JPS61212543A - Novel diamine, production thereof, and epoxy curing agent - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (Y and Z are -SO2-, or -CO-; m is 0-50; n is 0 or 1; m+n>=1). EXAMPLE:A compound shown by the formula II. USE:An epoxy curing agent, further a raw material for high polymers, drugs, agricultural chemicals, etc., having performance such as high heat resistance, high elongation, impact resistance, chemical resistance, water resistance, high strength, etc. PREPARATION:A compound shown by the formula III (M is alkali metal) is reacted with a compound shown by the formula IV (X is F, Cl, Br, or I) in a solvent containing a highly polar solvent, to give a compound shown by the formula V. This compound is reacted with a nitrobenzoic acid halide in the presence of an alkali compound such as pyridine, etc. optionally in an organic solvent such as benzene, etc., to synthesize a nitrobenzoic acid ester, the nitro group is reduced by the use of a metallic catalyst at normal pressure or under hydrogen pressure into the amino group, to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel aromatic diamine having a skeleton structure consisting of poly(11J-lene ether ketone), a method for producing the same, and an epoxy curing agent containing the aromatic diamine.

<Prior Art> Aromatic amine compounds are generally useful as raw materials for polymers, raw materials for pharmaceuticals and agricultural chemicals, or raw materials for various other useful compounds. It is known that it is also useful as a high-performance epoxy curing agent, and currently commonly used aromatic amine curing agents include metaphenylenediamine (MPD) and 4,
4'-diaminodiphenylmethane (DDM) or 4
, 4'-diaminodiphenylsulfone (DDS) is representative.

These aromatic amine curing agents for epoxy are used for epoxy adhesives, coating materials, laminated products such as FRP, cast products, etc. that require heat resistance, high toughness, water resistance, high elasticity, and other excellent mechanical properties. It is generally used as a sealant for molded products or ICs.

<Problems to be Solved by the Invention> However, in recent years, efforts have been made continuously and strongly to improve the performance of resin materials. It is.

The demands for improved performance of epoxy resins are similar or even more pronounced, and in all of the above-mentioned applications there is a strong need for further improvements in heat resistance, high strength, impact resistance, water resistance, or other mechanical properties. It is being

Under these circumstances, the present inventors conducted intensive research to develop a higher performance epoxy resin, and as a result, they arrived at the present invention. That is, the object of the present invention is to provide the general advantages of epoxy resins when used as a curing agent for epoxy resins, and to provide heat resistance, high elongation, impact resistance, chemical resistance, water resistance, high strength, and other properties. An object of the present invention is to provide a novel aromatic diamine that provides an epoxy resin with superior performance in mechanical properties. Still another object is to provide a novel aromatic diamine that is useful as a raw material for various polymers, pharmaceuticals and agricultural chemicals, or as a raw material for conversion into other useful compounds.

Means and Effects for Solving the Problems> The objects of the present invention have been conveniently achieved by the present invention shown in the following (1), (2), and (3).

(1) A novel diamine represented by the following general formula (1).

...Means [I] or -C-, and Y and Z may be the same or different. Also, m is 0.1.
2.3. -, 50, and n is O or 1. And m+n is 1 or more. ) (2) An epoxy curing agent characterized by containing a novel diamine represented by the following general formula (1).

・0... [I] Or -0-, and Y and Z may be the same or different. Also, m is 0.1.2
．． 3. ... is an integer in the range of 50, and n is O or l. And m+n is 1 or more. ) (3) A compound represented by the following general formula [I,] and a compound represented by the following general formula [direct] are reacted in a solvent containing a highly polar solvent to form a compound represented by the following general formula (IV). The product is characterized by the following general formula (1
) A method for producing a novel diamine represented by

...[]] or -〇-, and Y and Z may be the same or different. Also, m is 0.1.2
．． 3.・It is an integer in the range of 50, and n is 0 or 1. And m+n is 1 or more. ) MO<Kun(he)'5)-0M...
(1) (However, in the above formula (1), M is the alkali metal part 2to'lit u +, 'lt+to-#,
r I '1102-? ,,l-1ffi+”.

It is. )
In the above formula (1), X is F, Cl5Br.

Alternatively, it means I, and Z is the same as that in the above formula (1). ) ・――・−・ (W) (However, in the above formula [■], Y, Z, m, and n
are the same as those in the above formula [I]. ) The novel aromatic diamine according to the present invention is useful as a raw material for producing various polymers, such as a curing agent for producing polyurethane or a diamine for producing polyamide, polyamideimide, and polyamide. It is also useful as a raw material for medicines and agricultural chemicals, or as a raw material for conversion into other useful compounds.

Alternatively, when the novel aromatic diamine according to the present invention is used as an epoxy curing agent, it has properties such as heat resistance, high elongation, impact resistance, chemical resistance, water resistance, high strength, weather resistance, or other mechanical properties. A significantly superior epoxy resin can be obtained. Epoxy resins with such excellent properties are
In particular, for example, heat-resistant high-strength adhesives, weather-resistant high-toughness coating materials, water-resistant and heat-resistant sealants for ICs, etc., high-strength materials for FRP made of glass fibers, carbon fibers, fully aromatic polyamide fibers, etc. It is useful as a tough matrix resin or other high-performance epoxy products such as high-performance laminates, cast products, and molded products.

In order to produce the novel aromatic diamine of the present invention, first, a compound represented by the above general formula [厘] and the above general formula CI]
A long-chain diol represented by the general formula (IV) is synthesized by reacting the compound represented by the above in a solvent containing a highly polar solvent.

The synthesis of compound (IY) is described, for example, in Japanese Patent Publication No. 46-69
This can be carried out according to the method disclosed in No. 76. Examples of the highly polar solvent used here include phone, diisopropylsulfone, and tetramethylene sulfone. When a relatively large amount of water is present in the solvent, the value of n will be relatively small.

The reaction temperature is usually in the range of 50°C to 250°C.

The molar ratio of compound [■]/compound [■] is not particularly limited, but is usually 0.9 or more and 6 or less. When it is less than 0.9, the hydrolysis operation of the terminal chlorine becomes frequent, and when it is more than 6, the amount of the remaining compound (1) is too large, which is uneconomical.

Compounds of general formula CI) can be prepared by reacting the corresponding diol compounds with compounds such as alkali metals, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides or alkali metal alkyl compounds. Preferably, an alkali metal hydroxide is used and the reaction is carried out in the above-mentioned highly polar solvent used in the subsequent reaction.

After synthesizing compound CI], it is advisable to proceed to the synthesis of compound [■] under the conditions described above.

The synthesized compound (■) was separated by cooling the reaction solution to room temperature and separating the precipitated sodium chloride. J' [
This can be achieved by pouring into an acidic aqueous solution to obtain a precipitated solid. If necessary, this separation can be preceded by known methods of hydrolyzing the terminal halogen. The thus separated compound (IVI) can be redissolved in an aqueous alkaline solution if necessary, and then subjected to an acid precipitation operation again to improve its purity.

Compound (IV) is then converted into a compound represented by general formula [I], and various known methods can be applied. In principle, for example, in the presence of an alkaline compound such as pyridine, triethylamine, alkali metal hydroxide, benzene, dioxane, ethylene glycol, dimethyl ether, chloroform, carbon tetrachloride,
0 in organic solvents such as hexane, petroleum ether, and water solvents
Nitrobenzoic acid halide and the compound (ff) are reacted between ℃ and the boiling point of the solvent to first synthesize a nitrobenzoic acid ester, and then a metal catalyst such as platinum oxide, platinum supported on activated carbon, zinc, or Raney nickel is added. Compound [I] can be obtained by reducing a nitro group to a 7-mino group under normal pressure or pressurized hydrogen, at room temperature or with heating.

Alternatively, for example, compound (■) is first introduced into an alkali metal phenolate, and compound [I] is obtained by reacting this with aminobenzoic acid halide in a suspended state in a suitable solvent, for example, benzene, under a nitrogen atmosphere at the boiling point. You can also do that.

The novel aromatic diamine (1) thus obtained is a useful compound as described above.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

<Example> Example 1 (1) To Ho-o-5O) Ibe 1so2 (diooH (compound (y)) synthesis thermometer, stirrer, Dimroth cooler with distilled water separation mechanism, and nitrogen inlet tube In a 500 d four-eye flask, add 1 liter of dimethyl sulfoxide that has been dehydrated in advance.
00gg, 50y (0.2 mol) of 4,4'-dihydroxydiphenylsulfone, 26.4y (0.4 mol as purity 85%) of potassium hydroxide, and 40ml of benzene.
and stirred at 120° C. for 4 hours under a nitrogen atmosphere. During this period, distillation of an almost stoichiometric amount of water was observed. After cooling to room temperature, 4,4'-dichlorodiphenylsulfone 28
．． 71 (0.1 mol) dissolved in 100 d of dimethyl sulfoxide was added, and the mixture was heated to 125-130°C under stirring for 55 minutes.
Time processed. During this time, benzene and water in the system were removed to the outside of the yarn by evaporation. The reaction was further continued at 140° C. for 7.5 hours, then cooled to room temperature and filtered.

The P solution was dropped into 700 d of a 5% aqueous sulfuric acid solution while stirring. The precipitated light brown solid was separated from P, washed with water, and then 5%
It was dissolved in an aqueous solution of caustic soda of 6 Q O#1 (complete dissolution was confirmed at this time) and added dropwise again into an aqueous solution of 5% sulfuric acid of 700 d to perform an acid precipitation treatment. This produced fine white particles. When this is filtered, washed with water, and dried, the yield is 58 f1mp, 126-129°C. Table 1 shows the results of analysis by high performance liquid chromatography.

Table 1 (High performance liquid chromatography analysis conditions) Color A:
Chemcosorb 70DSH mobile phase: TH'
F/HzO=60/40-LO story/cod detection: 2
54 nm Next, the results of isolation of C component, which is the main component, are shown.

50f of the oligomer mixture thus obtained was dissolved in lAt1 amyl alcohol (80-82°C), and the apparatus was left to cool overnight to remove the generated tar-like substance (about 2.4F). To the supernatant, 360 ml of n-octane was added and dissolved by heating, and then allowed to stand to cool to separate into an oily substance (A, about 23.6 F) and a supernatant.

The thus obtained supernatant liquid was heated and dissolved again by adding 300 liters of n-octane, allowed to stand, and allowed to cool.The resulting oily substance (approximately 17.7 F) was separated, and this was mixed with 1 liter of amyl alcohol.
It was dissolved in a mixed solvent of 00 g/ln-octane 45 ml under heating. An oily substance (approximately 12.
Solid powder 651 (mp, 135-140 °C
) was obtained. The solid obtained by purifying Konoyouni was confirmed to be component C in Table 1 by high performance liquid chromatography.

Table 2 shows the elemental analysis values of this compound.

l) Calculated value for compound (V) described below. This product was further analyzed by FAB/MS and FD/MS. The result was 1! for the former! (MH) = (mlz 715
), but in the latter case CM+3 = (mlz 714)
was confirmed, and the molecular wind of this compound was determined to be 714. Further, the OH value of this compound was measured by a conventional method and found to be 369 (the calculated value for Compound (V) described below was 357.4).

From the above results, the compound obtained here is the following compound (
It was concluded that Y). This conclusion was also supported by IH-NMR and IR analysis.

C3s Hz s Ox. S3 ■-714 In addition, the oily substance A that was first separated in the above refining operation was also recovered and purified in the same manner, and the above compound (V
) A powder solid 8,7F identified as 8,7F was obtained.

Synthesis of (Compound [■]) Compound (V) 5F (purity 100%) obtained in (1) above
6.99xlO-3 mol] in 30 ml of pyridine
m-Nitrobenzoyl chloride 5.192
y (2,798xlO-" moles) in 60 ml of pyridine
Add dropwise to the dissolved solution. After stirring at 65° C. for 1 hour, the mixture was allowed to cool and filtered to obtain crystals 2.869. This was dissolved under heat in a mixed solvent of 66 g of a7ton/43 d of ethanol, and allowed to cool to remove the separated tar-like substance (0,081). The supernatant liquid was dropped into ethanol and the precipitated solid was filtered. ,
Dry. Yield is 2.78y (mp, 133-13
9°C).

High performance liquid chromatography analysis of this product revealed a purity of 96% (area % at 2541 m).

The thus obtained solid 2F, 5% Pt/CO, 2F, and 30 ml of dioxane were placed in a 100 mL tube equipped with an electromagnetic induction stirrer.
Put it in an autoclave and hydrogen pressure 3 kq/dG,
Hydrogenation treatment was carried out at room temperature for 15 hours. Next, 100 d of dioxane was added to dissolve the precipitate by heating, and the solid catalyst was removed by filtration.

The P solution was dried under reduced pressure, and the obtained solid powder was washed with hot ethanol and dried. Yield L5r%mp, is 145-15
The temperature was 1°C. This product was analyzed by high performance liquid chromatography and the purity was 95% (area % at 254 nm). About this IR and IH-NM
The results of the R analysis are shown in FIGS. 1 and 2. Moreover, the molecular weight of this product was determined to be 952 by FAB/MS analysis.

Furthermore, the results of elemental analysis were as shown in Table 3.

Table 3 From the above results, it was determined that the solid powder obtained here was the following compound.

(Compound [■]) Example 2 Basic evaluation as an epoxy curing agent Mutual solubility and reaction initiation temperature of the compound obtained in Example 1 (equivalent mixture of VN and the chemical monomer (Epicote 828 manufactured by Yuka Shell Co., Ltd.) (To), exothermic peak temperature (
) and 180°C for 2 hours Tg of cured product
Table 4 shows the measurement results.

Table 4 Despite being a long chain diamine, it shows a high Tg and has good solubility. This shows that it can be expected as an epoxy curing agent with good heat resistance.

In addition, measurements of T, , T, and Tg are carried out in 1. t du
Using a Pant DSC (model 99o), TO and T were measured at a heating rate of 10'C/body, and Tg at 40°C/gate.
was measured.

Example 3 (1) Ho-@-5o2-@-+o-@-so, -
@+, -oH (7) Synthesis Bisphenol 55QF (0.2 mol) in a 500 d four-way flask equipped with a stirrer, thermometer, Dimroth condenser, and nitrogen inlet tube
, KOH26,44 Da (0.4 mol based on purity of 85%) and 1 Q Oml of dimethyl sulfoxide were added, and the mixture was stirred at 120°C for 4 hours. After cooling, add 28.72y (0.1 mol) of dichlordiphenylsulfone dissolved in 100 ml of dimethyl sulfoxide, and heat to 122°C.
Stirring was continued for 6 hours at 135°C, 4.5 hours at 150°C, and 12 hours at 150°C. - After cooling overnight, the precipitate was removed by filtration, and the P solution was dropped into a 5% sulfuric acid aqueous solution (700 w). Separate the precipitate by decantation, dissolve it again in 500 d of 5% caustic soda aqueous solution, precipitate with acid as above (using 5% sulfuric acid aqueous solution 7 Q Q 11), filter, wash with water, and dry. ml), 129-135°C, and OH value 372 solid 615F was obtained. Table 5 shows the results of analyzing this product by high performance liquid chromatography.

Table 5 The OH value calculated from the composition shown in Table 5 is 376,
This showed good agreement with the separately measured OH number of 372.

Stirrer, condenser, dropping funnel with balance tube, Ca C
64.2 tt of m-nitrobenzoyl chloride (2.14 times the mole of the theoretically required amount calculated from the OH value) and 190 ml of pyridine were placed in a SOO* four-flask equipped with a 112 tube and a thermometer, and the mixture was stirred at the boiling point. While adding 60y of the solid obtained in (1) above from the dropping funnel to 120d of pyridine.
The diluted solution was added dropwise over a period of 35 minutes. After heating and stirring for 2 hours, the mixture was left to cool, and the entire amount of the reaction solution containing the precipitate was dropped into ethanol L51, and the precipitated crystals were separated in a furnace. The crystals were washed with 500 wl of 5% Naz CO,s aqueous solution, then washed with water, then washed with 500 ml of ethanol, and then dried. mp, 128-140℃, yield 75.23
y0 This solid 101 is converted into Pt (h IF , dioxane 1
500 liters of cod along with 50 liters of cod were charged into an autoclave equipped with a stirrer, and hydrogenated at a hydrogen pressure of 3#/dG and 127°C for 3 hours. The amount of hydrogen absorbed at this time was 1297 ml. This is calculated from the OH value of the raw material diol before nitrobenzoic acid esterification of 372, which is calculated when it ideally progresses to nitrobenzoic acid esterification and then reduction of the nitro group, and the diol molecular weight is 744 ( =372x2) Dinitroester molecular weight 1042 (=744+298) Diaminoester molecular weight 982 (=1042-60) 10/
It matches well with 11042X6X22400=1290/. After releasing the pressure, the P liquid from which the catalyst has been removed by filtration is dried under reduced pressure, and acetonitrile is added to dissolve it, and then dried under reduced pressure again to completely remove dioxane. The obtained solid is washed with ethanol and then dried under reduced pressure. Yield 8.59 f 1mp,
142-150℃.

The amine value of this product is 506, which is within the expected range from the amine value of 491 calculated in the same manner as the theoretical hydrogen absorption amount. IR and I H- of this
The NMR spectra are shown in FIGS. 3 and 4.

From these data, it was concluded that the following compound [■] was obtained.

[l That is, n=1.2, 3. It is a mixture of @@・. The average value of n, calculated from the amine value, is 2.26.

This value corresponds to the expected value n=2 based on the charge ratio of 52 moles of bisphenol and 1 mole of dichloride when synthesizing the raw material diol.

Example 4 The basic performance as an epoxy curing agent was evaluated in the same manner as in Example 2 for an equivalent mixture of the compound [■] obtained in Example 3 and an egoxy monomer (Epicoat 828 manufactured by Yuka Shell Co., Ltd.). The results are shown in Table 6.

Tg is 180°C x 2 hr curing.

Although it is a long-chain curing agent, it exhibits attractive performance as an epoxy curing agent, such as a high Tg and a moderate reaction initiation temperature (To).

Example 5 Evaluation as an adhesive A mixture of Epicoat 828 (manufactured by Yuka Shell Co., Ltd.) and an equivalent amount of the compound [■] obtained in Example 3 was subjected to a tensile shear test according to JIS K6580-1976. Ta. The adherend material was 75x25x3fi aluminum, and the curing conditions were 180°C x 2 hours. The measurement results are shown in Table 7 together with the results obtained in the same manner for two comparative curing agents. It is clear that the tensile shear strength is especially excellent at high temperatures.

l) Diaminodiphenylsulfone 2) Metaphenylenediamine 3) Adherent treated with trichlene 4) Adherent treated with sandpaper polishing <Effects of the Invention> According to the present invention, when used as an epoxy curing agent, the general epoxy resin A novel aromatic diamine and a method for producing the same that provide an epoxy resin having the following advantages and excellent performance in heat resistance, high elongation, impact resistance, chemical resistance, water resistance, high strength, and other mechanical properties. was provided. Further, according to the present invention, an excellent epoxy curing agent was provided.

[Brief explanation of the drawing]

FIGS. 1 and 3 show IR spectrograms of the compound according to the present invention, and FIGS. 2 and 4 show IH-NMR spectrograms of the compound according to the present invention, respectively.

Claims (3)

[Claims] (1) A novel diamine represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (However, in the above formula [I], Y and Z are ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲Mathematical formulas, chemical formulas, tables, etc.) etc. ▼ means Y and Z may be the same or different. Also, m is 0, 1, 2
, 3, . . . 50, and n is 0 or 1. And m+n is 1 or more. ) (2) An epoxy curing agent characterized by containing a novel diamine represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (However, in the above formula [I], Y and Z are ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲Mathematical formulas, chemical formulas, tables, etc.) etc. ▼ means Y and Z may be the same or different. Also, m is 0, 1, 2
, 3, . . . 50, and n is 0 or 1. And m+n is 1 or more. ) (3) A compound represented by the following general formula [IV] is obtained by reacting a compound represented by the following general formula [II] and a compound represented by the following general formula [III] in a solvent containing a highly polar solvent. A method for producing a novel diamine represented by the following general formula [I], characterized in that the -OH groups at both ends of the resulting compound are replaced with ▼ groups. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (However, in the above formula [I], Y and Z are ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲Mathematical formulas, chemical formulas, tables, etc.) etc. ▼ means Y and Z may be the same or different. Also, m is 0, 1, 2
, 3, . . . 50, and n is 0 or 1. And m+n is 1 or more. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] (However, in the above formula [II], M means an alkali metal atom, and Y is the same as that in the above formula [I]. .) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[III] (However, in the above formula [III], X means F, Cl, Br, or I, and Z means the above formula [I ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[IV] (However, in the above formula [IV], Y, Z, m, and n are the same as the above formula [I] (It is the same as those inside.)