JP2005272344A - Method for producing isobornyl acrylamide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple, industrially advantageous method for producing isobornyl acrylamide useful as a raw material for inks, coating materials, adhesives and the like in a high yield without requiring a measure to dispose of a large amount of waste due to the use of concentrated sulfuric acid, the production of drainage of the salt formed in its neutralization and the like. <P>SOLUTION: Isobornyl acrylamide is produced by reacting acrylonitrile with camphene in the presence of a strongly acidic cation exchange resin and water, preferably 5-25 g of the strongly acidic cation exchange resin per 1.0 mol acrylonitrile and 0.8-1.2 mol water per 1.0 mol camphene at 110-160°C for 1-24 hours. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a process for producing isobornylacrylamide useful as a raw material for inks, paints, adhesives and the like.

  Conventionally, it has been known to produce N-substituted acrylamide by reacting acrylonitrile with an olefin or alcohol in the presence of concentrated sulfuric acid, Lewis acid or the like, and various compounds have been reported (for example, Patent Document 1). Regarding isobornylacrylamide, Non-Patent Document 1 discloses that acrylonitrile and camphene were reacted in the presence of concentrated sulfuric acid in an acetic acid solvent, and the target product was obtained in a yield of 49%. However, these methods using concentrated sulfuric acid require a neutralization treatment and the like, which not only requires complicated operations for isolation of the target product, but also the yield of the target product depending on the type of olefin and alcohol. It was not satisfactory enough.

  Then, it replaced with concentrated sulfuric acid, Lewis acid, etc., the method of using a solid catalyst, especially a strong acidic cation exchange resin was examined, and patent document 2 describes that N-substituted acrylamide can be manufactured from acrylonitrile and alcohol. ing. According to this method, after completion of the reaction, the catalyst is removed by filtration, and the filtrate can be distilled or crystallized to isolate the target product, which is an extremely simple production method. However, in these reports, the alcohols used are limited to secondary or tertiary alcohols with relatively high reactivity, and the use of olefins is not studied at all.

On the other hand, there has also been reported an example in which camphene is converted into an isobornyl derivative using a strongly acidic cation exchange resin. For example, Patent Document 3 describes an example in which isobornyl acrylate is synthesized from camphene and acrylic acid. Yes. However, there is no disclosure that nitriles can be used instead of acids.
For example, Japanese Patent Publication No. 3-9898 Japanese Patent Application Laid-Open Nos. 11-209329 and 11-279131 Japanese Patent Laid-Open No. 9-20719 Bull. Chem. Soc. Jpn. 1970 43 1252

  Therefore, the present invention does not require a large amount of waste disposal measures associated with the use of concentrated sulfuric acid or the like, or the generation of salt drainage due to its neutralization, and the industrial production of isobornyl (meth) acrylamide that is simple and high yield. It is an object to provide an advantageous production method.

The main feature of the present invention is that the reaction is carried out in the presence of a strongly acidic cation exchange resin and water.
That is, the present invention
(1) A process for producing isobornylacrylamide, characterized by reacting acrylonitrile and camphene in the presence of a strongly acidic cation exchange resin and water,
(2) The process for producing isobornylacrylamide according to (1) above, wherein the molar ratio of camphene to water is 0.8 to 1.2,
Is to provide.

  According to the present invention, isobornyl acrylamide can be easily produced in a high yield without generating a large amount of waste.

Hereinafter, the present invention will be described in detail.
In the present invention, the reaction between acrylonitrile and camphene is carried out in the presence of a strongly acidic cation exchange resin and water.
The molar ratio of acrylonitrile and camphene is preferably about 0.1 to 1.0 mol with respect to 1.0 mol of acrylonitrile. When the molar ratio of camphene is 0.1 or less, the productivity is lowered, and when it exceeds 1.0, impurities are increased.

  The strongly acidic cation exchange resin used in the present invention is composed of a styrene group having a sulfonic acid group and a divinylbenzene copolymer, and may be either a porous type or a gel type. Can do. Specific examples include trade name Amberlist (Rohm & Haas), trade name Diaion (Mitsubishi Chemical), trade name Dowex (Dow Chemical) and the like. It is not a thing. Further, when the sulfonic acid group which is an ion exchange group is an alkali salt type, for example, a sodium salt type, it is necessary to make it an acid type by a known method.

  The amount of the strongly acidic cation exchange resin used is preferably 5 to 25 g (dry weight) with respect to 1.0 mol of acrylonitrile. If the amount of strongly acidic cation exchange resin used is less than 5 g, a sufficient reaction rate cannot be obtained. On the other hand, if it exceeds 25 g, stirring becomes difficult, and the yield decreases due to adsorption into the resin. Therefore, it is not preferable.

On the other hand, the water is preferably 0.08 to 1.2 mol with respect to 1.0 mol of acrylonitrile, and in particular, it may be used in the range of 0.8 to 1.2 mol with respect to 1.0 mol of camphene. Desirable, most preferably equimolar. The use of water is indispensable. If water is not added, the target product is not formed, and a polymer of acrylonitrile is mainly given.
When the water ratio is less than 0.8, the selectivity is significantly lowered, resulting in an increase in impurities, and when it is more than 1.2, a sufficient reaction rate cannot be obtained.

The reaction conditions vary depending on the ratio of acrylonitrile, camphene, strongly acidic cation exchange resin and water, but generally a reaction temperature of 110 to 160 ° C. and a reaction time of 1 to 24 hours are preferable.
When the reaction temperature is 110 ° C. or lower, the reaction does not proceed.

  For the reaction, an autoclave is usually used. The use of a polymerization inhibitor is not essential, but it is desirable to use a small amount of a known polymerization inhibitor.

  After completion of the reaction, the desired product is easily isolated by recrystallizing a crude crystal obtained by removing the catalyst by filtration and concentrating the reaction solution under reduced pressure with an organic solvent such as cyclohexane.

Hereinafter, the present invention will be described in detail with reference to examples.
Example 1
Acrylonitrile 53.1 g (1.0 mol), camphene 34.06 g (0.25 mol), ion-exchanged water 4.5 g (0.25 mol), Amberlyst 15E (Rohm and Haas, dried) in a 300 ml stainless steel autoclave ) 12.5 g and phenothiazine 0.04 g were added and reacted at 140 ° C. with stirring for 12 hours. After completion of the reaction, the reaction solution was filtered to separate Amberlyst, and the resin was further washed with a small amount of methanol. The filtrate and the washing solution were combined and analyzed by gas chromatography (packed column, PEG-20M manufactured by GL Sciences) to obtain camphene conversion and isobornylacrylamide production rate (camphene base).
The results are listed in Table 1.

Moreover, 43.6 g of crude isobornyl acrylamides were obtained by distilling off the filtrate and the washing solution under reduced pressure with an evaporator to remove excess acrylonitrile and methanol. This was recrystallized from cyclohexane to obtain white needle-shaped isobornylacrylamide (yield 76.3%).
Melting point: 135-137 ° C
The structure was confirmed by comparison with a standard mass spectrometer and an infrared absorption spectrum.

Examples 2-5
The reaction was carried out in the same manner as in Example 1 under the conditions described in Table 1 (strongly acidic cation exchange resin: Amberlyst 15E), and the conversion and production rate were measured by gas chromatography.
The results are shown in Table 1.

Example 6
The reaction was carried out in the same manner as in Example 1 except that the strongly acidic cation exchange resin was changed to Diaion RCP160H (Mitsubishi Chemical Co., Ltd., dried), and the conversion and production rate were measured by gas chromatography.
As a result, the conversion rate of camphene was 99.2%, and the production rate of isobornylacrylamide was 86.5%.

  As described above, according to the present invention, isobornyl acrylamide useful as a raw material for inks, paints, adhesives and the like can be produced simply and in high yield.

Claims (2)

  A process for producing isobornylacrylamide, characterized by reacting acrylonitrile and camphene in the presence of a strongly acidic cation exchange resin and water.   The process for producing isobornyl acrylamide according to claim 1, wherein the molar ratio of camphene to water is 0.8 to 1.2.