JPH06293719A - Production of primary amine having thermosetting group - Google Patents

Abstract

PURPOSE:To provide a method for producing a primary amine optimal for terminating the end of an oligomer and/or a polymer and synthesizing a low hygroscopic reactive resin. CONSTITUTION:Phenols expressed by formula I (R1 and R2 are H, O, S, lower alkyl, lower fluoroalkyl, phenyl, acetyl, benzyl or expressed by formula II or III; Ar is bivalent aromatic group) are made to react with a tosylate expressed by formula IV [R3 is H, lower alkyl or lower fluoroalkyl; R4 is CidenticalC, CH=CH or CH=C(CH3); (n) is 0-10; Ts is p-toluenesulfonate group] in the presence of a base in an aqueous solution and/or an organic solvent to provide a compound expressed by formula V which is an intermediate for a primary amine having a thermosetting group, e.g. 4-acetamidophenyl 1-allyl ether. The resultant compound is then subjected to either or both of reduction or dealkylation to afford the objective primary amine expressed by formula VI, e.g. 4-aminophenyl 1-allyl ether.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing a primary amine, more specifically, it is suitable for synthesizing a low hygroscopic reactive resin by terminating the end of an oligomer and / or polymer. The present invention relates to a method for producing a primary amine.

[0002]

BACKGROUND OF THE INVENTION Primary amines having a thermocrosslinking reactive group have been conventionally used as end-terminating monomers for thermosetting polyimides and polyamides.

Recently, for example, a thermosetting polyimide having a terminal terminated using 3-ethynylaniline as a primary amine has been put on the market as a thermid [Hughes.
Aircraft, JP-A-50-5348, etc.]. Several methods (for example, USP 4,125,563 etc.) are known for the synthesis of 3-ethynylaniline used here, but all have a problem that the synthesis route is long and the synthesis reagent is expensive. Was.

Further, a thermosetting polyimide in which terminals are terminated by using propargylamine as a primary amine has also been proposed [Ube Industries, Ltd., JP-A-2-284923, JP-A-3-174427]. . However, the thermal reaction initiation temperature of this resin is as high as 250 ° C., and the imide oligomer using this as a reactive group also has a high curing temperature and is known to be inferior in terms of processability [St. Clair, Anne K. . et al., Polym. En
g. Sci., 22 (1), 9-14 (1982)].

Various aromatic propargyl ethers have been proposed as a system utilizing a thermosetting reaction of a propargyl group [eg, Dow Chemical, JP-A-2-85275,
William E. Douglas et al., Eur. Polym. J., 27 (1
1), 1279-1287 (1991)]. Aromatic propargyl ether is obtained by reacting with various phenols and halogenated propargyl halide in an aqueous caustic solution in the presence of a phase transfer catalyst. Propargyl ether polymerizes via chromene by the application of heat to produce a thermoset polymer. It is known that the obtained cured product of the thermosetting polymer has low hygroscopicity. However, these aromatic propargyl ethers are, for example, those obtained by converting both ends of bisphenol A into propargyl ether, and since the polymerized product has a relatively low molecular weight, there is a problem that the cured product is inferior in heat resistance and mechanical strength. .

In view of such circumstances, the present inventor has arrived at the present invention as a result of intensive studies to solve these technical problems. That is, the first object of the present invention is to
By introducing an unsaturated alkyloxy group, such as propargyl ether / allyl ether, into a primary amine and using it as an amine-terminated amine of an imide oligomer, it has excellent heat resistance and mechanical strength and low moisture absorption. To provide thermosetting polyimide, polyamide, etc. having properties.

[0007]

The gist of the method for producing a primary amine having a thermosetting group according to the present invention is that the general formula (1) R ₁ R ₂ N-Ar-OH (1) (In the formula, R ₁ and R ₂ are hydrogen, oxygen, sulfur, lower alkyl,
Lower fluoroalkyl, phenyl, acetyl, benzyl or

[Chemical 4] The substituents selected from are shown below. Ar represents a divalent aromatic group. ) And a general formula (2) R ₃ -R ₄ -(-CH _2- ) _n -O-Ts (2) (wherein R ₃ is selected from hydrogen, lower alkyl, and lower fluoroalkyl). R ₄ is a substituent

[Chemical 5] The substituents selected from are shown below. n shows the positive integer of 0-10. Ts represents a p-toluenesulfonic acid group. ) Is obtained by reacting a tosylate represented by the formula (3) with R ₁ R ₂ N-Ar-O-(-CH _2- ) _n -R ₄ -R ₃ (3). A compound represented by the formula (4) H ₂ N-Ar-O-(-CH _2- ) _n -R ₄ -R ₃ (4) can be represented by the method of either reduction or dealkylation or both. To produce primary amines.

In the method for producing a primary amine having a thermosetting group, the Ar is

[Chemical 6] It is a divalent aromatic group selected from

[0009]

EXAMPLES Next, a first example having a thermosetting group according to the present invention
The method for producing a primary amine will be described.

First, paratoluene sulfonic acid chloride and the general formula (5) R ₃ -R ₄ -(-CH _2- ) _n -OH (5) (wherein R ₃ is hydrogen, lower alkyl or lower fluoroalkyl) R ₄ is a substituent selected from

[Chemical 7] An organic group selected from is shown. n shows the positive integer of 0-10. ) With a reactive alcohol,
A compound of the general formula (2) R ₃ —R ₄ — (— CH ₂ —) _n —O—Ts (2) (wherein R ₃ is a substituent selected from hydrogen, lower alkyl and lower fluoroalkyl, and R ₄ is

[Chemical 8] An organic group selected from is shown. n shows the positive integer of 0-10. Ts represents a paratoluene sulfonic acid group. ) Is obtained.

Here, the reactive alcohol used in the present invention represented by the above general formula (5) is more preferably propargyl or allyl alcohol from the viewpoint of cost and various properties. . The propargyl alcohol is preferably propargyl alcohol, and the allyl alcohol is preferably allyl alcohol or methacrylic alcohol.

Next, the obtained tosylate represented by the general formula (2) and the general formula (1) R ₁ R ₂ N-Ar-OH (1) (wherein R ₁ and R ₂ are hydrogen and oxygen) , Sulfur, lower alkyl,
Lower fluoroalkyl, phenyl, acetyl, benzyl or

[Chemical 9] The substituents selected from are shown below. Ar represents a divalent aromatic group. By reacting a phenol represented by the formula (1) with an aqueous solution and / or an organic solvent in the presence of a base,
A general formula (3) R ₁ R ₂ N-Ar-O-(-CH _2- ) _n -R ₄ -R ₃ (3) which is an intermediate of a primary amine having a thermosetting group (wherein R ₁ and R ₂ are hydrogen, oxygen, sulfur, lower alkyl,
Lower fluoroalkyl, phenyl, acetyl, benzyl or

[Chemical 10] The substituents selected from are shown below. Ar represents a divalent aromatic group. R ₃ represents a substituent selected from hydrogen, lower alkyl and lower fluoroalkyl. R ₄ is

[Chemical 11] An organic group selected from is shown. n shows the positive integer of 0-10. ) Is obtained.

The nitrophenols used in the present invention represented by the above general formula (1) are represented by the general formula (6)
Two

[Chemical 12] (In the formula, Z represents a lower alkyl residue or a lower fluoroalkyl residue, an aromatic residue such as Ph, a halogen group residue such as F, Cl, Br and I. m represents an integer of 0 to 4) .), Generally indicated. More specifically, 2-nitrophenol, 3-nitrophenol, or 4-nitrophenol is preferable in terms of the balance between cost and various characteristics.

The aminophenols used in the present invention represented by the above general formula (1) are represented by the general formula (7).

[Chemical 13] (In the formula, Z represents a lower alkyl residue or a lower fluoroalkyl residue, an aromatic residue such as Ph, a halogen group residue such as F, Cl, Br and I. m represents an integer of 0 to 4) .), Generally indicated. More specifically, 2-aminophenol, 3-aminophenol, or 4-aminophenol is preferable in terms of the balance between cost and various characteristics.

Further, although the divalent aromatic group Ar is not particularly limited,

[Chemical 14] A divalent aromatic group represented by is preferable.

The base catalyst used in the ether formation reaction from the tosylate and phenol of the present invention corresponds to a general alkaline catalyst based on the knowledge of those skilled in the art, but is preferably potassium hydroxide or sodium hydroxide. An aqueous solution of potassium carbonate or a mixture thereof is used.

In such an ether formation reaction from tosylate and phenols, a phase transfer catalyst can be used in order to obtain an ether product in a high yield. The phase transfer catalyst used here corresponds to all common catalysts known to those skilled in the art, but preferably a tetraalkylated ammonium halide or a tetraalkylated phosphonium halide is used. As the halide, iodide, bromide or chloride is used.

Further, an organic solvent can be used together with the aqueous solution in the reaction solution. The organic solvent used together is preferably a general-purpose organic solvent such as dimethylformamide, dimethylacetamide, toluene, benzene, chloroform and acetone. The solution concentration of the reaction solution is preferably 5 to 50%, more preferably 10 to 30%. If it exceeds this range, the reaction may not be sufficiently carried out or a reaction by-product may be easily produced, which is not preferable.

Then, the general formula (3) R ₁ R ₂ N-Ar-O-(-CH _2- ) _n -R ₄ -R ₃ (3) obtained by the above reaction (wherein R ₁ , R ₂ is hydrogen, oxygen, sulfur, lower alkyl,
Lower fluoroalkyl, phenyl, acetyl, benzyl or

[Chemical 15] The substituents selected from are shown below. Ar represents a divalent aromatic group. The compound represented by the formula (1) is represented by the general formula (4) H ₂ N-Ar-O-(-CH _2- ) _n -R ₄ -R ₃ (4) by a reduction or dealkylation method or both methods. (wherein, R ₃ represents hydrogen, lower alkyl, a substituent selected from lower fluoroalkyl. R ₄ is of 16

[Chemical 16] An organic group selected from is shown. n shows the positive integer of 0-10. A primary amine having a thermosetting group represented by) is produced.

When R ₁ and R ₂ are oxygen, that is, a nitro group, the reducing agent reduces the nitro group to an amino group. The reducing agent that can be used here corresponds to a general catalyst based on the knowledge of those skilled in the art, and is not limited in any way. For example, catalytic reduction with platinum black or palladium-carbon, reduction with metal hydride such as aluminum hydride or sodium hydride, reduction with hydrazine, and reduction with tin, tin chloride, iron or the like can be used. These can be appropriately selected and used (edited by The Chemical Society of Japan, "New Experimental Chemistry Lecture, Volume 14, Synthesis and Reactions of Organic Compounds (3), 1333-1335"). Other,
The reducing agent is applicable as long as it can be used for the reduction reaction of the nitro group. Here, the tin chloride / hydrochloric acid system is preferable from the viewpoint of cost and easy handling of the reaction. The temperature and reaction time are not particularly limited, but in the above example,
The reaction temperature at this time is preferably in the range of -15 to 120 ° C, and more preferably 0 to 100 ° C. The reaction time is preferably 1 to 24 hours.

R ₁ and R ₂ are hydrogen, oxygen, sulfur, lower alkyl, lower fluoroalkyl, phenyl, acetyl, benzyl, or

[Chemical 17] In the case of a so-called amide compound such as a substituent selected from, the amide group can be converted into an amino group by dealkylating the amino protecting group in an aqueous solution and / or an organic solvent.

As the dealkylating agent which can be used here, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc., sodium hydride, metallized lithium, lithium aluminum hydride, etc., sodium alcoholate, etc. can be used. A general alkaline catalyst based on the knowledge between the two corresponds and is not limited in any way (Organic Synthetic Chemistry Association, "Handbook of Organic Synthesis Experimental Methods, 398 pages", or Maruzen, "New Experimental Chemistry Course, Organic Compounds Synthesis and Reactions (5) Pages 2555-2556 ”
reference). Here, the boiling treatment in hydrochloric acid is preferable from the viewpoint of cost and easy handling of the reaction. The temperature and the reaction time are not particularly limited, but in the above example, the reaction temperature is -1.
The range of 5 to 150 ° C is suitable, and preferably 0 to 13
The range of 0 ° C is preferred.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples, and the present invention is within the scope of the present invention without departing from the spirit of the invention. It can be implemented in a mode in which various modifications, improvements and changes are made based on the knowledge of.

Example 1 (Synthesis Method 1 of Allyl Ether) A synthesis method of 4-acetamidophenyl-1-allyl ether will be described. First, a dropping funnel was attached to a 500 ml three-necked flask, and 6.52 g (32.6 mm)
ol) paratoluene sulfonic acid allyl ester 20
It was dissolved in milliliter of methanol and charged into a dropping funnel. Then, 1.30 g (32.6 mmol) of sodium hydroxide dissolved in 50 ml of water,
4.93 g (32.6 mmol) of 4-acetaminophen was charged into a reactor, the above allyl ester was added dropwise at 100 ° C., and the mixture was reacted for 12 hours. After the reaction, the mixture was treated according to a conventional method to obtain 5.01 g (yield: 81%) of 4-acetamidophenyl-1-allyl ether compound. The elemental analysis values and spectrum data of the obtained compound are as shown below.

[Elemental analysis value] Calculated value: C; 69.09, H; 6.85, N; 7.32 Actual value: C; 69.31, H; 6.64, N; 7.47 [Spectrum Data] IR (neat, cm ⁻¹ ) ν = 3500, 3300, 2
960, 1880, 1620, 1560, 1500, 1
470, 1370, 1270, 1240, 1220, 1
150, 1030, 860, 810, 660. ¹ H-NMR (CDCl ₃ , ppm) δ = 2.14
(S., 3H), 3.75 (s., J = 2.0Hz, 2
H), 5.23 (m., 2H), 5.96 (m., 1)
H), 8.0 (m., 4H)

Example 2 (Synthesis Method 2 of Allyl Ether) A synthesis method of 4-nitrophenyl-1-allyl ether will be described. A dropping funnel was attached to a 500 ml three-necked flask, and 6.52 g (32.6 mmol) of paratoluenesulfonic acid allyl ester was dissolved in 20 ml of methanol and charged into the dropping funnel. Then, 1.30 g (32.6 mmol) of sodium hydroxide dissolved in 50 ml of water and 4.53 g
(32.6 mmol) 4-nitrophenol was charged into a reactor, and the above allyl ester was added dropwise at 100 ° C.
Reacted for hours. After the reaction, the reaction was performed according to a conventional method, and then 5.30.
g (yield: 85%) of 4-nitrophenyl-1-allyl ether compound was obtained. The elemental analysis values and spectrum data of the obtained compound are as shown below.

[Elemental analysis value] Calculated value: C; 60.34, H; 5.03, N; 7.82 Measured value: C; 59.75, H; 5.08, N; 8.02 [Spectrum Data] IR (neat, cm ⁻¹ ) ν = 3600-3000, 3
000, 2950, 1620, 1600, 1580, 1
495, 1450, 1350, 1295, 1220, 1
160, 990, 905, 860, 780, 735, 6
90. ¹ H-NMR (chloroform-d, ppm) δ = 3.
8 (d., J = 2.0 Hz, 2H), 5.1 (m., 2)
H), 5.9 (m., 1H), 7.9 (m., 4H)

Example 3 (Synthetic Method 1 of Propargyl Ether) Next, a synthetic method of 4-acetamidophenyl-1-propargyl ether will be described. 3 of 500 ml
A dropping funnel was attached to the neck flask, and 6.45 g (3
Paratoluene sulfonic acid propargyl ester (2.6 mmol) was dissolved in 20 ml of methanol and charged into a dropping funnel. And 1.30g (32.6mm
ol) dissolved in 50 ml of water and 4.93 g (32.6 mmol) of N-acetaminophen were charged into a reactor, and the propargyl ester was added dropwise at 100 ° C. for 12 hours. It was made to react. After the reaction, the mixture was treated according to a conventional method to obtain 4.93 g (yield: 80%) of 4-acetamidophenyl-1-propargyl ether compound. The elemental analysis values and spectrum data of the obtained compound are as shown below.

[Elemental analysis value] Calculated value: C; 69.83, H; 5.86, N; 7.40 Actual value: C; 69.78, H; 5.98, N; 7.33 [Spectrum Data] IR (neat, cm ⁻¹ ) ν = 3500, 3300, 2
960, 2880, 1880, 1650, 1610, 1
560, 1510, 1450, 1370, 1270, 1
240, 1180, 1030, 840, 810, 66
0,630. ¹ H-NMR (CDCl ₃ , ppm) δ = 2.12
(S., 3H), 2.48 (tr., 1H), 4.61.
(D., J = 2.4 Hz, 2H), 6.77 to 7.6.
(M., 4H), 7.85 (br.s., 1H)

Example 4 (Synthesis method 2 of propargyl ether) A synthesis method of 4-nitrophenyl-1-propargyl ether will be described. A dropping funnel was attached to a 500 ml three-necked flask, and 6.52 g (32.6 mmol) of paratoluene sulfonic acid propargyl ester was added to 20 ml.
It was dissolved in milliliter of methanol and charged into a dropping funnel. Then, 1.30 g (32.6 mmol) of sodium hydroxide dissolved in 50 ml of water and 4.53 g (32.6 mmol) of 4-nitrophenol were charged into a reactor, and the above-mentioned propargyl was prepared at 100 ° C. The ester was added dropwise and reacted for 12 hours. After the reaction, the reaction was performed according to a conventional method to obtain 4.25 g (yield: 69%) of 4-nitrophenyl-1-propargyl ether compound. The elemental analysis values and spectrum data of the obtained compound are as shown below.

[Elemental analysis value] Calculated value: C; 61.02, H; 3.95, N; 7.91 Actual value: C; 59.82, H; 4.04, N; 7.72 [Spectrum Data] IR (neat, cm ⁻¹ ) ν = 3600-3000, 3
000, 2950, 1620, 1600, 1580, 1
495, 1450, 1350, 1295, 1220, 1
160, 990, 905, 860, 780, 735, 6
90. ¹ H-NMR (chloroform-d, ppm) δ = 3.
6 (tr., 1H), 5.7 (d., J = 2.0 Hz,
2H), 7.1 & 8.2 (dd., J = 6.0 Hz, 8
H)

Example 5 (Synthesis Method 1 of 4-Aminophenyl-1-allyl Ether) A 300 ml three-necked flask was equipped with a 50 ml dropping funnel, a three-way cock, and a seam cap, and dried under reduced pressure. It was replaced with nitrogen. 19.12 g (0.1 mol) of 4-acetamido-1-allyl edel synthesized in Example 1 and 200 g of 3N hydrochloric acid were charged into the reaction system and reacted under reflux for 4 hours. After the reaction, the reaction solution was put into a saturated sodium carbonate solution and extracted from methylene chloride. After dehydrating the organic layer, it was filtered and the solvent was distilled off. The precipitated crystals were recrystallized from ethanol to obtain 13.47 g (yield; 90.3%) of 4-aminophenyl-1-allyl ether.

Example 6 (Synthesis method 2 of 4-aminophenyl-1-allyl ether) A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock, and a seam cap, and dried under reduced pressure. It was replaced with argon. 23.67 g (0.14 mol) of 4-nitrophenyl-1-allyl ether synthesized in Example 2 and 270 ml of dioxane were charged into a reaction vessel. 260.4
9 g (1.16 mol) of tin chloride and 270 ml of concentrated hydrochloric acid were added dropwise over 2 hours under ice cooling. The reaction solution was stirred under ice cooling for 1 hour, then 1 liter of 10 wt
% Sodium hydroxide aqueous solution. After filtering out the precipitated tin hydroxide, the filtrate was extracted from methylene chloride. Then, after dehydration and filtration, the solvent was distilled off, and the precipitated crystals were separated by filtration and recrystallized from toluene. As a result, 2
1.62 g (yield; 93.2%) of 4-aminophenyl-1-allyl ether was obtained. The elemental analysis values and spectrum data of the obtained compound are as shown below.

[Elemental analysis value] Calculated value as C9H11N101: C; 80.74, H; 5.81, N; 13.4
5 Found: C; 80.53, H; 5.98, N; 13.8.
1 [Spectral data] IR (neat, cm ⁻¹ ) ν = 3600-3000,3
000, 2950, 1620, 1600, 1580, 1
495, 1450, 1350, 1295, 1220, 1
160, 990, 905, 860, 780, 735, 6
90. ¹ H-NMR (chloroform-d, ppm) δ = 3.
5 (tr., 1H), 4.2 (br.s., 2H),
5.15 (d., J = 1.2 Hz, 1H), 6.7
(M., 4H)

Example 7 (Synthesis method 1 of 4-aminophenyl-1-propargyl ether) A 300 ml three-necked flask was equipped with a 50 ml dropping funnel, a three-way cock, and a seam cap, and dried under reduced pressure to obtain nitrogen. Replaced with. 5.68 g (0.03 mol) of 4-acetamido-1-propargyl ether synthesized in Example 3 and 150 g of 3N hydrochloric acid were charged into the reaction system and reacted under reflux for 4 hours. After the reaction
The reaction solution was put into saturated sodium carbonate solution and extracted from methylene chloride. The organic layer was dehydrated, filtered, and the solvent was evaporated. The precipitated crystals were recrystallized from ethanol to obtain 4.18 g (yield; 94.7%) of 4-aminophenyl-1-propargyl ether.

Example 8 (Synthesis method 2 of 4-aminophenyl-1-propargyl ether) A 500-ml three-necked flask was equipped with a 200-ml dropping funnel, a three-way cock, and a seam cap, and dried under reduced pressure with argon. Replaced with. 26.91 g (0.16 mol) of 4-nitrophenyl-1-propargyl ether synthesized in Example 4 and 270 ml of dioxane were charged into a reaction vessel. 260.
49 g (1.16 mol) of tin chloride and 270 ml of concentrated hydrochloric acid were added dropwise over 2 hours under ice cooling. The reaction solution was stirred under ice cooling for 1 hour and then 1 liter of 10
It was dropped into a wt% sodium hydroxide aqueous solution. After filtering out the precipitated tin hydroxide, the filtrate was extracted from methylene chloride. After dehydration and filtration, the solvent was distilled off and the precipitated crystals were separated by filtration and recrystallized from toluene. As a result, 20.12.
(Yield; 89.2%) of 4-aminophenyl-1-propargyl ether was obtained. The elemental analysis values and spectrum data of the obtained compound are as shown below.

[Elemental analysis value] Calculated value as C9H9N101: C; 73.46, H; 6.12, N; 9.52 Actual value: C; 73.85, H; 5.98, N; 9.86 [Spectral data] IR (neat, cm ⁻¹ ) ν = 3600-3000,3
000, 2950, 1620, 1600, 1580, 1
495, 1450, 1350, 1295, 1220, 1
160, 990, 905, 860, 780, 735, 6
90. ¹ H-NMR (chloroform-d, ppm) δ = 2.
5 (tr., 1H), 3.5 (br.s., 2H),
4.75 (d., J = 1.2 Hz, 1H), 6.7
(M., 4H)

Application Example 1 A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock, and a seam cap, dried under reduced pressure, and then replaced with argon.
5.77 g (0.01 mol) of bisphenol-A bis (trimerylate) dianhydride, and 6.44 g
(0.02 mol) benzophenonetetracarboxylic dianhydride was charged to the reactor, and then 200 ml of distilled DMF dried over calcium hydride was added. 4.39 g (0.015 mol) of 1,3-bis (3-aminophenoxy) benzene dissolved in 50 ml of DMF was put into the dropping funnel and added dropwise. After stirring for 2 hours at 80 ° C., 4.42 g (0.03 mol) of 4-
Aminophenyl-1-propargyl ether was dissolved in 15 ml of DMF and added to obtain an oligoamic acid.

After the reaction temperature was returned to room temperature, 11 ml of acetic anhydride and 10 ml of pyridine were added to the obtained oligoamic acid to chemically dehydrate and ring it. After the reaction, the reaction solution was poured into 1 liter of methanol to precipitate the imide oligomer. When filtered under reduced pressure with an aspirator and dried in vacuum at 80 ° C. for 48 hours, 17.2 g (yield; 86.3%) of an oligomer was obtained as a pale yellow powder. The spectral data of the obtained oligomer are as shown below.

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3000, 2950, ¹
780, 1750, 1700, 1620, 1600, 1
580, 1495, 1450, 1350, 1295, 1
220, 1160, 990, 905, 860, 780,
735,690.

When the oligomer was B-staged by melting and defoaming in a vacuum oven at 220 ° C., it became a reddish brown powder. Using 8.3 g of B-staged imide oligomer, 220 ° C. for 20 minutes, 250 ° C. for 30 minutes.
Min 12 mm (width) × 12 with a density of 1.39 g / cm ³ by pressing under contact pressure for 1 hour at 270 ° C.
A casting plate of cm (length) × 3.4 mm (thickness) was obtained. When the properties of this casting plate were examined, the bending strength was 58.8 kg.
/ Mm ² , flexural modulus 315 kg / mm ² , impact strength 35
It was a resin having mechanical characteristics of kg · cm / cm ² and glass transition temperature (Tg) of 253 ° C. The moisture absorption rate is 0.2
It was 7%. The results are shown in Table 1.

[Table 1]

Regarding the electrical characteristics of this casting plate,
The dielectric constant and dielectric loss tangent at 1 MHz were examined. The measurement is Q
It was done with a meter. As a result, the dielectric constant was 2.83 and the dielectric loss tangent was 0.0032. The results are shown in Table 2.

[Table 2]

Application Example 2 A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock, and a seam cap, dried under reduced pressure, and then replaced with argon.
5.77 g (0.01 mol) of bisphenol-A bis (trimerylate) dianhydride, and 6.44 g
After charging (0.02 mol) of benzophenonetetracarboxylic dianhydride into the reactor, 200 ml of distilled DMF dried over calcium hydride was added. 4.39 g (0.015 mol) of 1,3-bis (3-) dissolved in 50 ml of DMF in a dropping funnel
Aminophenoxy) benzene was added and added dropwise. 80 ° C
After stirring for 2 hours at 4.12 g (0.03 mol) of 4
-Aminophenyl-1-allyl ether was dissolved in 15 ml of DMF and added to obtain an oligoamic acid.

After the reaction temperature was returned to room temperature, 11 ml of acetic anhydride and 10 ml of pyridine were added to the obtained oligoamic acid to chemically dehydrate and ring it. After the reaction, the reaction solution was poured into 1 liter of methanol to precipitate the imide oligomer. When filtered under reduced pressure with an aspirator and dried in vacuum at 80 ° C. for 48 hours, 18.9 g (yield; 91.5%) of an oligomer was obtained as a pale yellow powder. The spectral data of the obtained oligomer are as shown below.

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3000, 2950, ¹
780, 1750, 1700, 1620, 1600, 1
580, 1495, 1450, 1350, 1295, 1
220, 1160, 990, 905, 860, 780,
735,690.

When the oligomer was B-staged by melting and defoaming in a vacuum oven at 220 ° C., it became a reddish brown powder. Using 7.4 g of B-staged imide oligomer, 220 ° C. for 20 minutes, 250 ° C. for 30 minutes.
Min 12 mm (width) × 12 with a density of 1.41 g / cm ³ by pressing under contact pressure for 1 hour at 270 ° C.
A casting plate of cm (length) × 3.2 mm (thickness) was obtained. When the characteristics of this casting plate were examined, the bending strength was 56.2 kg.
/ Mm ² , flexural modulus 295 kg / mm ² , impact strength 31
The resin had mechanical properties of 231 ° C. and a glass transition temperature (Tg) of kg · cm / cm ² . The moisture absorption rate is 0.1
It was 9%. The results are shown in Table 1. The electrical characteristics were also measured in the same manner as in Application Example 1. As a result, the dielectric constant was 2.75 and the dielectric loss tangent was 0.0035. The results are shown in Table 2.

Application Comparative Example Commercially available imide type thermosetting oligomer (thermid,
Using 9.2 g of Kanebo NSC Co., Ltd.), 20 minutes at 220 ° C. and 3 minutes at 250 ° C. as in the above-mentioned application example.
12 minutes (width) x 12 having a density of 1.41 g / cm ³ by pressing under contact pressure for 0 minutes at 270 ° C for 1 hour, respectively.
A casting plate of cm (length) × 3.2 mm (thickness) was obtained. When the properties of this casting plate were examined in the same manner, the bending strength was 5
6.2 kg / mm ² , flexural modulus 365 kg / mm ² , impact strength 31 kg · cm / cm ² , glass transition temperature (Tg) 29
It was a resin having mechanical properties of 5 ° C. The moisture absorption rate was 0.45%. The results are shown in Table 1. The electrical characteristics were also measured in the same manner as in Application Example 1. As a result, the dielectric constant was 3.45 and the dielectric loss tangent was 0.0100. The results are shown in Table 2.

[0048]

INDUSTRIAL APPLICABILITY The present inventor has newly developed a novel method for producing a reactive primary amine and applied a reactive oligomer whose terminal is terminated with an amine monomer obtained by the production method. Specifically disclosed in the examples. Among them, it was clarified that by using the newly synthesized polyimide, it is possible to obtain a cured product having excellent processing characteristics and extremely high heat resistance that has never been obtained. Furthermore, the reactive imide oligomers exemplified in the present invention have excellent mechanical strength, dimensional stability, and electrical characteristics.
Sex, etc. had. In particular, it has been found that a polyimide having a low moisture absorption can be obtained in which voids and cracks are less likely to occur in the molded product.

That is, a reactive oligomer having a terminal terminated with a primary amine obtained by the novel primary amine production method of the present invention, and a polyimide resin, for example, is used. It can be seen that it is possible to provide materials with extremely high industrial value for a wide range of applications such as various laminated plates, heat-resistant paints, polymer materials for electronic devices, and molding materials. As described above, it is clear that the present invention is extremely useful because it has these many characteristics.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C07C 323/47 7419-4H // C08G 73/10 NTF 9285-4J

Claims (2)

[Claims] 1. A compound represented by the general formula (1) R ₁ R ₂ N-Ar-OH (1) (wherein R ₁ and R ₂ are hydrogen, oxygen, sulfur, lower alkyl,
Lower fluoroalkyl, phenyl, acetyl, benzyl or chemical formula 1 The substituents selected from are shown below. Ar represents a divalent aromatic group. ) And a general formula (2) R ₃ -R ₄ -(-CH _2- ) _n -O-Ts (2) (wherein R ₃ is selected from hydrogen, lower alkyl, and lower fluoroalkyl). R ₄ is a substituent represented by the following formula: The substituents selected from are shown below. n shows the positive integer of 0-10. Ts represents a p-toluenesulfonic acid group. ) Is obtained by reacting a tosylate represented by the formula (3) with R ₁ R ₂ N-Ar-O-(-CH _2- ) _n -R ₄ -R ₃ (3). A compound represented by the formula (4) H ₂ N-Ar-O-(-CH _2- ) _n -R ₄ -R ₃ (4) can be represented by the method of either reduction or dealkylation or both. A method for producing a primary amine having a thermosetting group, which comprises producing the primary amine described above. 2. The Ar is represented by Chemical Formula 3 The method for producing a primary amine having a thermosetting group according to claim 1, which is a divalent aromatic group selected from the group consisting of: