JP2001213958A - Ethyleneimine polymer and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrially advantageous, low-cost ethyleneimine polymer and a production method thereof. SOLUTION: This ethyleneimine polymer is produced by polymerizing crude ethyleneimine which is prepared by subjecting an ethyleneimine-containing reaction mixture formed by the intramolecular dehydration reaction of ethanolamine to a simple distillation operation, especially crude ethyleneimine which has an impurity content adjusted to a value in a specified range.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and industrially useful ethyleneimine polymer and a method for producing the same.

[0002]

2. Description of the Related Art It is known that monoethanolamine undergoes an intramolecular dehydration reaction in the presence of a catalyst to obtain ethyleneimine. As the catalyst, for example, a tantalum-based catalyst (US Pat. Nos. 4,289,656 and 4,337,175)
Nos. 4,477,591), silicon-
Alkali metal and / or alkaline earth metal catalysts (JP-B-5-13699, JP-A-5-13700, etc.), phosphorus-alkali metal and / or alkaline-earth metal catalysts (JP-B 5-76344, 5-873
Nos. 01, 5-76343, 5-55498, 5-16905, etc.), and a ceramic carrier formed by molding the silicon / phosphorus-alkali metal / alkaline earth metal catalyst composition. Supported catalysts (JP-A-9-132564, JP-A-9-194455, etc.) are known.

[0003] These catalysts are used in part for the production of ethyleneimine on an industrial scale. Then, the ethyleneimine-containing reaction mixture obtained by this reaction is purified through a high-level purification step, and the purified ethyleneimine is used for synthesizing various ethyleneimine polymers. That is, in the ethyleneimine-containing reaction mixture obtained by the intramolecular dehydration reaction of monoethanolamine, in addition to the target ethyleneimine, unreacted monoethanolamine and oligomers of ethyleneimine, ketones such as acetaldehyde, It contains heavy impurities such as Schiff bases generated by the reaction of acetaldehyde with the raw material monoethanolamine, light amines such as ammonia, methylamine and ethylamine, and light impurities such as acetonitrile. The purified ethyleneimine obtained after that is subjected to a polymerization reaction.

[0004]

The prior art for producing an ethyleneimine polymer using purified ethyleneimine obtained through an advanced purification step is unavoidable to increase the production cost accompanying the execution of the advanced purification step. It is not industrially advantageous.

The present invention solves the above-mentioned problems of the prior art,
It is an object of the present invention to provide an industrially advantageous ethyleneimine polymer having a reduced production cost and a method for producing the same.

[0006]

Means for Solving the Problems The inventors of the present invention have found that a reaction mixture containing ethyleneimine obtained by subjecting ethanolamine to intramolecular dehydration reaction is subjected to a simple distillation operation to obtain a crude ethyleneimine, particularly an impurity content. By using crude ethyleneimine adjusted to a specific range, it was found that an ethyleneimine polymer having exactly the same performance as a conventional ethyleneimine polymer obtained using purified ethyleneimine as a raw material could be produced, and based on this finding, Thus, the present invention has been completed.

That is, the present invention is an ethyleneimine polymer obtained by polymerizing crude ethyleneimine obtained by subjecting monoethanolamine to intramolecular dehydration reaction in the presence of a catalyst.

Further, the present invention provides a method for producing an ethyleneimine polymer, which comprises subjecting monoethanolamine to an intramolecular dehydration reaction in the presence of a catalyst to produce a crude ethyleneimine, and then polymerizing the crude ethyleneimine. Is the way.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an ethyleneimine-containing reaction mixture by subjecting monoethanolamine to intramolecular dehydration reaction in the presence of a catalyst is not particularly limited, and can be carried out by a generally well-known method. it can. Specifically, monoethanolamine is vaporized and optionally diluted with an inert gas such as nitrogen, or ammonia, water vapor, hydrogen, or the like is added for the purpose of suppressing side reactions, and the catalyst layer is used as a raw material gas. To be introduced. The reaction pressure may be normal pressure, reduced pressure or increased pressure. The reaction temperature is usually in the range of 300 to 500C. The space velocity of the source gas varies depending on the concentration of monoethanolamine, the type of catalyst used, and the like, and cannot be specified unconditionally.
It is in the range of 5000 h ^-1 . There is no particular limitation on the catalyst to be used, and the catalyst described in the above specification or publication can be used. Above all, Tokuho 5-13699
Nos. 5-13700, 5-76344, 5-
No. 87301, No. 5-76343, No. 5-55498
And the catalysts described in JP-A-5-16905 are preferably used.

The ethyleneimine-containing reaction mixture obtained by the above-mentioned gas-phase intramolecular dehydration reaction is collected using a collecting agent or condensed and collected. As the collecting agent, an amine compound is preferable, and in particular, monoethanolamine is also a raw material and most preferable. The ethyleneimine-containing reaction mixture mainly contains ethyleneimine, unreacted monoethanolamine and water, and as by-products, ammonia, light amines such as methylamine and ethylamine, acetonitrile, and ketones such as acetaldehyde; It contains Schiff bases formed by reacting acetaldehyde with monoethanolamine as a raw material.

In the present invention, the ethyleneimine-containing reaction mixture is subjected to a simple distillation operation, and the ethyleneimine content is 90% by mass or more, preferably 9% by mass, from the top of the distillation column.
5 to 99.9% by mass, monoethanolamine content is 1
Less than 000 ppm (mass; the same applies hereinafter), preferably 5
Crude ethyleneimine having a total content of light amines of less than 00 ppm, ammonia, methylamine and ethylamine of less than 2% by mass, preferably less than 1% by mass, and further containing less than 2% by mass, preferably less than 1% by mass of acetonitrile Get.

In addition, the crude ethyleneimine as described above can be obtained by contacting the ethyleneimine-containing reaction mixture with an organic solvent such as toluene or xylene to extract heavy components in the reaction mixture.

If the content of ethyleneimine in the crude ethyleneimine is less than 90% by mass or the content of impurities exceeds each of the above ranges, problems such as deterioration of the performance of the ethyleneimine polymer occur, which is not preferable.

In the present invention, the above crude ethyleneimine is recovered from the ethyleneimine-containing reaction mixture by a simple distillation or extraction operation, and then the crude ethyleneimine is polymerized to produce an ethyleneimine polymer.

There is no particular limitation on the method for producing an ethyleneimine polymer using crude ethyleneimine, and it can be produced by a method generally used for producing an ethyleneimine polymer. The polymerization catalyst, polymerization conditions, and the like can be appropriately selected from those generally used for the polymerization of ethyleneimine. For example, the crude ethyleneimine may be reacted at 0 to 200 ° C. in the presence of an effective amount of an acid catalyst such as hydrochloric acid. Further, the crude ethyleneimine may be subjected to addition polymerization based on the ethyleneimine polymer.
The ethyleneimine polymers of the present invention include ethyleneimine homopolymers and compounds copolymerizable with ethyleneimine, for example, copolymers with amines. For the method for producing such an ethyleneimine polymer, for example, JP-B-43-8828 and JP-B-49-33120 can be referred to.

The ethyleneimine polymer of the present invention has an average weight molecular weight of 1,000 to 1,000,000 (measured by gel permeation chromatography (GPC), in terms of pullulan). Agents, adhesives, paints, inks, fiber treatment agents, flocculants, cosmetics,
It is widely used in the fields of toiletries and dispersants.

[0017]

The ethyleneimine polymer of the present invention has the same performance as the ethyleneimine polymer obtained by using purified ethyleneimine, and uses the crude ethyleneimine obtained by a simple distillation operation as a raw material. It can be manufactured at low cost.

According to the method of the present invention, an ethyleneimine polymer can be produced industrially in terms of production cost and production process.

[0019]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In addition, ppm,%, and parts are based on mass unless otherwise specified. Example 1 900 g of aluminum nitrate (9-hydrate) was dissolved in 2.4 liters (L) of water, and triammonium phosphate 3 was added to the solution.
A solution of 57.6 g in 2.4 L of water was added with stirring. The obtained precipitate was filtered and washed with water, and kneaded well using 73.6 g of barium oxide and 100 ml of water.
The obtained viscous substance is formed into a cylindrical pellet having an outer diameter of about 5 mm and a length of about 5 mm, dried, and calcined at 1000 ° C. for 2 hours to obtain Al ₁ P ₁ B _{0.2 in} an atomic ratio excluding oxygen. A catalyst having the composition was obtained.

1 L of this catalyst was filled in a stainless steel reaction tube having an inner diameter of 25 mm, and heated to 430 ° C. with a heating medium.
A continuous reaction was carried out by passing the vaporized monoethanolamine into the reactor at an outlet pressure of the reaction tube of 400 mmHg and a space velocity of 1000 h ^-1 . The composition of the reaction mixture gas generated by the reaction was 67.6% by volume of monoethanolamine, 12.7% by volume of ethyleneimine, 15.6% by volume of water, 1.34% by volume of acetaldehyde, and the others were ammonia and dimers. there were.

After cooling the above reaction mixture gas to 100 ° C., it was introduced into a stainless steel distillation column having an inner diameter of 50 mm and a height of 2000 mm. The column is filled with 6.35 mm packing (McMahon Packing) to a height of 1600 mm, and the reaction mixture is introduced from the top of the packed tower to a height of 1/3, and a reflux ratio of 4 Distillation was carried out under the conditions to obtain crude ethyleneimine from the top of the column.

The contents of ethyleneimine and impurities contained in the crude ethyleneimine were as follows. Ethylene imine: 98.5% Monoethanolamine: 400 ppm Total of light amines: 9000 ppm Methylamine: 1000 ppm Ethylamine: 6000 ppm Ammonia: 2000 ppm Acetonitrile: 400 ppm Water: 400 ppm Ethylenediamine 60 in a reactor equipped with a stirrer, reflux condenser and thermometer. And 17 parts of 35% hydrochloric acid. After raising the temperature, 1140 parts of the crude ethyleneimine was added to 1 part.
It was added at 00-120 ° C under reflux over 10 hours. After completion of the addition, the mixture was aged at 100 to 120 ° C. for 2 hours to complete the reaction, thereby obtaining an ethyleneimine polymer (PEI-1). After cooling, the viscosity, pH, resin content and average molecular weight of this PEI-1 were measured by the following methods. Table 1 shows the results. Viscosity (mPa · s / 25 ° C.) Measured using a B-type viscometer. An aqueous solution having a pH of 5% was prepared and measured with a pH meter. Resin content (%) The water content was measured by the Karl Fischer method, and the remaining residue was taken as the resin content. Average weight molecular weight GPC was measured using pullulan as a standard substance. Example 2 In a reactor equipped with a stirrer, a reflux condenser and a thermometer, 72 parts of PEI-1 obtained in Example 1 and 35% hydrochloric acid 1 were added.
7 parts were charged and heated. After the temperature was raised, 1128 parts of the crude ethyleneimine obtained in Example 1 was added at 100 to 120 ° C under reflux over 10 hours. After completion of addition, 100 to 12
The reaction was completed by aging at 0 ° C. for 2 hours to obtain an ethyleneimine polymer (PEI-2). After cooling, the viscosity, pH, resin content and average molecular weight of PEI-2 were measured in the same manner as in Example 1. Table 1 shows the results.

[0023]

[Table 1]

Claims (3)

[Claims] 1. An ethyleneimine polymer obtained by polymerizing a crude ethyleneimine obtained by subjecting monoethanolamine to an intramolecular dehydration reaction in the presence of a catalyst. 2. The crude ethyleneimine has an ethyleneimine content of at least 90% by mass, and has
Monoethanolamine content is 1000ppm (mass)
The ethyleneimine polymer according to claim 1, wherein the total content of light amines composed of ammonia, methylamine and ethylamine is less than 2% by mass, and the acetonitrile content is less than 2% by mass. 3. The ethyleneimine polymer according to claim 1, wherein monoethanolamine is subjected to an intramolecular dehydration reaction in the presence of a catalyst to produce crude ethyleneimine, and then the crude ethyleneimine is polymerized. Manufacturing method.