JPH08165343A - Production of polyoxyalkylenemonoamine - Google Patents

Abstract

PURPOSE: To easily and conveniently produce a high-purity polyoxyalkylenemonoamine contg. no unreacted material nor by-product by subjecting a specific polyoxyalkylene compd. to cyanoethylation, hydrogenation, and purification. CONSTITUTION: A polyoxyalkylenemonoamine represented by formula II [wherein R<1> is a 1-24C hydrocarbon group or acyl; AO is 3-4C oxyalkylene; m is 1-1,000 and n is 0-1,000 provided m+n is 1-1,000 and n/(m+n) is 0.5 or lower; and when n is 1 or higher, oxyethylene units and AO are added in block or randomly] is obtd. by subjecting a polyoxyalkylene compd. of formula I (wherein R<1> , AO, m, and n are each the same as in formula II) to cyanoethylation in the presence of 0.0012wt.% (based on the reaction system) aq. soln. contg. 1-50wt.% at least one alkali catalyst selected from among potassium hydroxide, sodium hydroxide, and lithium hydroxide, then to hydrogenation with Raney nickel, and to purification with an ion-exchange resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyoxyalkylene used as a raw material and a method for producing a high-quality polyoxyalkylene monoamine which does not contain a polyamine produced as a by-product during the production.

[0002]

2. Description of the Related Art As a method for synthesizing an amine from a polyoxyalkylene derivative having a hydroxyl group, a method of directly obtaining an amine by reacting ammonia with a hydroxyl group in the presence of hydrogen using a Raney nickel / aluminum catalyst (Japanese Patent Application Laid-Open No. Sho-06-1999) 61-204225), a method of reacting a compound having a cyano group such as acrylonitrile with a hydroxyl group, and then hydrogenating it using a cobalt-based catalyst to obtain an amine (Japanese Patent Laid-Open No. 160-214214). Has been.

[0003]

However, in the above method for directly obtaining an amine from a hydroxyl group, it is necessary to react a Raney nickel / aluminum catalyst containing at least 25% aluminum at a reaction temperature of 200 ° C. or more under anhydrous conditions. Therefore, a special reaction vessel is required, and there is a drawback that side reactions such as decomposition of raw materials occur due to high temperature reaction. Furthermore, the method of hydrogenating the above hydroxyl group and then hydrogenating it to obtain an amine does not require a special apparatus, but since excess acrylonitrile is reacted to increase the amination rate, polyamine and the like are by-produced. There was a drawback to

Until now, polyoxyalkylene monoamines have been mainly used in the textile industry and resin additives,
Unreacted materials and by-products were not a major obstacle. However, in recent years, polyoxyalkylene monoamines have been used for chemical modification of bioactive proteins and drug delivery systems such as liposomes, and high-purity polyoxyalkylene monoamines with few by-products have been required. However, high-purity polyoxymonoamine could not be easily obtained by the above-mentioned production methods of and. An object of the present invention is to provide a simple method for producing high-purity polyoxyalkylene monoamine containing no unreacted substances and by-products.

[0005]

Means for Solving the Problems In producing a polyoxyalkylene monoamine, the present inventors have controlled the cyanoethylation rate of a polyoxyalkylene compound to be low under a specific solvent to prevent generation of polyacrylonitrile as a by-product. The present invention has been completed based on the finding that high-purity polyoxyalkylene monoamine can be obtained easily by a simple purification method by an ion exchange method after being suppressed and further hydrogenated.

That is, the present invention provides the following general formula (1) R ¹ O (C ₂ H ₄ ) _m (AO) _n C ₃ H ₆ NH ₂ (1) (where R ¹ is a carbon atom having 1 to 24 carbon atoms). Hydrogen group or acyl group,
AO is an oxyalkylene group having 3 or 4 carbon atoms, m and n are average addition mole numbers of oxyethylene group and oxyalkylene group, respectively, and m = 1 to 1000, n = 0 to 10
00 and m + n = 1 to 1000, {n / m + n} ≦ 0.
5, and when n ≧ 1, the oxyethylene group and the oxyalkylene group may be added in blocks or randomly. In the method for producing a polyoxyalkylene monoamine represented by the formula (1),
A method for producing a polyoxyalkylene monoamine, which comprises sequentially performing the step (3). (1) General formula (2) R ¹ O (C ₂ H ₄ O) _m (AO) _n H (2) (R ¹ is a hydrocarbon group having 1 to 24 carbon atoms or an acyl group,
AO is an oxyalkylene group having 3 or 4 carbon atoms, m and n are average addition mole numbers of oxyethylene group and oxyalkylene group, respectively, and m = 1 to 1000, n = 0 to 10
00 and m + n = 1 to 1000, {n / (m + n)} ≦
It is 0.5, and when n ≧ 1, the oxyethylene group and the oxyalkylene group may be added in blocks or randomly. ) A step of cyanoethylating the polyoxyalkylene compound, a step (2) of hydrogenating the obtained cyanoethylated compound, and a step of (3) purifying the obtained hydride with an ion exchange resin. Furthermore, the present invention provides 1-50% by weight of an alkali catalyst selected from potassium hydroxide, sodium hydroxide or lithium hydroxide as a catalyst in the cyanoethylation step.
0.001 to 2% by weight of an aqueous solution is added to the reaction system,
A method for producing a polyoxyalkylene monoamine, which comprises reacting a compound of the general formula (2) according to the following calculation formula (1) so that the blocking rate of hydroxyl groups is 40 to 95%. Calculation formula 1; Blocking rate (%) = (hydroxyl value of compound before reaction-remaining hydroxyl value after reaction) / (hydroxyl value of compound before reaction) x
100 (1) Further, in the hydrogenation step, a Raney nickel-based catalyst is used, and the reaction is performed in an ammonia atmosphere, which is a method for producing a polyoxyalkylene monoamine. Further, in the method for producing polyoxyalkylene monoamine, the catalyst is removed by filtration after completion of the hydrogenation step, and then a strong acid type ion exchange resin is used in the purification step.

Further, in the method for producing a polyoxyalkylene monoamine, (1) in the cyanoethylation step with acrylonitrile, acetonitrile is added as a reaction solvent in an amount of 100 to 500% by weight of the compound of the general formula (2), and acrylonitrile is generally used as a raw material. The compound of formula (2) is used in an amount of 100 to 500 mol% with respect to the hydroxyl group, and the reaction temperature is 10 to 10.
Reacting at 50 ° C., and making the blocking rate of the hydroxyl group with acrylonitrile in the calculation formula (1) to be 40 to 95%,
(2) After the completion of the cyanoethylation step, the catalyst is adsorbed and removed by an alkali adsorbent, then the reaction solvent acetonitrile and unreacted acrylonitrile are distilled off under reduced pressure, and the Raney nickel catalyst is used as a catalyst in the reduction step. ,
Reacting in an ammonia atmosphere at a temperature of 100 to 200 ° C., (3) after completion of the reduction step, the catalyst is removed by filtration, and then a strong acid type ion-exchange resin having the general formula in the reaction solution after the reduction step is completed. A step of removing the unreacted compound of the general formula (2) by adsorbing the compound of (1) and washing with ion-exchanged water; (4) washing with ion-exchanged water;
A purification step of desorbing the compound of general formula (1) from the ion exchange resin using 29% aqueous ammonia and (5) after that, an aqueous solution of general formula (1) purified by ion exchange is subjected to reduced pressure conditions or lyophilization, A method for producing a polyoxyalkylene monoamine, which comprises a concentration step of deammonification and dehydration.

Generally, in the cyanoethylation reaction of a polyoxyalkylene having a hydroxyl group, a by-product of polyacrylonitrile is inevitable, but it is difficult to completely remove this by-product before the reduction reaction with hydrogen, and hydrogenation is also difficult. It is also very difficult to completely remove the polyamine derived from the polyacrylonitrile produced as a by-product from the polyoxyalkylene monoamine later. In the present invention, by keeping the blocking rate of the above calculation formula (1) as low as 40 to 95%, and keeping the reaction temperature as low as 10 to 50 ° C., and using acetonitrile as a reaction solvent, polyacrylonitrile By suppressing by-products, after the hydrogenation, in the purification step by the ion-exchange resin method using ion-exchanged water and alkaline aqueous solution as the developing solvent, polyoxyalkylenes with unreacted hydroxyl groups are efficiently removed to obtain high-purity products. It is characterized by manufacturing.

The raw material used in the present invention is represented by the general formula (2), and R ¹ is a hydrocarbon group having 1 to 24 carbon atoms or an acyl group. Specific examples of the alkyl group having 1 to 24 carbon atoms represented by R ¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, Hexyl group, isoheptyl group, 2-ethylhexyl group, octyl group, isononyl group, decyl group, dodecyl group, isotridecyl group, tetradecyl group, hexadecyl group, isohexadecyl group, octadecyl group, isostearyl group, oleyl group, octyldodecyl group. , Saturated and unsaturated linear or branched hydrocarbon groups such as docosyl group and decyltetradecyl group, and further benzyl group, cresyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group. , Dodecylphenyl group, dioctylphenyl group, dinonylphenyl Aromatic hydrocarbon groups and the like. Further, as the acyl group represented by R ¹ , acetic acid, propionic acid, butyric acid, isobutyric acid,
Caprylic acid, 2-ethylhexanoic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid,
Isopalmitic acid, stearic acid, isostearic acid,
Acyl groups derived from saturated and unsaturated linear or branched fatty acids such as arachidic acid, behenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and erucic acid can be mentioned.

AO of the general formula (2) has 3 or 4 carbon atoms.
And oxypropylene group, oxybutylene group, oxytetramethylene group and the like. These oxyalkylene groups are groups obtained by addition-polymerizing alkylene oxides such as propylene oxide, 1,2-butylene oxide and tetrahydrofuran. m and n are the average number of moles of addition of oxyethylene group and oxyalkylene group, and m is 1 to 1,000.
It is not preferable that the amount is limited to 0 because at least 1 mol is required to give affinity to the living body, and when it exceeds 1,000, it becomes solid and the workability deteriorates. Furthermore n
Is limited to 0 to 1,000 because when it exceeds 1,000, the viscosity becomes high and the production becomes difficult. Also, 0.5 is limited to {n / m + n} ≦ 0.5.
If it exceeds, lipophilicity becomes strong and affinity with living organisms decreases, which is not preferable. More preferably {n / m + n} ≦
It is 0.3.

In the step of cyanoethylating the compound of the general formula (2) as a raw material, an alkali catalyst selected from potassium hydroxide, sodium hydroxide and lithium hydroxide is used as a catalyst. The concentration of the alkali to be used is 1 to 50% by weight, preferably 1 to 10% by weight. When the concentration is lower than 1% by weight, the reaction system has a large amount of water, so that the reaction between acrylonitrile and water increases and by-products are produced. A lot of things are produced, which is not preferable. Further, when the concentration of the alkali is higher than 50% by weight, the alkali becomes insoluble in water, which is not preferable. The amount of alkali added to the reaction system is 0.001 to 2
% By weight, preferably 0.5 to 1.5% by weight. If it is less than 0.001% by weight, the reaction is difficult to proceed,
If it exceeds 2% by weight, the reaction system has a large amount of water and a large amount of by-products, which is not preferable. The amount of acrylonitrile used in the cyanoethylation step is 100 to 500 mol%, preferably 250 to 450 mol% with respect to the hydroxyl group of the raw material, and the amount of acetonitrile as the solvent is 1 to 1 mol of the raw material.
It is from 0 to 500% by weight, and if it is less than 100% by weight, by-products such as polyacrylonitrile are generated, which is not preferable. Further, if the amount of acetonitrile is more than 500% by weight, it takes time to remove the solvent, which is not preferable. The reaction temperature in the cyanoethylation step is 10 to 50 ° C. If it is lower than 10 ° C., the reaction rate becomes slow and the reaction time becomes long, which is not preferable. Further, if the temperature is higher than 50 ° C., by-products such as polyacrylonitrile increase, which is not preferable. The blocking rate of the hydroxyl group of the raw material is 45 to 95%, more preferably 60 to 80%
If it is lower than 45%, the yield is lowered, which is not preferable, and if it is higher than 95%, polyamine derived from polyacrylonitrile produced as a by-product is increased and cannot be removed in the subsequent purification step, which is not preferable.

The reaction temperature in the hydrogenation step is 100 to 200 ° C.
If the temperature is lower than 100 ° C, the reaction is difficult to proceed,
If the temperature is higher than ℃, side reactions such as decomposition of raw materials occur, which is not preferable. More preferably, it is 100 to 150 ° C. Further, in the hydrogenation step, hydrocarbons such as n-hexane and cyclohexane and aromatic hydrocarbons such as toluene and xylene may be used as a diluting solvent, if necessary, from the viewpoint of physical properties of the raw materials, for example, melting point and viscosity. Is preferred.

Since the ion exchange resin used in the present invention is used for the purpose of removing polyoxyalkylene having a hydroxyl group from polyoxyalkylene monoamine, various structures can be used as long as it is a base exchange type. Ion-exchanged water can be used to remove the compound of the general formula (2) after adsorption of the compound of the general formula (1).
When the compound of formula (1) is desorbed, the compound of general formula (1) is desorbed from the ion exchange resin by using a stronger base than the compound of general formula (1). Therefore, ammonia water, potassium hydroxide, sodium hydroxide, etc. Use an alkaline aqueous solution. Considering the subsequent concentration step, it is more preferable to use ammonia water.

Ammonia or another alkali is used in the adsorption and purification steps with the ion exchange resin, and the concentration of the alkali is not particularly limited, but the concentration of the alkali is 1 to 1.
It is 50% by weight, preferably 1 to 30% by weight. Among the alkalis, ammonia is preferable from the viewpoint of the subsequent concentration step, and the concentration thereof is 1 to 29% by weight. If it is less than 1% by weight, the amount of elution increases and the concentration step becomes complicated, which is not preferable. %, It is difficult to obtain, and it is handled under pressure, which is not preferable. It is more preferably 1 to 10% by weight. When an aqueous solution of sodium hydroxide, potassium hydroxide or lithium hydroxide is used, it is preferable to remove the alkali by dialysis or the like, if necessary. The treated distillate is concentrated at low temperature under reduced pressure or by freeze-drying to obtain the desired product. If desired, the treated distillate may be used as an aqueous solution.

[0015]

INDUSTRIAL APPLICABILITY In the present invention, when a compound of the general formula (2) having a hydroxyl group is cyanoethylated, by suppressing the blocking rate of the hydroxyl group to 40 to 95%, by-product of polyacrylonitrile is suppressed, and by ion exchange. Since this is a method for producing a high-purity general formula (1) by removing the unreacted compound of the general formula (2), a high-purity poly-alkene can be easily prepared without using a special raw material, a reaction apparatus and a catalyst. An oxyalkylene monoamine can be obtained.

[0016]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. Example 1 A compound having the following composition was placed in a four-necked flask equipped with a reflux device, a nitrogen gas blowing tube, a thermometer, a stirring device, and a dropping funnel, and the mixture was maintained at 30 ° C. under a nitrogen gas stream while stirring. <Preparation composition> CH ₃ O (C ₂ H ₄ O) ₁₁₃ H 1000 g (about 0.2 mol) Acetonitrile 2000 g (200 wt% vs. raw material) 10% NaOH aqueous solution 6 g (0.6 wt% vs. raw material)

Then, 45 g of acrylonitrile (0.8 g
A mixture of 5 mol, 425 mol% with respect to the starting hydroxyl group) and 180 g of acetonitrile was placed in a dropping funnel and added dropwise at 30 ± 5 ° C. over 2 hours. After dripping, after aging for 2 hours at the same temperature, add 30 g of the alkaline adsorbent KYOWARD KW # 700 (Kyowa Chemical Industry Co., Ltd., product name), stir at the same temperature for 30 minutes, and then pressurize and filter. To remove the catalyst. Then, unreacted acrylonitrile and acetonitrile as a solvent were distilled off at 120 ± 5 ° C. under a reduced pressure of 5 to 30 mmHg while blowing nitrogen gas to obtain 970 g of cyanoethylated methoxypolyethylene glycol. The hydroxyl value of the obtained cyanoethylated methoxypolyethylene glycol was 3.8, and the blocking rate of hydroxyl groups calculated from the hydroxyl value was 66.1%.
The hydroxyl value is measured according to JIS K0070 (199
It carried out according to 2).

The gel permeation chromatogram of the raw material used, methoxypolyethylene glycol, is shown in FIG.
Fig. 2 shows the gel permeation chromatogram of the obtained cyanoethylated methoxy polyethylene glycol.
Shown in From FIG. 1 and FIG. 2, it can be confirmed that there is no byproduct of polyacrylonitrile. The measurement conditions of the gel permeation chromatogram are as follows. <Measurement conditions of gel permeation chromatogram> Column: SHODEX KF-801
KF-803, KF-804 Developing solvent: THF Column oven temperature: 40 ° C. Sample concentration: 0.15 (W / V)% Sample injection amount: 10 μl Flow rate: 1.0 ml / min

Next, 404.2 g of the obtained cyanoethylated methoxy polyethylene glycol and 200 g of toluene.
And Raney nickel catalyst Ni-5136P (E
NGELHARD DE MEERN B. V. Product)
18g was put into an autoclave for reduction with hydrogen, kept at 60 ° C with stirring, and kept at 7kg / c with ammonia gas.
Pressurized to m ² . Then, the temperature was controlled to 130 ± 10 ° C, hydrogen gas was gradually injected, and 35 ± 5 kg / cm ²
The reduction reaction with hydrogen was carried out while the pressure was maintained. After the reduction of the pressure due to the progress of the reduction reaction due to hydrogen is no longer observed, aging is carried out for another 2 hours, then the reactor is cooled to 70 ° C., then blown to return the reactor to atmospheric pressure, and blow in nitrogen gas. This removed the ammonia gas. Then, after removing the residual catalyst by filtration, the solvent acetonitrile and unreacted acrylonitrile under reduced pressure of 120 ± 5 ° C. and 5 to 30 mmHg were distilled off under reduced pressure to obtain crude methoxypolyethylene glycol monoamine 36.
7 g were obtained.

The total amine value of the obtained crude methoxypolyethylene glycol monoamine was 7.1, the primary amine value was 7.1, the secondary amine value and the tertiary amine value were 0, and the crude amine value calculated from the amine. The purity of methoxypolyethylene glycol monoamine was 63.5%. The amine value was measured according to the following method. <Measurement of total amine value> Total amine value is N / 10 perchloric acid-
The amount of perchloric acid required to neutralize 1 g of a sample by potentiometric titration using a glacial acetic acid titration solution, a Christel violet reagent, and a glacial acetic acid solvent was converted into mg of potassium hydroxide. <Measurement of Tertiary Amine Value> The tertiary amine value is a N / 10 perchloric acid-glacial acetic acid titrant, a Kristel violet reagent, and a mixed solvent of glacial acetic acid and acetic anhydride to neutralize 1 g of the sample by potentiometric titration. The amount of perchloric acid required to do this is converted to mg of potassium hydroxide. <Measurement of Total Amount of Secondary Amine Value and Tertiary Amine Value> Salicylaldehyde is added to a sample to react with a primary amine,
The amount of hydrochloric acid required to neutralize 1 g of a sample by potentiometric titration using an N / 10 hydrochloric acid ethanol titration solution and a bromcresol green reagent was converted into mg of potassium hydroxide. <Measurement of Secondary Amine Value> The secondary amine value is obtained by subtracting the measured value of the tertiary amine value from the measured value of the total amount of the secondary amine value and the tertiary amine value. <Measurement of Primary Amine Value> The primary amine value is obtained by subtracting the measured value of the total amount of the secondary amine value and the tertiary amine value from the measured value of the total amine value. Next, a liquid chromatogram of crude methoxy polyethylene glycol monoamine is shown in FIG.
Shown in The conditions of the liquid chromatogram are as follows. <Conditions for liquid chromatogram>Column; TSKgel SP-5PW
(Tosoh Corporation, trade name) Developing solvent; 2 mM phosphate buffer (pH 7.
4) Column oven temperature; 30 ° C. sample concentration; 0.5 (w / v)% sample injection amount; 20 μl flow rate; 0.5 ml / min

Subsequently, 100 g of the base exchange type ion exchange resin DIAION PK216 [product of Mitsubishi Kasei Co., Ltd., trade name] regenerated by a conventional method was packed in a column, and 10 g of the above-mentioned crude methoxypolyethylene glycol monoamine.
Was dissolved in 90 g of ion-exchanged water, and the column was filled with ion-exchanged water at a flow rate of 0.8 ml / min. When the liquid surface of the column reached the same level as the boundary surface of the packed resin, 1 liter of ion-exchanged water was flowed at a flow rate of 3.3 ml / min. Then, 0.5 liter of 5% ammonia water was added at a rate of 0.
Flowing at a flow rate of 8 ml, 550 ml of effluent was collected. Next, the collected effluent was freeze-dried to obtain 8 g of the desired high-purity methoxypolyethylene glycol monoamine.
I got The total amine value of the obtained methoxy polyethylene glycol monoamine is 10.9, and the primary amine value is 1
0.9, secondary amine value and tertiary amine value were 0. The purity of methoxypolyethylene glycol calculated from the amine value was 97.6%. The liquid chromatogram of the obtained methoxypolyethylene glycol monoamine is shown in FIG. From FIG. 4, it can be seen that the obtained methoxypolyethylene glycol monoamine has high purity.
The following formula was used for the conversion formula of purity by amine value. Calculation formula (2): Purity (%) = (A / B) × 100 (2) Here, the symbols represent the following. A: Measured primary amine value B: Theoretical primary amine value calculated from the raw material The raw material polyoxyalkylene compound is shown in Table 1, and the obtained polyoxyalkylene monoamine is shown in Table 2.

[0022]

[Table 1]

[0023]

[Table 2]

The GPC results in the table indicate gel permeation chromatograms, which are displayed as follows. No minor; indicates that there are no minor component peaks in addition to the major component. Secondary presence: Indicates that there is a peak of a secondary component in addition to the main component. Moreover, the purity% of the crude product and the purity% of the purified product are the purities calculated from the respective amine values, and are based on the above calculation formula (2).

Examples 2 to 7 In the same manner as in Example 1, using the starting compounds of the general formula (2) shown in Table 1, the corresponding polyoxyalkylene monoamines were obtained. The results are shown in Table 2.

Comparative Example 1 Using the compound of the general formula (2) used in Example 1, the reaction solvent in the cyanoethylation step was changed from acetonitrile to toluene, and a reaction was carried out in the same manner as in Example 1. . The results are shown in Table 2.

Comparative Example 2 Using the compound of the general formula (2) used in Example 1, 90 g of acrylonitrile was dropped in the cyanoethylation step.
Instead, cyanoethylated methoxypolyethylene glycol with a blocking rate of 98.5% was obtained. Then, the reaction was carried out in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 3 The reaction was carried out in the same manner as in Example 1 except that the amount of acetonitrile as a solvent before charging acrylonitrile in the cyanoethylation step was 500 g instead of 2000 g.

From the above Examples and Comparative Examples, it can be seen that high quality polyoxyalkylene monoamine can be obtained by the production method of the present invention.

[0030]

[Brief description of drawings]

FIG. 1 is a gel permeation chromatogram of a raw material methoxypolyethylene glycol of Example No. 1.

FIG. 2 is a gel permeation chromatogram of cyanoethylated methoxypolyethylene glycol of Example No. 1.

FIG. 3 shows Example No. 1 is a liquid chromatogram of crude methoxy polyethylene glycol monoamine of No. 1.

FIG. 4 shows Example No. 1 is a liquid chromatogram of 1 methoxypolyethylene glycol monoamine.

Claims (5)

[Claims] 1. A compound represented by the following general formula (1) R ¹ O (C ₂ H ₄ O) _m (AO) _n C ₃ H ₆ NH ₂ (1) (R ¹ is a hydrocarbon group having 1 to 24 carbon atoms or An acyl group,
AO is an oxyalkylene group having 3 or 4 carbon atoms, m and n are average addition mole numbers of oxyethylene group and oxyalkylene group, respectively, and m = 1 to 1000, n = 0 to 10
00 and m + n = 1 to 1000, {n / m + n} ≦ 0.
5, and when n ≧ 1, the oxyethylene group and the oxyalkylene group may be added in blocks or randomly. In the method for producing a polyoxyalkylene monoamine represented by the formula (1),
A method for producing a polyoxyalkylene monoamine, which comprises sequentially performing the step (3). (1) General formula (2) R ¹ O (C ₂ H ₄ O) _m (AO) _n H (2) (R ¹ is a hydrocarbon group having 1 to 24 carbon atoms or an acyl group,
AO is an oxyalkylene group having 3 or 4 carbon atoms, m and n are average addition mole numbers of oxyethylene group and oxyalkylene group, respectively, and m = 1 to 1000, n = 0 to 10
00 and m + n = 1 to 1000, {n / (m + n)} ≦
It is 0.5, and when n ≧ 1, the oxyethylene group and the oxyalkylene group may be added in blocks or randomly. ) A step of cyanoethylating a polyoxyalkylene compound represented by the formula (2), a step of hydrogenating the obtained cyanoethylated compound, and (3) a step of purifying the obtained hydride with an ion exchange resin, 2. In the cyanoethylation step, 0.001 to 2% by weight of a 1 to 50% by weight aqueous solution of an alkali catalyst selected from potassium hydroxide, sodium hydroxide or lithium hydroxide is added to the reaction system as a catalyst. The method for producing a polyoxyalkylene monoamine according to claim 1, wherein the compound of the general formula (2) is reacted so that the blocking rate of the hydroxyl group according to the following calculation formula (1) is 40 to 95%. Calculation formula 1; Blocking rate (%) = (hydroxyl value of compound before reaction-remaining hydroxyl value after reaction) / (hydroxyl value of compound before reaction) x
100 (1) 3. The method for producing a polyoxyalkylene monoamine according to claim 1, wherein in the hydrogenation step, a Raney nickel catalyst is used and the reaction is performed in an ammonia atmosphere. 4. The production of polyoxyalkylene monoamine according to claim 1, wherein a strong acid type ion exchange resin is used in the purification step after removing the catalyst by filtration after the hydrogenation step. Method. 5. A method for producing a polyoxyalkylene monoamine, wherein in the step (1) cyanoethylation with acrylonitrile, acetonitrile is added as a reaction solvent in an amount of 100 to 500% by weight of the compound of the general formula (2), and acrylonitrile is used as a starting material. The compound of formula (2) is used in an amount of 100 to 500 mol% based on the hydroxyl group, and the reaction temperature is 10 to 50.
Reacting at 0 ° C. to make the blocking rate of hydroxyl group with acrylonitrile in the above calculation formula (1) 40 to 95%, (2)
After completion of the cyanoethylation step, the catalyst is adsorbed and removed with an alkali adsorbent, then the reaction solvent acetonitrile and unreacted acrylonitrile are distilled off under reduced pressure, and the Raney nickel-based catalyst is used as the catalyst in the reduction step, and the ammonia atmosphere is used. Reacting under a temperature of 100 to 200 ° C.,
(3) After the reduction step, the catalyst is removed by filtration, and then the strongly acidic ion-exchange resin is allowed to adsorb the compound of the general formula (1) in the reaction solution after the reduction step and washed with ion-exchanged water. To remove the unreacted compound of the general formula (2) and (4) washing with ion-exchanged water,
A purification step of desorbing the compound of general formula (1) from the ion exchange resin using 29% aqueous ammonia, (5)
The method for producing a polyoxyalkylene monoamine according to claim 1, which comprises a step of deammonification and dehydration of the ion-exchange purified aqueous solution of the general formula (1) under reduced pressure or by freeze-drying.