JP2003055450A - Low odor polyamine polyether polyol and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamine polyether polyol wherein a formation amount of an impurity is small and the odor generation is controlled and its manufacturing method. SOLUTION: The polyamine polyether polyol having not more than 5 ppm of the 2,3-butanedione concentration is manufactured by adding 0.5-200 moles of an alkylene oxide to 1 mole of an NH bonding in a polyalkylene imine onto the polyalkylene imine having not more than 5 ppm of the acetonitrile concentration.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyamine polyether polyol obtained by adding an alkylene oxide to an amino group of a polyalkyleneimine, and more particularly to a polyamine polyether polyol having a low odor.

[0002]

2. Description of the Related Art Polyamine polyether polyol, which is an alkylene oxide adduct of polyalkyleneimine, is widely used in the fields of washing and metal working.
Polyamine polyether polyols are generally produced by a method of adding an alkylene oxide to an amino group of a polyalkyleneimine in the presence of an acid catalyst or a base catalyst.

However, in the manufacturing process of polyamine polyether polyol, odor caused by impurities generated during the process is a problem, and development of means for suppressing the generation of impurities has been desired.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a polyamine polyether polyol in which the amount of impurities produced is small and the generation of odor is suppressed, and a method for producing the same.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies on a mechanism of odor generation, a means for suppressing the amount of impurities generated, and the like. As a result, by reducing the concentration of 2,3-butanedione, polyamine polyether polyol The present invention has been completed by finding that odor can be dramatically reduced, and that it is effective to reduce the concentration of acetonitrile in polyalkyleneimine as a raw material in order to reduce the concentration of 2,3-butanedione. It is a thing.

That is, in the present invention, 0.5 mol per 1 mol of an NH bond (that is, a hydrogen atom bonded to an amino group: hereinafter also referred to as "active hydrogen") to an amino group of polyalkyleneimine.
A polyamine polyether polyol obtained by adding ˜200 mol of alkylene oxide, wherein the concentration of 2,3-butanedione contained in the polyamine polyether polyol is 5 ppm or less. .

Further, the present invention provides a polyalkyleneimine having an acetonitrile content of 5 ppm or less, in an amount of 0.5 to 20 with respect to 1 mol of NH bond of the polyalkyleneimine.
In this method, 0 mol of alkylene oxide is added to produce a polyamine polyether polyol having a 2,3-butanedione concentration of 5 ppm or less.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION First, the structure of the polyamine polyether polyol constituting the present invention will be described.
In the present application, the polyamine polyether polyol is
A compound in which an alkylene oxide is added to the active hydrogen of the amino group of polyalkyleneimine (represented by R—NH—R and R—NH ₂ when R is a residue other than a hydrogen atom).

The polyalkyleneimine is not particularly limited, but it is preferable that the alkylene units constituting the polyalkyleneimine have 2 to 4 carbon atoms. Such polyalkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine,
It can be obtained by homopolymerization or copolymerization of one or more kinds of alkyleneimines such as 2,3-butyleneimine by a conventional method. For example, polyethyleneimine, polypropyleneimine, polybutyleneimine, polyisopropyleneimine or a single amount thereof. Examples of the copolymer include a combination of bodies (ethyleneimine-propyleneimine copolymer, ethyleneimine-butyleneimine copolymer, etc.), and polyethyleneimine is preferable in view of production cost. Illustrating a specific structure of polyethyleneimine,
A linear one represented by the following general formula (1),

[0010]

[Chemical 1]

A branched one as exemplified by the following general formula (2),

[0012]

[Chemical 2]

Either of them may be used, or a mixture thereof may be used. The branched structure includes primary, secondary, and tertiary amines, but the structure is not uniquely specified and can be said to be a random structure.

The weight average molecular weight of the polyalkyleneimine is not particularly limited, but if the molecular weight is too low, the inherent properties of the polymer (dispersibility, stability, water resistance, etc.) may not be obtained, and it is too high. The viscosity may increase and it may be inconvenient to handle. From this viewpoint, the weight average molecular weight is preferably 150 or more, more preferably 300 or more, and particularly preferably 600 or more. With respect to the upper limit, it is preferably 2,000,000 or less, more preferably 500000 or less, still more preferably 10000 or less,
It is particularly preferably 5,000 or less. Although these polyalkyleneimines can be used as a raw material, an alkyleneimine synthesized by a liquid phase method, a wenker method, or a vapor phase method can be synthesized by using the alkyleneimine synthesized by a vapor phase method as a raw material by a method described later. It is preferable. This is because the amount of impurities such as polyethylene glycol produced can be reduced by using the gas phase method.

The polyamine polyether polyol relating to the present invention has 0.5 to 2 per 1 mol of active hydrogen in the amino group contained in the above-mentioned polyalkyleneimine structure.
About 100 moles of alkylene oxide are added. Structure in the case of adding an alkylene oxide, for example when adding ethylene oxide is N-H is a general formula N- (CH ₂ CH ₂ O) structure represented by _n -H.
Considering the easiness of the manufacturing process and the workability, it is preferable that 5 to 40 mol of alkylene oxide is added to 1 mol of active hydrogen. To give a specific example, a polyalkyleneimine containing 10 -NH- and 10 -NH ₂ has 30 NH bonds (active hydrogen).
Is included. Therefore, when 1 mol of this polyalkyleneimine is used, the case where 150 mol of alkylene oxide is added corresponds to the case where 5 mol of alkylene oxide is added to 1 mol of NH bond (active hydrogen) on average. To do.

The alkylene oxide is not particularly limited, but it is preferable that the alkylene units constituting the polyalkylene oxide have 2 to 4 carbon atoms. The alkylene oxides may be used alone or in combination of a plurality of alkylene oxides, and when they are used in combination, a product in which alkylene oxides are added in a block, random or alternating manner can be obtained.

The present invention is characterized in that the concentration of 2,3-butanedione contained in the polyamine polyether polyol having the above-mentioned constitution is low, and thereby the generation of odor as a product is suppressed. Specifically, it is necessary for the concentration of 2,3-butanedione to be 5 ppm or less in order to obtain the effect of the present invention.
It is preferably pm or less, more preferably 2 ppm or less, and particularly preferably 1 ppm or less. Of course, it is preferable that the concentration of impurities other than 2,3-butanedione is also low. Specifically, the concentration of acetaldehyde is 1 ppm or less, and the concentration of dioxane is 1 ppm.
The following are respectively preferable. By reducing such impurities and suppressing odor, the usefulness of the polyamine polyether polyol can be enhanced. For example, when used as a detergent, it is possible to prevent odor from adhering to the washed product, and the odorlessness of the present invention has a large effect in practice.

Next, one embodiment of the method for producing a polyamine polyether polyol according to the present invention will be described by taking the case of adding ethylene oxide to polyethyleneimine as an example. However, it does not exclude the use other than polyethyleneimine and ethylene oxide,
When other raw material compounds are used, it can be produced according to the following method. In that case, the conditions may be optimized as appropriate depending on the compound used.

Ethyleneimine, which is a raw material of polyethyleneimine, is generally monoethanolamine (HO-C).
H ₂ —CH ₂ —NH ₂ ) is prepared by an intramolecular dehydration reaction. The reactor is not particularly limited, and a known reactor can be used.

First, by vaporizing monoethanolamine,
If necessary, it is diluted with an inert gas (nitrogen, argon, etc.) and introduced into the catalyst layer as a raw material gas. The reaction pressure is not particularly limited and may be any of reduced pressure, normal pressure and increased pressure. The reaction temperature is generally 300 to 5
It is 00 ° C. The space velocity of the raw material gas must be appropriately determined according to the concentration of monoethanolamine, the type of catalyst used, etc., and cannot be specified unambiguously, but is usually 50.
It is about 5000 h ^-1 . Examples of the catalyst include niobium and tantalum catalysts; silicon-alkali metal and / or alkaline earth metal catalysts; phosphorus-alkali metal and / or alkaline earth metal catalysts; silicon / phosphorus-alkali metal / alkaline earth metal catalysts. Examples of the catalyst include a catalyst composition supported on ceramics. As a result, monoethanolamine undergoes an intramolecular dehydration reaction to produce ethyleneimine.

The reaction mixture containing ethyleneimine produced by the intramolecular dehydration reaction can be collected by using a collecting agent. You may collect and collect it as it is. An amine compound is preferable as the scavenger, and monoethanolamine used as a raw material is particularly preferable. The reaction mixture may contain, as impurities, ammonia, light amines such as methylamine and ethylamine, acetonitrile, ketones such as acetaldehyde, and a Schiff base formed by the reaction of acetaldehyde and monoethanolamine. These impurities can be removed by known techniques such as distillation and extraction with an organic solvent. As a result, ethyleneimine having a reduced impurity concentration can be obtained.

Next, polyethyleneimine is synthesized by polymerizing the ethyleneimine from which impurities have been removed. Polymerization is carried out by adding ethyleneimine in an effective amount of acid catalyst (HCl
Etc.) in the presence of the reaction at 0 to 200 ° C. Based on the synthesized polyethyleneimine, ethyleneimine may be further subjected to addition polymerization. The method for polymerizing ethyleneimine is not particularly limited, and is disclosed in Japanese Patent Publication No. 43-8828.
Japanese Examined Patent Publication No. 49-33120, Japanese Patent Publication No. 2000-501
Known techniques such as the method described in Japanese Patent No. 757 may be used.

The reaction system may be a batch system, a semi-batch system, or a continuous flow system, and is not particularly limited. In the case of the batch method, since the viscosity of the reaction solution becomes high during polymer production, a stirring blade for high viscosity (for example, Maxblend blade manufactured by Sumitomo Heavy Industries, Ltd.) was provided for heat removal, diffusion, and reaction acceleration. Preference is given to using stirred reactors. In order to improve the efficiency of heat removal, it is preferable to polymerize ethyleneimine under reflux using a vertical tube type cooler.

Impurities are present in the obtained crude polyethyleneimine as in the case of the raw material ethyleneimine. If the polyethyleneimine contains impurities, the resulting polyamine polyether polyol will cause an offensive odor. Acetonitrile is a compound that can have a particularly serious influence on the odor of the resultant product, and by reducing the concentration of acetonitrile in polyethyleneimine, the off-flavor of the polyamine polyether polyol produced can be effectively suppressed. As a result, the quality of the product can be improved. Further, by reducing the concentration of acetonitrile in polyethyleneimine, there is also an effect of enhancing the stability of the obtained polyamine polyether polyol, and in this respect also, the significance of reducing the concentration of acetonitrile is great. Specifically, it is necessary to set the content of polyethyleneimine to 5 ppm or less in order to obtain the effects of the present invention, more preferably 3 ppm or less, and particularly preferably 1 ppm or less. Of course, it is preferable that the concentration of impurities other than acetonitrile is as low as possible. Specifically, acetone is preferably 5 ppm or less, more preferably 3 ppm or less, and particularly preferably 1 ppm or less. The lower amine having 1 to 5 carbon atoms (methylamine, ethylenediamine, etc.) is preferably 0.1% by mass or less, more preferably 0.05% by mass or less,
It is more preferably 0.03 mass% or less,
It is particularly preferably not more than 01% by mass.

Examples of the method for removing acetonitrile from polyethyleneimine include a method of bubbling an inert gas into polyethyleneimine, a method of adding water to polyethyleneimine, mixing and then removing water by evaporation, and a method of combining these. To be

First, a method for bubbling polyethyleneimine with an inert gas will be described. One of the embodiments is a method of bubbling an inert gas into the polymer inside the reactor after the completion of the polymerization of ethyleneimine. As the inert gas, various gases inert to amines such as nitrogen gas, helium gas, and argon gas can be used. From the viewpoint of suppressing side reactions during bubbling, the temperature of the polymer during bubbling is 200 ° C.
The temperature is preferably set to the following, and more preferably set to 100 to 180 ° C. The inert gas supply means is not particularly limited, and in order to perform effective bubbling treatment, two or more inert gas outlets to the reaction solution are provided,
It is preferable to supply a foamy inert gas. The finer the bubble-like size, the more preferable, and specifically, the nozzle diameter is preferably 50 mm or less. When supplying the inert gas, it is preferable to use a stirring reactor provided with a supply means, for example, a ring-shaped inert gas supply means provided with a gas outlet is provided so as to be immersed in the reaction solution. Just do it. The supply amount of the inert gas is usually 0.001 to 10 liters (Normal) / min, and preferably 0.01 to 2 liters (Normal) / min, per 1 kg of polyethyleneimine. The bubbling time is usually 0.5 to 100 hours, preferably 1 to 20 hours. The bubbling treatment may be performed under either normal pressure or reduced pressure, and when performed under reduced pressure, 10 to 700
A value of about mmHg is suitable.

Next, a method of adding water to polyethyleneimine and mixing it and then removing the water by evaporation will be described. As one of the embodiments, after completion of the polymerization of ethyleneimine,
Water may be added to the polymer inside the reactor and mixed sufficiently, and the mixture may be heated to remove water by evaporation. The amount of water added is 1 to 9 relative to polyethyleneimine.
5 mass% is suitable, and 5-30 mass% is more preferable. From the viewpoint of suppressing side reactions during the evaporation treatment of water, the treatment is preferably performed so that the polymer temperature is 200 ° C. or lower, and more preferably 100 to 180 ° C.
The atmospheric gas pressure during the evaporation treatment may be either normal pressure or reduced pressure, and when performed under reduced pressure, it is 10 to 700 m.
About mHg is suitable.

The above bubbling treatment and water evaporation removal treatment may be combined, and by combining them, high-purity polyethyleneimine can be obtained in a shorter operation time. As one of the embodiments, after completion of the polymerization of ethyleneimine, water is added to the polymer inside the reactor,
Water is evaporated off while bubbling an inert gas through the mixture. The operating conditions can be set according to the above-mentioned conditions.

Then, ethylene oxide is added to the obtained polyethyleneimine having a low concentration of acetonitrile, and an attempt is made to add ethylene oxide to active hydrogen. Ethylene oxide addition can be carried out by a known method, for example, addition of alkylene oxide to active hydrogen, addition reaction with alkylene oxide having a substituent capable of reacting with active hydrogen, and the like can be used. On the other hand, when attempting to add about 3 to 40 mol of ethylene oxide, the method of supplying ethylene oxide described below in two batches is preferable from the viewpoint of preventing generation of impurities and coloring.

A) Supply of polyethyleneimine to the stirring reactor The obtained polyethyleneimine having a low concentration of acetonitrile is supplied to a stirring reactor provided with stirring blades. The method for supplying polyethyleneimine to the stirring reactor is not particularly limited, and the generally required consideration for the compound may be taken. The supply amount of polyethyleneimine cannot be uniquely determined because it is determined by the internal volume of the stirred reactor, the compound used, etc.
It is appropriate to supply about 50% by volume. Polyethyleneimine may be supplied alone, or may be supplied together with a solvent such as water or acetone in some cases. However, when added together with the solvent, it is necessary to pay attention to the generation of impurities due to the reaction with the solvent. Further, the solution containing polyethyleneimine preferably has a small difference from the polarity of the ethylene oxide supplied, in consideration of the solubility of ethylene oxide in the gas phase in the liquid phase and the distribution equilibrium.

The shape of the stirring reactor is not limited, and various shapes may be used. The stirring reactor scale is also not particularly limited, but in order to industrially obtain the effect of the present invention, the volume inside the stirring reactor is preferably 1 m ³ or more, more preferably 5 m ³ or more, It is particularly preferable that it is 10 m ³ or more. Further, it is preferable that a blade for stirring the reaction liquid is provided inside the stirring reactor. Specific examples of commercially available stirred reactors include Supermix HR-100, HR-320, HR.
-500i (all manufactured by Satake Chemical Machinery Co., Ltd.), Sunmelar (manufactured by Mitsubishi Heavy Industries, Ltd.), VCR (manufactured by Mitsubishi Heavy Industries, Ltd.), Bend Leaf (manufactured by Yako Sangyo Co., Ltd.),
Examples include Max Blend, Tornado, Super Blend (Sumitomo Heavy Industries, Ltd.), Full Zone, Logbone (Shinko Pantech Co., Ltd.), Torsion Lattice Blade (Hitachi, Ltd.), and the like.

B) Supply of ethylene oxide 0.7 to 1.2 mol, preferably 0.85 to 1.0 mol, based on 1 mol of active hydrogen contained in polyethyleneimine.
5 molar equivalents of ethylene oxide are used as they are or, if necessary, diluted with a solvent (water, acetone, etc.) and reacted according to the method of the present invention. However, when added together with the solvent, it is necessary to pay attention to the generation of impurities due to the reaction with the solvent. At this time, if the reaction temperature is too low, the reaction rate becomes slow, and if it is too high, the amount of impurities produced may increase. From this viewpoint, the reaction temperature is 100 to
180 degreeC is suitable and 120-170 degreeC is more suitable. The ethylene oxide addition may be performed in the presence of a solvent or in the absence of a solvent. It is difficult to uniquely define the preferable feed rate of ethylene oxide depending on the reaction system and the stirring reactor, but it is preferable to feed it so that the gas phase pressure does not exceed a certain value.
Specifically, it is suitable to supply the pressure so as to be about 0.05 to 1 mPa · s. Examples of the method for supplying ethylene oxide include a showering method and a method of providing an injection port on the lid or the upper part of the inner wall.

The atmosphere in the stirring reactor during the ethylene oxide addition reaction may be decompressed to supply alkylene oxide, and most of the atmosphere gas may be alkylene oxide gas, in order to reduce the explosiveness of alkylene oxide. The supply of alkylene oxide may be started after replacement with an inert gas such as nitrogen or argon.

The stirring power cannot be uniquely defined because it is a numerical value that should be appropriately selected depending on the type of blade, the type of ethylene oxide to be added, and the type of polyethyleneimine.
Generally, from the viewpoint of suppressing the occurrence of a heterogeneous reaction due to poor stirring and a decrease in reaction rate, the stirring power is 1 m in the reactor vessel.
With respect to ³ , 0.2 to ³ kW / m ³ is suitable, and 0.5 to
2.5 kW / m ³ is more suitable. It is not necessary to keep the stirring power constant, and the stirring power may be changed according to the reaction conditions.

C) Addition of catalyst A catalyst such as NaOH, KOH, NaOCH ₃ is added to the system. The catalyst may be added as it is, or may be added by dissolving it in water, methanol or the like. At this time, if the amount of catalyst added is too small, the reaction rate becomes slow, and if it is too large, the amount of impurities produced may increase. From this viewpoint, the amount of catalyst added is 0.
It is preferred to add 02 to 0.40 molar equivalents. Further, from the viewpoint of suppressing the generation of impurities, K is used as a catalyst.
Most preferably, OH is used. When the catalyst is added using a solvent, it is preferable to volatilize the catalyst by degassing and / or heating. The catalyst may be added from the initial ethylene oxide addition stage. By adding the catalyst from the initial stage of ethylene oxide addition, the distribution of EO chains to be added can be sparse.

D) Supply of ethylene oxide 2 to 40 mole equivalents of ethylene oxide and / or propylene oxide with respect to 1 mole of active hydrogen contained in polyethyleneimine are used as they are or, if necessary, diluted with a solvent to give 100 The reaction is carried out according to the method of the present invention at a temperature of ~ 200 ° C, preferably at a temperature of 150-175 ° C. The pressure during the reaction is 0.25 to 0.8.
About mPa · s is preferable.

E) Neutralization of catalyst Aging at a temperature of about 100 to 170 ° C. for about 0.5 to 3 hours to neutralize the catalyst, a carboxylic acid having 2 to 6 carbon atoms (CH ₃ COOH, CH _3). CH ₂ COOH, (CH ₃ ) ₂
CHCOOH, CH ₃ CH (OH) COOH, etc.), phosphoric acid, hydrochloric acid, sulfuric acid, etc. are used at about 40 to 60 ° C.

F) Purification of product The resulting product can be deodorized by bubbling an inert gas such as nitrogen or argon. You may deodorize by adding 1-10 mass% of volatile solvents, such as water and ethanol, with respect to the mass of polyamine polyether polyol, and reducing it to 0-0.01 MPa at 100-170 degreeC. These may be used in combination, and for example, while degassing with nitrogen, the pressure can be reduced to 0 to 0.01 MPa with water to deodorize. The deodorizing time is preferably 1 to 8 hours, more preferably 3 to 5 hours. Instead of or in combination with bubbling, impurities in the reaction solution may be removed by simple distillation, thin film distillation or spray dryer treatment. Simple distillation means batch distillation without rectification part,
It can be carried out by a general apparatus. Thin film distillation can be carried out using a Hickman type distiller, falling film distiller, rotor tray distiller, brush type molecular distiller, etc., pressure 0.1 mmHg or less, temperature 100-200.
It is suitable to carry out under the condition of ° C. In the spray dryer treatment, the target substance is sprayed from the top and 100 to 2 from the bottom.
It can be carried out by blowing a hot air inert gas at 00 ° C. In this case, since the target substance is granulated and dried, the evaporation surface area is large, the contact time between the droplet and the hot air is short, and the deterioration of the target substance due to the heat load can be reduced. Other deodorizing methods include activated carbon, molecular sieves, porous polymers and zeolites. However, it is necessary to note that post-treatment after use is required when deodorizing using these.

The polyamine polyether polyol thus produced can be further modified or cross-linked with a monomer or polymer having a reactive substituent by utilizing the primary to tertiary amino groups and hydroxyl groups. Examples include quaternization with an epoxy group, isocyanate group, carboxylic acid anhydride, aziridine group, epichlorohydrin, alkyl chloride, etc., esterification with a carboxylic acid or amidation, Michael addition with an unsaturated monomer, etc. To be Examples of compounds that can be used are carboxylic acid group-containing monomers such as (meth) acrylic acid and maleic acid, alkyl (meth) acrylate (C ₁ -C ₂₀ ) esters, alkylallyl having 1 to 20 carbon atoms. Monomers with unsaturated bonds such as ether,
Examples thereof include (meth) acrylic acid chloride, glycidyl (meth) acrylate, methylene chloride, dimethylsulfate, diethylsulfate, and isocyanate such as toluylene diisocyanate.

The most preferable combination for producing a polyamine polyether polyol by the above-mentioned steps a) to f) is KOH as a catalyst, and the catalyst amount is 10 to 25 mol per 1 mol of active hydrogen in polyethyleneimine. amount,
The addition temperature of ethylene oxide is 150 to 175 ° C.

The use of the obtained polyamine polyether polyol is not particularly limited, but examples thereof include lubricants, cutting fluids, viscosity index improvers, fluidizers, lubricants, water-based and oil-based paints, paper medicines, carbon black. Inorganic and organic dispersants such as silica, emulsifiers, emulsion polymerization activators, gelling agents, viscosity modifiers, liquid / gel or solid detergent compositions (dispersants, builders), flocculants, aqueous or oil-based ink compositions Object, an ink composition for an inkjet printer,
Examples include antistatic agents, solid electrolytes, anti-bleeding agents, dyes, and the like.

[0042]

EXAMPLES <Reference Example 1: Production of crude ethyleneimine> Ethyleneimine was produced according to the method described in Example 1 of JP-B-5-55498. That is, monoethanolamine was added in the presence of a phosphorus-alkaline earth metal-based catalyst at 430 ° C. under a reduced pressure of 400 mmHg at a space velocity of 1000.
The gas phase intramolecular dehydration reaction is carried out by continuously supplying with hr ⁻¹ ,
At the outlet of the reactor, it was cooled to 100 ° C. and condensed, and introduced into a continuous distillation column to distill crude ethyleneimine from the top of the column. In this crude ethyleneimine, 1000 ppm of methylamine,
Ethylamine 6000ppm, acetonitrile 400p
It contained pm and 400 ppm of water.

Reference Example 2: Production of Polymer A reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 60 g of ethylenediamine and 17 g of 35% by volume hydrochloric acid and heated. After heating, the crude ethyleneimine 11 obtained in Reference Example 1
40 g was added under reflux at 100 to 120 ° C. for 10 hours. After the addition was completed, the reaction was completed by aging at 100 to 120 ° C. for 2 hours. The obtained polyethyleneimine had an average weight molecular weight of 3610 (measured by gel permeation chromatography (GPC), converted to bulrun) and a viscosity of 6150 (mPa · s / 25 ° C., B-type viscometer). In addition, for polyethyleneimine, acetonitrile 4
00ppm, light amines such as ammonia 2000p
pm was included.

<Reference Example 3: Removal of impurities in polymer> 1 kg of polyethyleneimine obtained in Reference Example 2 was charged in a 2 liter flask on an oil bath, and 0.2 liter of nitrogen gas (Normal) was added at normal pressure. ) / Min was bubbled into the polymer. During bubbling, the temperature of the polymer was adjusted to 12
Maintained at 0 ° C. After bubbling for 5 hours, the polymer was analyzed and the contents of acetonitrile and light amines were both 1 ppm or less.

<Example 1> Polyethyleneimine of Reference Example 3 (172.3 g) was mixed with Maxblend stirring blade (Sumitomo Heavy Industries, Ltd.), ethylene oxide introducing tube,
A 1.2 L autoclave equipped with a nitrogen introduction tube and a pressure gauge was charged and the temperature was raised to 150 ° C. Thereafter, 167.4 g of ethylene oxide was fed to add about 0.95 mol of ethylene oxide to active hydrogen. The acetonitrile concentration in the used polyethyleneimine was 1 ppm or less as described above.

Next, the temperature was lowered to 80 ° C. and 49% KOH was added to 2%.
After charging 5 g and raising the temperature to 165 ° C., the pressure was reduced to 0.05 MPa while bubbling nitrogen at a flow rate of 20 ml / min.
After dehydration, 361 g of ethylene oxide was fed to add a total of about 3 mol of ethylene oxide to active hydrogen.

Then, the mixture was cooled to 80 ° C., 14 g of water and acetic acid were added to adjust the pH to 7, and the pressure was reduced to 0.005 MPa while bubbling nitrogen at a flow rate of 20 ml / min and kept for 5 hours. The concentration of 2,3-butanedione in the product polyamine polyether polyol is 1 ppm
It was below.

The concentration of acetonitrile contained in the used polyethyleneimine was determined by the headspace (TEKM).
Heat treatment at 80 ° C. for 10 minutes by ER), and GC353 (column: J & W Scientific) made by GL Sciences.
ic DB-1 (length 300m, inner diameter 0.53mm,
Using a film thickness of 1 μm and a detector of FID), the amount was quantified based on the calibration curve of acetonitrile. Quantitation limit is 1
It was ppm. Further, the concentration of 2,3-butanedione in the product was 80 in headspace (manufactured by TEKMER).
Heat-treated at 10 ° C for 10 minutes, GL Sciences Corporation GC353
(Column: DB-1 manufactured by J & W Scientific)
(Length 30 m, inner diameter 0.53 mm, film thickness 1 μm), detector: FID, using 2,3-butanedione,
A calibration curve was prepared with isoprene and quantified. The limit of quantification was 1 ppm.

The odor was evaluated by a sensory test by 5 people.
The test conditions were as follows: 1 g of a sample was placed in a 100 cc glass sample bottle, allowed to stand at 20 ° C. for 1 hour, and then smelled for evaluation according to the following criteria and scored.・ Unbearable odor 6 points ・ Unpleasant odor 5 points ・ Unpleasant odor 4 points ・ Slightly unpleasant odor 3 points ・ Slight odor 2 points ・ No odor 1 point The odor was 2 points. Further, the coloring was 400 as measured by APHA. The results are shown in Table 1.

Comparative Example 1 A polyamine polyether polyol was produced in the same manner as in Example 1 except that polyethyleneimine containing 195 ppm of acetonitrile was used as a raw material. The concentration of 2,3-butanedione in the polyamine polyether polyol was 8.5 ppm. In addition, the odor was measured to be 4 points, and the coloring was 7
It was 00. The results are shown in Table 1.

[0051]

[Table 1]

As shown in Table 1, Example 1 according to the present invention
The polyamine polyether polyols of (3) were excellent in both odor and color and were shown to be of high quality.

[0053]

EFFECTS OF THE INVENTION By reducing the concentration of acetonitrile in polyalkyleneimine, it is possible to suppress the production of impurities causing an offensive odor contained in the produced polyamine polyether polyol, and as a product of polyamine polyether polyol. The quality of can be improved. Furthermore, by reducing the concentration of acetonitrile in the polyalkyleneimine, the effect of increasing the stability of the obtained polyamine polyether polyol can be obtained.

Claims (2)

[Claims] 1. The amino group of polyalkyleneimine contains N
A polyamine polyether polyol in which 0.5 to 200 mol of alkylene oxide is added to 1 mol of H bond, which is contained in the polyamine polyether polyol.
A polyamine polyether polyol having a 3-butanedione concentration of 5 ppm or less. 2. A polyalkyleneimine having an acetonitrile content of 5 ppm or less is added with 0.5 to 200 moles of alkylene oxide to 1 mole of NH bond of the polyalkyleneimine to obtain 2,3-butanedione concentration. A method for producing a polyamine polyether polyol of 5 ppm or less.