KR20190064418A - Compound having anhydrosugar alcohol core and method for preparing the same - Google Patents

Abstract

The present invention relates to a compound having an anhydrosugar alcohol nucleus and a method for manufacturing the same. More particularly, the present invention relates to: the compound having the anhydrosugar alcohol nucleus which is manufactured by conducting a reaction with a nitrile compound and hydrogenation using a regenerable plant-based anhydrous alcohol as a raw material, and can be used a bio-based surfactant, a monomer of polymer condensation polymerization, or a curing agent for an epoxy resin; and the method for manufacturing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound having an alcohol-free alcohol nucleus and a method for producing the same.

The present invention relates to a compound having an anhydrosugar alcohol nucleus and a process for producing the same, and more particularly, to a process for producing a compound having an anhydride alcohol nucleus by reacting with a nitrile compound using a regenerable plant- Based surfactant, a monomer for polymer condensation polymerization or a curing agent for an epoxy resin, and a method for producing the same.

Hydrogenated sugar (also referred to as " sugar alcohol ") refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5 ), And classified into tetritol, pentitol, hexitol and heptitol (C 4, 5, 6 and 7, respectively), depending on the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like, and sorbitol and mannitol are particularly useful substances.

Anhydrosugar alcohol has a diol form with two hydroxyl groups in the molecule and can be prepared by utilizing hexitol derived from starch (for example, Korean Patent No. 10-1079518, Korean Patent Laid- -2012-0066904). Since alcohol-free alcohol is an eco-friendly substance derived from renewable natural resources, there has been much interest for a long time and studies on the manufacturing method have been carried out. Among these alcohol-free alcohols, isosorbide prepared from sorbitol has the widest industrial application currently.

The use of anhydrous alcohol is widely used in the treatment of cardiovascular diseases, patches, adhesives, oral cleansers and the like, solvents for compositions in the cosmetics industry, and emulsifiers in the food industry. In addition, it is possible to increase the glass transition temperature of a polymer substance such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, to improve the strength of these materials, and to be an environmentally friendly material derived from natural materials. useful. It is also known to be used as an environmentally friendly solvent for adhesives, environmentally friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

In recent years, demand for environmentally friendly chemical substances has increased sharply due to environmental pollution. In view of the fact that the above-mentioned alcohol-free alcohol is a renewable low cost raw material derived from plants, it can be used as a bio-based surfactant, a monomer for polymer condensation polymerization or a curing agent for epoxy resin And so on.

It is an object of the present invention to provide a method for producing a biodegradable polymer which can be used as a bio-based surfactant, a monomer for polymer condensation polymerization or a curing agent for an epoxy resin, by reacting with a nitril compound using a regenerable plant- A compound having an anhydride alcohol nucleus, and a process for producing the same.

In order to solve the above-mentioned technical problems, the present invention provides a compound represented by the following formula (A)

(A)

X-Y-O-M-O-Y-X

In the above formula (A)

X is each independently selected from -CN or -CH ₂ NH _2,

Each Y is independently -CR ₁ HCR ₂ H-,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl,

M is a divalent organic group derived from anhydrous alcohol.

According to another aspect of the present invention there is provided a process for the preparation of a compound of formula < RTI ID = 0.0 >

There is provided a process for preparing a compound represented by the formula (A '):

[Chemical formula A ']

X'-Y-O-M-O-Y-X '

In the above formula (A '),

X 'is -CN,

Each Y is independently -CR ₁ HCR ₂ H-,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl,

M is a divalent organic group derived from anhydrous alcohol.

According to another aspect of the present invention there is provided a process for the preparation of a compound of formula (I), which comprises the steps of: (1) carrying out a Michael reaction of an anhydride alcohol with a nitrile compound and (2) Lt; RTI ID = 0.0 > of: < / RTI &

[A '']

X " -Y-O-M-O-Y-X "

In the above formula (A "),

X " is -CH ₂ NH ₂ ,

Each Y is independently -CR ₁ HCR ₂ H-,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl,

M is a divalent organic group derived from anhydrous alcohol.

According to another aspect of the present invention, there is provided a surfactant prepared from the compound represented by the formula (A) according to the present invention.

According to still another aspect of the present invention, there is provided a curing agent for an epoxy resin comprising a compound represented by the formula (A) according to the present invention.

According to another aspect of the present invention, there is provided an epoxy resin composition comprising a curing agent for an epoxy resin and an epoxy resin according to the present invention.

According to another aspect of the present invention, there is provided a cured product obtained by curing an epoxy resin composition according to the present invention.

According to another aspect of the present invention, there is provided a molded article comprising a cured product according to the present invention.

The compound having an alcohol-free alcoholic nucleus of the present invention is produced through the reaction with a nitrile compound and a hydrogenation using a regenerable plant-based anhydrosugar alcohol as a raw material, so that it can be eco-friendly and the manufacturing cost can be reduced. In addition, when the compound having an alcohol-free alcohol nucleus of the present invention is used as a curing agent for an epoxy resin, an epoxy resin cured product in which the tensile strength and the glass transition temperature are remarkably improved can be produced.

Hereinafter, the present invention will be described in detail.

The present invention provides compounds represented by formula (A)

(A)

X-Y-O-M-O-Y-X

In the above formula (A)

X is each independently selected from -CN or -CH ₂ NH _2,

Each Y is independently -CR ₁ HCR ₂ H-,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl,

M is a divalent organic group derived from anhydrous alcohol.

The anhydrosugar alcohol is prepared from a hydrogenated sugar derived from a natural product.

Hydrogenated sugar (also referred to as " sugar alcohol ") refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5 ), And classified into tetritol, pentitol, hexitol and heptitol (C 4, 5, 6 and 7, respectively), depending on the number of carbon atoms.

Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like, and sorbitol and mannitol are particularly useful substances.

Anhydrosugar alcohol has a diol form with two hydroxyl groups in the molecule and can be prepared by utilizing hexitol derived from starch (for example, Korean Patent No. 10-1079518, Korean Patent Laid- -2012-0066904). Since alcohol-free alcohol is an eco-friendly substance derived from renewable natural resources, there has been much interest for a long time and studies on the manufacturing method have been carried out. Among these alcohol-free alcohols, isosorbide prepared from sorbitol has the widest industrial application currently.

In the compound represented by the general formula (A) of the present invention, M is isosorbide (1,4-3,6-dianhydroisorbitol), isanhydride (1,4-3,6-dianhydro- mannitol) Or a dihydric organic group derived from isoided (1,4-3,6-dianhydroiditol), and in one embodiment, M may be selected from the following formula:

In the compounds represented by the formula (A) of the present invention, R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl.

The alkyl is, for example, substituted or unsubstituted linear alkyl of 1 to 10 (more particularly 1 to 6) carbon atoms; Or a substituted or unsubstituted branched alkyl having 3 to 10 (more specifically 3 to 6) carbon atoms, and the aryl is, for example, a substituted or unsubstituted C6 to C14 (more specifically 6 to 12 ) Monocyclic aryl, polycyclic aryl, or fused cyclic aryl. Also, the heteroaryl is a substituted or unsubstituted 5 to 12-membered (more specifically 5 to 10-membered) monocyclic heteroaromatic ring containing one or more heteroatoms selected from N, O, Aryl, polycyclic heteroaryl, or fused cyclic heteroaryl, wherein the cycloalkyl may be, for example, a substituted or unsubstituted cycloalkyl of 3 to 8 carbon atoms (more specifically 3 to 6 carbon atoms).

These groups may be substituted with at least one substituent selected from alkyl having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, etc.) or aryl having 6 to 10 carbon atoms (e.g., phenyl, benzyl, .

With the proviso that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl.

In one embodiment, the compound represented by formula (A) of the present invention may be a compound represented by formula (1): < EMI ID =

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl.

In one embodiment, examples of the compound represented by the formula (1) may be the compounds represented by the following formulas (1-1) to (1-5).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In another embodiment, the compound represented by formula (A) of the present invention may be a compound represented by formula (2): < EMI ID =

(2)

In Formula 2,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl.

In one embodiment, examples of the compound represented by the formula (2) may be the compounds represented by the following formulas (2-1) to (2-5).

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

In one embodiment, the compound represented by formula (A) of the present invention may be a compound represented by formula (3): < EMI ID =

(3)

In Formula 3,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl.

In one embodiment, examples of the compound represented by the general formula (3) may be the compounds represented by the following general formulas (3-1) to (3-5).

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

In another embodiment, the compound represented by formula (A) of the present invention may be a compound represented by formula (4): < EMI ID =

[Chemical Formula 4]

In Formula 4,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl.

In one embodiment, examples of the compound represented by the general formula (4) may be the compounds represented by the following general formulas (4-1) to (4-5).

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

In one embodiment, the compound represented by formula (A) of the present invention may be a compound represented by formula (5): < EMI ID =

[Chemical Formula 5]

In Formula 5,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl.

In one embodiment, examples of the compound represented by the general formula (5) may be the compounds represented by the following general formulas (5-1) to (5-5).

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

In another embodiment, the compound represented by formula (A) of the present invention may be a compound represented by formula (6): < EMI ID =

[Chemical Formula 6]

In Formula 6,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl.

In one embodiment, examples of the compound represented by the formula (6) may be the compounds represented by the following formulas (6-1) to (6-5).

[Formula 6-1]

[Formula 6-2]

[Formula 6-3]

[Formula 6-4]

[Formula 6-5]

According to another aspect of the present invention, there is provided a process for preparing a compound represented by the formula (A ') comprising the step of carrying out a Michael reaction of an alcohol with an anhydride and a nitrile compound:

[Chemical formula A ']

X'-Y-O-M-O-Y-X '

In the above formula (A '),

X 'is -CN,

Each Y is independently -CR ₁ HCR ₂ H-,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl,

M is a divalent organic group derived from anhydrous alcohol.

In carrying out the Michael reaction of anhydrosugar alcohol and nitrile compound, the anhydrosugar alcohol is selected from the group consisting of isosorbide (1,4-3,6-dianhydrosorbitol), isomannide (1,4-3,6-dian Hydro mannitol) or isoidide (1,4-3,6-dianhydroiditol).

The nitrile compound used in the production method of the present invention includes crotononitrile, methacrylonitrile, cinnamonitrile, 3- (furan-2-yl) prop-2-enone nitrile, cyclohexane acrylonitrile, , But the present invention is not limited thereto.

In carrying out the Michael reaction of anhydrosugar alcohol and a nitrile compound, the reaction can be carried out at an equivalent ratio of 2 to 3 molar equivalents of the nitrile compound to 1 molar equivalent of an alcohol without anhydride. When the molar equivalent of the nitrile compound is too low, the yield of the compound represented by the formula (A ') is lowered. On the other hand, when the molar equivalent is too high, an additional effect is not expected and the manufacturing cost is increased.

The Michael reaction can be carried out in the presence of a base catalyst, and the Michael reaction can be carried out in the presence of 0.005 to 0.05 molar equivalent of a base catalyst per 1 molar equivalent of an alcohol without anhydride. If the content of the base catalyst is too low, the reaction rate of the Michael reaction becomes slow. On the other hand, if the content of the base catalyst is too high, it is difficult to expect an additional effect and the manufacturing cost increases.

Examples of the base catalyst include, but are not particularly limited to, hydroxides of alkali metals (specifically, hydroxides of Li, Na, K, Rb or Cs etc.), hydroxides of alkaline earth metals (specifically, Mg, Ca, Sr (Specifically, a carbonate of Li, Na, K, Rb or Cs), an alcoholate of an alkali metal or an alkaline earth metal (specifically, sodium methylate, sodium ethylate or potassium hydroxide) t-butylate, etc.) or basic organic catalysts (specifically, 1,8-diazabicyclo [5.4.0] undec-7-ene ), 4- (dimethylamino) pyridine, etc.), and preferably a basic organic catalyst can be used. When a basic organic catalyst is used as a base catalyst, the rate of Michael reaction (nitrile addition reaction) is accelerated as compared with that of a basic inorganic catalyst, thereby solving the problem of severe heat generation due to the accumulation of unreacted starting materials upon addition of the nitrile compound.

In the step of performing the Michael reaction of the anhydride alcohol with the nitrile compound, the Michael reaction product may be stirred for 1 to 10 hours. If the stirring time is too short, the yield of the compound represented by the formula (A ') may be lowered, and conversely, if the stirring time is too long, no further effect is expected.

The product of the Michael reaction can be cooled to room temperature after the stirring step and the product of the cooled Michael reaction is reacted with an organic solvent (for example, ethyl acetate, dichloromethane, 2-methyltetrahydrofuran, diethyl ether, etc.) After dilution, it may be sequentially washed with an aqueous solution of hydrochloric acid, an aqueous solution of sodium hydroxide and distilled water. Thereafter, a step of concentration under reduced pressure can be further carried out.

In the process for producing the compound represented by the above formula (A '), the matters relating to anhydrosugar alcohol, nitrile compound, R ₁ and R ₂ are the same as described above.

According to another aspect of the present invention, there is provided a process for preparing a nitrile compound, comprising: (1) performing a Michael reaction of an alcohol with no alcohol and a nitrile compound; And (2) a step of adding hydrogen to the compound obtained from the Michael reaction.

[A '']

X " -Y-O-M-O-Y-X "

In the above formula (A "),

X " is -CH ₂ NH ₂ ,

Each Y is independently -CR ₁ HCR ₂ H-,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,

Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl,

M is a divalent organic group derived from anhydrous alcohol.

The compound obtained from the Michael reaction in the step (2) may be a compound represented by the above formula (A ').

The step (2) of adding the hydrogen to the compound represented by the formula (A '') obtained from the Michael reaction to obtain the compound represented by the formula (A ") can be advantageously carried out in the presence of ammonia, .

The step (2) may be carried out at a temperature of 40 to 180 DEG C, preferably 50 to 130 DEG C, a hydrogen pressure of 5 to 20 bar, and a hydrogen pressure of 0.1 to 20 Preferably 0.5 part by weight to 10 parts by weight, of a hydrogenation catalyst.

If the hydrogen pressure is too low, the hydrogen is not sufficiently added and the yield of the compound of formula (A ") may be lowered. On the other hand, if the hydrogen pressure is too high, no additional effect is expected.

The step (2) may be carried out without using a solvent or may be carried out in a solvent. When the step (2) is carried out in a solvent, the solvent may be selected from water, or a linear or branched C1-C5 alcohol.

According to another aspect of the present invention, there is provided a surfactant prepared from a compound represented by the formula A, preferably a diamine compound represented by the formula A ". The diamine compound represented by the formula (A ") of the present invention can be used as a bio-based surfactant or as a monomer for polymer condensation polymerization.

According to another aspect of the present invention, there is provided a curing agent for an epoxy resin comprising a compound represented by the formula (A), preferably a diamine compound represented by the formula (A ").

The curing agent for an epoxy resin of the present invention is environmentally friendly and can reduce the manufacturing cost. Especially when the epoxy resin is cured using the epoxy resin curing agent, the tensile strength and the glass transition temperature of the epoxy resin cured product can be remarkably improved.

The curing agent for an epoxy resin of the present invention may further comprise a compound usable as an epoxy resin curing agent which is generally known in the art, in addition to the compound represented by the formula (A) (preferably a diamine compound represented by the formula (A)).

According to another aspect of the present invention, there is provided a curing agent for an epoxy resin according to the present invention; And an epoxy resin composition.

In one embodiment, examples of the epoxy resin include bisphenol A-epichlorohydrin resin, epoxy novolac resin, alicyclic epoxy resin, aliphatic epoxy resin, cyclic epoxy resin, glycidyl ester type epoxy resin, brominated epoxy resin, But are not limited to, those selected from the group consisting of bio-derived epoxy resin, epoxidized soybean oil, or a combination thereof.

In another embodiment, examples of the epoxy resin include novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin; Bisphenol A type epoxy resins, and bisphenol F type epoxy resins; Aromatic glycidylamine type epoxy resins such as N, N-diglycidyl aniline, N, N-diglycidyl toluidine, diaminodiphenyl methane type glycidyl amine and aminophenol type glycidyl amine; Hydroquinone type epoxy resins; Biphenyl type epoxy resins; Stilbene type epoxy resin; Triphenol methane type epoxy resin; Triphenolpropane type epoxy resin; Alkyl-modified triphenolmethane type epoxy resin; A triazine nucleus-containing epoxy resin; A dicyclopentadiene-modified phenol-type epoxy resin; Naphthol type epoxy resin; Naphthalene type epoxy resin; Phenolic aralkyl type epoxy resins having phenylene and / or biphenylene skeleton, aralkyl type epoxy resins such as naphthol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton; But are not limited to, aliphatic epoxy resins such as alicyclic epoxy resins such as vinylcyclohexene dioxide, dicyclopentadiene oxide and alicyclic diepoxy-adipate, and combinations thereof.

In another embodiment, examples of the epoxy resin include bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, steel type epoxy resin, hydroquinone type epoxy resin, naphthalene skeleton Type epoxy resin, tetraphenylol ethane type epoxy resin, diphenyl phosphate (DPP) type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol A ethylene oxide adduct diglycidyl Ether, glycidyl ether having one epoxy group such as diglycidyl ether of bisphenol A propylene oxide adduct, diglycidyl ether of bisphenol A, phenyl glycidyl ether and cresyl glycidyl ether, A nucleus-modified epoxy resin which is a nuclear hydrogenation product of a resin, or a combination thereof. I, and the like.

In the epoxy resin composition of the present invention, the content ratio of the epoxy resin and the curing agent for epoxy resin is such that the equivalent ratio of the curing agent for the epoxy resin to the epoxy resin (equivalent to curing agent for epoxy resin / equivalent to epoxy resin) 1.75. More specifically, the equivalence ratio may be in the range of 0.75 to 1.25, and more specifically, the equivalence ratio may be in the range of 0.95 to 1.05. If the equivalent weight of the epoxy resin curing agent is too small relative to the equivalent weight of the epoxy resin, the mechanical strength may be lowered and the physical properties may deteriorate from the viewpoints of thermal and adhesive strength. Conversely, the equivalent of the epoxy resin curing agent In case of too many cases, the physical properties may deteriorate in terms of mechanical strength, thermal and adhesive strength.

The epoxy resin composition of the present invention may further comprise a curing catalyst for the curing promoting effect.

Examples of the curing catalyst usable in the present invention include amine compounds (e.g., tertiary amines) such as benzyldimethylamine, tris (dimethylaminomethyl) phenol and dimethylcyclohexylamine; Imidazole compounds such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole and 1-benzyl-2-methylimidazole; Organophosphorus compounds such as triphenylphosphine, triphenyl phosphite and the like; Quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide; Diazabicyclo [5.4.0] undecene-7 and the like, and organic acid salts thereof; Organometallic compounds such as zinc octylate, tin octylate or aluminum acetyl acetone complex; Quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide; Boron compounds such as boron trifluoride, triphenylborate and the like; Metal halides such as zinc chloride and tin chloride; A latent curing catalyst (for example, a high melting point dispersed latent amine adduct in which dicyandiamide, an amine is added to an epoxy resin or the like, a microcapsule type latent catalyst in which a surface of an imidazole, phosphorus, or phosphine accelerator is coated with a polymer ; Amine salt type latent catalyst; latent acid dissociation type thermal cationic polymerization type latent catalyst such as Lewis acid salt and Bronsted acid salt, etc.), or a combination thereof, but the present invention is not limited thereto.

In one embodiment, the curing catalyst may be selected from the group consisting of an amine compound, an imidazole compound, an organic phosphorus compound, or a combination thereof.

When the curing catalyst is contained in the epoxy resin composition of the present invention, the amount of the curing catalyst may be 0.01 part by weight to 1.0 part by weight, more specifically 0.05 part by weight to 100 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent for epoxy resin. 0.5 part by weight, more specifically 0.08 part by weight to 0.2 part by weight, but is not limited thereto. If the amount of the curing catalyst to be used is too small, the curing reaction of the epoxy resin may not proceed sufficiently, resulting in deterioration of mechanical properties and thermal properties. On the other hand, if the amount of the curing catalyst is excessively large, The viscosity may be increased.

The epoxy resin composition of the present invention may further contain at least one additive component which is usually used in the epoxy resin composition, if necessary.

Such additive components include, for example, antioxidants, UV absorbers, fillers, resin modifiers, silane coupling agents, diluents, colorants, defoamers, defoamers, dispersants, viscosity modifiers, gloss modifiers, wetting agents, May be used.

The antioxidant may be used in order to further improve the heat-resistant stability of the resulting cured product, and is not particularly limited. For example, a phenolic antioxidant (dibutylhydroxytoluene), a sulfur-based antioxidant (mercaptopropionic acid derivative, etc.) (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.) or a combination thereof. The content of the antioxidant in the composition may be 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent for an epoxy resin.

Examples of the UV absorber include, but are not limited to, a benzotriazole UV absorber represented by TINUBIN P or TINUVIN 234 manufactured by BASF Japan Ltd.; Triazine based UV absorbers such as TINUVIN 1577ED; A hindered amine-based UV absorber such as CHIMASSOLV 2020FDL, or a combination thereof. The content of the UV absorber in the composition may be 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent for epoxy resin.

The filler is used mainly for the purpose of improving the mechanical properties of the cured product by mixing with an epoxy resin or a curing agent. In general, when the amount of the filler is increased, mechanical properties are improved. Examples of inorganic fillers include fillers such as talc, sand, silica, talc, and calcium carbonate; Reinforcing fillers such as mica, quartz, and glass fiber; There is a specific use such as quartz powder, graphite, alumina, Aerosil (for the purpose of imparting plasticity), and the metallic material contributes to thermal expansion coefficient, abrasion resistance, thermal conductivity and adhesion of aluminum, aluminum oxide, iron, iron oxide, (SB2O3); barium titanate; and lightweight fillers such as fine plastic spheres (phenol resin, urea resin, etc.) as the organic material. In addition, as a filler having a reinforcing property, various kinds of glass fiber or chemical fiber can be treated as a filler in a wide range in the production of a laminate. Thixotropic (Thixotropic) is a phenomenon in which a resin adhered by a vertical surface or dipping method or impregnated in a laminated material does not flow down or is lost during curing. Fine particles having a large unit surface area are used. For example, colloidal silica (Aerosil) or bentonite-based clay is used.

In one embodiment, the filler is not particularly limited, but may be selected from the group consisting of, for example, glass fiber, carbon fiber, titanium oxide, alumina, talc, mica, aluminum hydroxide or a combination thereof. The content of the filler in the composition may be 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent for epoxy resin.

Examples of the resin modifier include, but are not limited to, flexibility imparting agents such as polypropylene glycidyl ether, polymerized fatty acid polyglycidyl ether, polypropylene glycol, urethane prepolymer, and the like. The content of the resin modifier in the composition may be 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent for epoxy resin.

Examples of the silane coupling agent include, but are not limited to, chloropropyltrimethoxysilane, vinyltrichlorosilane,? -Methacryloxypropyltrimethoxysilane,? -Aminopropyltriethoxysilane, and the like. . The content of the silane coupling agent in the composition may be 0.01 to 20 parts by weight, or 0.05 to 10 parts by weight, or 0.1 to 5 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent for an epoxy resin.

The diluent is used for the main purpose of decreasing the viscosity by adding it to an epoxy resin or a curing agent, and it plays a role of improving the flowability, the defoaming property at the time of use, improving penetration into the details of the parts, . The diluent is generally not volatilized unlike the solvent and remains in the cured product when the resin is cured, and is divided into a reactive and a non-reactive diluent. Wherein the reactive diluent has one or more epoxy groups and participates in the reaction to enter the crosslinked structure in the cured product while the non-reactive diluent is only physically mixed and dispersed in the cured product. The most commonly used reactive diluents are butyl glycidyl ether (BGE), phenyl glycidyl ether (PGE), aliphatic glycidyl ether (C12-C14) , Modified t-carboxyl glycidyl ester, and the like. Examples of commonly used non-reactive diluents include di-butyl phthalate (DBP), di-octyl phthalate (DOP), nonyl-phenol, and hy- dro.

In one embodiment, the diluent is not particularly limited and includes, for example, n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, vinyl cyclohexene dioxide, diglycidyl aniline, Glycerin triglycidyl ether, or a combination thereof. The content of the diluent in the composition may be 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent for epoxy resin.

As a coloring agent for coloring the resin, a pigment or a dye is used. Colorants such as titanium dioxide, cadmium red, shading green, carbon black, chrome green, chrome yellow, navy blue, and shining blue are generally used as pigments.

In addition, a defoaming agent and a defoaming agent used for the purpose of removing bubbles of resin, a dispersing agent for enhancing the dispersing effect of the resin and the pigment, a wetting agent for improving the adhesion between the epoxy resin and the material, , A gloss-adjusting agent for adjusting the gloss of a resin, an additive for improving adhesion, an additive for imparting electrical properties, and the like.

According to still another aspect of the present invention, there is provided a cured product obtained by curing the epoxy resin composition of the present invention.

The curing method of the epoxy resin composition of the present invention is not particularly limited, and for example, conventionally known curing apparatus such as a closed curing furnace or a tunnel furnace capable of continuous curing can be used. The heating method used for the curing is not particularly limited, and can be performed by conventionally known methods such as hot air circulation, infrared heating, high frequency heating, and the like.

The curing temperature and curing time may range from 80 ° C to 250 ° C for 30 seconds to 10 hours. In one specific example, post-curing can be carried out under the conditions of 120 ° C to 180 ° C and 0.1 hour to 5 hours after the precursor is cured under the conditions of 80 ° C to 120 ° C and 0.5 hours to 5 hours. In one specific example, curing can be carried out under the conditions of 150 ° C to 250 ° C for 30 seconds to 30 minutes for short time curing.

According to another aspect of the present invention, there is provided a molded article comprising a cured product according to the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[ Example ]

<Isosorbide Dinitrile  Preparation of compound (compound of formula A ') >

Example  A1: isosorbide Diketononitrile  Produce

10 g (0.068 mol, 0.01 eq.) Of 1,8-Diazabicyclo [5.4.0] undec-7-ene were placed in a glass reactor and the internal temperature was adjusted to 70-75 ° C After completely dissolving the isosorbide, 1,140 g (17 mol, 2.5 eq.) Of crotononitrile was slowly added dropwise for about 4 hours so that the internal temperature did not exceed 80 캜. After completion of dropwise addition, the mixture was stirred for 3 hours while keeping the internal temperature at 70 to 75 ° C, and then cooled to room temperature. The reaction mixture was diluted with 4 kg of ethyl acetate, washed successively with 2 kg of 1N hydrochloric acid aqueous solution, 2 kg of 1N sodium hydroxide aqueous solution and 2kg distilled water, and then concentrated under reduced pressure to obtain isosorbide dimethanol 1,750 g of nitrile was obtained. The yield was 92%.

[Formula 1-1]

^{1 H NMR (δ ppm; DMSO-} d 6): 1.18 (3H, d), 1.21 (3H, d), 2.35 (1H, dd), 2.39 (1H, dd), 2.66 (1H, dd), 2.70 ( (1H, dd), 3.00 (1H, m), 3.12 (1H, m), 3.49 , 4.01 (1H, dd), 4.01 (1H, d), 4.09

MS ( m / e ): 280

Example  A2: isosorbide Of methacrylonitrile  Produce

Except that 1,140 g (17 mol, 2.5 eq.) Of methacrylonitrile was used in place of 1,140 g (17 mol, 2.5 eq.) Of crotononitrile in the same manner as in Example A1, 1,710 g of bead dimethacrylonitrile was obtained. The yield was 91%.

[Formula 1-2]

^{1 H NMR (δ ppm; DMSO-} d 6): 1.41 (3H, d), 1.43 (3H, d), 2.99 (1H, m), 3.04 (1H, m), 3.49-3.64 (6H, m), (1H, dd), 3.91 (1H, dd), 3.91 (1H, dd)

MS ( m / e ): 280

Example  A3: isosorbide Dicyanonitrile  Produce

The procedure of Example A1 was repeated except that 2,196 g (17 mol, 2.5 eq.) Of cinnamonitrile was used instead of 1,140 g (17 mol, 2.5 eq.) Of crotononitrile and stirring time after dropwise addition was changed from 3 hours to 6 hours. 2,500 g of isosorbide dicyanomonitrile, which is a compound of the following formula 1-3, was obtained in the same manner as in the above. The yield was 91%.

[Formula 1-3]

^{1 H NMR (δ ppm; DMSO-} d 6): 2.74 (1H, dd), 2.80 (1H, dd), 2.99 (1H, dd), 3.07 (1H, dd), 3.48 (1H, m), 3.53 ( (1H, dd), 3.76 (1H, dd), 3.80 (1H, dd) , t), 4.29 (1H, t), 7.18-7.40 (10H, m)

MS ( m / e ): 404

Example  A4: isosorbide Of di (3-furyl) acrylonitrile  Produce

(17 moles, 2.5 eq.) Instead of 1,140 g (17 moles, 2.5 eq.) Of crotononitrile was used in place of 2,125 g (17 moles, 2.5 eq.) Of 3- (furan-2-yl) prop- (3-furyl) acrylate, which is a compound of the following formula (1-4), was used in the same manner as in Example A1 except that the stirring time after completion of dropwise addition was changed from 3 hours to 9 hours And 2,450 g of ronitryl was obtained. The yield was 90%.

[Formula 1-4]

^{1 H NMR (δ ppm; DMSO-} d 6): 2.79 (1H, dd), 2.88 (1H, dd), 3.04 (1H, dd), 3.12 (1H, dd), 3.50 (1H, m), 3.55 ( (1H, m), 3.81 (1H, dd), 3.88 (1H, dd), 4.05 (1H, dd), 4.10 (4H, m), 7.30-7.35 (2H, m)

MS ( m / e ): 384

Example  A5: Isosorbide Of di (3-cyclohexyl) acrylonitrile  Produce

Except that 2,299 g (17 mol, 2.5 eq.) Of cyclohexane acrylonitrile was used instead of 1,140 g (17 mol, 2.5 eq.) Of crotononitrile, and stirring time after completion of dropwise addition was changed from 3 hours to 5 hours In the same manner as in Example A1, 2,785 g of isosorbide di (3-cyclohexyl) acrylonitrile, which is a compound of the following Formula 1-5, was obtained. The yield was 88%.

[Formula 1-5]

^{1 H NMR (δ ppm; DMSO-} d 6): 1.27-1.77 (22H, m), 2.49 (1H, dd), 2.53 (1H, dd), 2.70 (1H, dd), 2.74 (1H, dd), D), 3.80 (1H, dd), 3.88 (1H, dd), 3.88 (1H, dd), 4.05 (1H, t), 4.09 (1H, t)

MS ( m / e ): 416

<Isosorbide Diamine  Preparation of compound (compound of formula A &quot;) >

Example  B1: isosorbide Of dichlorotonamines  Produce

1,000 g of isosorbide dichlorotononitrile as the compound of Formula 1-1, 2,000 g of purified water, 50 g of Raney nickel, and 300 g of ammonia water were placed in a high-pressure reactor and then hydrogen was introduced at a pressure of 10 bar. While maintaining the hydrogen pressure, the internal temperature was heated to 130 DEG C and stirred for 4 hours. After completion of the reaction, the catalyst was recovered through filtration, and the filtrate was concentrated to obtain 875 g of isosorbide dinitroamine represented by the following formula (2-1). The yield was 85%.

[Formula 2-1]

^{1 H NMR (δ ppm; DMSO-} d 6): 1.21 (3H, d), 1.23 (3H, d), 1.68 (2H, m), 1.72 (2H, m), 2.65 (2H, t), 2.70 ( 2H), 3.01 (1H, m), 3.14 (1H, m), 3.52 (1H, m), 3.58 d), 3.99 (1H, d), 4.02 (1H, dd), 4.08

MS ( m / e ): 288

Example  B2: isosorbide Dimethacryloamine  Produce

Except that 1,000 g of isosorbide dimethacrylonitrile of Example A2 was used instead of 1,000 g of isosorbide dichlorotononitrile of Example A1, the compound of Formula 2-2 905 g of isosorbide dimethacryloamine was obtained. The yield was 88%.

[Formula 2-2]

^{1 H NMR (δ ppm; DMSO-} d 6): 1.06 (3H, d), 1.09 (3H, d), 2.22 (2H, m), 2.25 (2H, m), 2.48 (1H, dd), 2.54 ( (1H, dd), 2.73 (1H, dd), 2.77 (1H, dd), 3.20 (1H, dd), 3.28 (1H, d), 4.03 (1H, d), 3.57 (1H, m), 3.74 (1H, dd), 3.79 dd)

MS ( m / e ): 288

Example  B3: Isosorbide Dicinamoamine  Produce

Isosorbide of Example A1 The same procedure as in Example B1 was repeated except that 1000 g of isosorbide dincyanonitrile of Example A3 was used instead of 1,000 g of dichlorononitrile, 815 g of bead dicinamoamine was obtained. The yield was 80%.

[Formula 2-3]

^{1 H NMR (δ ppm; DMSO-} d 6): 2.01 (4H, m), 2.65 (3H, t), 2.69 (3H, t), 3.52 (1H, m), 3.61 (1H, m), 3.76 ( (1H, dd), 3.82 (1H, dd), 3.94 (1H, d), 3.98 (1H, d), 4.01 , t), 7.19-7.40 (10 H, m)

MS ( m / e ): 412

Example  B4: Isosorbide Of di (3-furyl) acrylamines  Produce

Isosorbide of Example A1 The procedure of Example B1 was repeated except that 1,000 g of isosorbide di (3-furyl) acrylonitrile of Example A4 was used instead of 1,000 g of dichlorotononitrile of Example A4. (3-furyl) acryloamine, which is a compound of formula (I). The yield was 83%.

[Chemical Formula 2-4]

^{1 H NMR (δ ppm; DMSO-} d 6): 2.01 (4H, m), 2.67 (4H, m), 3.50-3.62 (4H, m), 3.81 (1H, dd), 3.88 (1H, dd), M), 7.25-7.35 (2H, m), 4.04 (1H, dd)

MS ( m / e ): 392

Example  B5: Isosorbide Of di (3-cyclohexyl) acrylamines  Produce

Except that 1,000 g of isosorbide di (3-cyclohexyl) acrylonitrile of Example A5 was used instead of 1,000 g of dichlorosilonitrile of Example A1 in place of 1,000 g of dichlorotononitrile of Example A1. (3-cyclohexyl) acryloamine, which is a compound of formula (I-5). The yield was 79%.

[Chemical Formula 2-5]

^{1 H NMR (δ ppm; DMSO-} d 6): 1.24-1.78 (26H, m), 2.65 (4H, m), 2.79 (1H, m), 2.88 (1H, m), 3.51-3.59 (4H, m ), 3.62 (1H, dd), 3.70 (1H, dd)

MS ( m / e ): 422

&Lt; Epoxy resin Hardened  Manufacturing>

Example  C1 to C5: Epoxy resins using the compounds of the formulas (2-1) to (2-5) Hardened  Produce

18.5 g of bisphenol A diglycidyl ether-based difunctional epoxy resin (YD-128, Kukdo Chemical Co., Ltd., epoxy equivalent: 185 g / equiv.) And 18.5 g of 2- 1 to 2-5 were mixed in the ratios shown in Table 1 below to prepare an epoxy resin composition.

Subsequently, the epoxy resin composition was put into a mold coated with a Teflon film, and cured at 80 ° C for 2 hours and at 125 ° C for 2 hours to obtain an epoxy resin cured product.

Comparative Example  C1: Hexamethylenediamine (HMDA)  Epoxy resin used Hardened  Produce

18.5 g of bisphenol A diglycidyl ether-based difunctional epoxy resin (YD-128, Kido Chemical Co., Ltd., epoxy equivalent: 185 g / equiv.) And 11.6 g of hexamethylenediamine (Sigma Aldrich) as a curing agent were mixed To prepare an epoxy resin composition.

Subsequently, the epoxy resin composition was put into a mold coated with a Teflon film, and cured at 80 ° C for 2 hours and at 125 ° C for 2 hours to obtain an epoxy resin cured product.

Comparative Example  C2: Isophorone Diamine (IPDA)  Epoxy resin used Hardened  Produce

18.5 g of bisphenol A diglycidyl ether-based difunctional epoxy resin (YD-128, Kukdo Chemical Co., epoxy equivalent: 185 g / equiv.) And isophoronediamine (cis- and trans- ) Were mixed to prepare an epoxy resin composition.

Subsequently, the epoxy resin composition was put into a mold coated with a Teflon film, and cured at 80 ° C for 2 hours and at 125 ° C for 2 hours to obtain an epoxy resin cured product.

Comparative Example  C3: 2,5- Bis -O- (3-aminopropyl) isosorbide ( BAI ) &Lt; / RTI &gt; Hardened  Produce

2,5-bis-O- (3-aminopropyl) isosorbide of the following formula 7 was prepared by the method described in the example of U.S. Patent Application Publication No. 2010-0130759.

18.5 g of bisphenol A diglycidyl ether-based difunctional epoxy resin (YD-128, National Kagaku Kogyo Co., Ltd., epoxy equivalent: 185 g / equiv.) And 2.5 g of 2,5- - (3-aminopropyl) isosorbide were mixed to prepare an epoxy resin composition.

Subsequently, the epoxy resin composition was put into a mold coated with a Teflon film, and cured at 80 ° C for 2 hours and at 125 ° C for 2 hours to obtain an epoxy resin cured product.

 (7)

&Lt; Method for measuring physical properties &

Tensile Strength: The tensile strength of the epoxy resin cured product was measured using a universal tensile tester in accordance with ASTM D412.

- Glass transition temperature: The glass transition temperature of the cured epoxy resin was measured using a differential scanning calorimeter (Perkin-Elmer DSC-7 & Robotic).

The compositions of the epoxy resin compositions of Examples C1 to C5 and Comparative Examples C1 to C3 are shown in the following Table 1, and physical properties of the respective epoxy resin compositions with respect to the cured products are shown in Table 1 below.

As shown in Table 1, the epoxy resin cured products of Examples C1 to C5 prepared by using the diamine compound according to the present invention as a curing agent for an epoxy resin had an excellent tensile strength of 86 MPa or more and a glass transition temperature And the heat resistance was remarkably high at 149 ° C or more.

On the other hand, in the case of epoxy resins cured with C1 and C2 prepared by using HMDA and IPDA which are commonly used epoxy resin curing agents (aliphatic diamine compounds), the tensile strength was poor to 70 MPa or less and the glass transition temperature 128 ° C or less. Also, the epoxy resin cured product of Comparative Example C3, which was prepared by using BAI as a curing agent for epoxy resin, exhibited relatively poor tensile strength and glass transition temperature as compared with the epoxy resin cured product of Examples C1 to C5 .

Claims (23)

A compound represented by the following formula (A):
(A)
XYOMOYX
In the above formula (A)
X is each independently selected from -CN or -CH ₂ NH _2,
Each Y is independently -CR ₁ HCR ₂ H-,
R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl,
M is a divalent organic group derived from anhydrous alcohol. The compound according to claim 1, wherein M is a divalent organic group derived from isosorbide, isomannide or isoidide. 2. A compound according to claim 1, wherein M is selected from the group consisting of:

The compound according to claim 1, which is represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl. The compound according to claim 1, which is represented by the following formula (2):
(2)

In Formula 2,
R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl. The compound according to claim 1, which is represented by the following formula (3):
(3)

In Formula 3,
R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl. The compound according to claim 1, which is represented by the following formula (4):
[Chemical Formula 4]

In Formula 4,
R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl. The compound according to claim 1, which is represented by the following formula (5):
[Chemical Formula 5]

In Formula 5,
R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl. The compound according to claim 1, which is represented by the following formula (6):
[Chemical Formula 6]

In Formula 6,
R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl. Performing a Michael reaction of an anhydride alcohol with a nitrile compound,
Process for preparing a compound represented by the formula (A '):
[Chemical formula A ']
X'-YOMOY-X '
In the above formula (A '),
X 'is -CN,
Each Y is independently -CR ₁ HCR ₂ H-,
R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl,
M is a divalent organic group derived from anhydrous alcohol. 11. The method according to claim 10, wherein M is a divalent organic group derived from isosorbide, isomannide or isoidide. 11. The method according to claim 10, wherein M is selected from the following formula:

11. The composition of claim 10 wherein the nitrile compound is selected from the group consisting of crotononitrile, methacrylonitrile, cinnamonitrile, 3- (furan-2yl) prop-2- enonitrile, cyclohexane acrylonitrile, Lt; RTI ID = 0.0 &gt; (A). &Lt; / RTI &gt; The process for producing a compound represented by the formula (A ') according to claim 10, wherein the nitrile compound is reacted in an amount of 2 to 3 molar equivalents based on 1 molar equivalent of an alcohol without anhydride. 11. The process according to claim 10, wherein the Michael reaction is carried out in the presence of 0.005 to 0.05 molar equivalents of a base catalyst with respect to 1 molar equivalent of an alcohol without anhydride. The process for producing a compound represented by the formula (A ') according to claim 10, which comprises stirring the product of the Michael reaction for 1 to 10 hours. (1) carrying out a Michael reaction of an alcohol without anhydride and a nitrile compound; And
(2) adding hydrogen to the compound obtained from the Michael reaction.
Process for producing a compound represented by the formula (A "):
[A '']
X &quot; - YOMOY-X &quot;
In the above formula (A &quot;),
X &quot; is -CH ₂ NH ₂ ,
Each Y is independently -CR ₁ HCR ₂ H-,
R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, heteroaryl or cycloalkyl,
Provided that at least one of R ₁ and R ₂ is alkyl, aryl, heteroaryl or cycloalkyl,
M is a divalent organic group derived from anhydrous alcohol. A process for producing a compound represented by the formula (A "), wherein hydrogenation is carried out under a hydrogen pressure of 5 to 20 bar, 9. Surfactant prepared from a compound represented by the formula (A) according to any one of claims 1 to 9. A curing agent for an epoxy resin comprising a compound represented by the formula (A) according to any one of claims 1 to 9. A curing agent for an epoxy resin according to claim 20; And an epoxy resin. A cured product obtained by curing the epoxy resin composition according to claim 21. A molded article comprising the cured product according to claim 22.