JP4904775B2 - Hydroxyalkylated polyalkylene polyamine composition, method for producing the same, and method for producing polyurethane resin using the same - Google Patents

Description

  The present invention relates to a hydroxyalkylated polyalkylene polyamine composition containing a tertiary amino group such as a methylamino group or a dimethylamino group (hereinafter sometimes referred to as a tertiary amino group), a production method thereof, and The present invention relates to a method for producing a polyurethane resin using.

  The hydroxyalkylated polyalkylene polyamine composition of the present invention is useful as an epoxy curing agent, urethane raw material, surfactant, fiber treatment agent, paper strength enhancer, resin modifier, lubricating oil additive, etc. In the production of a polyurethane resin, the composition is extremely useful as a composition for producing a polyurethane resin or polyurethane foam having almost no volatile amine catalyst or harmful metal catalyst. Since the hydroxyalkylated polyalkylene polyamine composition of the present invention has catalytic ability, the amount of conventional amine catalyst used can be reduced, and a polyurethane resin can be produced with high productivity.

  The polyurethane resin is produced by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a flame retardant, a crosslinking agent and the like. It is known that many metal compounds and tertiary amine compounds are used as catalysts for the production of polyurethane resins. These catalysts are often used industrially when used alone or in combination.

  In the production of polyurethane foam using water and / or a low-boiling organic compound as a foaming agent, among these catalysts, tertiary amine compounds are widely used because of their excellent productivity and moldability. Examples of such tertiary amine compounds include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N , N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine and the like. (For example, refer nonpatent literature 1). In most cases, the metal compound is often used in combination with a tertiary amine catalyst because the productivity and moldability are deteriorated, and the metal compound is rarely used alone.

  The above-mentioned tertiary amine catalyst is gradually discharged from the polyurethane product as a volatile amine, and causes, for example, an odor problem due to the volatile amine and a discoloration problem of other materials such as a skin vinyl chloride in an automobile interior material or the like. Further, the tertiary amine catalyst generally has a strong bad odor, and the working environment during the production of the polyurethane resin is significantly deteriorated. For these volatile tertiary amine catalysts, as a method for solving this problem, amine catalysts having primary and secondary amino groups or hydroxyl groups capable of reacting with polyisocyanates in the molecule (hereinafter referred to as reactive catalysts). And a method using a bifunctional crosslinking agent having a tertiary amino group in the molecule has been proposed (see, for example, Patent Documents 1 to 4).

  The method using the above reactive catalyst is said to be able to avoid the above problem because it is immobilized in the polyurethane resin skeleton in a form reacted with polyisocyanate, and is certainly effective in reducing the odor of the final resin product. However, since these amine catalysts have volatility, they are not a production method for improving the working environment when producing polyurethane resins. Moreover, the problem which reduces physical properties, such as the hardness of a polyurethane resin, also arises.

  The method using the above-mentioned crosslinking agent is effective in reducing the odor of the final resin product and improving the working environment when producing the polyurethane resin, but the physical properties such as hardness of the polyurethane resin are insufficient.

  On the other hand, an alkylene oxide adduct of N, N-dimethyldipropylenetriamine has been proposed as a trifunctional polyol having a tertiary amino group in the molecule (see, for example, Patent Document 5). This polyol has 3 hydroxyl groups in the molecule, and there is a possibility that the above problems can be solved. However, since the raw material compound for preparing this polyol is expensive, when this is used for the production of polyurethane resin, This causes problems such as an increase in manufacturing cost.

  In order to reduce the amount of tertiary amine catalyst used, many alkylene oxide adducts of ethylenediamine (hereinafter sometimes referred to as amine-based polyols) are commercially available. These amine-based polyols have a small unpleasant odor and are effective in improving the working environment because the amount of tertiary amine catalyst used can be reduced. However, since the catalyst activity is small, it is necessary to use a large amount of rigid polyurethane foam. Problems such as reduced flame retardancy occur.

  On the other hand, the metal catalyst does not cause the odor problem and the problem of degrading other materials like the above-mentioned tertiary amine catalyst. However, when the metal catalyst is used alone, as described above, the productivity and physical properties are improved. In addition, the moldability has deteriorated, and further, toxicity problems and environmental problems due to heavy metals remaining in the products have been addressed.

JP-A-46-4846 Japanese Patent Publication No. 61-31727 Japanese Patent No. 2971979 Japanese Unexamined Patent Publication No. 63-265909 JP-A-5-214091 Keiji Iwata "Polyurethane Resin Handbook" (1987 first edition) Nikkan Kogyo Shimbun, p. 118

  The present invention has been made in view of the above-described background art, and its purpose is to provide a novel hydroxyalkylated polyalkylene polyamine composition, an inexpensive production method thereof, and an odor problem, toxicity, and environment using the same. An object of the present invention is to provide a production method capable of obtaining a polyurethane product with good productivity and moldability without causing problems.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

  That is, the present invention is a hydroxyalkylated polyalkylene polyamine composition, a production method thereof, and a polyurethane resin production method using the same as shown below.

  [1] The following general formula (1)

［式中、Ｒ_１〜Ｒ_５は各々独立して炭素数１〜３のアルキル基、又は下記一般式（２）

[Wherein R _{1 to} R ₅ are each independently an alkyl group having 1 to 3 carbon atoms, or the following general formula (2)

（式中、Ｒ_６、Ｒ_７は各々独立して水素原子、又は炭素数１〜４のアルキル基を表し、ｐは１〜３の整数を表す。）
で示される置換基を表し、Ｒ_５とＲ_１、Ｒ_２、Ｒ_３又はＲ_４とが任意に結合して環を形成しても良い。ただし、Ｒ_１〜Ｒ_５のうち少なくとも１つは上記一般式（２）で示される置換基を表し、なおかつＲ_１〜Ｒ_５の全てが上記一般式（２）で示される置換基になることはない。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。］
で示されるヒドロキシアルキル化ポリアルキレンポリアミンを２種以上含有することを特徴とするヒドロキシアルキル化ポリアルキレンポリアミン組成物。

(In formula, R < ₆ >, R < ₇ > respectively independently represents a hydrogen atom or a C1-C4 alkyl group, and p represents the integer of 1-3.)
R ₅ and R ₁ , R ₂ , R ₃ or R ₄ may be optionally combined to form a ring. Provided that at least one of R ₁ to R ₅ represents a substituent represented by the general formula (2), yet that all R ₁ to R ₅ is a substituent represented by the general formula (2) There is no. n and m each independently represents an integer of 1 to 5. a represents an integer of 1 to 6. ]
A hydroxyalkylated polyalkylene polyamine composition comprising two or more hydroxyalkylated polyalkylene polyamines represented by the formula:

[2] In the general formula (1), the ratio of the alkyl group having 1 to 3 carbon atoms and the substituent represented by the general formula (2) among R _{1 to} R ₅ is [alkyl having 1 to 3 carbon atoms]. Group] / [substituent represented by the general formula (2)] = 80/20 to 20/80 (molar ratio) in the range of hydroxyalkylated polyalkylene polyamine composition according to the above [1] object.

  [3] The hydroxyalkylated polyalkylene polyamine composition according to the above [1] or [2], wherein the hydroxyl value is in the range of 20 to 800.

  [4] The following general formula (3)

（式中、Ｒ_１〜Ｒ_５は各々独立して水素原子又は炭素数１〜３のアルキル基を表し、Ｒ_５が炭素数１〜３のアルキル基の場合、Ｒ_５とＲ_１、Ｒ_２、Ｒ_３又はＲ_４とが任意に結合して環を形成しても良い。ただし、Ｒ_１〜Ｒ_５のうち少なくとも１つは水素原子を表す。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。）
で示されるＮ−アルキル化ポリアルキレンポリアミンを２種以上含有することを特徴とするＮ−アルキル化ポリアルキレンポリアミン組成物。

_(Wherein, R 1 to R ₅ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms each independently, when _{R 5} is an alkyl group having 1 to 3 carbon atoms, _{R 5} and _R 1, _{R 2} , R ₃ or R ₄ may be optionally combined to form a ring, provided that at least one of R _{1 to} R ₅ represents a hydrogen atom, and n and m are each independently 1 to 5 A represents an integer of 1 to 6.)
An N-alkylated polyalkylene polyamine composition comprising two or more N-alkylated polyalkylene polyamines represented by the formula:

[5] In the general formula (3), the ratio of the alkyl group having 1 to 3 carbon atoms to the hydrogen atom in R _{1 to} R ₅ is [alkyl group having 1 to 3 carbon atoms] / [hydrogen atom] = The hydroxyalkylated polyalkylene polyamine composition according to the above [4], which is in the range of 80/20 to 20/80 (molar ratio).

  [6] The following general formula (4)

（式中、Ｒ_１〜Ｒ_４は水素原子を表し、Ｒ_５は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ_５が炭素数１〜３のアルキル基の場合、Ｒ_５とＲ_１、Ｒ_２、Ｒ_３又はＲ_４とが任意に結合して環を形成しても良い。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。）
で示されるポリアルキレンポリアミンを、炭素数１〜３のアルキル化剤により部分的にＮ−アルキル化することを特徴とする上記［４］又は［５］に記載のＮ−アルキル化ポリアルキレンポリアミン組成物の製造方法。

_(Wherein, R 1 to R ₄ represents a hydrogen atom, _{R 5} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, when _{R 5} is an alkyl group having 1 to 3 carbon atoms, _{R 5} and R ₁ , R ₂ , R ₃ or R ₄ may be optionally combined to form a ring, n and m each independently represent an integer of 1 to 5, and a represents an integer of 1 to 6. .)
The N-alkylated polyalkylene polyamine composition according to the above [4] or [5], wherein the polyalkylene polyamine represented by the formula is partially N-alkylated with an alkylating agent having 1 to 3 carbon atoms. Manufacturing method.

  [7] The method for producing an N-alkylated polyalkylene polyamine composition as described in [6] above, wherein the alkylating agent is formaldehyde.

  [8] The polyalkylene polyamine represented by the general formula (4) is diethylenetriamine, dipropylenetriamine, dihexamethylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, N-2 (2′-aminoethyl) aminoethylpiperazine, N, N′-bis (2-aminoethyl) piperazine, N-2 (2 ′ (2 ″ -aminoethyl) aminoethyl) aminoethylpiperazine, N— 2 (2′-aminoethyl) aminoethyl-N′-aminoethylpiperazine, N, N′-bis (3-aminopropyl) piperazine, tris (2-aminoethyl) amine, tris (3-aminopropyl) amine, N, N-bis (2-aminoethyl) diethylenetri The N-alkylated polyalkylene polyamine composition according to the above [6] or [7], wherein the N-alkylated polyalkylene polyamine composition is selected from the group consisting of amine and N ″ -bis (2-aminoethyl) -N-aminoethylpiperazine Manufacturing method.

  [9] The above [1] to [3], wherein the N-alkylated polyalkylene polyamine composition according to [4] or [5] is oxyalkylated with an alkylene oxide having 2 to 4 carbon atoms. ] The manufacturing method of the hydroxyalkylated polyalkylene polyamine composition in any one of.

  [10] The hydroxy according to the above [9], wherein the alkylene oxide is one or more selected from the group consisting of ethylene oxide, 1,2-propylene oxide and 1,2-butylene oxide. A method for producing an alkylated polyalkylene polyamine composition.

  [11] The following general formula (4)

（式中、Ｒ_１〜Ｒ_４は水素原子を表し、Ｒ_５は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ_５が炭素数１〜３のアルキル基の場合、Ｒ_５とＲ_１、Ｒ_２、Ｒ_３又はＲ_４とが任意に結合して環を形成しても良い。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。）
で示されるポリアルキレンポリアミンを、炭素数１〜３のアルキル化剤により部分的にＮ−アルキル化し、次いで炭素数１〜４のアルキレンオキサイドによりオキシアルキル化することを特徴とする上記［１］乃至［３］のいずれかに記載のヒドロキシル化ポリアルキレンポリアミン組成物の製造方法。

_(Wherein, R 1 to R ₄ represents a hydrogen atom, _{R 5} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, when _{R 5} is an alkyl group having 1 to 3 carbon atoms, _{R 5} and R ₁ , R ₂ , R ₃ or R ₄ may be optionally combined to form a ring, n and m each independently represent an integer of 1 to 5, and a represents an integer of 1 to 6. .)
[1] to [1], wherein the polyalkylene polyamine represented by the above formula is partially N-alkylated with an alkylating agent having 1 to 3 carbon atoms and then oxyalkylated with an alkylene oxide having 1 to 4 carbon atoms. [3] The method for producing a hydroxylated polyalkylene polyamine composition according to any one of [3].

  [12] The method for producing a hydroxyalkylated polyalkylene polyamine composition as described in [11] above, wherein the alkylating agent is formaldehyde.

  [13] The polyalkylene polyamine represented by the general formula (4) is diethylenetriamine, dipropylenetriamine, dihexamethylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, N-2 (2′-aminoethyl) aminoethylpiperazine, N, N′-bis (2-aminoethyl) piperazine, N-2 (2 ′ (2 ″ -aminoethyl) aminoethyl) aminoethylpiperazine, N— 2 (2′-aminoethyl) aminoethyl-N′-aminoethylpiperazine, N, N′-bis (3-aminopropyl) piperazine, tris (2-aminoethyl) amine, tris (3-aminopropyl) amine, N, N-bis (2-aminoethyl) diethyleneto The hydroxyalkylated polyalkylene polyamine composition according to [11] or [12] above, which is selected from the group consisting of an amine and N ″ -bis (2-aminoethyl) -N-aminoethylpiperazine. Production method.

  [14] A method for producing a polyurethane resin, comprising reacting a polyol and an isocyanate in the presence of the hydroxyalkylated polyalkylene polyamine composition according to any one of [1] to [3].

  [15] A process for producing a polyurethane resin, comprising reacting a polyol and an isocyanate in the presence of a hydroxyalkylated polyalkylene polyamine composition obtained by the process according to any one of [9] to [13].

  [16] A method for producing a polyurethane foam, comprising reacting a polyol and an isocyanate in the presence of the hydroxyalkylated polyalkylenepolyamine composition according to any one of [1] to [3] above and a foaming agent.

  [17] A polyurethane foam characterized by reacting a polyol and an isocyanate in the presence of a hydroxyalkylated polyalkylene polyamine composition obtained by the production method according to any one of [9] to [13] above and a foaming agent. Production method.

  [18] The method for producing a polyurethane foam according to [16] or [17], wherein the reaction is carried out using water and / or a low-boiling organic compound as a foaming agent.

  According to the present invention, there are provided a novel hydroxyalkylated polyalkylenepolyamine composition, an inexpensive production method thereof, and a polyurethane resin production method using the composition.

  Since the hydroxyalkylated polyalkylene polyamine composition of the present invention has a plurality of hydroxyl groups, has a relatively large molecular weight, and has catalytic ability, when it is used in a method for producing a polyurethane resin, the physical properties of the polyurethane resin are lowered. Therefore, it is possible to reduce the amount of the conventional amine catalyst used, and to obtain a polyurethane product with good productivity and moldability at low cost without causing odor problems, toxicity and environmental problems.

The hydroxyalkylated polyalkylene polyamine composition of the present invention contains two or more hydroxyalkylated polyalkylene polyamines represented by the general formula (1).
In the said General formula (1), a represents the integer of 1-6. When the molecular weight is small, the reaction activity of the hydroxyalkylated polyalkylene polyamine is low. Moreover, as the value of a increases, the boiling point of the primary and secondary amines as raw materials increases, making it difficult to industrially purify the raw materials. For this reason, a is more preferably in the range of 2-5.
In the said General formula (1), m and n represent the integer of 1-5 each independently. When these m and n are increased, the reaction activity of the hydroxyalkylated polyalkylene polyamine is decreased, but when used for the production of a polyurethane resin, the moldability of the resulting polyurethane resin product is improved. In order to produce industrially inexpensively, m and n are each more preferably in the range of 1-2.

  In the said General formula (2), p value is an integer of 1-3. The larger the p value, the lower the reactivity and viscosity of the terminal hydroxyl group.

  The hydroxyalkylated polyalkylene polyamine composition of the present invention is not particularly limited, but is preferably in the range of 20 to 800 mgKOH / g, particularly preferably in the range of 100 to 700 mgKOH / g.

  In the present invention, the hydroxyl value of the hydroxyalkylated polyalkylene polyamine composition means a hydroxyl value per average molecular weight of the composition, and is defined by the following formula.

      Hydroxyl value (mg / KOH) = number of OH groups in molecule ÷ average molecular weight × 56.11 × 1000.

The hydroxyalkylated polyalkylene polyamine composition of the present invention can be easily produced by methods known in the literature.
For example, the polyalkylene polyamine represented by the general formula (4) is partially N-alkylated with an N-alkylating agent such as monoalcohols, aldehydes, alkyl halides, etc. It can be produced by preparing an N-alkylene polyamine composition containing two or more of the indicated N-alkylated polyalkylene polyamines, and further adding an alkylene oxide to the active hydrogen site of the N-alkylene polyamine composition. .

  The hydroxyalkylated polyalkylene polyamine composition of the present invention can be produced by adding an alkylene oxide to the active hydrogen site of the N-alkylated polyalkylene polyamine represented by the general formula (3).

In the method of the present invention, the ratio of alkylation to oxyalkylation is determined by the production rate (ie, curing rate) of the resulting polyurethane resin when the hydroxyalkylated polyalkylene polyamine composition of the present invention is used for the production of polyurethane resin. ) And the suppression of volatile amines. For example, increasing the proportion of oxyalkylation results in less volatile amines but slower polyurethane resin cure. On the other hand, when the ratio of oxyalkylation decreases, the polyurethane resin cures faster, but the volatile amine increases, and the hardness of the polyurethane resin decreases. Therefore, it is preferable to alkylate in the range of 20 to 80%, more preferably in the range of 30 to 70% with respect to the active hydrogen group of the polyalkylene polyamine represented by the general formula (4). In the general formula (3), the ratio of the alkyl group having 1 to 3 carbon atoms and the hydrogen atom in R _{1 to} R ₅ is [alkyl group having 1 to 3 carbon atoms] / [hydrogen atom] = It is preferably in the range of 80/20 to 20/80 (molar ratio), more preferably in the range of 70/30 to 30/70 (molar ratio).

In the above general formula _(1), of the R 1 to R _5, the ratio of the substituent represented by an alkyl group and the formula 1 to 3 carbon atoms (2), [1 to 3 carbon atoms Of the alkyl group] / [substituent represented by the general formula (2)] = 80/20 to 20/80 (molar ratio) is preferable, and 70/30 to 30/70 (molar ratio) is more preferable. ).
In the method of the present invention, the polyalkylene polyamine represented by the general formula (4) is not particularly limited. Specifically, diethylenetriamine, dipropylenetriamine, dihexamethylenetriamine, triethylenetetramine, triethylene Propylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, N-2 (2′-aminoethyl) aminoethylpiperazine, N, N′-bis (2-aminoethyl) piperazine, N-2 ( 2 ′ (2 ″ -aminoethyl) aminoethyl) aminoethylpiperazine, N-2 (2′-aminoethyl) aminoethyl-N′-aminoethylpiperazine, N, N′-bis (3-aminopropyl) piperazine, Tris (2-aminoethyl) amine, tris (3-aminopropy ) Amine, N, N-bis (2-aminoethyl) diethylenetriamine, N "- bis (2-aminoethyl) -N- aminoethylpiperazine and the like. These polyalkylene polyamines are easily and inexpensively available industrially and have a relatively large molecular weight, so that the hydroxyalkylated polyalkylene polyamine composition of the present invention having a plurality of hydroxyl groups can be easily and inexpensively produced. can do.

  In the method of the present invention, as the N-alkylation method, specifically, the polyalkylene polyamine represented by the general formula (4) and formaldehyde used as the N-alkylating agent are hydrogenated under hydrogen pressure. Examples thereof include a reductive methylation method in which the reaction is carried out in the presence of a catalyst. When formaldehyde is used as the N-alkylating agent, not only the hydroxyalkylated polyalkylene polyamine composition of the present invention can be obtained at low cost, but also high catalytic ability can be imparted thereto.

  According to the N-alkylation method described above, N-alkylated polyalkylene polyamines having different numbers of added methyl groups can be obtained by changing the molar ratio of the polyalkylene polyamine represented by the general formula (4) to formaldehyde. And if alkylene oxides, such as 1, 2- propylene oxide, are added to these, the hydroxyalkylated polyalkylene polyamine shown by the said General formula (1) will be obtained.

  Since the hydroxyalkylated polyalkylene polyamine obtained by this method exists as a mixture of several kinds having different numbers and positions of added methyl groups after the reaction and is difficult to separate by distillation, the above-mentioned general formula is substantially eliminated. It is obtained as a composition comprising two or more hydroxyalkylated polyalkylene polyamines represented by (1).

In the method of the present invention, the alkylene oxide is not particularly limited, and examples thereof include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide and the like.
As the hydroxyalkylated polyalkylene polyamine composition of the present invention prepared by the method of the present invention, for example, when diethylenetriamine is used as the polyalkylene polyamine represented by the general formula (4), a monomethylated product is used. Includes compounds having four 1,2-propylene oxides added thereto to compounds having two 1,2-propylene oxides added to the trimethyl body, specifically, depending on the position of the methyl group, N-methyl-N , N ′, N ″, N ″ -tetrakis (2-hydroxypropyl) diethylenetriamine, N′-methyl-N, N, N ″, N ″ -tetra (2-hydroxypropyl) diethylenetriamine, N, N-dimethyl-N ', N ", N" -tris (2-hydroxypropyl) diethylenetriamine, N, N'-dimethyl -N, N ", N" -tris (2-hydroxypropyl) diethylenetriamine, N, N, N'-trimethyl-N ", N" -bis (2-hydroxypropyl) diethylenetriamine, N, N, N "-trimethyl -N ', N "-bis (2-hydroxypropyl) diethylenetriamine and the like are exemplified, and a mixture in which these are arbitrarily combined. N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ″, N ″ -tetramethyl-N ′-(2-hydroxypropyl) diethylenetriamine, N, N, N ′, N ″ -tetramethyl-N ″-(2-hydroxypropyl) diethylenetriamine, N, N, N ′, N ″, N ″ -pentakis (2-hydroxypropyl) diethylenetriamine may be contained in any proportion.

  Similarly, in the case where the polyalkylene polyamine represented by the general formula (4) is triethylenetetramine, a compound in which 1,2-propylene oxide is added to the active hydrogen site of the compound from monomethyl to tetramethyl is exemplified. It is done. When the polyalkylene polyamine represented by the general formula (4) is tetraethylenepentamine, a compound in which 1,2-propylene oxide is added to the active hydrogen site of the compound from the monomethyl body to the pentamethyl body can be mentioned. When the polyalkylene polyamine represented by the general formula (4) is pentaethylenehexamine, a compound in which 1,2-propylene oxide is added to the active hydrogen site of the compound from monomethyl to hexamethyl is exemplified. When the polyalkylene polyamine represented by the general formula (4) is dipropylene triamine, a compound obtained by adding 1,2-propylene oxide to an active hydrogen site of a compound from a monomethyl body to a trimethyl body is exemplified. When the polyalkylene polyamine represented by the general formula (4) is dihexamethylene triamine, a compound obtained by adding 1,2-propylene oxide to an active hydrogen site of a compound from a monomethyl body to a trimethyl body can be mentioned. When the polyalkylene polyamine represented by the general formula (4) is tripropylenetetramine, a compound obtained by adding 1,2-propylene oxide to the active hydrogen site of the compound from the monomethyl body to the tetramethyl body is exemplified. When the polyalkylene polyamine represented by the general formula (4) is N-aminoethylpiperazine, a compound in which 1,2-propylene oxide is added to the active hydrogen site of the monomethyl compound is exemplified. When the polyalkylene polyamine represented by the general formula (4) is N-2- (2′-aminoethyl) aminoethylpiperazine, 1,2-propylene oxide is added to the active hydrogen site of the compound from monomethyl to dimethyl. The added compound is mentioned. When the polyalkylene polyamine represented by the general formula (4) is N, N′-bis (2-aminoethyl) piperazine, 1,2-propylene oxide is added to the active hydrogen site of the compound from monomethyl to dimethyl. The compound made to be mentioned is mentioned. When the polyalkylene polyamine represented by the general formula (4) is N-2- (2 ′-(2 ″ -aminoethyl) aminoethyl) aminoethylpiperazine, the active hydrogen site of the compound from the monomethyl body to the trimethyl body is used. In the case where the polyalkylene polyamine represented by the general formula (4) is N-2- (2′-aminoethyl) aminoethyl-N′-aminoethylpiperazine And a compound in which 1,2-propylene oxide is added to the active hydrogen moiety of a compound from a monomethyl compound to a trimethyl compound, and the polyalkylene polyamine represented by the general formula (4) is N, N′-bis (3 In the case of -aminopropyl) piperazine, 1,2-to the active hydrogen site of the monomethyl to dimethyl compounds. In the case where the polyalkylene polyamine represented by the general formula (4) is tris (2-aminoethyl) amine, 1 is added to the active hydrogen site of the compound from the monomethyl body to the tetramethyl body. In the case where the polyalkylene polyamine represented by the general formula (4) is tris (3-aminopropyl) amine, the active hydrogen of the compound from monomethyl to tetramethyl is added. In the case where the polyalkylene polyamine represented by the general formula (4) is N, N-bis (2-aminoethyl) diethylenetriamine, the monomethyl compound is converted to tetramethyl. 1,2-propyleneoxy at the active hydrogen site of the compound up to the body Compounds obtained by adding id and the like. These compounds may include by-products in any proportion.

  The hydroxyalkylated polyalkylene polyamine composition of the present invention is a polyurethane resin in which a polyol and a polyisocyanate are reacted in the presence of other foaming agents, surfactants, flame retardants, crosslinking agents, catalysts, etc. as necessary. In the production method, it is used as a part of a polyol or a crosslinking agent.

  The method for producing a polyurethane resin of the present invention is characterized in that a polyol and an isocyanate are reacted in the presence of the above-described hydroxyalkylated polyalkylene polyamine composition of the present invention. The method for producing a polyurethane foam according to the present invention is characterized in that, in the above-described method for producing a polyurethane resin, a polyol and an isocyanate are further reacted in the presence of a foaming agent.

  Examples of other polyols used in the method for producing a polyurethane resin of the present invention include conventionally known polyether polyols, polyester polyols, polymer polyols, and flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. Can be mentioned. These polyols can be used alone or in combination as appropriate.

  Examples of the polyether polyol include at least two of polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol, amines such as ethylenediamine, and alkanolamines such as ethanolamine and diethanolamine. The compound having the above active hydrogen group is used as a starting material, and is produced by addition reaction of this with an alkylene oxide such as ethylene oxide or propylene oxide [for example, Gunter Oeltel, “Polyurethane Handbook” (1985 edition) Hanser Publishers (Germany) p. See 42-53 etc. ].

  Polyester polyols can be obtained from the dehydration condensation reaction of dibasic acids (mainly adipic acid) with glycols and triols, wastes from the production of nylon, trimethylolpropane, pentaerythritol wastes, and phthalic polyester wastes. And polyester polyols obtained by treating waste products [for example, Keiji Iwata “Polyurethane Resin Handbook” (first edition in 1987), Nikkan Kogyo Shimbun, p. See 117 etc. ].

  Examples of the polymer polyol include a polymer polyol obtained by reacting the polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst.

  Examples of the flame retardant polyol include phosphorus-containing polyols obtained by adding alkylene oxide to a phosphoric acid compound, halogen-containing polyols obtained by ring-opening polymerization of epichlorohydrin and trichlorobutylene oxide, and phenol polyols.

  These polyols can have an average hydroxyl value of about 20 to 1000 mg KOH / g, but 20 to 100 mg KOH / g for flexible polyurethane foam and semi-rigid polyurethane foam products, and 100 to 800 mg KOH for spray type rigid polyurethane foam. / G is preferably used.

  The polyisocyanate used in the method for producing a polyurethane resin of the present invention includes toluene diisocyanate (hereinafter sometimes referred to as TDI), diphenylmethane diisocyanate (hereinafter sometimes referred to as MDI), naphthylene diisocyanate, and xylylene. Examples thereof include aromatic polyisocyanates such as range isocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate, and mixtures thereof. Among these, TDI and its derivatives or MDI and its derivatives are preferable, and these may be used in combination.

  Examples of TDI and its derivatives include a mixture of 2,4-TDI and 2,6-TDI or a terminal isocyanate prepolymer derivative of TDI. Examples of MDI and its derivatives include a mixture of MDI and its polymer polyphenyl polymethylene diisocyanate, and / or a diphenylmethane diisocyanate derivative having a terminal isocyanate group.

  Among these isocyanates, flexible polyurethane foam and semi-rigid polyurethane foam products include TDI and derivatives thereof, or MDI and derivatives thereof, and mixtures thereof, and spray-type rigid polyurethane foams include MDI and its polymer polyphenylpolymethylene diisocyanate. The mixture of is preferably used.

  The mixing ratio of these polyisocyanates and polyols is not particularly limited, but is generally in the range of 60 to 400 in terms of isocyanate index (isocyanate groups / active hydrogen groups capable of reacting with isocyanate groups).

  In the method for producing a polyurethane resin of the present invention, a catalyst can be used without departing from the present invention. Examples of the catalyst include organic metal catalysts, carboxylic acid metal salts, tertiary amines and quaternary ammonium salts.

  The organometallic catalyst is a metal compound other than lead, tin, and mercury, and may be any conventionally known compound, and is not particularly limited. For example, bismuth octoate, bismuth neodecanoate, zinc octoate, Preferred examples include zinc neodecanoate, zinc naphthenate, nickel octoate, nickel naphthenate, cobalt naphthenate and the like. Heavy metals such as lead, tin and mercury cause toxicity problems and environmental problems, so it is desirable to use less.

  The carboxylic acid metal salt is not particularly limited as long as it is a conventionally known metal salt, and examples thereof include alkali metal salts and alkaline earth metal salts of carboxylic acids. The carboxylic acid is not particularly limited, but examples thereof include aliphatic mono- and dicarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid and adipic acid, and aromatic mono- and dicarboxylic acids such as benzoic acid and phthalic acid. Etc. Moreover, as a metal which should form carboxylate, alkaline earth metals, such as alkali metals, such as lithium, sodium, and potassium, and calcium, magnesium, are mentioned as a suitable example.

  The tertiary amines may be any conventionally known ones and are not particularly limited. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ′ can be used. -Tetramethylpropylenediamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, N, N, N', N ", N" -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N′-dimethyl Perazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethyl There may be mentioned tertiary amine compounds such as aminopropylimidazole.

  The quaternary ammonium salts are not particularly limited as long as they are conventionally known. For example, tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium salts such as tetramethylammonium hydroxide salts, and the like. Examples thereof include tetraalkylammonium organic acid salts such as hydroxide, tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

  In the method for producing a polyurethane resin of the present invention, the amount of the catalyst used is usually 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the polyol used. . If it is less than 0.01 part by weight, the polyurethane resin is slowly cured and the moldability is deteriorated. On the other hand, if it exceeds 20 parts by weight, not only the effect of increasing the catalyst is not obtained, but also the moldability may be deteriorated.

  Specifically as a foaming agent used for the manufacturing method of the polyurethane resin of this invention, a fluorocarbon compound, a low boiling point hydrocarbon, water, and mixtures thereof are mentioned. Examples of fluorocarbon compounds include dichloromonofluoroethane (HCFC-141b), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC). -365mfc) and the like, but from the problem of ozone layer destruction, 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC- 365 mfc) is preferred. As the low-boiling hydrocarbons, hydrocarbons having a boiling point of 0 to 70 ° C. are usually used, and specific examples include propane, butane, pentane, cyclopentane, hexane, and mixtures thereof. Of these foaming agents, water is particularly preferred.

  In the method for producing a polyurethane resin of the present invention, a surfactant can be used as a foam stabilizer if necessary. Examples of the surfactant to be used include conventionally known organosilicone surfactants, and specifically, nonionic systems such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers. Surfactant or a mixture thereof is exemplified. Their use amount is usually 0.1 to 10 parts by weight per 100 parts by weight of polyol.

  In the method for producing a polyurethane resin of the present invention, a crosslinking agent or a chain extender can be used if necessary. Examples of the crosslinking agent or chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol and glycerin, low molecular weight amine polyols such as diethanolamine and triethanolamine, or ethylenediamine and xylylene. Examples include polyamines such as range amine and methylene bisorthochloroaniline.

  In the method for producing a polyurethane resin of the present invention, a flame retardant can be used if necessary. Examples of the flame retardant used include reactive flame retardants such as phosphorus-containing polyols such as propoxylated phosphoric acid and propoxylated dibutyl pyrophosphate obtained by addition reaction of phosphoric acid and alkylene oxide, tricresyl Tertiary phosphates such as phosphate, halogen-containing tertiary phosphates such as tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, halogens such as dibromopropanol, dibromoneopentyl glycol, tetrabromobisphenol A Examples include organic compounds, inorganic compounds such as antimony oxide, magnesium carbonate, calcium carbonate, and aluminum phosphate. The amount is not particularly limited and varies depending on the required flame retardancy, but is usually 4 to 20 parts by weight with respect to 100 parts by weight of the polyol.

  In the method for producing a polyurethane resin of the present invention, a colorant, an antiaging agent, and other conventionally known additives can be used as necessary. The type and amount of these additives may be within the normal usage range of the additive used.

  The method for producing the polyurethane resin of the present invention is carried out by rapidly mixing and stirring the mixed solution in which the raw materials are mixed, and then injecting the mixture into a suitable container or mold to perform foam molding. Mixing and stirring may be performed using a general stirrer or a dedicated polyurethane foaming machine. As the polyurethane foaming machine, high-pressure, low-pressure and spray-type devices can be used.

  Examples of polyurethane resin products include elastomers that do not use a foaming agent and polyurethane foams that use a foaming agent. Among them, the production of polyurethane foam products is preferred. Polyurethane foam products include soft, semi-rigid, rigid, etc., but in particular, they are manufactured with soft car seats, semi-rigid instrument panels and handles, and spray-type rigid foams used as automotive interior materials. Thermal insulation building materials are preferred.

  Hereinafter, although demonstrated based on an Example, this invention is not limited only to these Examples. The hydroxyl value of each hydroxyalkylated polyalkylene polyamine was measured according to JIS-K1557-1970 (namely, a method abbreviated as phthalic anhydride method).

  As in the present invention, polyhydric alcohols obtained by adding alkylene oxide to a raw material compound become a mixture of a plurality of compounds having a distribution in molecular weight, and it is difficult to isolate and identify these compounds. Is used to calculate the number of hydroxyl groups per average molecular weight of the product. The hydroxyl value (mgKOH / g) is defined by the following formula as described above.

Hydroxyl value = number of OH groups in molecule ÷ average molecular weight × 56.11 × 1000.
Example 1
In a 1000 ml autoclave equipped with a stirrer, 150 g (1.45 mol) of diethylenetriamine (DETA manufactured by Tosoh Corp.), 150 g of water and 0.5 g of catalyst Pd-C (5% supported) were charged. The autoclave was sealed, purged with hydrogen, and then heated to 120 ° C. with stirring. Subsequently, 295 g (3.63 mol) of 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 distillation apparatus, the product, N-methylated diethylenetriamines, was distilled off under reduced pressure to obtain 159 g. As a result of gas chromatographic analysis and ¹ H-NMR analysis of this product, 53% of the hydrogen group bonded to the nitrogen atom of diethylenetriamine was converted to a methyl group [ie, in the above general formula (3), Among R _{1 to} R ₅ , the ratio of the alkyl group having 1 to 3 carbon atoms and the hydrogen atom is [alkyl group having 1 to 3 carbon atoms] / [hydrogen atom] = 53/47 (molar ratio)], and The gas chromatogram revealed that the composition was 14% monomethyl, 33% dimethyl, 36% trimethyl, and 17% tetramethyl. This amine compound was designated as Compound A.

  In an autoclave, 70.2 g of compound A was charged, sealed, purged with nitrogen, and heated to 120 ° C. with stirring. Subsequently, 71.7 g of 1,2-propylene oxide was pumped over 4 hours. After aging reaction for 1 hour, the reaction solution is cooled and taken out, evaporated for 2 hours under the condition of 60 ° C./20 mmHg, and then hydroxyalkylated polyalkylene polyamine composition 1 (hereinafter sometimes referred to as polyol 1). ) Was obtained. Its hydroxyl value was 465 mg KOH / g. As a result, the average molecular weight of the hydroxyalkylated polyalkylene polyamine composition 1 is estimated to be 284.

Example 2
In an autoclave, 77.2 g of compound A was charged, sealed, purged with nitrogen, and then heated to 80 ° C. with stirring. Subsequently, 62.6 g of ethylene oxide was supplied stepwise from the pressure vessel over 4 hours. After a ripening reaction at 100 ° C. for 1 hour, the reaction solution was cooled and taken out, and evaporated for 2 hours under the conditions of 60 ° C./20 mmHg to obtain 134 g of a hydroxyalkylated polyalkylene polyamine composition 2. Its hydroxyl value was 529 mgKOH / g. As a result, the average molecular weight of the hydroxyalkylated polyalkylene polyamine composition 2 is estimated to be 249.

Example 3
Except that the amount of the 37% formalin aqueous solution was changed to 470 g (5.80 mol), the reaction and distillation were performed under the same conditions as in Example 1 to obtain 182 g of N-methylated diethylenetriamines. As a result of analyzing this product in the same manner as in Example 1, it was found that 79% of the hydrogen group bonded to the nitrogen atom of diethylenetriamine was converted to a methyl group [that is, in the above general formula (3), R ₁ to In R ₅ , the ratio of the alkyl group having 1 to 3 carbon atoms and the hydrogen atom is [alkyl group having 1 to 3 carbon atoms] / [hydrogen atom] = 79/21 (molar ratio)], and the composition is The composition was found to be 4% dimethyl, 19% trimethyl, 52% tetramethyl, and 25% pentamethyl. This amine compound was designated as Compound B.

  In an autoclave, 111 g of compound B was charged, sealed, purged with nitrogen, and heated to 120 ° C. with stirring. Subsequently, 45 g of 1,2-propylene oxide was supplied by a pump over 4 hours. After aging reaction for 1 hour, the reaction solution was cooled and taken out, and evaporated for 2 hours under the condition of 60 ° C./20 mmHg to obtain 151 g of a hydroxyalkylated polyalkylene polyamine composition 3. Its hydroxyl value was 265 mg KOH / g. As a result, the average molecular weight of the hydroxyalkylated polyalkylene polyamine composition 3 is estimated to be 222.

Example 4
In a 200 ml autoclave equipped with a stirrer, 111 g of compound B was charged, sealed, purged with nitrogen, and heated to 80 ° C. with stirring. Subsequently, 36 g of ethylene oxide was supplied stepwise from the pressure vessel over 4 hours. After aging reaction at 100 ° C. for 1 hour, the reaction solution was cooled and taken out and evaporated under the conditions of 60 ° C./20 mmHg for 2 hours to obtain 140 g of hydroxyalkylated polyalkylene polyamine composition 4. The hydroxyl value was 284 mgKOH / g. As a result, the average molecular weight of the hydroxyalkylated polyalkylene polyamine composition 4 is estimated to be 207.

Example 5
In a 1000 ml autoclave equipped with a stirrer, 375 g of tetraethylenepentamine (TEPA manufactured by Tosoh Corp.) and 1.3 g of catalyst Pd-C (supporting 5%) containing a branched chain and a cyclic product in addition to a straight chain were charged. . The autoclave was sealed, purged with hydrogen, and then heated to 120 ° C. with stirring. Subsequently, while introducing hydrogen at a pressure of 3 MPa into the autoclave, 480 g of 37% formalin aqueous solution was supplied by a pump over 9 hours. After aging reaction for 1 hour, the reaction solution was taken out by cooling.

After distilling off water from the reaction solution using a distillation apparatus, 335 g of N-methylated tetraethylenepentamines as a product was obtained under reduced pressure. As a result of analyzing this product in the same manner as in Example 1, it was found that 52% of the hydrogen group bonded to the nitrogen atom of tetraethylenepentamine was converted to a methyl group [that is, in the above general formula (3), Among R _{1 to} R ₅ , the ratio of the alkyl group having 1 to 3 carbon atoms and the hydrogen atom is [alkyl group having 1 to 3 carbon atoms] / [hydrogen atom] = 52/48 (molar ratio)], and Although it was found that the trimethyl body and tetramethyl body were the main components, the composition could not be specified. This amine compound was designated as Compound C.

  In an autoclave, 97.7 g of compound C was charged, sealed, purged with nitrogen, and heated to 80 ° C. with stirring. Subsequently, 58 g of ethylene oxide was supplied stepwise from the pressure vessel over 4 hours. After aging reaction at 100 ° C. for 1 hour, the reaction solution was taken out by cooling and evaporated for 2 hours under the conditions of 60 ° C./20 mmHg to obtain 150 g of hydroxyalkylated polyalkylene polyamine composition 5. Its hydroxyl value was 439 mgKOH / g.

Example 6
In a 200 ml autoclave equipped with a stirrer, 97.7 g of compound C was charged, sealed, purged with nitrogen, and heated to 120 ° C. with stirring. Subsequently, 74 g of 1,2-propylene oxide was pumped over 4 hours. After conducting the aging reaction for 1 hour, the reaction solution is cooled and taken out, and evaporated for 2 hours under the condition of 60 ° C./20 mmHg. 166 g was obtained. Its hydroxyl value was 395 mg KOH / g.

Example 7
In a 200 ml autoclave equipped with a stirrer, 80.1 g of compound C was charged, sealed, purged with nitrogen, and heated to 120 ° C. with stirring. Subsequently, 79 g of 1,2-butylene oxide was pumped over 4 hours. After the aging reaction for 1 hour, the reaction solution was cooled and taken out, and evaporated for 2 hours under the conditions of 60 ° C./20 mmHg, and then the hydroxyalkylated polyalkylene polyamine composition 7 (hereinafter sometimes referred to as polyol 7). 150 g was obtained. Its hydroxyl value was 376 mgKOH / g.

Example 8
In a 500 ml autoclave equipped with a stirrer, 150 g (1.14 mol, reagent) of dipropylene triamine and 0.5 g of catalyst Pd-C (5% supported) were charged. The autoclave was sealed, purged with hydrogen, and then heated to 120 ° C. with stirring. Subsequently, while introducing hydrogen at a pressure of 3 MPa into the autoclave, 232 g of 37% formalin aqueous solution was supplied by a pump over 4 hours. After aging reaction for 1 hour, the reaction solution was taken out by cooling.

After distilling off water from the reaction solution using a distillation apparatus, distillation was performed under reduced pressure to obtain 142 g of N-methylated dipropylene triamines as a product. As a result of analyzing this product in the same manner as in Example 1, it was found that 51% of the hydrogen group bonded to the nitrogen atom of dipropylenetriamine was converted to a methyl group [ie, in the above general formula (3), R _{1 to} R ₅ , the ratio of the alkyl group having 1 to 3 carbon atoms and the hydrogen atom is [alkyl group having 1 to 3 carbon atoms] / [hydrogen atom] = 51/49 (molar ratio)], and monomethyl The composition was found to be 13% body, 36% dimethyl body, 38% trimethyl body, and 13% tetramethyl body. This amine compound was designated as Compound D.

  In a 200 ml autoclave with a stirrer, 90.5 g of compound D was charged, sealed, purged with nitrogen, and heated to 120 ° C. with stirring. Subsequently, 75 g of 1,2-propylene oxide was supplied by a pump over 4 hours. After the aging reaction for 1 hour, the reaction solution is cooled and taken out, evaporated for 2 hours under the condition of 60 ° C./20 mmHg, and then hydroxyalkylated polyalkylene polyamine composition 8 (hereinafter sometimes referred to as polyol 8). ) Was obtained. The hydroxyl value was 420 mgKOH / g.

Example 9
In a 200 ml autoclave equipped with a stirrer, 83.7 g of compound D was charged, sealed, purged with nitrogen, and heated to 80 ° C. with stirring. Subsequently, 59 g of ethylene oxide was supplied stepwise from the pressure vessel over 4 hours. After aging reaction at 100 ° C. for 1 hour, the reaction solution was cooled and taken out, and evaporated for 2 hours under the conditions of 60 ° C./20 mmHg to obtain 137 g of a hydroxyalkylated polyalkylene polyamine composition 9. Its hydroxyl value was 490 mgKOH / g.

Example 10
In a 200 ml autoclave equipped with a stirrer, 75.3 g of compound D was charged, sealed, purged with nitrogen, and heated to 120 ° C. with stirring. Subsequently, 84 g of 1,2-butylene oxide was pumped over 4 hours. After aging reaction for 1 hour, the reaction solution was cooled and taken out, and evaporated for 2 hours under the condition of 60 ° C./20 mmHg to obtain 151 g of a hydroxyalkylated polyalkylene polyamine composition 10. Its hydroxyl value was 400 mgKOH / g.

Example 11
In a 200 ml autoclave equipped with a stirrer, 147 g (3.32 mol) of 37% formalin aqueous solution was reacted and distilled under the same conditions as in Example 5 to obtain 147 g of N-methylated tetraethylenepentamines. It was. As a result of the analysis, it was found that 71% of the hydrogen group bonded to the nitrogen atom of tetraethylenepentamine was converted to a methyl group, and that the pentamethyl body was the main component. The composition could not be specified. This amine compound was designated as Compound E.

  In a 200 ml autoclave equipped with a stirrer, 104.4 g of compound E was charged, sealed, purged with nitrogen, and heated to 120 ° C. with stirring. Subsequently, 45 g of 1,2-propylene oxide was supplied by a pump over 4 hours. After aging reaction for 1 hour, the reaction solution was cooled and taken out, and evaporated for 2 hours under the conditions of 60 ° C./20 mmHg to obtain 147 g of hydroxyalkylated polyalkylene polyamine composition 11. Its hydroxyl value was 275 mg KOH / g.

Example 12
In a 200 ml autoclave equipped with a stirrer, 104.4 g of compound E was charged, sealed, purged with nitrogen, and heated to 80 ° C. with stirring. Subsequently, 35 g of ethylene oxide was supplied stepwise from the pressure vessel over 4 hours. After aging reaction at 100 ° C. for 1 hour, the reaction solution was cooled and taken out, and evaporated for 2 hours under the condition of 60 ° C./20 mmHg to obtain 134 g of a hydroxyalkylated polyalkylene polyamine composition 12. Its hydroxyl value was 296 mgKOH / g.

Example 13
The reaction and distillation were performed under the same conditions as in Example 5 except that the 37% formalin aqueous solution was changed to 115 g (1.42 mol) to obtain 125 g of N-methylated tetraethylenepentamines. As a result of analysis, it was found that 30% of the hydrogen group bonded to the nitrogen atom of tetraethylenepentamine was converted to a methyl group, and that the dimethyl body was the main component. The composition could not be specified. This amine compound was designated as Compound F.

  In an autoclave, 71.7 g of compound F was charged, sealed, purged with nitrogen, and heated to 120 ° C. with stirring. Subsequently, 85.4 g of 1,2-propylene oxide was pumped over 4 hours. After aging reaction for 1 hour, the reaction solution was cooled and taken out, and evaporated for 2 hours under the condition of 60 ° C./20 mmHg to obtain 152 g of a hydroxyalkylated polyalkylene polyamine composition 13. Its hydroxyl value was 500 mg KOH / g.

Example 14
In an autoclave, 71.7 g of compound F was charged, sealed, purged with nitrogen, and then heated to 80 ° C. with stirring. Subsequently, 68 g of ethylene oxide was supplied stepwise from the pressure vessel over 4 hours. After aging reaction at 100 ° C. for 1 hour, the reaction solution was cooled and taken out, and evaporated for 2 hours under the conditions of 60 ° C./20 mmHg to obtain 134 g of a hydroxyalkylated polyalkylene polyamine composition 14. Its hydroxyl value was 576 mg KOH / g.

Examples 15 to 18 and Comparative Examples 1 to 4
As an example of producing a semi-rigid polyurethane foam using the hydroxyalkylated polyalkylene polyamine composition of the present invention, a semi-rigid polyurethane foam was prepared using various catalysts instead of using the hydroxyalkylated polyalkylene polyamine composition of the present invention. An example of producing a rigid polyurethane foam is shown below as a comparative example.

  Premix A was prepared at the raw material mixing ratio shown in Table 1. The amount of triethanolamine was adjusted according to the amount of each hydroxyalkylated polyalkylene polyamine added so that the crosslink density of the polymer would be the same.

１）ＦＡ７０３、三洋化成社製ポリエーテルポリオール
２）イソシアネート（ＭＤＩ）：ＭＲ２００（日本ポリウレタン社製）
３）ＩＮＤＥＸ＝（ＮＣＯ基モル数／ＯＨ基モル数）×１００。

1) FA703, polyether polyol manufactured by Sanyo Kasei Co., Ltd. 2) Isocyanate (MDI): MR200 (manufactured by Nippon Polyurethane Co., Ltd.)
3) INDEX = (number of moles of NCO group / number of moles of OH group) × 100.

  Take 105.8 g of Premix A in a 300 ml polyethylene cup, add the hydroxyalkylated polyalkylene polyamine composition of the present invention or various catalysts shown in Table 2 in an amount such that the reactivity is 50 seconds at the following gel times, The temperature was adjusted to 25 ° C. Put the isocyanate liquid whose temperature is adjusted to 25 ° C. in a separate container into the premix A cup in an amount that the isocyanate index [= isocyanate group / OH group (molar ratio) × 100)] is 105, and quickly use a stirrer. Stir for 5 seconds at 3000 rpm. The mixed and stirred liquid mixture was transferred to a 2 liter polyethylene cup whose temperature was adjusted to 40 ° C., and the reactivity during foaming was measured.

Next, the liquid mixture is put in a mold (inner dimensions, made of aluminum of 295 × 305 × 25 mm) whose temperature is adjusted to 40 ° C. so that the total foam density becomes 94 kg / m ³ by the same operation, and the lid is closed. Foam molding was performed. The foam was demolded 3 minutes after the start of mixing, and the foam hardness at the time of demolding was measured 1 minute later. In addition, foam hardness and foam odor were measured and compared from molded foam. 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, foam start time visually. Gel time: Measure time when reaction progresses and change from liquid to resinous material. Rise time: Foam rise Visually measure the time to stop.

(2) Odor during work Three monitors were set up 1 meter behind the worker who was preparing the reaction liquid, and the odor was observed and evaluated as follows as the odor during work. ○: Unpleasant odor Small Δ: Slightly unpleasant odor ×: Very unpleasant odor

(3) 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.

(4) Hardness of foam The foam was removed 3 minutes after the start of mixing, and the hardness of the foam was measured 24 hours later.

(5) Vinyl chloride sheet contamination test (PVC discoloration)
The foam containing the epidermis is cut to a size of 7 × 7 × 2.5 cm, charged into a 2000 ml separable flask, a white vinyl chloride sheet 5 × 5 cm is hung in the air, the lid is closed and sealed, 100 ° C. × 72 After standing for a period of time, the degree of contamination of the vinyl chloride sheet was visually confirmed, and the color change was evaluated as follows: ○: No change in color ×: Change in color to red.

  Since the vinyl chloride sheet turns red due to the amine volatilized from the foam, if the sheet changes color, it indicates that the amine has been discharged from the foam. I can say no.

１）トリエタノールアミン（関東化学（株）社製）
２）トリエチレンジアミン３３．３％ジプロピレングリコール溶液（東ソー（株）社製ＴＥＤＡ−Ｌ３３）
３）Ｎ，Ｎ−ジメチルプロパンジアミン（試薬）
４）直鎖以外に分岐鎖及び環状体も含むテトラエチレンペンタミン（東ソー（株）社製ＴＥＰＡ）の１００％メチル化品
５）Ｎ−（２−ヒドロキシプロピル）−Ｎ，Ｎ’，Ｎ”，Ｎ”−テトラメチルジエチレントリアミン（合成品）。

1) Triethanolamine (manufactured by Kanto Chemical Co., Inc.)
2) Triethylenediamine 33.3% dipropylene glycol solution (TEDA-L33 manufactured by Tosoh Corporation)
3) N, N-dimethylpropanediamine (reagent)
4) 100% methylated product of tetraethylenepentamine (TEPA manufactured by Tosoh Co., Ltd.) including branched and cyclic products in addition to straight chain 5) N- (2-hydroxypropyl) -N, N ′, N ″ , N ″ -tetramethyldiethylenetriamine (synthetic product).

  As is apparent from the above table, Examples 15 to 18 are examples using the hydroxyalkylated polyalkylene polyamine composition of the present invention, but the obtained polyurethane foam has a high hardness at the time of demolding, and at the time of work. There is almost no odor and does not contaminate the vinyl chloride sheet.

  On the other hand, Comparative Example 1 is an example using a general-purpose tertiary amine catalyst, but the obtained polyurethane foam has low hardness at the time of demolding, has an odor during work, and contaminates the vinyl chloride sheet. To do. Comparative Example 2 is an example using a general-purpose reactive amine catalyst, but the resulting polyurethane foam has low odor during working and at the time of demolding and foam. Comparative Example 3 is an example using a compound in which all active hydrogen groups of the polyalkylene polyamine are substituted with methyl groups. However, there is an odor during operation and the vinyl chloride sheet is contaminated. Comparative Example 4 is an example using a compound in which one of the active hydrogen groups of the polyalkylene polyamine was oxyalkylated using 1,2-propylene oxide and the other active hydrogen groups were substituted with methyl groups. The polyurethane foam to be obtained has a low hardness at the time of demolding and has a odor during work.

Examples 19 to 22 and Comparative Examples 5 to 7
As an example of the production of a flexible polyurethane foam using the hydroxyalkylated polyalkylene polyamine composition of the present invention, a flexible polyurethane using various catalysts instead of not using the hydroxyalkylated polyalkylene polyamine composition of the present invention. The example which manufactured the foam is shown below as a comparative example.

  Premix B was prepared at the raw material mixing ratio shown in Table 3.

１）ＣＰ４７１１、ダウ社製ポリエーテルポリオール
２）ＣＰ１４２１、ダウ社製ポリエーテルポリオール
３）ジエタノールアミン（関東化学（株）社製）
４）Ｂ４１１３ＬＦ（ゴールドシュミット社製シリコーン系界面活性剤）
５）ＮＥ１１２、ダウ社製イソシアネート（ＭＤＩ）
６）ＩＮＤＥＸ＝（ＮＣＯ基モル数／ＯＨ基モル数）×１００。

1) CP4711, Dow Polyether Polyol 2) CP1421, Dow Polyether Polyol 3) Diethanolamine (Kanto Chemical Co., Ltd.)
4) B4113LF (silicone surfactant made by Goldschmidt)
5) NE112, Dow isocyanate (MDI)
6) INDEX = (number of moles of NCO group / number of moles of OH group) × 100.

  100.4 g of Premix B was placed in a 300 ml polyethylene cup, the hydroxyalkylated polyalkylene polyamine composition of the present invention shown in Table 4 or various catalysts were added, and the temperature was adjusted to 20 ° C. In a separate container, 56.2 g of an isocyanate liquid whose temperature was adjusted to 20 ° C. with an isocyanate index [= isocyanate group / OH group (molar ratio) × 100)] of 100 was placed in a premix B cup, and quickly put into a stirrer. And stirred at 6000 rpm for 5 seconds. The mixed and stirred liquid mixture was transferred to a 2 liter polyethylene cup whose temperature was adjusted to 40 ° C., and the reactivity during foaming was measured.

  Next, the liquid mixture was put in from the end in a mold (inner dimensions, made of aluminum of 250 × 250 × 80 mm) whose temperature was adjusted to 60 ° C. by the same operation and scale, and then foam molding was performed. The foam was demolded 3 minutes after the mixed solution was added. The results are shown in Table 4. In addition, the measuring method of each measurement item is as follows.

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

(2) Odor during work Three monitors were set up 1 meter behind the worker who was preparing the reaction liquid, and the odor was observed and evaluated as follows as the odor during work. ○: Unpleasant odor Small Δ: Slightly unpleasant odor ×: Very unpleasant odor

(3) Hardness of foam The foam was removed 3 minutes after the start of mixing, and the hardness of the foam was measured 24 hours later.

(4) Amine amine odor Foam with a core core density of 5 × 5 × 5 cm was cut, put into a mayonnaise bottle, capped, and heated at 50 ° C. for 1 day for 10 monitors. The smell of the foam was smelled and the strength of amine odor was measured. ○: Almost no odor △: Slightly odor ×: Strong odor.

１）トリエチレンジアミン３３．３％ジプロピレングリコール溶液（東ソー（株）社製ＴＥＤＡ−Ｌ３３）
２）Ｎ，Ｎ−ジメチルエタノールアミン（関東化学（株）社製）。

1) Triethylenediamine 33.3% dipropylene glycol solution (TEDA-L33 manufactured by Tosoh Corporation)
2) N, N-dimethylethanolamine (manufactured by Kanto Chemical Co., Inc.).

  As is apparent from the above table, Examples 19 to 20 are examples using the hydroxyalkylated polyalkylene polyamine composition of the present invention, but the resulting polyurethane foam has sufficient hardness and is in operation. And almost no foam odor. Examples 21 to 22 are examples in which the hydroxyalkylated polyalkylene polyamine of the present invention is used and the amount of general-purpose tertiary amine catalyst used is halved. The resulting polyurethane foam has sufficient hardness. Also, there is little odor during work and foam.

On the other hand, Comparative Example 5 is an example using a general-purpose reaction type catalyst. However, the hardness of the resulting polyurethane foam is insufficient, and there is an odor of the foam during work. Comparative Example 6 is an example in which a general-purpose tertiary amine catalyst is used, but it smells during work and foam. Comparative Example 7 is an example in which a general-purpose reaction type catalyst and a general-purpose tertiary amine catalyst are used in combination, but the polyurethane foam obtained has insufficient hardness, and there is an odor during working and foam.

Claims (14)

The following general formula (1)

[Wherein R _{1 to} R ₅ are each independently a methyl group , or the following general formula (2)

(In formula, R < ₆ >, R < ₇ > represents a hydrogen atom and p represents the integer of 1-3.)
The substituent shown by is represented. Provided that at least one of R ₁ to R ₅ represents a substituent represented by the general formula (2), yet that all R ₁ to R ₅ is a substituent represented by the general formula (2) There is no. n and m each independently represent an integer of 1 or 2 . a represents an integer of 1 to 2 ; ]
In the general formula (1), the ratio of the methyl group to the substituent represented by the general formula (2) among R _{1 to} R ₅ is [methyl group] / [general formula (2) A hydroxyalkylated polyalkylene polyamine composition containing two or more hydroxyalkylated polyalkylene polyamines in a range of 70/30 to 30/70 (molar ratio) . The following general formulas (1a) to (1c)

[In the general formulas (1a) to (1c), R ₁ ~ R ₅ Are each independently a methyl group or the following general formula (2)

(Wherein R ₆ , R ₇ Represents a hydrogen atom, and p represents an integer of 1 to 3. )
The substituent shown by is represented. However, R ₁ ~ R ₅ At least one of them represents a substituent represented by the general formula (2), and R ₁ ~ R ₅ Are not all the substituents represented by the general formula (2). ]
And in the above general formulas (1a) to (1c), R ₁ ~ R ₅ Among them, the ratio of the methyl group to the substituent represented by the general formula (2) is [methyl group] / [substituent represented by the general formula (2)] = 70/30 to 30/70 (molar ratio). A hydroxyalkylated polyalkylene polyamine composition comprising two or more hydroxyalkylated polyalkylene polyamines having the above-mentioned range. The hydroxyalkylated polyalkylene polyamine composition according to claim 1 or 2, wherein the hydroxyl value is in the range of 20 to 800. The following general formula (3)

(Wherein R _{1 to} R ₅ each independently represents a hydrogen atom or a methyl group . However, at least one of R _{1 to} R ₅ represents a hydrogen atom. N and m are each independently 1 to 1) Represents an integer of 2. a represents an integer of 1 to 2 )
In the general formula (3), the ratio of the methyl group to the hydrogen atom in R _{1 to} R ₅ is [methyl group] / [hydrogen atom] = 70/30 to 30/70 (moles) N-methylated polyalkylene polyamine composition containing two or more kinds of N-alkylated polyalkylene polyamines in the range of the ratio) . The following general formula (4)

(In formula, R < ₁ > -R < ₅ > represents a hydrogen atom . N and m represent the integer of 1-2 each independently. A represents the integer of 1-2 .)
The method for producing an N-methylated polyalkylene polyamine composition according to claim 4, wherein the polyalkylene polyamine represented by the formula is partially N-methylated with formaldehyde . 6. The N-methylated polyalkylene polyamine composition according to claim 5, wherein the polyalkylene polyamine represented by the general formula (4) is selected from the group consisting of diethylenetriamine, dipropylenetriamine, and tetraethylenepentamine . Manufacturing method. The N-methylated polyalkylene polyamine composition according to claim 4 is oxidized with one or more alkylene oxides selected from the group consisting of ethylene oxide, 1,2-propylene oxide and 1,2-butylene oxide. The method for producing a hydroxyalkylated polyalkylene polyamine composition according to any one of claims 1 to 3, wherein the alkylation is performed. The following general formula (4)

(In formula, R < ₁ > -R < ₅ > represents a hydrogen atom . N and m represent the integer of 1-2 each independently. A represents the integer of 1-2 .)
Polyalkylene polyamine represented in, partially N- alkylated with formaldehyde, followed by ethylene oxide, one or more alkylene oxides selected from the group consisting of 1,2-propylene oxide and 1,2-butylene oxide The method for producing a hydroxylated polyalkylene polyamine composition according to any one of claims 1 to 3, wherein the oxyalkylation is carried out by the method. 9. The hydroxyalkylated polyalkylene polyamine composition according to claim 8, wherein the polyalkylene polyamine represented by the general formula (4) is selected from the group consisting of diethylenetriamine, dipropylenetriamine, and tetraethylenepentamine . Production method. A process for producing a polyurethane resin comprising reacting a polyol and an isocyanate in the presence of the hydroxyalkylated polyalkylene polyamine composition according to any one of claims 1 to 3. A method for producing a polyurethane resin, comprising reacting a polyol and an isocyanate in the presence of a hydroxyalkylated polyalkylene polyamine composition obtained by the production method according to any one of claims 7 to 9 . A process for producing a polyurethane foam, comprising reacting a polyol and an isocyanate in the presence of the hydroxyalkylated polyalkylene polyamine composition according to any one of claims 1 to 3 and a foaming agent. A method for producing a polyurethane foam, comprising reacting a polyol and an isocyanate in the presence of a hydroxyalkylated polyalkylene polyamine composition obtained by the production method according to any one of claims 7 to 9 and a foaming agent. Water, dichloromonofluoroethane (HCFC-141b), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), The method for producing a polyurethane foam according to claim 12 or 13, wherein the reaction is performed using a blowing agent selected from the group consisting of propane, butane, pentane, cyclopentane, and hexane .