | Process for preparing n-isobornylacrylamide |
| US5446083A (en) * | 1991-06-05 | 1995-08-29 | Zeneca Resins Bv | Aqueous coating compositions |
| JP2005272344A (en) * | 2004-03-24 | 2005-10-06 | Kohjin Co Ltd | Method for producing isobornyl acrylamide |
| CN105461852A (en) * | 2014-09-03 | 2016-04-06 | 中国石油化工股份有限公司 | Acrylamide copolymer, preparation method therefor and application of acrylamide copolymer |
| CN105461599A (en) * | 2014-09-03 | 2016-04-06 | 中国石油化工股份有限公司 | Acrylamide monomer and preparation method therefor |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5446083A (en) * | 1991-06-05 | 1995-08-29 | Zeneca Resins Bv | Aqueous coating compositions |
| RU2024494C1 (en) * | 1991-07-08 | 1994-12-15 | Данов Сергей Михайлович | Process for preparing n-isobornylacrylamide |
| JP2005272344A (en) * | 2004-03-24 | 2005-10-06 | Kohjin Co Ltd | Method for producing isobornyl acrylamide |
| CN105461852A (en) * | 2014-09-03 | 2016-04-06 | 中国石油化工股份有限公司 | Acrylamide copolymer, preparation method therefor and application of acrylamide copolymer |
| CN105461599A (en) * | 2014-09-03 | 2016-04-06 | 中国石油化工股份有限公司 | Acrylamide monomer and preparation method therefor |
Non-Patent Citations (3)
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| Heteropolyacids as new catalysts of the Ritter reaction;Kartashov, V. R.等;《Russian Journal of Organic Chemistry》;20061231;第42卷(第7期);第968页右栏第二段 * |
| Indium-Triflate-Catalyzed Ritter Reaction in Liquid Sulfur Dioxide;Daniels Posevins等;《Eur. J. Org. Chem.》;20161231;第1414-1419页 * |
| Iron (III) perchlorate - a novel reagent in synthesis;Kumar, Baldev等;《Indian Journal of Chemistry》;19911231;第30B卷(第5期);第460页右栏最后一段，第461页左栏第一段 * |
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