JPH06184090A - Sulfur-containing compound and its production - Google Patents

Abstract

PURPOSE:To obtain a sulfur-containing new compound excellent in chemical resistance and water resistance and useful as a curing agent for epoxy resins capable of exhibiting rapidly curable property and low temperature curable property without addition of a basic substance because of having amino group and mercapto group high in reactivity. CONSTITUTION:The compound of formula I {R<1> to R<4> are H, alkyl or aromatic group; (a) to (e) are 0 or 1-5 and 1<=(a+b+c+d+e)<=5; (n), (p), (q), (u), (v), (w) and (x) are 0 or l-10 and 1<=[p+q+an+b(dx+w)+eu+v]<=400. This compound is obtained by reacting an amino compound of formula II (e.g. ethylenediamine) with a thirane compound of formula III (preferably ethylene sulfide or propylene sulfide), normally in an inert organic solvent at ambient temperature to 150 deg.C. Furthermore, as the inert organic solvent, an ether-based organic solvent such as THF is preferably used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a sulfur-containing compound and a method for producing the same. More specifically, it relates to a compound having a highly reactive amino group and a mercapto group in the molecule and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, polyamino compounds have been widely used at room temperature as a curing agent for epoxy resins. However, there is a problem in quick-curing property or low-temperature curing property. On the other hand, a polythiol compound is used when fast curability or low temperature curability is required. However, the polythiol compound alone does not exhibit fast-curing properties and low-temperature curing properties, and it is necessary to use a basic substance in combination. Furthermore, most of the polythiol compounds that are often used at present are polythioalkylcarboxylic acid esters obtained by reacting a thioalkylcarboxylic acid with a polyhydric alcohol. Since it has a bond, it has poor chemical resistance, water resistance, particularly alkali resistance, and cannot be used for applications where the cured epoxy resin comes into contact with alkali.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above problems of the prior art. That is, the object of the present invention is to produce a novel sulfur-containing compound having a highly reactive amino group and a mercapto group in the molecule that exhibits excellent performance as a curing agent for epoxy resins and to industrially efficiently produce the compound. Is to provide a method.

[0004]

The present invention is based on the general formula (1)

[0005]

[Chemical 5]

(However, in the general formula (1), R ¹ ,
R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group or an aromatic group, and may be the same or different,
a, b, d and e are 0 or positive integers of 1 to 5 and satisfy the relationship of 1 ≦ a + b + d + e ≦ 5, and n, p, q, u, v, w and x are Each is 0 or a positive integer from 1 to 10 and 1 ≦ p + q
The relationship of + an + b (dx + w) + eu + v ≦ 40 is satisfied. )
The present invention relates to a sulfur-containing compound represented by

The method for producing the sulfur-containing compound of the present invention is not particularly limited, but the general formula (2)

[0008]

[Chemical 6]

(However, in the general formula (2), a, b,
d and e are 0 or a positive integer of 1 to 5 and 1 ≦ a +
This satisfies the relationship of b + d + e ≦ 5. ) To the amino compound represented by the general formula (3)

[0010]

[Chemical 7]

(However, in the general formula (3), R ¹ ,
R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group or an aromatic group, and may be the same or different. )
It can be produced by reacting a thiirane compound represented by

[0012]

The amino compound used in the above production method is
A compound having at least two amino groups in the molecule represented by the general formula (2), such as ethylenediamine, diethylenetriamine, triethylenetetramine,
Examples thereof include tetraethylene pentamine and pentaethylene hexamine.

The thiirane compound is a general term for the three-membered ring sulfide compound represented by the above general formula (3), and is also called alkylene sulfide or episulfide. Among the thiirane compounds, ethylene sulfide and propylene sulfide, which are easily available and have a low boiling point, are preferable.

The reaction molar ratio between the amino compound and the thiirane compound is not particularly limited, but normally, the thiirane compound is added to 1 equivalent of active hydrogen of the amino group in the amino compound.
It is from 01 to 10 mol. The reaction ratio of the thiirane compound is 0.
When it is less than 01, the ratio of the mercapto group introduced into the molecule is small, and the effect of the mercapto group cannot be recognized. Conversely, if the reaction ratio of the thiirane compound is greater than 10,
The thioether bond portion is increased, and the ratio of highly reactive amino group and mercapto group present in the molecule is relatively reduced.

The reaction method is not particularly limited, but is usually carried out in an inert organic solvent which does not react with the amino compound or thiirane compound. Examples of such an inert organic solvent include aromatic organic solvents and ether organic solvents. Among them, preferred solvents are ether organic solvents. Examples of such compounds include ether compounds such as diethyl ether, tetrahydrofuran and dioxane. Although the reaction temperature is not particularly limited, it is usually from room temperature to 150 ° C.

Since the production method of the present invention is a liquid phase reaction in which the reaction is easily controlled and is based on a ring-opening addition reaction of a three-membered ring sulfide to an amino group, a side compound containing a malodorous sulfur compound Does not produce organisms, waste, wastewater, etc. Therefore, according to the production method of the present invention, it is not necessary to treat waste, and the sulfur-containing compound can be produced environmentally and industrially advantageously.

[0017]

The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0018]

Example 1 Triethylenetetramine 21.9 was added to a flask equipped with a stirrer, a dropping tube, a thermometer and a reflux condenser.
g and tetrahydrofuran (hereinafter THF) 140 g were charged, and the mixture was heated under reflux in a nitrogen stream to replace nitrogen. Then 20.0 g of THF was added to ethylene sulfide 18.1
The solution in which g was dissolved was added dropwise over 2 hours while maintaining the temperature in the flask at 50 ° C. After the dropwise addition was completed, the reaction was completed by maintaining the temperature at 50 ° C. for 5 hours.

After the reaction was completed, the solvent was removed under reduced pressure to obtain 40.0 g of a pale yellow turbid liquid product.

The results of the elemental analysis, infrared absorption analysis, NMR analysis and SH group content measurement (Ellman method) of the obtained product are shown in Table 1. It was found that a compound having 0 mol added was obtained. The infrared absorption spectrum is shown in FIG. 1 and the NMR spectrum is shown in FIG.

[0021]

[Table 1]

[0022]

Example 2 A reaction was carried out in the same manner as in Example 1 except that 25.8 g of diethylenetriamine was used instead of triethylenetetramine and the amount of ethylene sulfide used was changed to 30.1 g.

After the completion of the reaction, the solvent was removed under reduced pressure to obtain 55.8 g of a pale yellow cloudy liquid product.

The results of the elemental analysis, infrared absorption analysis, NMR analysis and SH group content measurement of the obtained product are shown in Table 2. It turned out that it was obtained. The infrared absorption spectrum is shown in FIG.
The spectrum is shown in FIG.

[0025]

[Table 2]

[0026]

Example 3 Example 1 was repeated except that 22.3 g of propylene sulfide was used in place of ethylene sulfide, the dropping time was 3 hours, and the reaction was finished by holding at 50 ° C. for 22 hours after the dropping. The reaction was carried out in the same manner as in.

After the reaction was completed, the solvent was removed under reduced pressure to obtain 44.2 g of a pale yellow transparent liquid product.

The results of elemental analysis, infrared absorption analysis, NMR analysis and SH group content measurement of the obtained product are shown in Table 3, and 2.1 mol of propylene sulfide was added to the amino groups of triethylenetetramine on average. It was found that the compound was obtained. The infrared absorption spectrum is shown in FIG.
The NMR spectrum is shown in FIG.

[0029]

[Table 3]

[0030]

The sulfur-containing compound of the present invention has a highly reactive amino group and mercapto group in the molecule, and therefore, when used as a curing agent for an epoxy resin, it cures rapidly without adding a basic substance. And low temperature curability. Further, since the molecule has a plurality of functional groups, the crosslink density is high.
Furthermore, since it does not contain a weak bond such as an ester bond in the molecule, it has excellent chemical resistance, water resistance, alkali resistance and the like.

Further, since the sulfur-containing compound of the present invention has highly reactive amino group and mercapto group in the molecule,
It can be used not only as a curing agent for epoxy resins, but also in a wide range of applications such as a crosslinking agent, a vulcanizing agent, a polymerization regulator, an antioxidant, a metal chelating agent, and a lubricating oil additive.

Further, the production method of the present invention is easy to control the reaction and does not generate by-products, wastes, waste water and the like containing sulfur compounds which give off a bad odor, so that there is no need to treat wastes and it is environmentally friendly Moreover, it is an industrially preferable method.

[Brief description of drawings]

FIG. 1 shows an infrared absorption spectrum of the compound obtained in Example 1.

FIG. 2 shows an NMR spectrum of the compound obtained in Example 1.

FIG. 3 shows an infrared absorption spectrum of the compound obtained in Example 2.

FIG. 4 shows an NMR spectrum of the compound obtained in Example 2.

FIG. 5 shows an infrared absorption spectrum of the compound obtained in Example 3.

FIG. 6 shows an NMR spectrum of the compound obtained in Example 3.

Claims (3)

[Claims] 1. A compound represented by the general formula (1): (However, in the general formula (1), R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group or an aromatic group,
They may be the same or different, and a, b, d and e are each 0 or a positive integer of 1 to 5 and 1 ≦ a + b + d + e.
The relation of ≦ 5 is satisfied, and n, p, q, u, v, w and x are 0 or positive integers of 1 to 10, respectively, and 1 ≦ p + q + an + b (dx + w)
It satisfies the relationship of + eu + v ≦ 40. ) A sulfur-containing compound represented by. 2. A general formula (2): (However, in the general formula (2), a, b, d and e are 0 or positive integers of 1 to 5, respectively, and satisfy the relationship of 1 ≦ a + b + d + e ≦ 5.). The amino compound represented by the general formula (3): (However, in the general formula (3), R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group or an aromatic group,
They may be the same or different. ), A thiirane compound represented by the general formula (1): (However, in the general formula (1), R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group or an aromatic group,
They may be the same or different, and a, b, d and e are each 0 or a positive integer of 1 to 5 and 1 ≦ a + b + d + e.
The relation of ≦ 5 is satisfied, and n, p, q, u, v, w and x are 0 or positive integers of 1 to 10, respectively, and 1 ≦ p + q + an + b (dx + w)
It satisfies the relationship of + eu + v ≦ 40. The manufacturing method of the sulfur-containing compound represented by these. 3. The production method according to claim 2, wherein an ether compound is used as a reaction solvent.