Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2001-12-17
2003-06-10
Davis, Brian (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S493000, C568S697000
Reexamination Certificate
active
06576794
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to processes for producing an ether amine, an ether tertiary amine and an ether quaternary ammonium salt which are useful as softening agents, rinse bases or raw materials thereof, or raw materials for production of surfactants, dyes, acid gas removers, functional polymers, etc.
2. Description of the Prior Art
In a production process of an alkyloxypropylamine, an alkoxypropionitrile is at first prepared from an alcohol and acrylonitrile and then the product is hydrogenated. For example, the process by Uter Morene et al. [J. Am. Chem. Soc., Vol. 67, p. 1505 (1945)], the process described in British Patent No. 869,405 and the like are known. In these processes, however, a hydrogenation reaction is conducted under a high hydrogen pressure of about 100 kg/cm
2
, and thus an expensive apparatus is required, and an operation for removing ammonia used in the process is essential. Therefore, these processes cannot be said to be industrially useful. On the other hand, Japanese Patent Application Laid-Open No. 103505/1973 discloses a process in which an alkali metal hydroxide is used to obtain a nitrile, and the resulting nitrile is hydrogenated under a hydrogen pressure of about 25 kg/cm
2
or lower after the alkali metal hydroxide is removed. This process requires a complicated operation for removing the alkali metal hydroxide, and its yield is low. So the process has not been satisfactory as a process for producing an alkyloxypropylamine through an alkyloxypropionitrile on an industrial scale.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for producing industrially advantageously an ether amine containing neither unreacted compounds nor by-products, having a high purity and scarcely colored, and processes for directly producing an ether tertiary amine and an ether quaternary ammonium salt from the ether amine thus obtained.
The present inventors have found that when the amount of the alkali metal hydroxide used in the step of cyanoethylating an alcohol is decreased to an amount less than that conventionally used, the purity of the alkyloxypropionitrile obtained as an intermediate is markedly increased, and the resulting reaction product can be subjected to a subsequent hydrogenation step without removing the alkali metal hydroxide therefrom to obtain an intended ether amine with a high purity and industrial advantages. The present inventors have also found that an ether tertiary amine and an ether quaternary ammonium salt each having a high purity can be efficiently produced from the ether amine thus obtained without need of any purification step.
According to the present invention, there is thus provided a process for producing an ether amine represented by the general formula (3):
ROCH
2
CH
2
CH
2
NH
2
(3)
wherein R denotes a linear or branched alkyl or alkenyl group having 6 to 24 carbon atoms, which comprises reacting a primary or secondary alcohol represented by the general formula (1):
ROH (1)
wherein R has the same meaning as defined above, with an acrylonitrile in an amount of 0.8 to 1.2 equivalents relative to the amount of the alcohol (1) in the presence of an alkali metal hydroxide in an amount of not less than 0.01 part by weight but less than 0.05 part by weight per 100 parts by weight of the alcohol (cyanoethylation step) to give an alkyloxypropionitrile represented by the general formula (2):
ROCH
2
CH
2
CN (2)
wherein R has the same meaning as defined above, and then adding water in an amount of 0.5 to 20 parts by weight per 100 parts by weight of the alkyloxy-propionitrile to the reaction system without removing the alkali metal hydroxide from the reaction system and effecting hydrogenation using a hydrogenation catalyst (hydrogenation step).
According to the present invention, there is also provided a process for producing an ether tertiary amine represented by the general formula (5):
R—O—CH
2
—CH
2
—CH
2
—N (CH
2
R
1
)
2
(5)
wherein R
1
denotes hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms, and R has the same meaning as defined above, which comprises, subsequent to the above-described hydrogenation step, adding an aldehyde represented by the general formula (4):
R
1
CHO (4)
wherein R
1
has the same meaning as defined above, to the ether amine represented by the general formula (3) defined above at a reaction temperature of 60 to 200° C. under a hydrogen pressure of at least 0.5 MPa (gauge pressure) in the presence of a metal catalyst containing at least one element selected from the group consisting of Pd, Pt, Rh, Re and Ru, or a Raney nickel catalyst (tertiary amine forming step).
According to the present invention, there is also provided a process for producing an ether quaternary ammonium salt represented by the general formula (6):
R—O—CH
2
—CH
2
—CH
2
—N (CH
2
R
1
)
2
(R
2
) (6)
wherein R
2
denotes a linear or branched alkyl or hydroxyalkyl group having 1 to 5 carbon atoms, and R and R
1
have the same meanings as defined above, which comprises, subsequent to the above-described tertiary amine forming step, reacting the ether tertiary amine represented by the general formula (5) defined above with a quaternary salt forming agent (quaternary ammonium salt forming step).
According to the present invention, there can be produced industrially advantageously an ether amine containing neither unreacted compounds nor by-products, having a high purity and less colored. In addition, an ether tertiary amine and an ether quaternary ammonium salt each having a high purity can be efficiently produced from the ether amine thus obtained without need of any purification step.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The process for production of an ether amine according to the present invention comprises a cyanoethylation step and a hydrogenation step.
Cyanoethylation Step
The cyanoethylation step is a step for producing an alkyloxypropionitrile (2) from a primary or secondary alcohol (1) and acrylonitrile.
Examples of the primary or secondary alcohol (1) include n-hexanol, 2-ethylhexanol, isodecanol, lauryl alcohol, tridecanol, palmityl alcohol, stearyl alcohol, isostearyl alcohol and 2-octyldodecanol. Among these, linear alcohols are preferred.
The amount of acrylonitrile to be used is 0.8 to 1.2 equivalents, preferably 0.9 to 1.2 equivalents, more preferably 0.95 to 1.1 equivalents relative to that of the alcohol (1). If the amount of acrylonitrile exceeds 1.2 equivalents, hydrogenation activity is lowered, thereby lowering selectivity. If the amount of acrylonitrile is less than 0.8 equivalent, unreacted alcohol remains to lower the yield.
Examples of the alkali metal hydroxide used in this step include lithium hydroxide, sodium hydroxide and potassium hydroxide, with potassium hydroxide and sodium hydroxide being particularly preferred from the viewpoint of reactivity. One or more of these alkali metal hydroxides can be used, and the amount thereof is not less than 0.01 part by weight, but less than 0.05 part by weight, and is preferably 0.01 to 0.04 part by weight per 100 parts by weight of the raw material alcohol (1) because unreacted acrylonitrile is decomposed or polymerized, or the resulting alkyloxypropionitrile is decomposed to lower the yield of the intended product if an higher amount of the alkali metal hydroxide relative to the raw material alcohol (1) is present.
The reaction temperature in this step is preferably 45 to 70° C., particularly preferably 50 to 65° C. The reaction time is preferably 0.5 to 5 hours.
Hydrogenation Step
The hydrogenating step is a step for obtaining the intended ether amine (3) by the hydrogenation reaction of the alkyloxypropionitrile (2).
In the present invention, the reaction product obtained in the above-described cyanoethylation step is used in the hydrogenation step without removing the alkali metal hydroxide from the reaction system. In this step, the reaction is conducted by adding
Abe Hiroshi
Fukushima Tetsuaki
Masuda Hiroyuki
Nishimoto Uichiro
Davis Brian
Kao Corporation
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