JP2003096061A - Amine imide compound and epoxy resin hardening agent containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide amine imide compounds having properties of high safety and easy to handle, further having high speed for hardening, as compared with those of shown by conventional ones and an epoxy resin hardening agent containing said compound as the effective ingrediet. SOLUTION: The amine imide compounds comprises compounds represented by formula (I): R<1> CH(OH)CH2 N<+> [-(CH2 )4 -] N<-> C(=O)R<2> [wherein, R<1> represents an alkyl group having 1 to 4 carbon number or a phenoxymethyl group; R<2> represents as alkyl group having 1 to 8 carbon number, an alkenyl group having 2 to 4 carbon number or a phenyl group which is substituted with an alkoxy group having 1 to 4 carbon number], and formula (2): PhOCH2 CH(OH)CH2 N<+> [-(CH2 )4 N-C(=O)(CH2 )n C(=O)N<-> N<+> [-(CH2 )4 ] CH2 CH(OH)CH2 OPh [wherein, n is an integer of 1 to 8] and the epoxy resin hardening agent comprises said compounds.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel amine imide compound and a curing agent for an epoxy resin containing the same as an active ingredient.

[0002]

2. Description of the Related Art Amine imide compounds are known as compounds useful as resin monomers, cross-linking agents, detergents, surfactants, intermediates for medical and agricultural chemicals, surface treatment agents and the like. Further, the amine imide compound is decomposed by heating to generate an isocyanate and a tertiary amine, and the generated tertiary amine acts as a curing agent for the epoxy resin. Due to the properties of the amine imide compound, the amine imide compound is used as a curing agent for latent epoxy resins.

[0003]

However, various conventionally known amine imide compounds still have a problem that the curing rate thereof is insufficient. In addition, conventional amine imide has 1,1-dimethylhydrazine (UDMH) introduced into its skeleton, and UDMH is used in the production of amine imide. However, UDMH is a poisonous substance designated as a deleterious substance, and the range of explosion limit is further increased. However, it had a drawback that it was not easy to handle widely. An object of the present invention is to provide an amine imide compound which is safer, easier to handle and has a higher curing rate than ever before, and an epoxy resin curing agent containing the same as an active ingredient.

[0004]

[In the formula, n represents a number of 1 to 8]

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds of the formulas (1) and (2) of the present invention are represented by the following formula.

[0006]

[Chemical 1]

[0007]

[Chemical 2]

In the amineimide compound represented by the formula (1) of the present invention, the alkyl group having 1 to 4 carbon atoms in R ¹ is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-. Butyl, s-
Butyl etc. can be illustrated.

The alkyl group having 1 to 8 carbon atoms for R ² is, for example, methyl, ethyl, n-propyl,
Isopropyl, n-butyl, isobutyl, t-butyl,
Examples thereof include s-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, n-hexyl, isohexyl, heptyl and octyl. Examples of the alkenyl group having 2 to 4 carbon atoms include vinyl, allyl, propenyl,
Examples include isopropenyl, 2-methyl-1-propenyl, 2-methylallyl, 2-butenyl, 1,3-butadienyl and the like. Examples of the phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, s-butoxy group, etc. A phenyl group substituted with can be exemplified.

Of these amine imide compounds, compounds particularly suitable as a curing agent for epoxy resins include 1-
(2-Hydroxy-3-phenoxypropyl) -1,1
-Tetramethyleneamine pivalimide [compound of formula (1) in which R ¹ is a phenoxymethyl group and R ² is a t-butyl group], 1- (2-hydroxy-3-phenoxypropyl) -1,1-tetra Methyleneamine-2-methoxybenzimide [compound of formula (1) in which R ¹ is a phenoxymethyl group and R ² is a 2-methoxyphenyl group], 1- (2
-Hydroxypropyl) -1,1-tetramethyleneamine propionimide [compound of formula (1) in which R ¹ is a methyl group and R ² is an ethyl group], 1- (2-hydroxy-3
-Phenoxypropyl) -1,1-tetramethyleneamine methacrylimide [R ¹ is a phenoxymethyl group, R ²
A compound of formula (1) in which is an isopropenyl group], N,
N'-bis {[1- (2-hydroxy-3-phenoxypropyl) -1,1-tetramethyleneamine] adipinimide} [compound of formula (2) in which m = 4] and the like can be mentioned.

The amine imides of the present invention are produced by reacting (a) 1-aminopyrrolidine with (b) acid chloride or ester, and (c) phenylglycidyl ether or 1,2-epoxyalkanes. be able to. As the acid chloride, monocarboxylic acid chloride can be used when producing the compound of formula (1), and dicarboxylic acid dichloride can be used when producing the compound of formula (2).

Monocarboxylic acid chlorides include R ² C
A compound represented by OCl (R ² is the same as above) can be used, and specifically, acetic acid chloride, propionic acid chloride, butyric acid chloride, isobutyric acid chloride, valeric acid chloride, isovaleric acid chloride, pivalic acid chloride ( Two and two
-Dimethylpropanoic acid chloride), heptanoic acid chloride, octanoic acid chloride, acrylic acid chloride, methacrylic acid chloride, crotonic acid chloride, isocrotonic acid chloride, 2-methoxybenzoyl chloride, 3-methoxybenzoyl chloride, 4-methoxybenzoyl chloride, 2 Examples include -ethoxybenzoyl chloride and 4-t-butoxybenzoyl chloride.

Examples of the dicarboxylic acid dichloride include ClC
A compound represented by O (CH ₂ ) n COCl (n is the same as above) can be used, and specifically, malonic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, pimelic acid dichloride, suberic acid dichloride. , Adeline acid dichloride, sebacic acid dichloride and the like.

When these acid chlorides are used as raw materials, as alkalis, amines such as triethylamine, trimethylamine, triethanolamine, pyridine and / or sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, carbonic acid. It is desirable to use an inorganic alkali such as potassium together or use 1-aminopyrrolidine in a predetermined amount or more to trap hydrochloric acid generated by the reaction.

As the ester, a monocarboxylic acid ester can be used when producing the compound of the formula (1), and a dicarboxylic acid ester can be used when producing the compound of the formula (2).

Taking the methyl ester as an example of the monocarboxylic acid ester, a compound represented by R ² COOCH ₃ (R ² is the same as above) can be used. Specifically, methyl acetate, methyl propionate, Methyl butyrate, Methyl isobutyrate, Methyl valerate, Methyl isovalerate, Methyl pivalate (Methyl 2,2-dimethylpropanoate), Methyl heptanoate, Methyl octoate, Methyl acrylate, Methyl methacrylate, Methyl crotonate, Isocrotonic acid methyl, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl,
2-ethoxybenzoylmethyl, 4-t-butoxybenzoylmethyl and the like can be exemplified. Instead of these, ethyl ester, propyl ester and the like may be used.

Taking methyl ester as an example of the dicarboxylic acid ester, CH ₃ OCO (CH ₂ ) nCOOC
A compound represented by H ₃ (n is the same as above) can be used, and specifically, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelic acid, dimethyl suberate, dimethyl adelaine acid can be used. Examples include dimethyl sebacate and the like. Instead of these, ethyl ester, propyl ester and the like may be used.

Examples of 1,2-epoxyalkanes include propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, and 1,2-epoxyhexane. The reaction can be carried out in a suitable solvent. Such solvents include tetrahydrofuran, toluene, 1,
4-dioxane, diethyl ether, chloroform, methylene chloride, methanol, ethanol, n-propanol, isopropanol, water, hexane and the like can be preferably used. In the reaction, each raw material may be reacted at the same time, or 1-aminopyrrolidine and acid chloride or ester may be previously reacted to form a hydrazide, and then phenylglycidyl ether or 1,2-epoxyalkanes may be reacted.

When the starting materials are reacted at the same time, the reaction is carried out in a suitable solvent with (b) acid chloride or ester and (c) phenylglycidyl ether or 1,2-
After mixing epoxy alkanes and further adding alkalis when acid chloride is used, 1-aminopyrrolidine is preferably added dropwise, and a raw material usually having a temperature of 5 to 80 ° C. and a boiling point of less than 80 ° C. (eg, propylene oxide). In the case of using (1), it can be carried out by reacting at a temperature up to the boiling point of the raw material for about 30 minutes to 30 hours.

When 1-aminopyrrolidine is previously reacted with acid chloride or ester to form a hydrazide, and then phenylglycidyl ether or 1,2-epoxyalkane is reacted, 1-aminopyrrolidine and, if necessary, a solvent are used in a solvent. After mixing alkalis such as amines, acid chloride or ester is added dropwise and reacted for about 1 to 30 hours to obtain the corresponding hydrazides, then the hydrazides are separated, and then the hydrazides are added. After mixing in a solvent and preferably dropwise adding phenyl glycidyl ether or 1,2-epoxyalkane under reflux,
A method of reacting for about 1 to 30 hours can be exemplified. The target product can be separated from the reaction product by a conventional method such as concentration, crystallization and filtration.

When the amine imide compound of the present invention is used as a curing agent for an epoxy resin, the epoxy resin that can be cured is not particularly limited, and various epoxy resins can be used. For example, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin and the like can be exemplified.

As the glycidyl ether type epoxy resin, bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl type,
Naphthalene type, fluorene type, phenol novolac type, cresol novolac type, DPP novolac type, 3
Examples thereof include functional type, tris-hydroxyphenylmethane type, tetraphenylolethane type and the like.

Examples of the glycidyl ester type epoxy resin include hexahydrophthalic acid ester type and phthalic acid ester type. As the glycidyl amine type epoxy resin, tetraglycidyl amino diphenyl methane,
Triglycidyl isocyanurate, hydantoin type,
Examples thereof include 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, aminophenol type, aniline type, toluidine type and the like.

The ratio of the amine imide compound of the present invention to the epoxy resin used is epoxy resin 10
1 to 50 parts by weight, more preferably 5 to 0 parts by weight
It is desirable to use 20 parts by weight. The amine imide of the present invention is a compound that can be expected to be useful as a curing agent for epoxy resins, as well as a resin monomer, a cross-linking agent, a detergent, a surfactant, a pharmaceutical / agrochemical intermediate, a surface treatment agent, and the like. is there.

[0025]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the invention is not limited thereto.

Example 1 1- (2-hydroxy-3-phenoxypropyl)-
Synthesis of 1,1-tetramethyleneamine pivalimide 1-aminopyrrolidine 17.1 g (0.198 mol), triethylamine 20.0 g (0.198 mol), and isopropanol 300 ml were mixed, and the mixed solution was cooled to 10 ° C. After that, 10.85 g (0.09 mol) of pivaloyl chloride
Was added dropwise over 1 hour. After the dropping, the temperature is gradually raised,
The mixture was stirred at room temperature for 20 hours. The reaction mixture was concentrated, isopropanol was removed, and the mixture was extracted with water / chloroform. The organic layer was washed with water and dried using anhydrous magnesium sulfate. This was filtered and concentrated to give dihydrazide 32.
0 g was obtained. 400 ml of isopropanol was added to 32.0 g of the obtained dihydrazide and heated, and under reflux, 13.48 g (0.09 mol) of phenyl glycidyl ether was added to 3 ml.
It was added dropwise over 0 minutes. After completion of the dropping, the reaction was completed by stirring for 20 hours, the concentrate of the reaction solution was dissolved in hexane / toluene, cooled to -20 ° C to crystallize, filtered and dried to obtain white crystals of the target compound. 25.9 g (yield 89.9
%) Was obtained. Melting point 146 ° C

¹ H-NMR (CDCl ₃ ) δ (ppm) 7.27-7.32 (m, 2H),
6.89-7.01 (m, 3H), 4.46-4.64.
(M, 2H), 4.24-4.32 (m, 1H), 4.
07-4.13 (m, 1H), 3.89 (dd, 1
H), 3.57-3.71 (m, 2H), 3.33-
3.41 (m, 1H), 3.19-3.28 (m, 1
H), 2.33-2.53 (m, 2H), 1.86-
2.07 (m, 3H), 1.14 (s, 9H)

Example 2 Synthesis of N, N'-bis {[1- (2-hydroxy-3-phenoxypropyl) -1,1-tetramethyleneamine] adipinimide 17.1 g (0.198 g) of 1-aminopyrrolidine Mol), 20.0 g (0.198 mol) of triethylamine and 300 ml of isopropanol were mixed, the mixed solution was cooled to 10 ° C., and then 16.5 g of adipic acid dichloride was added dropwise over 1 hour. After the dropping, the temperature is gradually raised to 20 at room temperature.
Stir for hours. The reaction mixture was concentrated, isopropanol was removed, and the mixture was extracted with water / chloroform. The organic layer was washed with water and dried using anhydrous magnesium sulfate. This was filtered and concentrated to obtain 24.1 g of dihydrazide. Isopropanol 40 was added to 24.1 g of the obtained dihydrazide.
0 ml was added and heated, and 27.0 g (0.180 mol) of phenyl glycidyl ether was added dropwise under reflux over 30 minutes. After completion of dropping, the reaction is completed by stirring for 20 hours,
Dissolve the reaction solution concentrate in hexane / toluene, and
After cooling to ℃ and crystallization, it was filtered and dried to obtain 44.8 g (yield 85.5%) of white crystals of the target compound. Melting point 184 ° C

¹ H-NMR (CDCl ₃ ) δ (ppm) 7.24-7.31 (m, 4H),
6.86-6.98 (m, 6H), 5.90 (b, 2)
H), 4.50-4.56 (m, 2H), 4.29-
4.41 (m, 3H), 4.12-4.21 (m, 2)
H), 3.90-4.04 (m, 4H), 3.49-
3.56 (m, 2H), 3.30-3.39 (m, 3
H), 2.73 (b, 3H), 1.80-2.33
(M, 11H), 1.65 (b, 4H)

Example 3 1- (2-hydroxy-3-phenoxypropyl)-
Synthesis of 1,1-tetramethyleneamine-2-methoxybenzimide 15.35 g (0.09 mol) of 2-methoxybenzoyl chloride was used in place of pivaloyl chloride, and diethyl ether was used for crystallization. The reaction was performed in the same manner as in Example 1 to obtain 28.3 g of slightly brown crystals of the target compound (yield 85.0).
%) Was obtained. Melting point 126 ° C

¹ H-NMR (CDCl ₃ ) δ (ppm) 7.46 (d, 1H), 7.22-
7.32 (m, 4H), 6.84-7.00 (m, 5
H), 4.69-4.75 (m, 1H), 4.54-
4.60 (m, 1H), 4.42-4.49 (m, 1
H), 4.16 (d, 1H), 4.02-4.07
(M, 1H), 3.78-3.90 (m, 2H), 3.
81 (s, 3H), 3.37-3.49 (m, 2H),
2.35-2.43 (m, 2H), 2.01-2.07
(M, 2H)

Example 4 Synthesis of 1- (2-hydroxypropyl) -1,1-tetramethyleneaminepropionimide Methyl propionate 9.7 g (0.110 mol), propylene oxide 6.4 g (0.110 mol) And methanol 8
0 ml was mixed and 1-aminopyrrolidine 8.6 was added at room temperature.
g (0.10 mol) was added dropwise over 30 minutes and then reacted for 20 hours. The reaction solution was concentrated, and the obtained concentrate was dissolved in a hexane / toluene mixed solvent, cooled to -20 ° C to crystallize, filtered and dried to obtain white crystals of the target compound 1.
7.0 g (yield 85.0%) was obtained. Melting point 117 ° C

¹ H-NMR (CDCl ₃ ) δ (ppm) 4.43-4.51 (m, 1H),
4.23-4.35 (m, 2H), 3.70 (dd, 2)
H), 3.30-3.40 (m, 3H), 2.23-
2.33 (m, 2H), 2.07 (q, 2H), 1.
92-2.03 (m, 2H), 1.20 (d, 3H),
1.10 (t, 3H)

Example 5 1- (2-hydroxy-3-phenoxypropyl)-
Synthesis of 1,1-tetramethyleneamine methacrylimide 16.5 g (0.110 mol) of phenyl glycidyl ether, 11.0 g (0.110 mol) of methyl methacrylate and 100 ml of isopropanol were mixed and 1-aminopyrrolidine was added at room temperature. 30 g of 8.6 g (0.100 mol)
After dripping over a period of time, heat up to 60 ° C. and keep at that temperature for 2
The reaction was allowed for 0 hours. The concentrate obtained by concentrating the reaction solution was dissolved in a hexane / toluene mixed solvent, cooled to −20 ° C. to crystallize, filtered and dried to obtain white crystals of the target compound 2
4.9 g (yield 81.9%) was obtained. Melting point 132 ° C

¹ H-NMR (CDCl ₃ ) δ (ppm) 7.26-7.31 (m, 2H),
6.87-7.00 (m, 3H), 5.75 (s, 1
H), 5.11 (s, 1H), 4.49-4.56
(M, 2H), 4.36-4.44 (m, 1H),
3.90-4.01 (m, 3H), 3.57-3.64.
(M, 1H), 3.31-3.47 (m, 2H),
2.36-2.44 (m, 2H), 1.99-2.06
(M, 2H), 1.92 (s, 3H)

Comparative Example 1 Synthesis of 1,1-dimethyl-1- (2-hydroxypropyl) aminepropionimide 1,1-dimethylhydrazine 6.01 g (0.100 mol) was used in place of 1-aminopyrrolidine. Others are Example 4
White crystals of the target compound (13.9 g, yield 7)
9.9%). Melting point 111 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm) 4.35-4.40 (m, 1H),
3.55 (s, 3H), 3.52 (s, 3H), 3.3
9 (t, 2H), 3.10 (dd, 1H), 2.05
(Q, 2H), 1.22 (d, 3H), 1.08
(T, 3H)

Comparative Example 2 Synthesis of 1,1-dimethyl-1- (2-hydroxy-3-phenoxy) amine methacrylimide 6.01 g (0.100 mol) of 1,1-dimethylhydrazine in place of 1-aminopyrrolidine Example 5 except that
23.6 g of white crystals of the target compound (yield 8
4.9%). Melting point 92 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm) 7.28-7.33 (m, 2H),
6.89-7.01 (m, 3H), 5.82 (s, 1
H), 5.15 (s, 1H), 4.55-4.62
(M, 1H), 4.15 (dd, 1H), 3.90
(Dd, 1H), 3.65 (s, 3H), 3.63
(S, 3H), 3.57-3.61 (m, 1H), 3.
46 (dd, 2H), 1.90 (s, 3H)

Test Example 1 The amine imide prepared in Examples 4 and 5 and Comparative Examples 1 and 2 was replaced with an epoxy resin (bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd., trade name Epicoat 82).
8. Epoxy equivalent 190) 100 parts by weight were added and mixed in a ratio shown in Table 1. The mixture was heated to 120 ° C. and the cure status was measured at 10 minute intervals. The results are shown in Table 2.

[0039]

[Table 1]

[0040]

[Table 2]

From the results shown in Table 2, it can be seen that the amine imide compound of the present invention is a compound useful as a latent curing agent capable of curing an epoxy resin more rapidly than conventional amine imide compounds. Although the mechanism by which the amine imide compound of the present invention exerts such a remarkable effect is not necessarily clear, as compared with the conventional chain alkyl amine type amine imide compound, the amine imide compound of the present invention is a cyclic amine type and therefore sterically hinders. It is presumed that it is because it is small.

[0042]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain an amine imide compound which is safer, easier to handle and has a higher curing rate than before, and a curing agent for an epoxy resin containing the same as an active ingredient.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takashi Kitajima             463 Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture             Gaku Co., Ltd. Tokushima Factory (72) Inventor Ryohiro Nabeshima             463 Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture             Gaku Co., Ltd. Tokushima Factory F term (reference) 4J036 DC36

Claims (3)

[Claims] 1. An amine imide compound represented by the formula (1). _{^{R 1 CH (OH) CH 2}} N + [- (CH _{2) 4} -] ^{N - C (= O) R} 2 (1) wherein, ^{R 1} represents an alkyl group or a phenoxymethyl group having 1 to 4 carbon atoms Indicates. R ² is an alkyl group having 1 to 8 carbon atoms,
Shows a phenyl group substituted with an alkenyl group having 2 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms] 2. An amine imide compound represented by the formula (2). _{PhOCH 2 CH (OH) CH 2} N + [- (CH _{2) 4} -] ^{N - C (= O) (} CH 2) n C (= O) N - -N + [- (CH _{2) 4} -] CH ₂ CH (OH) CH ₂ OPh (2) [wherein n represents a number from 1 to 8] 3. A compound represented by formula (1) and formula (2)
A curing agent for an epoxy resin, containing as an active ingredient at least one selected from the compounds represented by: