JP5486537B2 - Polyamine compound, process for producing the polyamine compound, and epoxy curing agent - Google Patents

Description

  The present invention relates to a novel polyamine compound, a method for producing the polyamine compound, and an epoxy curing agent.

Epoxy resin is a thermosetting resin produced by the reaction between an epoxy compound and a curing agent. Due to its excellent characteristics and versatility, adhesives for civil engineering and construction, sealing agents for semiconductors, printed circuit boards and high-voltage power It is used in various fields such as insulating materials for molding equipment and paints for cans and automobiles.
Curing agents used for epoxy resins vary widely depending on the application, but polyaddition type curing agents are typically polyamine compounds such as aliphatic polyamines, alicyclic polyamines, and aromatic polyamines ( Non-patent document 1).

In particular, aliphatic polyamines have high curability and are used as room temperature curing type curing agents. The cured product is excellent in mechanical properties and excellent in adhesion and chemical resistance. Examples of such aliphatic polyamines include diethylenetriamine, triethylenetetramine, trimethylhexamethylenediamine, and 2-methylpentamethylenediamine.
On the other hand, development of a new epoxy curing agent using a new compound is desired.

Epoxy Resin Technology Association, Review Epoxy Resin Vol. 1 Fundamentals I, Epoxy Resin Technology Association, 123-146 (2003)

  The present invention relates to a novel polyamine compound, a method for producing the polyamine compound, and an adhesive for civil engineering and construction, a sealing agent for semiconductor, an insulating material for a printed circuit board, a molded device for high voltage power, a can, an automobile, etc. It is an object of the present invention to provide an epoxy curing agent having excellent curing performance that is useful for various coating materials.

  As a result of intensive studies, the present inventors have achieved the above-mentioned problem by the following means.

(1) A polyamine compound represented by the following general formula (1).

In general formula (1), R represents a hydrogen atom or a methyl group.
(2) An epoxy curing agent represented by the following general formula (1).

  In general formula (1), R represents a hydrogen atom or a methyl group.

(3) From the step of reacting tris (hydroxymethyl) aminomethane with acrylonitrile or methacrylonitrile to obtain a compound represented by the following general formula (2) and the step of reducing the compound represented by the general formula (2) The manufacturing method of the polyamine compound represented by following General formula (1).

  In the general formulas (1) and (2), R represents a hydrogen atom or a methyl group.

  According to the present invention, a novel polyamine compound, a method for producing the polyamine compound, and an adhesive for civil engineering and construction, a sealing agent for semiconductor, an insulating material for a printed circuit board, a molded device for high voltage power, a can, an automobile, etc. It is possible to provide an epoxy curing agent having excellent curing performance that is useful for various coating materials.

1 is a chart of ¹ H-NMR spectrum of polyamine compound 1 synthesized in Example 1. FIG. 2 is a chart of ¹³ C-NMR spectrum of polyamine compound 1 synthesized in Example 1. FIG. 2 is a chart of an infrared absorption spectrum of polyamine compound 1 synthesized in Example 1. FIG.

  The present inventors have found a novel polyamine compound and have found that the polyamine compound exhibits an excellent effect as a curing agent for an epoxy resin.

(New polyamine compound)
The compound represented by the general formula (1) of the present invention will be described.

  In general formula (1), R represents a hydrogen atom or a methyl group. Here, R is preferably a hydrogen atom.

(Method for producing polyamine compound)
The manufacturing method of the polyamine compound represented by General formula (1) of this invention is demonstrated.
The process for producing a polyamine compound represented by the general formula (1) of the present invention is a step of reacting tris (hydroxymethyl) aminomethane with acrylonitrile or methacrylonitrile to obtain a compound represented by the following general formula (2). (First step) and a step of reducing the compound represented by the general formula (2) (second step).

  In the general formulas (1) and (2), R represents a hydrogen atom or a methyl group.

In the first step, the hydroxyl group of tris (hydroxymethyl) aminomethane is subjected to a Michael addition reaction with acrylonitrile or methacrylonitrile in the presence of a base to obtain a compound represented by the general formula (2) as an intermediate. The Michael addition reaction can be carried out by a homogeneous reaction or a two-layer reaction, but a homogeneous reaction is preferred from the viewpoint of suppressing by-products.
In the homogeneous reaction, either a method in which acrylonitrile is used in a large excess and a reaction is carried out without a solvent or a method in which a reaction is carried out using a solvent may be used.

Preferable solvents include aromatic solvents such as toluene, nitrile solvents such as acetonitrile, ether solvents such as tetrahydrofuran, amide solvents such as N, N-dimethylacetamide, and sulfoxide solvents such as dimethyl sulfoxide. Among these, from the viewpoint of solubility of tris (hydroxymethyl) aminomethane as a raw material and solvent distillation after the reaction, a nitrile solvent or an ether solvent is more preferable, acetonitrile or tetrahydrofuran is more preferable, and acetonitrile is particularly preferable. preferable.
As the base, a strong base having a pKa of a conjugate acid of 13 or more can be used. Examples of such strong bases include hydroxides such as sodium hydroxide and potassium hydroxide, metal alkoxides such as sodium methoxide, sodium t-butoxide, and potassium t-butoxide, metal hydrides such as sodium hydride, guanidine, Examples include organic strong bases such as DBU. Among these, from the viewpoint of suppressing by-products, a conjugated base of a tertiary alcohol such as sodium t-butoxide or potassium t-butoxide is preferable. The amount of base added is preferably in the range of 0.00001 to 0.1 mol, more preferably 0.0001 to 0.01 mol, and more preferably 0.0005 to 0, per 1 mol of tris (hydroxymethyl) aminomethane. 0.002 mol is particularly preferred.

The amount of acrylonitrile or methacrylonitrile added is preferably in the range of 3 to 30 mol, more preferably 4 to 10 mol, with respect to 1 mol of tris (hydroxymethyl) aminomethane, when the reaction is carried out without solvent. 8 moles are particularly preferred. When performing reaction using a solvent, the range of 3-10 mol is preferable with respect to 1 mol of tris (hydroxymethyl) aminomethane, 3.3-7 mol is still more preferable, 3.6-6 mol is Particularly preferred.
The reaction temperature is preferably in the range of −20 ° C. to 90 ° C., more preferably 0 ° C. to 80 ° C., and particularly preferably 20 ° C. to 70 ° C. from the viewpoint of shortening the reaction time and suppressing side reactions.
The reaction atmosphere may be air or an inert gas, but is preferably an inert gas in order to avoid deactivation of the base by carbon dioxide in the air. Examples of the inert gas include nitrogen and argon.

  After completion of the reaction, it is preferable to stop the reaction by adding a compound having a pKa of 12 or less. There is no particular limitation as long as the compound has a pKa of 12 or less, but inorganic compounds such as sodium hydrogen carbonate and sodium hydrogen sulfate are preferred because the post-treatment is simple. The reaction is preferably stopped after cooling at 30 ° C. or less, more preferably at 20 ° C. or less, and particularly preferably at 10 ° C. or less.

In the second step, the nitrile group of the intermediate represented by the general formula (2) is reduced to an amino group. This reduction reaction may be any reduction reaction, but a hydrogenation reaction is preferred in the present invention.
The hydrogenation reaction is not particularly limited as long as it is a known method, but can be performed, for example, by a heterogeneous catalytic hydrogenation reaction.
Examples of the catalyst used in the heterogeneous catalytic hydrogenation reaction include Raney catalysts such as Raney nickel and Raney cobalt, and supported catalysts in which a catalytic metal such as palladium, platinum, rhodium, and ruthenium is supported on a carrier such as carbon. Of these, Raney catalysts are preferred from the viewpoint of reaction selectivity.
The solvent is preferably water and an alcohol solvent, more preferably a cosolvent of water and alcohol, and particularly preferably a cosolvent of water and methanol.
In order to suppress a side reaction, it is preferable to make ammonia coexist in the reaction solution. The method of adding ammonia may be a method of adding aqueous ammonia as a solvent or a method of introducing ammonia gas. The amount of ammonia added is preferably 1 mol / kg or more, more preferably 3 mol / kg or more, and particularly preferably 5 mol / kg or more with respect to the reaction solution.
The hydrogen pressure is not particularly limited and can be 0.1 to 10 MPa.
The reaction temperature is preferably in the range of 0 to 100 ° C, more preferably 10 to 50 ° C, and particularly preferably 20 to 35 ° C from the viewpoint of shortening the reaction time and suppressing by-products.

(Epoxy curing agent)
The polyamine compound represented by the general formula (1) of the present invention has four amino groups, particularly, a highly reactive primary amino group (—NH ₂ ) in the molecule. Moreover, since these amino groups are sterically distributed at a specific distance in the molecular structure, the performance as an epoxy curing agent is excellent.
The epoxy curing agent represented by the general formula (1) of the present invention is cured by a polyaddition reaction by mixing with an epoxy compound to produce a so-called epoxy resin. In this curing, even if the polyamine compound represented by the general formula (1) of the present invention is contained alone, the polyamine compound represented by the general formula (1) of the present invention and at least one known curing agent or A curing accelerator may be used in combination, and these known curing agents or curing accelerators may be contained in the epoxy curing agent of the present invention.

  As known curing agents that may be used in combination, aliphatic polyamines, alicyclic polyamines, aromatic polyamines, and special polyamines can be used. Examples of the aliphatic polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, and diethylaminopropylamine. Alicyclic polyamines include isophorone diamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, bis (4-amino-3-methylcyclohexyl). Examples include methane. Examples of the aromatic polyamine include diaminodiphenylmethane, m-phenylenediamine, and diaminodiphenylsulfone. Special polyamines include polyoxypropylene diamine, polyoxypropylene triamine, polycyclohexyl polyamine mixture, 3,9-bis (3-aminopropyl) -2,4,5,10-tetraspiro [5.5] undecane, N- Aminoethylpiperazine etc. are mentioned.

As known curing accelerators that may be used in combination, fatty acids, benzoic acids, alcohols, phenols, mercaptos, and the like can be used. Specifically, Epoxy Resin Technical Association, Review Epoxy Resin 1 The compounds listed in Table 5 in Chapter 3, Item 2, Volume I, Epoxy Resin Technology Association (2003).
When the epoxy curing agent represented by the general formula (1) of the present invention and these known curing agents and accelerators are used in combination, the known curing agent and curing are different depending on the purpose of use and the epoxy compound used. The accelerator is preferably less than 50 mass, more preferably less than 25 mass relative to 100 mass of the epoxy curing agent represented by the general formula (1) of the present invention, and epoxy curing represented by the general formula (1) of the present invention. More preferably, the agent is used alone.

As the epoxy compound, known epoxy compounds such as glycidyl ether type, glycidyl ester type, glycidyl amine type, and oxidized type can be used.
Examples of the glycidyl ether type include a Bis-A type epoxy compound, a Bis-F type epoxy compound, a High-Br type epoxy compound, a novolac type epoxy compound, and an alcohol type epoxy compound. Examples of the glycidyl ester type include hydrophthalic acid type epoxy compounds and dimer acid type epoxy compounds. Examples of the glycidylamine type include aromatic amine type epoxy compounds and aminophenol type epoxy compounds. An alicyclic epoxy compound is mentioned as an oxidation type.
The blending ratio of the polyamine compound represented by the general formula (1) of the present invention and the epoxy compound is 0.1, assuming that A = (polyamine blending amount / active hydrogen equivalent) / (epoxy blending amount / epoxy equivalent). The range of <A <10 is preferable, 0.5 <A <2 is more preferable, and 0.8 <A <1.2 is particularly preferable.
Here, the active hydrogen equivalent is a value obtained by dividing the molecular weight of the polyamine compound by the number of hydrogen atoms of the amino group. The epoxy equivalent is a value obtained by dividing the molecular weight of the epoxy compound by the number of epoxy groups.
The epoxy curing agent of the present invention can be preferably used for civil engineering and building adhesives, semiconductor encapsulants, insulating materials for printed circuit boards and high-voltage power molding equipment, paints for cans and automobiles, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited by this.

Example 1
-Synthesis of polyamine compound of the present invention-
According to the following scheme, the following polyamine compound 1 (R is a hydrogen atom) of the present invention was synthesized.

To a 3 L three-necked flask, 145.3 g (1.2 mol) of tris (hydroxymethyl) aminomethane, 115 mg (1.2 mmol) of sodium t-butoxide and 1.2 L of acetonitrile were added and stirred. Heated to ° C. Next, 286.7 g (5.4 mol) of acrylonitrile was added dropwise over 30 minutes, and then stirred at 55 ° C. for 1 hour until the reaction solution became uniform. Then, it cooled to 20 degreeC and stirred for 1 hour, and also stirred at 0 degreeC for 4 hours. While stirring at 0 ° C., 6.0 g of sodium bicarbonate was added to stop the reaction, followed by filtration to remove inorganic salts. The filtrate was concentrated under reduced pressure, yielding 343.3 g of intermediate.
A 1 L autoclave was sealed with 24.0 g of the intermediate obtained above, 48.0 g of Ni catalyst (Raney nickel 2400, manufactured by WR Grace & Co.), 300 ml of methanol, and 300 ml of 25% aqueous ammonia. After the inside of the autoclave was replaced twice with nitrogen, 10 Mpa of hydrogen was introduced and reacted at 25 ° C. for 16 hours. After completion of the reaction, the inside of the autoclave was replaced with nitrogen, and then the reaction solution was taken out. The Ni catalyst in the reaction solution was filtered off through Celite filtration, and then the filtrate was concentrated under reduced pressure to obtain 23.8 g of the polyamine compound of the present invention.

The resulting polyamine compound 1 was identified by ¹ H-NMR spectrum, ¹³ C-NMR spectrum, and infrared absorption spectrum. The chart of identification data is shown in FIGS.
Here, both ¹ H-NMR spectrum and ¹³ C-NMR spectrum have TMS as the internal standard and deuterated chloroform as the measurement solvent.

Example 2
-Evaluation of epoxy curability-
A sample solution A was prepared by mixing 0.37 g of the polyamine compound 1 of the present invention and 1.70 g of 2,2-bis (4-glycidyloxyphenyl) propane (Tokyo Kasei) with sufficient stirring. After allowing the sample liquid A to stand at 25 ° C. for 3 days, it was confirmed by visual observation and touch that the sample liquid A was cured.

Example 3
-Evaluation of epoxy curability-
Sample solution B was prepared by stirring 0.37 g of polyamine compound 1 of the present invention and 1.01 g of 1,4-butanediglycidyl ether (Wako Pure Chemical Industries, Ltd.) and mixing them well. After allowing the sample liquid B to stand at 25 ° C. for 3 days, it was confirmed by visual observation and touch that the sample liquid B was cured.

Example 4
-Evaluation of epoxy curability-
A sample solution C was prepared by stirring 0.37 g of the polyamine compound 1 of the present invention and 1.42 g of 1,2-cyclohexanedicarboxylic acid diglycidyl (Tokyo Kasei) and mixing them well. After allowing the sample liquid C to stand at 25 ° C. for 3 days, it was confirmed by visual observation and touch that the sample liquid C was cured.

Example 5
0.426 g of the polyamine compound 2 of the present invention (R is a methyl group) and 1.70 g of 2,2-bis (4-glycidyloxyphenyl) propane (Tokyo Kasei) are stirred and mixed well, and sample solution D Was prepared. After allowing the sample liquid D to stand at 25 ° C. for 3 days, it was confirmed by visual observation and touch that the sample liquid D was cured.

Claims (3)

A polyamine compound represented by the following general formula (1).

In general formula (1), R represents a hydrogen atom or a methyl group. An epoxy curing agent represented by the following general formula (1).

In general formula (1), R represents a hydrogen atom or a methyl group. The following general procedure consisting of a step of reacting tris (hydroxymethyl) aminomethane with acrylonitrile or methacrylonitrile to obtain a compound represented by the following general formula (2) and a step of reducing the compound represented by the general formula (2) The manufacturing method of the polyamine compound represented by Formula (1).

In the general formulas (1) and (2), R represents a hydrogen atom or a methyl group.

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