JP2021147528A - Polyurethane polyamine composition, method for producing polyurethane polyamine, and method for producing polyurethane polyamine composition - Google Patents

Abstract

To provide a method for efficiently synthesizing polyurethane polyamine, a polyurethane polyamine composition with low toxicity and high stability, in which an aziridine compound remaining in a polyurethane polyamine crude product is removed, and a method for producing the composition.SOLUTION: Introducing ethylene imine under high-pressure CO2 heated in a reactor makes it possible to efficiently synthesize a polyurethane polyamine (I) including constitutional units with urethane units and amine units linked together. Adding a specific solvent after the reaction and removing the solvent with heat makes it possible to remove an aziridine compound remaining in a polyurethane polyamine resin composition.SELECTED DRAWING: None

Description

The present invention relates to a polyurethane polyamine composition, a method for producing a polyurethane polyamine, and a method for producing a polyurethane polyamine composition.

Conventionally, when producing polyurethane polyamine (polyurethane polyamine resin), ethyleneimine, which is a concern for toxicity, is used as a raw material, but unreacted ethyleneimine remains in the product polyurethane polyamine resin, which is safe. , There was a problem that adversely affected the stability. In the formulation of Non-Patent Document 1, the raw materials are mixed in a reactor cooled to liquid nitrogen temperature, then heated to 80 ° C. and reacted under high pressure for 18 hours, and ethyleneimine is removed under reduced pressure to remove solid content. It was an inefficient process in terms of energy consumption and complicated operation.

In Non-Patent Document 2, 2-methylaziridine (propyleneimine) is introduced into an autoclave filled with argon gas, cooled CO ₂ is added, and the mixture is reacted at 100 ° C. for 24 hours to obtain 2-methylaziridine and CO ₂ . It is described that the copolymer was synthesized. However, Non-Patent Document 2 does not describe the synthesis of polyurethane polyamines using ethyleneimine as a raw material. Ethylene imine and propylene imine are structurally similar but have completely different reactivity.

K. Soga, et. al. , Die Macintosh Chemie 1974, 175, 3309-3313 T. Ikariya et. al. , Macromolecules 2005, 38, 6429-6434

An object of the present invention is to provide a method capable of efficiently synthesizing a polyurethane polyamine using ethyleneimine as a raw material. Another object of the present invention is to provide a low-toxicity, high-stability polyurethane polyamine composition in which the aziridine compound remaining in the polyurethane polyamine is removed, and a method for producing the composition.

The present inventor has found that a polyurethane polyamine can be efficiently synthesized by introducing ethyleneimine under _{high pressure CO 2 which has been} heated in a reactor, and has completed the present invention.
Further, by adding a specific solvent after the reaction and distilling off the solvent while heating, it becomes possible to remove the aziridine compound remaining in the crude polyurethane polyamine, and the polyurethane has low toxicity and high stability. They have found that a polyamine composition can be produced and provided, and have completed the present invention.

That is, the polyurethane polyamine composition of the present invention is a polyurethane containing a structural unit in which a urethane unit represented by the following formulas (1) to (3) and an amine unit represented by the following formulas (4) to (6) are connected. It contains polyamine (I), and the content of ethyleneimine is less than 0.1% by mass with respect to 100% by mass of the polyurethane polyamine (I).

Further, in the method for producing a polyurethane polyamine of the present invention, ethyleneimine is added and mixed with carbon dioxide in a supercritical state to react with the urethane unit represented by the above formulas (1) to (3) and the above formula. It is characterized by including a step of producing the polyurethane polyamine (I) including a structural unit in which the amine units represented by (4) to (6) are connected.

The present invention also comprises a polyurethane polyamine (G) containing a structural unit in which a urethane unit represented by the following formulas (19) to (21) and an amine unit represented by the following formulas (22) to (24) are connected. With respect to the crude polyurethane polyamine containing 0.1% by mass or more of the aziridine compound with respect to 100% by mass of the polyurethane polyamine (G), a solvent having a boiling point higher than that of the aziridine compound is added to 100% by mass of the crude product. It is a method for producing a polyurethane polyamine composition, which comprises a step of adding 1% by mass or more thereof and distilling off 1% by mass or more of the solvent in 100% by mass.

In the above formula, A _{1 to} A ₃ , B _{1 to} B ₂ , C _{1 to} C ₃ , D _{1 to} D ₃ , E _{1 to} E ₂ , and F ₁ have the same or different substituents, respectively. It may be a methylene group.

According to the present invention, it is possible to provide an efficient method for synthesizing a polyurethane polyamine using ethyleneimine as a raw material. In addition, the aziridine compound remaining in the crude polyurethane polyamine is removed, and a polyurethane polyamine composition having low toxicity and high stability, and a method for producing the composition can be provided.

1. 1. Polyurethane polyamine composition The polyurethane polyamine composition of the present invention is a constituent unit in which urethane units represented by the following formulas (1) to (3) and amine units represented by the following formulas (4) to (6) are connected. Contains polyurethane polyamine (I) containing, and the content of ethyleneimine is less than 0.1% by mass with respect to 100% by mass of the polyurethane polyamine (I). The polyurethane polyamine (I) preferably contains the following structural units.
-A structural unit in which a urethane unit represented by the following formula (1) and an amine unit represented by the following formula (4) are connected.
A structural unit in which the urethane unit represented by the following formula (1) and the amine unit represented by the following formula (5) are connected.
-A structural unit in which a urethane unit represented by the following formula (1) and an amine unit represented by the following formula (6) are connected.
-A structural unit in which a urethane unit represented by the following formula (2) and an amine unit represented by the following formula (4) are connected.
-A structural unit in which a urethane unit represented by the following formula (2) and an amine unit represented by the following formula (5) are connected.
-A structural unit in which a urethane unit represented by the following formula (2) and an amine unit represented by the following formula (6) are connected.
-A structural unit in which a urethane unit represented by the following formula (3) and an amine unit represented by the following formula (4) are connected.
-A structural unit in which a urethane unit represented by the following formula (3) and an amine unit represented by the following formula (5) are connected, and-a urethane unit represented by the following formula (3) and the following formula (6). A structural unit connected to the amine unit represented by.

Further, the polyurethane polyamine (I) is a carbamic acid unit represented by the following formulas (7) to (9), an aziridine unit represented by the following formulas (10) to (11), and the following formulas (12) to ( It may contain a urea unit represented by 18).

In the present specification, the polyurethane polyamine refers to a material having a urethane ratio of 7% or more. Here, the urethane ratio in the polyurethane polyamine (I) is a ^{value obtained from the area ratio of 1} HNMR as the urethane unit-derived methylene peak area / total methylene peak area = mol%.

The polyurethane polyamine (I) is preferably a polyurethane polyamine having 70% by mass or more of the structural units represented by the above formulas (1) to (18) in terms of mass ratio, and is preferably a polyurethane polyamine having 80% by mass or more. Is more preferable, and a polyurethane polyamine having 90% by mass or more is further preferable. The upper limit is 100% by mass.

The urethane ratio in the polyurethane polyamine (I) can be arbitrarily selected depending on the intended use, but is preferably 10% or more, more preferably 15% or more, and more preferably 20% or more. More preferred. The upper limit is about 100%. When the urethane ratio is in a preferable range, the performance such as dispersibility and adhesion derived from the urethane structure can be sufficiently exhibited. Here, the method for measuring the urethane ratio in the polyurethane polyamine (I) is as described above.

The preferable range of the average molecular weight of the polyurethane polyamine (I) varies depending on the application, but when it is used as a dispersant or the like, the weight average molecular weight Mw is preferably about 1,000 to 20,000. The number average molecular weight Mn is preferably about 500 to 10,000. The Mw / Mn is preferably about 1.0 to 3.0. When used as a molding material or an adhesive, a high molecular weight substance is preferable, and the weight average molecular weight Mw is preferably about 3,000 to 300,000. The number average molecular weight Mn is preferably about 2,000 to 200,000. The Mw / Mn is preferably about 1.0 to 5.0.

The content of ethyleneimine in the polyurethane polyamine composition of the present invention is preferably 1000 ppm or less with respect to 100% by mass of the polyurethane polyamine (I). The Industrial Safety and Health Act also designates substances containing 1000 ppm or more of ethyleneimine as substances subject to labeling and notification obligations from the viewpoint of hazards. In order to enhance safety in handling, it is more preferably 100 ppm or less, further preferably 10 ppm or less, and particularly preferably 1 ppm or less. The lower limit of the ethyleneimine content is 0 ppm.

The content of the polyurethane polyamine (I) in the polyurethane polyamine composition of the present invention can be arbitrarily selected according to the purpose of use, but from the viewpoint of functional imparting and transport efficiency, 100% by mass of the composition It is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 40% by mass or more. The upper limit is 100% by mass.

The polyurethane polyamine composition of the present invention may contain a solvent. Examples of the solvent include water; alcohols such as methanol, ethanol and isopropyl alcohol; ethers such as tetrahydrofuran and diethylene glycol dimethyl ether: esters such as ethyl acetate and cellsolve acetate; acetonitrile, N, N-dimethylformamide, N, N- Examples thereof include aprotic polar solvents such as dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone. The content of the solvent is preferably 0 to 90% by mass, more preferably 0 to 80% by mass, still more preferably 0 to 60% by mass, based on 100% by mass of the composition.

Since the polyurethane polyamine composition of the present invention has low toxicity and high stability, it can be used in various applications such as dispersants, coating agents, adhesives, gas barrier films, and gas separation membranes. Polyurethane is functionally adopted in all fields, and in particular, polyurethane polyamine (I) having a structural unit represented by the above formulas (4) to (6) has high reactivity with an electrophile1. Since it is a polyurethane having a secondary amine and / or a secondary amine, various functionalizations can be expected by using various electrophiles.

2. Method for Producing Polyurethane Polyamine In the method for producing polyurethane polyamine of the present invention, ethyleneimine is added and mixed with carbon dioxide in a supercritical state and reacted, and the urethane unit represented by the above formulas (1) to (3) is formed. It is characterized by including a step of producing a polyurethane polyamine (I) containing a structural unit in which the amine unit represented by the above formulas (4) to (6) is connected.

Carbon dioxide in a supercritical state is obtained by introducing carbon dioxide into a reaction vessel and setting the temperature and pressure inside the reaction vessel to a temperature and pressure equal to or higher than the critical point of carbon dioxide. The reaction vessel may be heated to a temperature equal to or higher than the critical point of carbon dioxide, and carbon dioxide may be introduced to bring the pressure above the critical point of carbon dioxide. As the temperature and pressure above the critical point of carbon dioxide, the temperature is preferably 31.1 to 180 ° C. and the pressure is 7.38 to 60 MPa, more preferably the temperature is 50 to 150 ° C. and the pressure is 10 to 50 MPa, and the temperature is 70 to 120 ° C. A pressure of 20-40 MPa is more preferred. If the pressure drops due to the consumption of carbon dioxide as the reaction progresses, it is particularly preferred to add carbon dioxide and maintain a preferred pressure range until the end of the reaction. When the temperature is raised after mixing carbon dioxide and ethyleneimine that are not in the supercritical state, the introduction rate of the urethane unit is low, polyurethane polyamine cannot be obtained, and polyethyleneimine is mainly obtained.

Further, carbon dioxide in a supercritical state may contain a solvent. Examples of the solvent include alcohols such as methanol, ethanol and propanol; ethers such as tetrahydrofuran and diethylene glycol dimethyl ether; esters such as ethyl acetate and cellsolve acetate; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, etc. Aprotic polar solvents such as dimethyl sulfoxide and N-methylpyrrolidone are preferable. One type of these solvents may be used, or two or more types may be mixed and used. The amount of the solvent used is preferably 0 to 500% by mass, more preferably 0 to 200% by mass, still more preferably 0 to 100% by mass, based on 100% by mass of carbon dioxide.

The mixing ratio of carbon dioxide and ethyleneimine is preferably carbon dioxide / ethyleneimine = 100 to 0.2, more preferably 50 to 0.5, and even more preferably 20 to 1.0 in terms of molar ratio. A mixing method in which ethyleneimine is sequentially introduced so that carbon dioxide is always present in excess in the reaction vessel is preferable when increasing the urethane ratio.

The above ethyleneimine may be diluted with a solvent and added to the reaction system. Examples of the solvent include alcohols such as methanol, ethanol and propanol; ethers such as tetrahydrofuran and diethylene glycol dimethyl ether; esters such as ethyl acetate and cellsolve acetate; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, etc. Aprotic polar solvents such as dimethyl sulfoxide and N-methylpyrrolidone are preferable. One type of these solvents may be used, or two or more types may be mixed and used. The amount of the solvent used is preferably 20 to 1000% by mass, more preferably 50 to 500% by mass, still more preferably 100 to 200% by mass, based on 100% by mass of ethyleneimine.

The method for producing a polyurethane polyamine of the present invention does not particularly require a catalyst, but the use of a catalyst or a polymerization initiator makes it possible to moderate the reaction conditions and control the molecular weight. As the catalyst, both an acid catalyst and a base catalyst can be used, but a base catalyst is preferable, and inorganic strong bases such as sodium hydroxide and potassium hydroxide; 1,8-bis (dimethylamino) naphthalene, 1, Examples thereof include organic strong bases such as 8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclooctane, metal alkoxide, and metal phenoxide. The amount of the catalyst used is preferably about 0.001 to 10% by mass with respect to 100% by mass of ethyleneimine.

When adding / mixing ethyleneimine to carbon dioxide in a supercritical state and reacting it, it is necessary to adjust the addition / mixing rate so that the heat generated by the reaction can be sufficiently slowed down, so it is set appropriately according to the scale. However, the addition / mixing time is preferably 1 minute or longer, more preferably 5 minutes or longer, and even more preferably 30 minutes or longer. The aging time for completing the reaction after addition and mixing is preferably 10 minutes or more, more preferably 30 minutes or more, still more preferably 1 hour or more. The upper limit of the total time required for addition / mixing and aging is preferably 48 hours or less, more preferably 24 hours or less from the viewpoint of economy and the like.

In the method for producing a polyurethane polyamine of the present invention, a distribution system reactor can also be used, and as the reactor, a tube type, a continuous tank type, or the like can be arbitrarily selected. The reaction conditions can be arbitrarily selected from the above-mentioned preferable forms, but in order to avoid clogging in the distribution system, it is preferable to dilute with a solvent and send the liquid. The amount of the solvent used is preferably 20 to 1000% by mass, more preferably 50 to 800% by mass, still more preferably 100 to 600% by mass, based on 100% by mass of ethyleneimine.

3. 3. Method for Producing Polyamine Polyamine Composition The method for producing the polyurethane polyamine composition of the present invention is a urethane unit represented by the following formulas (19) to (21) and an amine unit represented by the following formulas (22) to (24). The aziridine compound with respect to the crude product of the polyurethane polyamine containing 0.1% by mass or more of the aziridine compound with respect to 100% by mass of the polyurethane polyamine (G) and the polyurethane polyamine (G) containing the structural unit connected to the above. It is characterized by comprising a step of adding 1% by mass or more of a solvent having a higher boiling point to 100% by mass of the crude product and distilling off 1% by mass or more of the 100% by mass of the solvent.

In the above formula, A _{1 to} A ₃ , B _{1 to} B ₂ , C _{1 to} C ₃ , D _{1 to} D ₃ , E _{1 to} E ₂ , and F ₁ have the same or different substituents, respectively. It may be a methylene group. Examples of the substituent include a methyl group and an ethyl group. The polyurethane polyamine (G) may contain the polyurethane polyamine (I) or may be the polyurethane polyamine (I).

The content of the polyurethane polyamine (G) contained in the crude polyurethane polyamine can be arbitrarily selected according to the purpose of use, but from the viewpoint of function addition and transportation efficiency, it is contained in 100% by mass of the crude product. 10% by mass or more is preferable, 20% by mass or more is more preferable, and 50% by mass or more is further preferable.

Examples of the aziridine compound contained in the crude polyurethane polyamine include ethyleneimine, propyleneimine, 2,2-dimethylaziridine, and 2-ethylaziridine.

Examples of the solvent having a higher boiling point than the aziridine compound include water; alcohols such as ethanol and propanol; ethers such as tetrahydrofuran and diethylene glycol dimethyl ether; esters such as ethyl acetate and cellsolve acetate; acetonitrile, N, N-dimethylformamide, Examples thereof include aprotic polar solvents such as N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and gamma-butyrolactone. One type of these solvents may be used, or two or more types may be mixed and used. The type of solvent can be appropriately selected depending on the purpose of use, but water, ethanol, propanol and tetrahydrofuran are preferable. The amount of the solvent added can be appropriately selected depending on the type of solvent and the purpose of use of the polyurethane polyamine composition, but is 1% by mass or more and 10 to 1000% by mass with respect to 100% by mass of the composition. % Is preferable, 20 to 500% by mass is more preferable, and 50 to 200% by mass is further preferable. As a method for adding the solvent, a method of sequentially adding the solvent while distilling off the solvent is particularly preferable.

The distilling conditions for a solvent having a boiling point higher than that of the aziridine compound can be appropriately selected depending on the type and concentration of the solvent, but the temperature is 60 to 120 ° C. and the pressure is −0.1 to 0.20 MPa (gauge pressure). ), And the time can be appropriately adjusted depending on the type of solvent and the concentration of the polyurethane polyamine composition to be obtained, but it is preferably about 1 to 24 hours.

The amount of the solvent having a boiling point higher than that of the aziridine compound can be appropriately adjusted depending on the content of the aziridine compound and the concentration of the polyurethane polyamine composition to be obtained, but in 100% by mass of the solvent. It is 1% by mass or more, preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass. It is particularly preferable that the amount of the solvent having a boiling point higher than that of the aziridine compound is approximately ½ (mass ratio) of the amount added, which is approximately equal to the amount of the bottom residual solvent.

According to the method for producing a polyurethane polyamine composition of the present invention, the content of the aziridine compound is less than 0.1% by mass with respect to 100% by mass of the polyurethane polyamine (G), and the polyurethane polyamine composition has low toxicity and high stability. You get things.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

The urethane ratio of the reaction product was calculated from the peak area ratio by measuring ^{1 1 HNMR by the following method.}
Equipment: JEOL ECA400
Frequency: 400MHz
Solvent: D ₂ O
Formula: Urethane ratio (mol%) = Urethane unit-derived methylene peak area / total methylene peak area x 100

The molecular weight of the reaction product was calculated by GPC measurement by the following method. Polyethylene glycol (PEG) was used as the reference material to create the composition curve. As the buffer solution, an acetic acid aqueous solution to which monoethanolamine was added was used.
Device: Agilent Technologies. LC1620, Biotage ELSD A-120
Column: Asahipak GF-710HQ, 510HQ, 310HQ

The content of ethyleneimine in the composition was measured by gas chromatography by the following method and calculated from the peak area by the absolute calibration curve method.
Equipment: Perkin Turbomatrix 40, Shimadzu GC-2014
Capillary column: GL Science Inert Cap 210

Example 1
While press-fitting carbon dioxide into the autoclave, the temperature was raised to 120 ° C. The pressure in the autoclave was 27 MPa, and carbon dioxide was in a supercritical state. A solution prepared by mixing 4.9 g of ethyleneimine (manufactured by Nippon Shokubai Co., Ltd.) with 4.9 g of ethanol was introduced over 5 minutes, aged for 3 hours, cooled to room temperature, and then stepped down to obtain a reaction product. .. 20 g of water was added to the above reaction product to dissolve the reaction product. The mixture was distilled off under reduced pressure at a temperature of 90 ° C. and a pressure of 0.05 MPa for 2 hours. The reservoir was 4 g of ethanol and 20 g of water, and 3.75 g of polyurethane polyamine was obtained as the final product.
The urethane ratio of the obtained polyurethane polyamine was 21%, Mw was 27,000, Mn was 3,900, and the content of ethyleneimine in the above mixture was below the detection limit (1 ppm or less).

Comparative Example 1 1 g of ethyleneimine (manufactured by Nippon Shokubai Co., Ltd.) was placed in a prescription autoclave of Non-Patent Document 1, cooled to −70 ° C., and 29 g of carbon dioxide was introduced and sealed. When the autoclave was heated to 100 ° C., the internal pressure reached 20 MPa and the reaction was carried out for 16 hours. Then, unreacted carbon dioxide was discharged, and the reaction product was dried at room temperature at a pressure of −0.1 MPa to obtain 1.4 g of the reaction product.
The urethane ratio of the reaction product was 23%, Mw was 6,000, Mn was 2,400, and the content of ethyleneimine was 1200 ppm.

Comparative Example 2 When 1.6 g of ethyleneimine (manufactured by Nippon Shokubai Co., Ltd.) was placed in a prescription autoclave of Non-Patent Document 2 using ethyleneimine as a raw material and 12 g of carbon dioxide was introduced at 30 ° C., the polymerization reaction started. , The internal temperature of the autoclave rose to 150 ° C. or higher. The pressure in the autoclave increased from 6 MPa to 20 MPa. After cooling to room temperature, unreacted carbon dioxide was discharged to obtain 1.9 g of a reaction product. The urethane ratio of the reaction product was 6%, Mw was 23,000, Mn was 6,500, polyurethane polyamine was not obtained, and polyethyleneimine was obtained.

Example 2
300 g of carbon dioxide was placed in an autoclave and the temperature was raised to 100 ° C. The pressure in the autoclave was 10 MPa, and carbon dioxide was in a supercritical state. 50 g of acetonitrile is added thereto, and 300 g of a solution prepared by mixing ethyleneimine (manufactured by Nippon Shokubai Co., Ltd.) and acetonitrile in a weight ratio of 1: 1 is introduced over 90 minutes and aged at 100 to 117 ° C. for 1 hour to 50 ° C. After cooling, 300 g of water was added to the autoclave to dissolve the reaction product and discharge unreacted carbon dioxide to obtain a crude polyurethane polyamine. The content of ethyleneimine was 1160 ppm.
The solvent was distilled off from the crude polyurethane polyamine product at a temperature of 60 to 90 ° C. and a pressure of −0.09 to 0.05 MPa for 2 hours under reduced pressure. The reservoir was 200 g of acetonitrile and 180 g of water, and as a final product, a mixture of 146 g of polyurethane polyamine and 110 g of water was obtained.
The urethane ratio of the obtained polyurethane polyamine was 19%, Mw was 63,000, Mn was 3,700, and the content of ethyleneimine in the above mixture was 54 ppm.

Example 3
300 g of carbon dioxide was placed in an autoclave and the temperature was raised to 105 ° C. The pressure in the autoclave was 10 MPa, and carbon dioxide was in a supercritical state. To this, 1100 g of a solution prepared by mixing ethyleneimine (manufactured by Nippon Shokubai Co., Ltd.), methanol and tetrahydrofuran in a weight ratio of 1: 1: 1 was introduced over 210 minutes, and aged at 105-119 ° C. for 1 hour to 100 ° C. 200 g of water was added to dissolve the reaction product. Unreacted carbon dioxide was discharged, and the mixture was distilled off under reduced pressure at a temperature of 80 to 90 ° C. and a pressure of −0.05 to 0 MPa for 5 hours while introducing 1000 g of water. The reservoir was 210 g of methanol, 150 g of tetrahydrofuran and 700 g of water, and as a final product, a mixture of 680 g of polyurethane polyamine and 460 g of water was obtained.
The urethane ratio of the obtained polyurethane polyamine was 17%, Mw was 3,900, Mn was 2,000, and the content of ethyleneimine in the above mixture was below the detection limit (1 ppm or less).

Example 4
340 g of carbon dioxide was placed in an autoclave and the temperature was raised to 85 ° C. The pressure in the autoclave was 10 MPa, and carbon dioxide was in a supercritical state. To this, 800 g of a solution prepared by mixing ethyleneimine (manufactured by Nippon Shokubai Co., Ltd.) with isopropyl alcohol at a weight ratio of 1: 2 was introduced over 90 minutes, aged at 85 to 100 ° C. for 1 hour, and 310 g of water was added to generate a reaction. The thing was dissolved. Unreacted carbon dioxide was discharged and distilled off at a temperature of 90 ° C. and a pressure of 0 MPa for 0.5 hours. The reservoir was 400 g of isopropyl alcohol and 200 g of water, and as a final product, a mixture of 250 g of polyurethane polyamine and 110 g of water was obtained.
The urethane ratio of the obtained polyurethane polyamine was 23%, Mw was 5,200, Mn was 3,200, and the content of ethyleneimine in the above mixture was 2 ppm.

Example 5
300 g of carbon dioxide and 0.2 g of sodium hydroxide as a catalyst were placed in an autoclave, and the temperature was raised to 90 ° C. The pressure in the autoclave was 10 MPa, and carbon dioxide was in a supercritical state. To this, 840 g of a solution prepared by mixing ethyleneimine (manufactured by Nippon Shokubai Co., Ltd.) with ethanol at a weight ratio of 1: 2 was introduced over 90 minutes, aged at 110 to 118 ° C. for 1 hour, cooled to 100 ° C., and then 260 g of water. Was added to dissolve the reaction product. Unreacted carbon dioxide was discharged, and 360 g of water was introduced at a temperature of 90 ° C. and a pressure of −0.05 to 0 MPa, and the mixture was distilled off under reduced pressure for 2 hours. The reservoir was 470 g of ethanol and 240 g of water, and as a final product, a mixture of 340 g of polyurethane polyamine and 310 g of water was obtained.
The urethane ratio of the obtained polyurethane polyamine was 26%, Mw was 3,000, Mn was 1800, and the content of ethyleneimine in the above mixture was below the detection limit (1 ppm or less).

Example 6
The autoclave was filled with argon gas, and 2 g of propyleneimine (manufactured by Tokyo Kasei Co., Ltd.) was added at room temperature of 30 ° C. or lower. Further, 30 g of carbon dioxide was introduced and sealed, and then the temperature of the autoclave was raised to 100 ° C. The pressure in the autoclave was 22 MPa, and the reaction was carried out in this state for 20 hours. After cooling to room temperature, unreacted carbon dioxide was discharged to obtain 3 g of a reaction product. The reaction product was a polyurethane polyamine having a urethane ratio of 48%. This polyurethane polyamine had a methyl group as a substituent on the methylene group.
10 g of water was added to 3 g of the above reaction product to dissolve the reaction product to obtain a polyurethane polyamine composition. The content of propyleneimine was 5000 ppm. The solvent was distilled off under reduced pressure at a temperature of 90 ° C. and a pressure of −0.06 MPa for 2 hours. The reservoir was 9 g of water and a mixture of 2.5 g of polyurethane polyamine and 1 g of water was obtained as the final product.
The urethane ratio of the obtained polyurethane polyamine was 48%, and the content of propyleneimine in the above mixture was 50 ppm.

Example 7
35 g of carbon dioxide was placed in an autoclave and the temperature was raised to 100 ° C. The pressure in the autoclave was 30 MPa, and carbon dioxide was in a supercritical state. To this, 15 g of a solution prepared by mixing ethyleneimine (manufactured by Nippon Shokubai Co., Ltd.) with ethanol at a weight ratio of 1: 2 was introduced over 30 minutes, aged at 100 ° C. for 16 hours, and 15 g of water was added to dissolve the reaction product. , Unreacted carbon dioxide was discharged to obtain 30 g of a polyurethane polyamine composition. The content of ethyleneimine was 1600 ppm.
From the obtained polyurethane polyamine composition, the solvent was distilled off under reduced pressure at a temperature of 90 ° C. and a pressure of −0.06 MPa for 2 hours. The reservoir was ethanol and water, and 4.9 g of polyurethane polyamine composition was obtained as the final product.
The urethane ratio of the obtained polyurethane polyamine was 36%, Mw was 4,700, Mn was 1,900, and the content of ethyleneimine in the above composition was 30 ppm.

Example 8
35 g of carbon dioxide was placed in an autoclave and the temperature was raised to 100 ° C. The pressure in the autoclave was 30 MPa, and carbon dioxide was in a supercritical state. To this, 13 g of a solution prepared by mixing ethyleneimine (manufactured by Nippon Shokubai Co., Ltd.) with isopropyl alcohol at a weight ratio of 1: 2 was introduced over 30 minutes, aged at 100 ° C. for 16 hours, and 15 g of water was added to dissolve the reaction product. Then, unreacted carbon dioxide was discharged to obtain 30 g of a crude polyurethane polyamine product. The content of ethyleneimine was 1800 ppm.
From the obtained crude polyurethane polyamine, the solvent was distilled off under reduced pressure at a temperature of 90 ° C. and a pressure of −0.06 MPa for 2 hours. The reservoir was ethanol and water, and 4.3 g of the polyurethane polyamine composition was obtained as the final product.
The urethane ratio of the obtained polyurethane polyamine was 31%, Mw was 8,400, Mn was 2,600, and the content of ethyleneimine in the above composition was 20 ppm.

As shown in Examples 1 to 8, polyurethane polyamines could be efficiently synthesized by introducing ethyleneimine under _{high-pressure CO 2 heated in the reactor.} Further, as shown in Examples 1 to 8, the aziridine compound remaining in the crude polyurethane polyamine can be removed by adding a specific solvent after the reaction and distilling off the solvent while heating, resulting in low toxicity. , A highly stable polyurethane polyamine composition could be produced.

Claims (3)

It contains polyurethane polyamine (I) containing a structural unit in which a urethane unit represented by the following formulas (1) to (3) and an amine unit represented by the following formulas (4) to (6) are connected, and is an ethyleneimine. The content of the polyurethane polyamine (I) is less than 0.1% by mass with respect to 100% by mass of the polyurethane polyamine (I).

Ethylene imine is added and mixed with carbon dioxide in a supercritical state and reacted, and the urethane unit represented by the following formulas (1) to (3) and the amine represented by the following formulas (4) to (6) are reacted. A method for producing a polyurethane polyamine, which comprises a step of producing a polyurethane polyamine (I) containing a structural unit connected to a unit.

A polyurethane polyamine (G) containing a structural unit in which a urethane unit represented by the following formulas (19) to (21) and an amine unit represented by the following formulas (22) to (24) are connected, and the polyurethane polyamine ( G) With respect to the crude polyurethane polyamine containing 0.1% by mass or more of the aziridine compound with respect to 100% by mass, a solvent having a boiling point higher than that of the aziridine compound is added in an amount of 1% by mass based on 100% by mass of the crude product. A method for producing a polyurethane polyamine composition, which comprises a step of adding the above and distilling off 1% by mass or more of the solvent in 100% by mass.

In the above formula, A _{1 to} A ₃ , B _{1 to} B ₂ , C _{1 to} C ₃ , D _{1 to} D ₃ , E _{1 to} E ₂ , and F ₁ have the same or different substituents, respectively. It may be a methylene group.