JP2007022955A - Alkylated polyalkylene polyamine composition and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkylated polyalkylene polyamine composition useful in producing polyurethane resins and epoxy resins and its inexpensive and commercial manufacturing method. <P>SOLUTION: The alkylated polyalkylene polyamine composition comprises one or more kinds selected from the group consisting of amine compounds represented by formula (1) (wherein R<SB>1</SB>-R<SB>4</SB>and R<SB>6</SB>-R<SB>9</SB>are each independently a 1-3C alkyl group; R<SB>5</SB>is a 1-3C alkyl group or a 2C or 3C N,N-dimethylaminoalkyl group; n and m are each independently an integer of 1-5; and a is an integer of 1-6). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an alkylated polyalkylene polyamine composition and a method for producing the same. The alkylated polyalkylene polyamine composition is a useful compound as an organic alkali source.

  Alkylated polyalkylene polyamines are useful compounds that are widely used as catalysts for polyurethane resins and curing accelerators for epoxy resins. Also, as an organic alkali source useful in the field of electronic materials and battery materials in which alkali metals such as photosensitive resins, antistatic agents, resist strippers, semiconductor cleaners, electrolytes, charge transport materials, and abrasives are restricted. Widely used.

  In the production of polyurethane resins, polyols having active hydrogen or tertiary amines are used as catalysts in the reaction of water and isocyanates. Tris (2-dimethylaminoethyl) amine is particularly useful as a highly active catalyst. It has been proposed (see, for example, Patent Document 1).

  As a method for producing tris (2-dimethylaminoethyl) amine, a method in which tris (2-chloroethyl) amine is aminated with dimethylamine is known (for example, see Non-Patent Document 1), but the toxicity of the raw material is high. However, since it is difficult to obtain, there is a problem as an industrial production method. Further, a method is known in which a chelate complex compound is separated from polyethylene polyamines having a large amount of impurities, and further purified by a solvent extraction method (see, for example, Patent Document 2), but requires a complicated multi-step process. There was a problem with the implementation. Thus, development of alkylated polyalkylene polyamines that are suitable for the production methods of polyurethane resins and epoxy resins and that have industrial utility value is strongly desired.

US Pat. No. 3,836,488 Japanese Patent Laid-Open No. 48-57902 Journal of the American Chemical Society, Vol. 76, Part 2, 2414-17 (1954)

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an alkylated polyalkylene polyamine composition useful in a method for producing a polyurethane resin or an epoxy resin, and an industrially inexpensive production method thereof. That is.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, certain alkylated polyalkylene polyamine compositions are useful as catalysts or amine-based organic ligands in polyurethane resin and epoxy resin production processes, and more easily than industrially available polyalkylene polyamine mixtures. It has been found that it can be produced, and the present invention has been completed.

  That is, this invention is an alkylated polyalkylene polyamine composition as shown below, and its manufacturing method.

  1. An alkylated polyalkylene polyamine composition comprising one or more amine compounds selected from the group consisting of amine compounds represented by the following general formula (1).

（式中、Ｒ_１〜Ｒ_４及びＲ_６〜Ｒ_９は各々独立して炭素数１〜３のアルキル基を表し、Ｒ_５は炭素数１〜３のアルキル基、又は炭素数が２若しくは３のＮ，Ｎ−ジメチルアミノアルキル基を表す。ｎ、ｍは各々独立して１〜５の整数を表す。ａは１〜６の整数を表す。）
２．上記一般式（１）で示されるアミン化合物として、トリス（２−ジメチルアミノエチル）アミンとＮ，Ｎ’−ビス（２−ジメチルアミノエチル）−Ｎ，Ｎ’−ジメチルエチレンジアミンを含有することを特徴とする上記１．に記載のアルキル化ポリアルキレンポリアミン組成物。

(In the formula, R _{1 to} R ₄ and R _{6 to} R ₉ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ₅ represents an alkyl group having 1 to 3 carbon atoms, or 2 or 3 carbon atoms. N, N-dimethylaminoalkyl group of n, n and m each independently represents an integer of 1 to 5. a represents an integer of 1 to 6.)
2. It contains tris (2-dimethylaminoethyl) amine and N, N′-bis (2-dimethylaminoethyl) -N, N′-dimethylethylenediamine as the amine compound represented by the general formula (1). The above 1. The alkylated polyalkylene polyamine composition described in 1.

  3. When the mixing ratio of tris (2-dimethylaminoethyl) amine and N, N′-bis (2-dimethylaminoethyl) -N, N′-dimethylethylenediamine is in the range of 10 to 98/90 to 2 (% by weight). The above-mentioned 2. characterized in that there is. The alkylated polyalkylene polyamine composition described in 1.

  4). As the amine compound represented by the general formula (1), N, N-bis (2-dimethylaminoethyl) -N ′, N ″, N ″ -trimethyldiethylenetriamine and N, N ″ -bis (2-dimethylaminoethyl) ) -N, N ′, N ″ -trimethyldiethylenetriamine. The alkylated polyalkylene polyamine composition described in 1.

  5. N, N-bis (2-dimethylaminoethyl) -N ′, N ″, N ″ -trimethyldiethylenetriamine and N, N ″ -bis (2-dimethylaminoethyl) -N, N ′, N ″ -trimethyldiethylenetriamine 3. The mixing ratio is in the range of 10 to 98/90 to 2 (% by weight). The alkylated polyalkylene polyamine composition described in 1.

  6. A mixture containing three or more types of polyalkylene polyamines is purified by distillation and then alkylated. To 5. The manufacturing method of the alkylated polyalkylene polyamine composition in any one of.

  7). Polyalkylene polyamines are triethylenetetramine, tris (2-aminoethyl) amine, N, N′-bis (aminoethyl) piperazine, N-2 (2′-aminoethyl) aminoethylpiperazine, tetraethylenepentamine, N -2 (2 '(2 "-aminoethyl) aminoethyl) aminoethylpiperazine, N-2 (2'-aminoethyl) aminoethyl-N'-aminoethylpiperazine, N", N "-bis (2-amino 6. The alkylated polyalkylene polyamine according to 6 above, which is a compound selected from the group consisting of ethyl) -N- (2-aminoethyl) piperazine and N, N-bis (2-aminoethyl) diethylenetriamine. A method for producing the composition.

  8. A mixture containing three or more alkylated polyalkylene polyamines is purified by distillation. To 5. The manufacturing method of the alkylated polyalkylene polyamine composition in any one of.

  9. Alkylated polyalkylene polyamines are triethylenetetramine, tris (2-aminoethyl) amine, N, N′-bis (aminoethyl) piperazine, N-2 (2′-aminoethyl) aminoethylpiperazine, tetraethylenepentamine N-2 (2 ′ (2 ″ -aminoethyl) aminoethyl) aminoethylpiperazine, N-2 (2′-aminoethyl) aminoethyl-N′-aminoethylpiperazine, N ″, N ″ -bis (2 7. A compound selected from the group consisting of alkylated forms of -aminoethyl) -N- (2-aminoethyl) piperazine and N, N-bis (2-aminoethyl) diethylenetriamine. A process for producing an alkylated polyalkylene polyamine composition of

  According to the present invention, an alkylated polyalkylene polyamine composition effective for producing a polyurethane resin or an epoxy resin can be easily provided industrially.

  In addition, when the composition of the present invention is applied to the above polymer production method, a polymer having high catalytic activity and excellent physical properties and moldability of the obtained resin can be obtained. Industrial utility value is great.

  The alkylated polyalkylene polyamine composition of the present invention contains one or more amine compounds selected from the group consisting of amine compounds represented by the following general formula (1).

（式中、Ｒ_１〜Ｒ_４及びＲ_６〜Ｒ_９は各々独立して炭素数１〜３のアルキル基を表し、Ｒ_５は炭素数１〜３のアルキル基、又は炭素数が２若しくは３のＮ，Ｎ−ジメチルアミノアルキル基を表す。ｎ、ｍは各々独立して１〜５の整数を表す。ａは１〜６の整数を表す。）
上記一般式（１）は、ポリアルキル化ポリアルキレンポリアミン構造を有し、置換基Ｒ_１〜Ｒ_４及びＲ_６〜Ｒ_９は各々独立して炭素数１〜３のアルキル基を表す。置換基Ｒ_１〜Ｒ_４、Ｒ_６〜Ｒ_９としては、ポリウレタン樹脂やエポキシ樹脂の製造法において、触媒としての活性が高く、得られた樹脂の物性、成形性に優れることから、炭素数１のメチル基が特に好ましい。

(In the formula, R _{1 to} R ₄ and R _{6 to} R ₉ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ₅ represents an alkyl group having 1 to 3 carbon atoms, or 2 or 3 carbon atoms. N, N-dimethylaminoalkyl group of n, n and m each independently represents an integer of 1 to 5. a represents an integer of 1 to 6.)
The general formula (1) has a polyalkylated polyalkylene polyamine structure, and the substituents R _{1 to} R ₄ and R _{6 to} R ₉ each independently represent an alkyl group having 1 to 3 carbon atoms. The substituents R _{1 to} R ₄ and R _{6 to} R ₉ have a high activity as a catalyst in the production method of polyurethane resins and epoxy resins, and are excellent in physical properties and moldability of the obtained resin. The methyl group is particularly preferred.

In the general formula (1), when R represents an integer of 2 to 6, each of the substituents R ₅ is independently an alkyl group having 1 to 3 carbon atoms, or N, N- having 2 or 3 carbon atoms. Although it represents a dimethylaminoalkyl group, it has excellent catalytic activity, physical properties and moldability of the resulting resin in the production method of polyurethane resin and epoxy resin, so that it has a C1 methyl group or N, N-dimethylaminoethyl group. Is particularly preferred.

  Although a is 1-6 in the said General formula (1), in the manufacturing method of a polyurethane resin or an epoxy resin, since it is excellent in catalyst activity, the physical property of the obtained resin, and a moldability, a is the range of 1-3. Is more preferable.

  In the above general formula (1), n and m are each independently an integer of 1 to 5. However, when this alkyl chain becomes long, the catalyst activity decreases in the production method of polyurethane resin or epoxy resin, and the resulting resin N and m are more preferably in the range of 1-2.

  The alkylated polyalkylene polyamine represented by the general formula (1) is an amine compound obtained by N-alkylating a linear or branched polyalkylene polyamine with monoalcohols, aldehydes, alkyl halides or the like. Although not particularly limited, diethylenetriamine, dipropylenetriamine, dihexamethylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tris (2-aminoethyl) amine, tris ( Examples include N-alkylated compounds such as 3-aminopropyl) amine and N, N-bis (2-aminoethyl) diethylenetriamine. Among these, those in which the N-alkyl group is a methyl group are preferable because they have particularly high activity in the process for producing polyurethane resins and epoxy resins, and are excellent in the physical properties and moldability of the obtained resins.

  In the alkylated polyalkylene polyamine represented by the general formula (1), specific examples of these N-methylated products include N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ', N ″, N ″ -pentamethyldipropylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldihexamethylenetriamine, N, N′-bis (2-dimethylaminoethyl) -N, N′-dimethylethylenediamine, N, N′-bis (3-dimethylaminopropyl) -N, N′-dimethylpropylenediamine, N, N ″ -bis (2-dimethylaminoethyl) -N, N ′, N ″ -Trimethyldiethylenetriamine, N, N '"-bis (2-dimethylaminoethyl) -N, N', N", N '"-tetramethyltriethylenetetramine, tris ( Examples include amine compounds such as -dimethylaminoethyl) amine, tris (3-dimethylaminopropyl) amine, and N, N-bis (2-dimethylaminoethyl) -N ', N ", N" -trimethyldiethylenetriamine. Among them, in the production method of polyurethane resin and epoxy resin, the activity as a catalyst is high, and the obtained resin is excellent in physical properties and moldability. Therefore, tris (2-dimethylaminoethyl) amine and N, N′-bis Compositions containing (2-dimethylaminoethyl) -N, N′-dimethylethylenediamine, N, N-bis (2-dimethylaminoethyl) -N ′, N ″, N ″ -trimethyldiethylenetriamine and N, N ″ A composition containing -bis (2-dimethylaminoethyl) -N, N ', N "-trimethyldiethylenetriamine Preferred.

  In the present invention, the mixing ratio of tris (2-dimethylaminoethyl) amine and N, N′-bis (2-dimethylaminoethyl) -N, N′-dimethylethylenediamine is 10 to 98/90 to 2 (wt%). ) Is preferable, and a range of 20 to 98/80 to 2 (% by weight) is more preferable. N, N-bis (2-dimethylaminoethyl) -N ′, N ″, N ″ -trimethyldiethylenetriamine and N, N ″ -bis (2-dimethylaminoethyl) -N, N ′, N ″ -trimethyl The mixing ratio of diethylenetriamine is preferably in the range of 10 to 98/90 to 2 (% by weight), and more preferably in the range of 20 to 98/80 to 2 (% by weight). A composition comprising 98% by weight or more of tris (2-dimethylaminoethyl) amine or N, N-bis (2-dimethylaminoethyl) -N ′, N ″, N ″ -trimethyldiethylenetriamine (branched body) In this case, distillation equipment with a high number of distillation stages is required for distillation purification, and the productivity of distillation purification is low and expensive, which may be industrially disadvantageous. On the other hand, when the branching body is 10% or less, since the activity is low, the polymerization time becomes long and it may be difficult to obtain a high molecular weight polymer.

  The alkylated polyalkylene polyamine composition of the present invention can be easily produced by reactions known in the literature. For example, a mixture containing three or more polyalkylene polyamines such as a linear polyalkylene polyamine, a branched polyalkylene polyamine, and a cyclic polyalkylene polyamine containing a piperazine ring is purified by distillation and then alkylated or these polyalkylene polyamine alkyls. It can be easily produced by distilling and purifying a mixture containing three or more alkylated polyalkylene polyamines.

  Mixtures containing these polyalkylene polyamines can be obtained as by-products by reacting ethylene dichloride with ammonia to obtain ethylene diamine, or obtaining polyethylene imine by the reaction of ethylene imine and ammonia. An amine component containing 4 or more nitrogen atoms can be used.

  Examples of a method for tertiaryizing a mixture containing these polyalkylene polyamines include a method by reductive methylation in which formaldehyde is reacted in the presence of a hydrogenation catalyst under hydrogen pressure. The amine compound obtained by this production method is obtained as a mixture containing a permethylated polyalkylene polyamine, and further purified by distillation separation to obtain the alkylated polyalkylene polyamine composition of the present invention.

  In the present invention, a distillation column having a theoretical distillation plate number of 5 or more, preferably 10 or more is used for distillation separation. If the number of distillation stages is less than 5, not only is the separation of the composition of the present invention difficult to distill, but also distillation purification takes time, which may make industrial application difficult.

  The alkylated polyalkylene polyamine composition of the present invention can be used not only as a catalyst for polyurethane resin production and as a curing accelerator for epoxy resin production, but also can be used in a wide range of applications as an organic alkali source. For example, phenol resin production catalyst, positive photosensitive resin composition, antistatic agent, resist stripper, semiconductor cleaning agent, electrolyte, luminescent material, charge transport material, abrasive composition, inkjet ink composition, photocuring It can be used for a functional resin composition.

  Hereinafter, although demonstrated based on an Example and a comparative example, this invention is not limited only to these Examples.

Example 1 Production Example (1) of Alkylated Polyalkylene Polyamine Composition
A 1000 ml autoclave equipped with a stirrer was charged with 150 g of triethylenetetramine (TETA, TESO) containing a branched chain and a cyclic product in addition to a straight chain, 150 g of water, and 6.0 g of catalyst Raney nickel. The autoclave was sealed, purged with hydrogen, and then heated to 120 ° C. with stirring. Subsequently, 464 g (5.72 mol) of a 37% formalin aqueous solution was supplied by a pump over 4 hours while introducing hydrogen into the autoclave at a pressure of 3 MPa. After aging reaction for 1 hour, the reaction solution was taken out by cooling.

  After distilling off water from the reaction solution using a rotary evaporator, the product, N-methylated triethylenetetramine, was distilled and purified under reduced pressure using a 40-stage old distillation apparatus. As a result of gas chromatograph and H-NMR analysis of this product, the mixing ratio of tris (2-dimethylaminoethyl) amine and N, N′-bis (2-dimethylaminoethyl) -N, N′-dimethylethylenediamine was 85. 6.5 / 14.4 (weight% ratio) of fraction-1 8.5 g, mixing ratio 35.2 / 64.8 (weight% ratio) of fraction-2 9.0 g, mixing ratio 0 8.5g of fraction-3 of .5 / 99.5 (weight% ratio) was obtained. These fractions-1, 2, and 3 were designated as alkylated polyalkylene polyamine compositions A-1, A-2, and A-3, respectively.

Example 2 Production Example of Alkylated Polyalkylene Polyamine Composition (2)
Under the same conditions as in Example 1, except that 150 g of tetraethylenepentamine (TEPA, manufactured by Tosoh Corporation) and 384 g (4.74 mol) of a 37% formalin aqueous solution were used in addition to the straight chain. Reaction and distillation were carried out to purify N-methylated triethylenetetramine by distillation. As a result of gas chromatograph and H-NMR analysis of the distilled purified product, N, N-bis (2-dimethylaminoethyl) -N ′, N ″, N ″ -trimethyldiethylenetriamine and N, N ″ -bis (2-dimethyl) were obtained. Aminoethyl) -N, N ′, N ″ -trimethyldiethylenetriamine has a mixing ratio of 95.5 / 4.5 (weight% ratio), a fraction-4 of 6.5 g, and a mixing ratio of 40.5 / 59.5. Fraction-5 (7.0% by weight ratio) was obtained in an amount of 7.0 g, and 7.5 g of a fraction-6 having a mixing ratio of 0.5 / 99.5 (weight% ratio) was obtained. These fractions -4, 5, and 6 were designated as alkylated polyalkylene polyamine compositions B-1, B-2, and B-3, respectively.

Examples 3 to 6 and Comparative Examples 1 to 3
The example which manufactured the semi-rigid polyurethane foam using the alkylated polyalkylene polyamine composition of this invention and a comparative example is shown.

  Premix A was prepared by mixing the polyol A, water, and triethanolamine at the raw material mixing ratio shown in Table 1.

105.8 g of Premix A was placed in a 300 ml polyethylene cup, a predetermined amount of the alkylated polyalkylene polyamine composition of the present invention and Comparative Example was added, and the temperature was adjusted to 25 ° C. The amount of the isocyanate liquid whose isocyanate index {isocyanate group / OH group (molar ratio) × 100)} is 105 is placed in a premix A cup in an isocyanate liquid whose temperature has been adjusted to 25 ° C. in a separate container, and quickly 6000 rpm with a stirrer. Stir for 5 seconds. The mixed and stirred liquid mixture was transferred to a 2 l polyethylene cup whose temperature was adjusted to 40 ° C., and the reactivity during foaming was measured. Next, an aluminum mold having a length of 50 cm, a width of 12 cm, and a thickness of 0.5 cm is inclined at 25 °, and a mixed solution is injected from the bottom of the mold so that the foam density is 95 kg / m ^3. A certain amount was produced and foam-molded. In this case, the premix A was prepared in the same manner as described above, and the alkylated polyalkylene polyamine compositions of the present invention and comparative examples were prepared so as to have a gel time of 50 seconds, mixed with isocyanate, and reaction molded. After foam molding, the hardness and moldability of the molded foam were measured.

  The results are shown in Table 2.

  The measurement method for each measurement item is as follows.

(1) Reactive measurement items Cream time: Measure foaming start time and foam rise start time visually Gel time: Measure time when reaction progresses and changes from liquid to resinous material Rise time: Foam rise Visually measure the time to stop.

(2) Hardness at the time of demolding The foam was demolded 3 minutes after the start of mixing, and the hardness at the time of demolding of the foam was measured 1 minute later.

(3) Evaluation of formability Expressed as follows from the size of the voids in the foam: ◎: very good ○: good △: bad ×: very bad.

上記表から明らかなとおり、実施例３〜実施例６は本発明のアルキル化ポリアルキレンポリアミン組成物を用いた例であるが、これらは、同じ使用量で反応速度が高く触媒活性が高いことを示している。また、脱型時の硬度が高く硬化速度が高いだけでなく、成形性に優れたフォームを形成する。

As is apparent from the above table, Examples 3 to 6 are examples using the alkylated polyalkylene polyamine composition of the present invention, but these show that the reaction rate is high and the catalytic activity is high at the same use amount. Show. Moreover, not only the hardness at the time of mold removal is high and the curing rate is high, but also a foam excellent in moldability is formed.

  On the other hand, Comparative Examples 1 and 2 are linear alkylated polyalkylene polyamine compositions, but have low activity and inferior curing speed and moldability. Further, Comparative Example 3 is a composition containing a cyclic alkylated polyalkylene polyamine, which produces a foam having particularly low activity and inferior curing speed and moldability.

Examples 7 to 10 and Comparative Examples 4 to 6
The example which manufactured the epoxy resin coating film using the alkylated polyalkylene polyamine composition of this invention and a comparative example is shown.

  Epoxy resin A, a curing agent, and a curing accelerator were mixed at the raw material blending ratio shown in Table 3, and stirred and mixed with a spatula in a cup at 20 ° C. to obtain an epoxy resin composition. The epoxy resin composition thus obtained was measured for curability and flexibility at 5 ° C., and the results are shown in Table 4.

  The measurement method for each measurement item is as follows.

(1) Low temperature curability An epoxy resin composition is applied to the surface of a glass plate (25 × 353 × 1.8 mm) using a 75 micron doctor blade, and an RCI coating film drying measurement time measuring device at a curing temperature of 5 ° C. Evaluation of curability. The curability was evaluated based on the secondary line streak start time indicated in this test.

(2) Flexibility The epoxy resin composition was applied onto a tin plate (150 × 50 × 0.3 mm) using a 500-micron doctor blade, dried and cured at 19 to 21 ° C. for 7 days. Thereafter, a bending test was performed using a coating film bending tester, and the presence or absence of cracking or peeling of the coating film on the test piece was observed. The mandrel was 2 mm or 3 mm (based on JIS K-5400: 1997). From the cracked state of the resin, it was expressed as follows: ◎: No abnormality ○: Slightly cracked △: Cracked ×: Cracked.

上記表から明らかなとおり、実施例７〜実施例１０は本発明のアルキル化ポリアルキレンポリアミン組成物を用いた例であるが、これらは、同じ使用量で低温の硬化速度が高く塗膜乾燥性が高い。また、得られた塗膜の可撓性が高い。

As is apparent from the above table, Examples 7 to 10 are examples using the alkylated polyalkylene polyamine composition of the present invention. Is expensive. Moreover, the flexibility of the obtained coating film is high.

On the other hand, Comparative Examples 4 and 5 are linear alkylated polyalkylene polyamine compositions, but the coating film drying rate at low temperatures was slow, and the flexibility of the coating film was poor. . Further, Comparative Example 6 is a composition containing a cyclic alkylated polyalkylene polyamine, but similarly, the coating film drying rate at a low temperature was slow, and the flexibility of the coating film was inferior.

Claims (9)

An alkylated polyalkylene polyamine composition comprising one or more amine compounds selected from the group consisting of amine compounds represented by the following general formula (1).

(In the formula, R _{1 to} R ₄ and R _{6 to} R ₉ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ₅ represents an alkyl group having 1 to 3 carbon atoms, or 2 or 3 carbon atoms. N, N-dimethylaminoalkyl group of n, n and m each independently represents an integer of 1 to 5. a represents an integer of 1 to 6.) It contains tris (2-dimethylaminoethyl) amine and N, N′-bis (2-dimethylaminoethyl) -N, N′-dimethylethylenediamine as the amine compound represented by the general formula (1). The alkylated polyalkylene polyamine composition according to claim 1. The mixing ratio of tris (2-dimethylaminoethyl) amine and N, N′-bis (2-dimethylaminoethyl) -N, N′-dimethylethylenediamine ranges from 10 to 98/90 to 2 (weight% ratio). The alkylated polyalkylene polyamine composition according to claim 2, wherein As the amine compound represented by the general formula (1), N, N-bis (2-dimethylaminoethyl) -N ′, N ″, N ″ -trimethyldiethylenetriamine and N, N ″ -bis (2-dimethylaminoethyl) 2. The alkylated polyalkylene polyamine composition according to claim 1, which comprises:)-N, N ′, N ″ -trimethyldiethylenetriamine. N, N-bis (2-dimethylaminoethyl) -N ′, N ″, N ″ -trimethyldiethylenetriamine and N, N ″ -bis (2-dimethylaminoethyl) -N, N ′, N ″ -trimethyldiethylenetriamine 5. The alkylated polyalkylene polyamine composition according to claim 4, wherein the mixing ratio is in the range of 10 to 98/90 to 2 (weight% ratio). The method for producing an alkylated polyalkylene polyamine composition according to any one of claims 1 to 5, wherein a mixture containing three or more types of polyalkylene polyamines is purified by distillation and then alkylated. Polyalkylene polyamines are triethylenetetramine, tris (2-aminoethyl) amine, N, N′-bis (aminoethyl) piperazine, N-2 (2′-aminoethyl) aminoethylpiperazine, tetraethylenepentamine, N -2 (2 '(2 "-aminoethyl) aminoethyl) aminoethylpiperazine, N-2 (2'-aminoethyl) aminoethyl-N'-aminoethylpiperazine, N", N "-bis (2-amino The alkylated polyalkylene polyamine according to claim 6, which is a compound selected from the group consisting of ethyl) -N- (2-aminoethyl) piperazine and N, N-bis (2-aminoethyl) diethylenetriamine. A method for producing the composition. The method for producing an alkylated polyalkylene polyamine composition according to any one of claims 1 to 5, wherein a mixture containing three or more kinds of alkylated polyalkylene polyamine is purified by distillation. Alkylated polyalkylene polyamines are triethylenetetramine, tris (2-aminoethyl) amine, N, N′-bis (aminoethyl) piperazine, N-2 (2′-aminoethyl) aminoethylpiperazine, tetraethylenepentamine N-2 (2 ′ (2 ″ -aminoethyl) aminoethyl) aminoethylpiperazine, N-2 (2′-aminoethyl) aminoethyl-N′-aminoethylpiperazine, N ″, N ″ -bis (2 9. A compound selected from the group consisting of alkylated forms of -aminoethyl) -N- (2-aminoethyl) piperazine and N, N-bis (2-aminoethyl) diethylenetriamine. A process for producing an alkylated polyalkylene polyamine composition of