JPH054955A - New azomethine group-containing norbornene derivative, production thereof and production of polymer thereof - Google Patents

Abstract

PURPOSE:To obtain a new azomethine group-containing norbornene derivative useful as structural member, electric and electronic part material, having specific various functions such as heat resistance, conductivity, liquid crystal and biodegradability. CONSTITUTION:An azomethine group-containing norbornene derivative shown by formula I (R is H, 1-3C alkyl or 2-5C alkenyl; X is 6-18C aromatic residue) such as a compound shown by formula II. The compound shown by formula I is obtained by heating a 2-formylnorbornene compound shown by formula III with an aromatic diamine shown by the formula H2N-X-NH2 at room temperature to about 180 deg.C. The compound shown by formula I has good workability such as a low melting point and ready solvent solubility and is made into a high molecular weight compound by ready reaction of norbornene ring.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel azomethine group-containing norbornene derivative obtained from a 2-formylnorbornene compound and an aromatic diamine, a process for producing the same, and a process for producing a polymer thereof. The azomethine group-containing norbornene derivative of the present invention Provides polymers excellent in heat resistance and flame retardancy by molding methods such as cast molding, injection molding and compression molding, and they are useful as structural members, electric and electronic parts materials.

[0002]

2. Description of the Related Art Materials used with the progress of science and technology are required to have higher performance and higher functions, and various materials have been developed to meet the demand.

Under such circumstances, azomethine group-containing compounds and polymers thereof have recently attracted attention because they have various unique functions such as heat resistance, conductivity, liquid crystallinity and biodegradability.

Since polyazomethine can be obtained very easily (for example, at room temperature) by reacting a dialdehyde with a diamine, and the polymer has excellent heat resistance, various studies have been conducted for a long time. However, since this polymerization reaction is a condensation type, there is a drawback that condensation water is generated during the polymerization, and as the polymer has a higher molecular weight, the solubility in a solvent is decreased and the water is precipitated out of the system.

On the other hand, various high-performance polymers called so-called super engineering plastics (engineering plastics) such as polyetherketone, polyphenylene sulfide, and polyimide are on the market, and expectations for polyimide are particularly great.

Aromatic imide compounds having a norbornene ring at both ends (bisnadiimide compound) have been attracting attention as an addition type polyimide resin raw material having extremely high heat resistance, and a part of them has been put to practical use as a matrix for so-called advanced composite materials. ing. However, aromatic bisnadiimide compounds generally have high melting points and poor solubility in solvents, and are therefore difficult to handle. Further, since the nadimide compound is poor in reactivity, harsh reaction conditions (for example, high temperature such as 300 ° C.) are required to make the compound have a high molecular weight. However, under such reaction conditions, in addition to the intended high molecular weight reaction, the reverse Diels-Al of the norbornene ring is
It is said that the der reaction partially occurs, and the highly volatile cyclopentadiene generated therein causes significant bubbles (voids) in the molded body.

In order to suppress such foaming, the molding method is limited to a method of reacting under high temperature and pressure (for example, an autoclave molding method), or an acid anhydride (ester) which is a raw material of imide and a diamine are used as solvents. There is a drawback in that its usage is considerably limited, such as melting and oligomerization to use as a varnish.

[0008]

The object of the present invention to solve the above-mentioned drawbacks of the prior art is that it has a low melting point, is easily soluble in a solvent, has good workability, and the norbornene ring easily reacts. It is an object of the present invention to provide a novel compound having a high molecular weight, a method for producing the same, and a method for easily producing a polymer having excellent heat resistance and flame retardancy.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a novel azomethine group-containing norbornene derivative having a certain structure satisfies these conditions, The present invention has been completed.

The gist of the present invention is, firstly, the general formula [1]

[Chemical 3] (Wherein R represents hydrogen, a C _{1 to} C ₃ , preferably a C _{1 to} C ₂ alkyl group or a C _{2 to} C ₅ , preferably a C _{2 to} C ₄ alkenyl group, and X represents C _{6 to} C ₁₈ , Preferably C _{6 to} C
Represents ₁₄ aromatic residues. ) Azomethine group-containing norbornene derivative (hereinafter referred to as compound [1]) represented by the following), secondly in the method for producing compound [1], and thirdly, heat resistance and flame retardancy using compound [1] as a polymerization raw material. A method for producing a polymer having excellent properties.

The present invention will be described in detail. The compound [1] is represented by the following general formula [3]:

[Chemical 4] (Wherein R represents hydrogen, a C _{1 to} C ₃ , preferably a C _{1 to} C ₂ alkyl group, or a C _{2 to} C ₅ , preferably a C _{2 to} C ₄ alkenyl group) Norbornene compound (hereinafter referred to as compound [3]) and general formula [4] H ₂ N—X—NH ₂ (where X is C _{6 to} C ₁₈ ,
Aromatic diamine compound represented by preferably C _{6 to} C ₁₄ aromatic residue) (hereinafter referred to as compound [4])
Is synthesized as a raw material.

As typical ones of the above compound [3],
For example, 2-formylnorbornene; an alkyl-substituted-2-formylnorbornene compound such as methyl-, ethyl- or propyl-2-formylnorbornene, preferably methyl-2-formylnorbornene; vinyl-, propenyl-, butenyl- or Examples include alkenyl-substituted 2-formylnorbornene compounds such as pentenyl-2-formylnorbornene, preferably allyl-2-formylnorbornene and isopropenyl-2-formylnorbornene.

Representative examples of the above compound [4] include, for example, o-, m-, p-phenylenediamine,
Tolylenediamine, dimethylphenylenediamine, xylylenediamine, benzidine, o-tolidine, diaminoterphenyl, diaminodiphenylether, diaminodiphenylsulfone, diaminodiphenylsulfide, diaminobenzophenone, methylenedianiline, ethylenedianiline, propylenedianiline or isopropylidene. Examples thereof include dendianiline, preferably o-,
m-, p-phenylenediamine, tolylene-2,4-diamine, o-tolidine, or 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'- Examples thereof include diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, isopropylidenedianiline and the like.

The compound [1] is obtained by reacting the compound [3] and the compound [4] as described above in the presence or absence of a solvent at room temperature to 180 ° C., preferably 50 to 150 ° C. It is synthesized by reacting for 1 to 10 hours, preferably 1 to 8 hours. The reaction pressure is not important in this reaction and is not particularly limited. As the reaction solvent, a general-purpose solvent is used, and examples thereof include benzene, hexane, ether, ethyl acetate, pyridine and the like. In this case, an acid catalyst such as hydrochloric acid or sulfuric acid or an alkali catalyst such as sodium hydroxide or potassium carbonate may be used as the catalyst. Since the reaction between the compound [3] and the compound [4] proceeds extremely easily, a catalyst is not usually required.

The compound [1] thus synthesized is usually a viscous liquid, a semi-solid or a solid at room temperature and has a melting point of about 120 ° C. or lower. And, they are easily dissolved in general-purpose solvents such as ketones, ethers, esters, aromatic hydrocarbons and halogenated hydrocarbons, and special polar solvents such as pyridine, DMF, DMSO and N-methylpyrrolidone.

In order to polymerize the compound [1], a molding method such as direct casting, injection molding, compression molding or the like can be used.
At a temperature of 250 ° C., preferably 150-220 ° C.,
Polymerization is carried out by heating for 5 to 30 hours, preferably 1 to 20 hours. Depending on the purpose of use and the ease of molding, the compound [1] may be previously oligomerized and then polymerized and molded under the above conditions. In this case, the compound [1] is treated under atmospheric pressure or under reduced pressure, preferably under reduced pressure,
The oligomerization is carried out by heat treatment at a temperature of 80 to 150 ° C., preferably 100 to 130 ° C. for 0.1 to 20 hours, preferably 1 to 10 hours.

The molded body obtained by the above molding method is
0.5 to 30 at a temperature of 200 to 350 ° C. if necessary
You may heat-process for a further time.

During the polymerization molding, various fillers, if necessary,
For example, glass fiber, carbon fiber, metal fiber, calcium phosphate, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, antimony oxide, gypsum, silica, alumina, clay, talc, quartz powder, carbon black, etc. are used as the compound [1]. 10 to 100 copies
There is no problem even if 500 parts are mixed.

When the starting compound [3] used in the method of the present invention is a substituted-2-formylnorbornene, such as methyl-2-formylnorbornene, it contains 20 types of isomer structures, Isolation of each of the isomers is virtually impossible and industrially wasteful. Similarly, the compound [1] synthesized from such a substituted-2-formyl norbornene consists of a very large number of isomers, isolation of those isomers is essentially impossible, and industrially no It is meaningless.

[0020]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 287.5 g was added to a flask having a volume of 1 l and being purged with nitrogen.
(1.45 mol) of 4,4′-diaminodiphenylmethane (hereinafter referred to as DDM) was added, and the mixture was heated to 120 ° C. and melted under stirring to give 389.8 g (3.20 mol) of 5-norbornene- 2-carbaldehyde (hereinafter N-Al
d)) was added dropwise. In a nitrogen atmosphere, with stirring 1
After heating at 20 ℃ for 1 hour, under reduced pressure of 2-3 mmHg, 100
When water and unreacted substances formed by treatment at ℃ were removed, 562.5 g of a substance having a melting point of 50 to 60 ° C. (by a trace melting point measuring device, the same applies hereinafter) was obtained. It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 40.
6 (theoretical value 406.25), elemental analysis value (wt%) is C:
The values were 85.77 (theoretical value 85.66), H: 8.01 (theoretical value 7.44), and N: 6.85 (theoretical value 6.90). The IR spectrum is shown in FIG. 1 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 720 cm ⁻¹ : Norbornene ring C-H bending vibration based on cis-2 substituted alkene structure

Example 2 13.4 g (0.
11 mol) N-Ald and 10.0 g (0.05 mol) 4,4'-diaminodiphenyl ether (hereinafter D
DE)) was added and heated at 100 ° C. for 1 hour with stirring. Then, under a reduced pressure of 2 to 3 mmHg, the mixture was treated at 80 to 90 ° C. to remove water and unreacted substances.
19.5 g of a substance having a melting point of 75 to 84 ° C. was obtained.
It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 40.
8 (theoretical value 408.24), elemental analysis value (wt%) is C:
It was 82.21 (theoretical value 82.31), H: 7.01 (theoretical value 6.91), and N: 6.83 (theoretical value 6.86). The IR spectrum is shown in FIG. 3 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 1240 cm ⁻¹ : Ether C-O-C antisymmetric vibration 720 cm ^-1 : C-H bending vibration based on cis-2 substituted alkene structure of norbornene ring

EXAMPLE 3 13.4 g (0.
11 mol) N-Ald and 5.4 g (0.05 mol) p-phenylenediamine (hereinafter referred to as p-PD).
Was added and heated at 100 ° C. for 1 hour with stirring, and then treated at 80 to 90 ° C. under a reduced pressure of 2 to 3 mmHg to remove water and unreacted products, which showed a melting point of 75 to 76 ° C. 15.1 g of material was obtained. This material is I
From the results of R, NMR, mass spectrometry and elemental analysis, it was found to be the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 31.
6 (theoretical value: 316.20), elemental analysis value (wt%) is C:
It was 83.55 (theoretical value 83.49), H: 7.82 (theoretical value 7.65), and N: 8.90 (theoretical value 8.86). The IR spectrum is shown in FIG. 5 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 720 cm ⁻¹ : Norbornene ring C-H bending vibration based on cis-2 substituted alkene structure

EXAMPLE 4 9.9 g (0.0
5 mol) of DDM, and heated to 100 ° C. to melt,
15.0 g (0.11 mol) of methyl-5-norbornene-2-carbaldehyde (hereinafter referred to as MN-Ald) was added dropwise and heated at 100 ° C. for 1 hour while stirring. Then, the reaction mixture was treated at 80 to 90 ° C. under a reduced pressure of 2 to 3 mmHg to remove water and unreacted substances, and 20.5 g of a semisolid substance at room temperature was obtained. This substance is IR, NM
From the results of R, mass spectrometry and elemental analysis, it was found to be the compound shown in Table 1. 94% yield based on diamine
Met.

The molecular weight of this substance by mass spectrometry is 43.
4 (theoretical value 434.28), elemental analysis value (wt%) is C:
The values were 85.33 (theoretical value 85.66), H: 8.00 (theoretical value 7.89), and N: 16.55 (theoretical value 16.45). The IR spectrum is shown in FIG. 7 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 1450 cm ⁻¹ : CH ₃ antisymmetric deformation vibration 1380cm of ^-1: CH ₃ symmetric deformation vibration 720 cm ^-1: CH deformation vibration based on cis-disubstituted alkene structure norbornene ring

Example 5 15.0 (0.1
1 mol) g MN-Ald and 10.0 g (0.05
Mol) of DDE was added and heated at 100 ° C. for 1 hour with stirring. Then, under reduced pressure of 2-3 mmHg, 80-90 ° C
When the water and unreacted substances produced by the treatment with were removed, 21.0 g of a semi-solid substance at room temperature was obtained. It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 43.
6 (theoretical value 436.27), elemental analysis value (wt%) is C:
It was 82.46 (theoretical value 82.52), H: 7.52 (theoretical value 7.39), and N: 6.46 (theoretical value 6.42). The IR spectrum is shown in FIG. 9 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 1450 cm ⁻¹ : CH ₃ Antisymmetric bending vibration of 1380 cm ⁻¹ : CH ₃ symmetric bending vibration of 1240 cm ⁻¹ : C—O—C antisymmetric stretching vibration of ether 720 cm ⁻¹ : C—H based on cis-2 substituted alkene structure of norbornene ring Bending vibration

Example 6 15.0 g (0.
11 mol) MN-Ald and 5.4 g (0.05
Mol) of p-PD was added, and the mixture was heated with stirring at 100 ° C. for 1 hour. Then, under reduced pressure of 2-3 mmHg, 80-90
When water and unreacted substances formed by treatment at ℃ were removed, 16.5 g of a semi-solid substance was obtained at room temperature. It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 34.
4 (theoretical value 344.24), elemental analysis value (wt%) is C:
The values were 83.80 (theoretical value 83.66), H: 8.50 (theoretical value 8.20), and N: 8.22 (theoretical value 8.14). The IR spectrum is shown in FIG. 11 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 1450 cm ⁻¹ : CH ₃ antisymmetric deformation vibration 1380cm of ^-1: CH ₃ symmetric deformation vibration 720 cm ^-1: CH deformation vibration based on cis-disubstituted alkene structure norbornene ring

Example 7 In a flask having a volume of 50 l and being purged with nitrogen, 9.9 g (0.
(05 mol) DDM was added, and the mixture was heated to 100 ° C. and melted, and 17.8 g (0.12 mol) of allyl-5 was added.
-Norbornene-2-carbaldehyde (hereinafter AN-Al
d) was added dropwise, and the mixture was heated with stirring at 100 ° C. for 1 hour. Then, under a reduced pressure of 2 to 3 mmHg, the mixture was treated at 80 to 90 ° C. to remove water and unreacted substances.
22.3 g of a semi-solid substance was obtained at room temperature. This substance is shown in Table 1 from the results of IR, NMR, mass spectrometry and elemental analysis.
It was found to be the compound shown in. The yield based on diamine was 92%.

The molecular weight of this substance by mass spectrometry is 48.
6 (theoretical value 486.32), elemental analysis value (wt%) is C:
It was 86.52 (theoretical value 86.36), H: 7.93 (theoretical value 7.88), and N: 5.80 (theoretical value 5.76). The IR spectrum is shown in FIG. 13 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 910, 990 cm ⁻¹ : Out-of-plane bending vibration of allyl group C—H 720 cm ⁻¹ : CH bending vibration based on cis-2-substituted alkene structure of norbornene ring

Example 8 17.8 g (0.
12 moles of AN-Ald and 10.0 g (0.05
Mol) of DDE was added and heated at 100 ° C. for 1 hour with stirring. Then, under reduced pressure of 2-3 mmHg, 80-90 ° C
When the water and unreacted substances generated by the treatment with were removed, 23.5 g of a semi-solid substance at room temperature was obtained. It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 48.
8 (theoretical value 488.30), elemental analysis value (wt%) is C:
It was 83.46 (theoretical value 83.56), H: 7.52 (theoretical value 7.43), and N: 5.71 (theoretical value 5.74). The IR spectrum is shown in FIG. 15 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 1240 cm ⁻¹ : Ether C-O-C antisymmetric stretching vibration 910, 990 cm ^-1 : out-of-plane bending vibration of allyl group C-H 1240 cm ^-1 : ether C-O-C antisymmetric stretching vibration 720 cm ^-1 : cis of norbornene ring C-H bending vibration based on -2-substituted alkene structure

Example 9 17.8 g (0.
12 mol) of AN-Ald and 5.4 g (0.05 mol) of p-PD were added and heated with stirring at 100 ° C for 1 hour. Then, under reduced pressure of 2-3 mmHg, 80-90 ° C
When the water and unreacted substances generated by the treatment with were removed, 19.2 g of a semi-solid substance at room temperature was obtained. It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 39.
6 (theoretical value 396.27), elemental analysis value (wt%) is C:
The values were 84.71 (theoretical value 84.79), H: 8.30 (theoretical value 8.14), and N: 7.07 (theoretical value 7.07). The IR spectrum is shown in FIG. 17 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 910, 990 cm ⁻¹ : Out-of-plane bending vibration of allyl group C—H 720 cm ⁻¹ : CH bending vibration based on cis-2-substituted alkene structure of norbornene ring

[0047]

[Table 1]

Example 10 100 g of the azomethine group-containing norbornene derivative obtained in Example 1 was heated at 120 ° C. for 10 hours under reduced pressure of 2-3 mmHg.
After the time treatment, 99 g of an oligomer having a melting point of 97 to 105 ° C. was obtained.

Example 11 The polymer obtained by heat-treating the azomethine group-containing norbornene derivative obtained in Example 1 under reduced pressure of 3 mmHg at 160 to 170 ° C. for 1 hour and then at 190 to 200 ° C. for 1 hour was obtained. Further, it was post-cured at 250 ° C. for 6 hours under atmospheric pressure to be completely cured.

The cured product was insoluble in various solvents and exhibited a glossy black color, and its specific gravity was 1.158. Further, when a thermal analysis test was conducted on this product, the following results were obtained.

Thermal loss onset temperature of fine powder: 298 ° C. Glass transition temperature (Tg): 281 ° C. Thermal expansion coefficient (25 ° C. to Tg): 1.10 × 10 ⁻⁴ (1 /
℃)

It is considered that the polymer obtained by this reaction was not obtained by simply reacting only the norbornene ring, but was also obtained by reacting the double bond of the azomethine group in the polymerization raw material. That is, the IR of the polymer obtained in this Example
This is also supported by the weaker absorption based on C = N at 1640 cm ^{−1 in} the spectrum as compared with FIG. 1, which is the IR spectrum of the polymerization raw material. Example 12 A cured product obtained by heat-treating under exactly the same conditions as in Example 11 except that the post-cure conditions were changed as follows was subjected to the same thermal analysis test, and the following results were obtained. Was obtained.

[0053]

[Table 2]

Example 13 The azomethine group-containing norbornene derivative obtained in Example 2 was heat-treated at 180 ° C. for 5 hours under normal pressure, and then 200
It was post-cured at 24 ° C. for 24 hours to be completely cured. The cured product was insoluble in various solvents and exhibited a glossy black color. When a thermal analysis test was conducted, the decomposition start temperature was 300 ° C.

Example 14 In Example 13, the post cure conditions were 250 ° C. and 5
When the same heat treatment was performed except that the time was changed, the obtained cured product was insoluble in various solvents and exhibited a glossy black color. When a thermal analysis test was performed, the decomposition start temperature was 308 ° C.

Example 15 The azomethine group-containing norbornene derivative obtained in Example 3 was subjected to the same heat treatment and post cure as in Example 13 to completely cure it. The cured product is insoluble in various solvents,
When it showed a glossy black color and was subjected to a thermal analysis test, the decomposition initiation temperature was 338 ° C.

Example 16 The azomethine group-containing norbornene derivative obtained in Example 4 was subjected to the same heat treatment and post cure as in Example 13 to completely cure it. The cured product is insoluble in various solvents,
It showed a glossy black color and was subjected to a thermal analysis test to find that the decomposition initiation temperature was 252 ° C.

Example 17 In Example 16, the post cure conditions were 250 ° C. and 8 ° C.
When the same heat treatment was performed except that the time was changed, the obtained cured product was insoluble in various solvents and exhibited a glossy black color. When a thermal decomposition test was performed, the decomposition start temperature was 266 ° C. Example 18 The azomethine group-containing norbornene derivative obtained in Example 5 was subjected to the same heat treatment and post cure as in Example 13 to be completely cured. The cured product is insoluble in various solvents,
When it showed a glossy black color and was subjected to a thermal analysis test, the decomposition initiation temperature was 273 ° C.

Example 19 The azomethine group-containing norbornene derivative obtained in Example 6 was subjected to the same heat treatment and post cure as in Example 13 to completely cure it. The cured product is insoluble in various solvents,
When it showed a glossy black color and was subjected to a thermal analysis test, the decomposition start temperature was 281 ° C.

Example 20 The azomethine group-containing norbornene derivative obtained in Example 7 was subjected to the same heat treatment and post cure as in Example 13 to completely cure it. The cured product is insoluble in various solvents,
It showed a glossy black color and was subjected to a thermal analysis test to find that the decomposition start temperature was 317 ° C.

Example 21 In Example 20, the post cure conditions were 250 ° C. and 8 ° C.
When the same heat treatment was performed except that the time was changed, the obtained cured product was insoluble in various solvents and exhibited a glossy black color. When a thermal analysis test was performed, the decomposition start temperature was 328 ° C. Example 22 The azomethine group-containing norbornene derivative obtained in Example 8 was subjected to the same heat treatment and post cure as in Example 13 to be completely cured. The cured product is insoluble in various solvents,
When it showed a glossy black color and was subjected to a thermal analysis test, the decomposition start temperature was 337 ° C.

Example 23 The azomethine group-containing norbornene derivative oligomer obtained in Example 10 was heat-treated at 180 ° C. for 5 hours under atmospheric pressure, and postcured at 210 ° C. for 20 hours under atmospheric pressure to obtain a black cured product. Got This cured product had a glass transition temperature (Tg) of 277 ° C and a thermal decomposition initiation temperature of 296 ° C.

[0063]

The azomethine group-containing norbornene derivative of the present invention has a low melting point and is soluble in various solvents, so that it is easy to handle. Further, since harsh polymerization conditions are not required, polymerization molding can be easily performed by molding methods such as cast molding, injection molding and compression molding. Further, since the molded product is excellent in heat resistance, flame retardancy, etc., it is useful as a structural member, a material for electric and electronic parts.

[0064]

[Brief description of drawings]

1 is an IR spectrum of an azomethine group-containing norbornene derivative obtained in Example 1.

2 is a ¹ H-NMR spectrum of the azomethine group-containing norbornene derivative obtained in Example 1. FIG.

FIG. 3 is an IR spectrum of the azomethine group-containing norbornene derivative obtained in Example 2.

FIG. 4 is a ¹ H-NMR spectrum of the azomethine group-containing norbornene derivative obtained in Example 2.

5 is an IR spectrum of the azomethine group-containing norbornene derivative obtained in Example 3. FIG.

FIG. 6 is a ¹ H-NMR spectrum of the azomethine group-containing norbornene derivative obtained in Example 3.

FIG. 7 is an IR spectrum of the azomethine group-containing norbornene derivative obtained in Example 4.

8 is a ¹ H-NMR spectrum of the azomethine group-containing norbornene derivative obtained in Example 4. FIG.

9 is an IR spectrum of the azomethine group-containing norbornene derivative obtained in Example 5. FIG.

FIG. 10 is a ¹ H-NMR spectrum of the azomethine group-containing norbornene derivative obtained in Example 5.

11 is an IR spectrum of the azomethine group-containing norbornene derivative obtained in Example 6. FIG.

FIG. 12 is a ¹ H-NMR spectrum of an azomethine group-containing norbornene derivative obtained in Example 6.

13 is an IR spectrum of the azomethine group-containing norbornene derivative obtained in Example 7. FIG.

FIG. 14 is a ¹ H-NMR spectrum of an azomethine group-containing norbornene derivative obtained in Example 7.

15 is an IR spectrum of the azomethine group-containing norbornene derivative obtained in Example 8. FIG.

16 is a ¹ H-NMR spectrum of the azomethine group-containing norbornene derivative obtained in Example 8. FIG.

FIG. 17 is an IR spectrum of the azomethine group-containing norbornene derivative obtained in Example 9.

18 is a ¹ H-NMR spectrum of the azomethine group-containing norbornene derivative obtained in Example 9. FIG.

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[Procedure amendment]

[Submission date] June 4, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 8

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel azomethine group-containing norbornene derivative obtained from a 2-formylnorbornene compound and an aromatic diamine, a process for producing the same, and a process for producing a polymer thereof. The azomethine group-containing norbornene derivative of the present invention Provides polymers excellent in heat resistance and flame retardancy by molding methods such as cast molding, injection molding and compression molding, and they are useful as structural members, electric and electronic parts materials.

[0002]

2. Description of the Related Art Materials used with the progress of science and technology are required to have higher performance and higher functions, and various materials have been developed to meet the demand.

Under such circumstances, azomethine group-containing compounds and polymers thereof have recently attracted attention because they have various unique functions such as heat resistance, conductivity, liquid crystallinity and biodegradability.

Since polyazomethine can be obtained very easily (for example, at room temperature) by reacting a dialdehyde with a diamine, and the polymer has excellent heat resistance, various studies have been conducted for a long time. However, since this polymerization reaction is a condensation type, there is a drawback that condensation water is generated during the polymerization, and as the polymer has a higher molecular weight, the solubility in a solvent is decreased and the water is precipitated out of the system.

On the other hand, various high-performance polymers called so-called super engineering plastics (engineering plastics) such as polyetherketone, polyphenylene sulfide, and polyimide are on the market, and expectations for polyimide are particularly great.

Aromatic imide compounds having a norbornene ring at both ends (bisnadiimide compound) have been attracting attention as an addition type polyimide resin raw material having extremely high heat resistance, and a part of them has been put to practical use as a matrix for so-called advanced composite materials. ing. However, aromatic bisnadiimide compounds generally have high melting points and poor solubility in solvents, and are therefore difficult to handle. Further, since the nadimide compound is poor in reactivity, harsh reaction conditions (for example, high temperature such as 300 ° C.) are required to make the compound have a high molecular weight. However, under such reaction conditions, in addition to the intended high molecular weight reaction, the reverse Diels-Al of the norbornene ring is
It is said that the der reaction partially occurs, and the highly volatile cyclopentadiene generated therein causes significant bubbles (voids) in the molded body.

In order to suppress such foaming, the molding method is limited to a method of reacting under high temperature and pressure (for example, an autoclave molding method), or an acid anhydride (ester) which is a raw material of imide and a diamine are used as solvents. There is a drawback in that its usage is considerably limited, such as melting and oligomerization to use as a varnish.

[0008]

The object of the present invention to solve the above-mentioned drawbacks of the prior art is that it has a low melting point, is easily soluble in a solvent, has good workability, and the norbornene ring easily reacts. It is an object of the present invention to provide a novel compound having a high molecular weight, a method for producing the same, and a method for easily producing a polymer having excellent heat resistance and flame retardancy.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a novel azomethine group-containing norbornene derivative having a certain structure satisfies these conditions, The present invention has been completed.

The gist of the present invention is, firstly, the general formula [1]

[Chemical 3] (Wherein R represents hydrogen, a C _{1 to} C ₃ , preferably a C _{1 to} C ₂ alkyl group or a C _{2 to} C ₅ , preferably a C _{2 to} C ₄ alkenyl group, and X represents C _{6 to} C ₁₈ , Preferably C _{6 to} C
Represents ₁₄ aromatic residues. ) Azomethine group-containing norbornene derivative (hereinafter referred to as compound [1]) represented by the following), secondly in the method for producing compound [1], and thirdly, heat resistance and flame retardancy using compound [1] as a polymerization raw material. A method for producing a polymer having excellent properties.

The present invention will be described in detail. The compound [1] is represented by the following general formula [3]:

[Chemical 4] (Wherein R represents hydrogen, a C _{1 to} C ₃ , preferably a C _{1 to} C ₂ alkyl group, or a C _{2 to} C ₅ , preferably a C _{2 to} C ₄ alkenyl group) Norbornene compound (hereinafter referred to as compound [3]) and general formula [4] H ₂ N—X—NH ₂ (where X is C _{6 to} C ₁₈ ,
Aromatic diamine compound represented by preferably C _{6 to} C ₁₄ aromatic residue) (hereinafter referred to as compound [4])
Is synthesized as a raw material.

As typical ones of the above compound [3],
For example, 2-formylnorbornene; an alkyl-substituted-2-formylnorbornene compound such as methyl-, ethyl- or propyl-2-formylnorbornene, preferably methyl-2-formylnorbornene; vinyl-, propenyl-, butenyl- or Examples include alkenyl-substituted 2-formylnorbornene compounds such as pentenyl-2-formylnorbornene, preferably allyl-2-formylnorbornene and isopropenyl-2-formylnorbornene.

Representative examples of the above compound [4] include, for example, o-, m-, p-phenylenediamine,
Tolylenediamine, dimethylphenylenediamine, xylylenediamine, benzidine, o-tolidine, diaminoterphenyl, diaminodiphenylether, diaminodiphenylsulfone, diaminodiphenylsulfide, diaminobenzophenone, methylenedianiline, ethylenedianiline, propylenedianiline or isopropylidene. Examples thereof include dendianiline, preferably o-,
m-, p-phenylenediamine, tolylene-2,4-diamine, o-tolidine, or 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'- Examples thereof include diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, isopropylidenedianiline and the like.

The compound [1] is obtained by reacting the compound [3] and the compound [4] as described above in the presence or absence of a solvent at room temperature to 180 ° C., preferably 50 to 150 ° C. It is synthesized by reacting for 1 to 10 hours, preferably 1 to 8 hours. The reaction pressure is not important in this reaction and is not particularly limited. As the reaction solvent, a general-purpose solvent is used, and examples thereof include benzene, hexane, ether, ethyl acetate, pyridine and the like. In this case, an acid catalyst such as hydrochloric acid or sulfuric acid or an alkali catalyst such as sodium hydroxide or potassium carbonate may be used as the catalyst. Since the reaction between the compound [3] and the compound [4] proceeds extremely easily, a catalyst is not usually required.

The compound [1] thus synthesized is usually a viscous liquid, a semi-solid or a solid at room temperature and has a melting point of about 120 ° C. or lower. And, they are easily dissolved in general-purpose solvents such as ketones, ethers, esters, aromatic hydrocarbons and halogenated hydrocarbons, and special polar solvents such as pyridine, DMF, DMSO and N-methylpyrrolidone.

In order to polymerize the compound [1], a molding method such as direct casting, injection molding, compression molding or the like can be used.
At a temperature of 250 ° C., preferably 150-220 ° C.,
Polymerization is carried out by heating for 5 to 30 hours, preferably 1 to 20 hours. Depending on the purpose of use and the ease of molding, the compound [1] may be previously oligomerized and then polymerized and molded under the above conditions. In this case, the compound [1] is treated under atmospheric pressure or under reduced pressure, preferably under reduced pressure,
The oligomerization is carried out by heat treatment at a temperature of 80 to 150 ° C., preferably 100 to 130 ° C. for 0.1 to 20 hours, preferably 1 to 10 hours.

The molded body obtained by the above molding method is
0.5 to 30 at a temperature of 200 to 350 ° C. if necessary
You may heat-process for a further time.

During the polymerization molding, various fillers, if necessary,
For example, glass fiber, carbon fiber, metal fiber, calcium phosphate, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, antimony oxide, gypsum, silica, alumina, clay, talc, quartz powder, carbon black, etc. are used as the compound [1]. 10 to 100 copies
There is no problem even if 500 parts are mixed.

When the starting compound [3] used in the method of the present invention is a substituted-2-formylnorbornene, such as methyl-2-formylnorbornene, it contains 20 types of isomer structures, Isolation of each of the isomers is virtually impossible and industrially wasteful. Similarly, the compound [1] synthesized from such a substituted-2-formyl norbornene consists of a very large number of isomers, isolation of those isomers is essentially impossible, and industrially no It is meaningless.

[0020]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 287.5 g was added to a flask having a volume of 1 l and being purged with nitrogen.
(1.45 mol) of 4,4′-diaminodiphenylmethane (hereinafter referred to as DDM) was added, and the mixture was heated to 120 ° C. and melted under stirring to give 389.8 g (3.20 mol) of 5-norbornene- 2-carbaldehyde (hereinafter N-Al
d)) was added dropwise. In a nitrogen atmosphere, with stirring 1
After heating at 20 ℃ for 1 hour, under reduced pressure of 2-3 mmHg, 100
When water and unreacted substances formed by treatment at ℃ were removed, 562.5 g of a substance having a melting point of 50 to 60 ° C. (by a trace melting point measuring device, the same applies hereinafter) was obtained. It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 40.
6 (theoretical value 406.25), elemental analysis value (wt%) is C:
The values were 85.77 (theoretical value 85.66), H: 8.01 (theoretical value 7.44), and N: 6.85 (theoretical value 6.90). The IR spectrum is shown in FIG. 1 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 720 cm ⁻¹ : Norbornene ring C-H bending vibration based on cis-2 substituted alkene structure

Example 2 13.4 g (0.
11 mol) N-Ald and 10.0 g (0.05 mol) 4,4'-diaminodiphenyl ether (hereinafter D
DE)) was added and heated at 100 ° C. for 1 hour with stirring. Then, under a reduced pressure of 2 to 3 mmHg, the mixture was treated at 80 to 90 ° C. to remove water and unreacted substances.
19.5 g of a substance having a melting point of 75 to 84 ° C. was obtained.
It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 40.
8 (theoretical value 408.24), elemental analysis value (wt%) is C:
It was 82.21 (theoretical value 82.31), H: 7.01 (theoretical value 6.91), and N: 6.83 (theoretical value 6.86). The IR spectrum is shown in FIG. 3 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows: 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 1240 cm ⁻¹ : Ether C-O-C antisymmetric vibration 720 cm ^-1 : C-H bending vibration based on cis-2 substituted alkene structure of norbornene ring

EXAMPLE 3 13.4 g (0.
11 mol) N-Ald and 5.4 g (0.05 mol) p-phenylenediamine (hereinafter referred to as p-PD).
Was added and heated at 100 ° C. for 1 hour with stirring, and then treated at 80 to 90 ° C. under a reduced pressure of 2 to 3 mmHg to remove water and unreacted products, which showed a melting point of 75 to 76 ° C. 15.1 g of material was obtained. This material is I
From the results of R, NMR, mass spectrometry and elemental analysis, it was found to be the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 31.
6 (theoretical value: 316.20), elemental analysis value (wt%) is C:
It was 83.55 (theoretical value 83.49), H: 7.82 (theoretical value 7.65), and N: 8.90 (theoretical value 8.86). The IR spectrum is shown in FIG. 5 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 720 cm ⁻¹ : Norbornene ring C-H bending vibration based on cis-2 substituted alkene structure

EXAMPLE 4 9.9 g (0.0
5 mol) of DDM, and heated to 100 ° C. to melt,
15.0 g (0.11 mol) of methyl-5-norbornene-2-carbaldehyde (hereinafter referred to as MN-Ald) was added dropwise and heated at 100 ° C. for 1 hour while stirring. Then, the reaction mixture was treated at 80 to 90 ° C. under a reduced pressure of 2 to 3 mmHg to remove water and unreacted substances, and 20.5 g of a semisolid substance at room temperature was obtained. This substance is IR, NM
From the results of R, mass spectrometry and elemental analysis, it was found to be the compound shown in Table 1. 94% yield based on diamine
Met.

The molecular weight of this substance by mass spectrometry is 43.
4 (theoretical value 434.28), elemental analysis value (wt%) is C:
The values were 85.33 (theoretical value 85.66), H: 8.00 (theoretical value 7.89), and N: 16.55 (theoretical value 16.45). The IR spectrum is shown in FIG. 7 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 1450 cm ⁻¹ : CH ₃ antisymmetric deformation vibration 1380cm of ^-1: CH ₃ symmetric deformation vibration 720 cm ^-1: CH deformation vibration based on cis-disubstituted alkene structure norbornene ring

Example 5 15.0 (0.1
1 mol) g MN-Ald and 10.0 g (0.05
Mol) of DDE was added and heated at 100 ° C. for 1 hour with stirring. Then, under reduced pressure of 2-3 mmHg, 80-90 ° C
When the water and unreacted substances produced by the treatment with were removed, 21.0 g of a semi-solid substance at room temperature was obtained. It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 43.
6 (theoretical value 436.27), elemental analysis value (wt%) is C:
It was 82.46 (theoretical value 82.52), H: 7.52 (theoretical value 7.39), and N: 6.46 (theoretical value 6.42). The IR spectrum is shown in FIG. 9 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 1450 cm ⁻¹ : CH ₃ Antisymmetric bending vibration of 1380 cm ⁻¹ : CH ₃ symmetric bending vibration of 1240 cm ⁻¹ : C—O—C antisymmetric stretching vibration of ether 720 cm ⁻¹ : C—H based on cis-2 substituted alkene structure of norbornene ring Bending vibration

Example 6 15.0 g (0.
11 mol) MN-Ald and 5.4 g (0.05
Mol) of p-PD was added, and the mixture was heated with stirring at 100 ° C. for 1 hour. Then, under reduced pressure of 2-3 mmHg, 80-90
When water and unreacted substances formed by treatment at ℃ were removed, 16.5 g of a semi-solid substance was obtained at room temperature. It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 34.
4 (theoretical value 344.24), elemental analysis value (wt%) is C:
The values were 83.80 (theoretical value 83.66), H: 8.50 (theoretical value 8.20), and N: 8.22 (theoretical value 8.14). The IR spectrum is shown in FIG. 11 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 1450 cm ⁻¹ : CH ₃ antisymmetric deformation vibration 1380cm of ^-1: CH ₃ symmetric deformation vibration 720 cm ^-1: CH deformation vibration based on cis-disubstituted alkene structure norbornene ring

Example 7 In a flask having a volume of 50 l and being purged with nitrogen, 9.9 g (0.
(05 mol) DDM was added, and the mixture was heated to 100 ° C. and melted, and 17.8 g (0.12 mol) of allyl-5 was added.
-Norbornene-2-carbaldehyde (hereinafter AN-Al
d) was added dropwise, and the mixture was heated with stirring at 100 ° C. for 1 hour. Then, under a reduced pressure of 2 to 3 mmHg, the mixture was treated at 80 to 90 ° C. to remove water and unreacted substances.
22.3 g of a semi-solid substance was obtained at room temperature. This substance is shown in Table 1 from the results of IR, NMR, mass spectrometry and elemental analysis.
It was found to be the compound shown in. The yield based on diamine was 92%.

The molecular weight of this substance by mass spectrometry is 48.
6 (theoretical value 486.32), elemental analysis value (wt%) is C:
It was 86.52 (theoretical value 86.36), H: 7.93 (theoretical value 7.88), and N: 5.80 (theoretical value 5.76). The IR spectrum is shown in FIG. 13 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 910, 990 cm ⁻¹ : Out-of-plane bending vibration of allyl group C—H 720 cm ⁻¹ : CH bending vibration based on cis-2-substituted alkene structure of norbornene ring

Example 8 17.8 g (0.
12 moles of AN-Ald and 10.0 g (0.05
Mol) of DDE was added and heated at 100 ° C. for 1 hour with stirring. Then, under reduced pressure of 2-3 mmHg, 80-90 ° C
When the water and unreacted substances generated by the treatment with were removed, 23.5 g of a semi-solid substance at room temperature was obtained. It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 48.
8 (theoretical value 488.30), elemental analysis value (wt%) is C:
It was 83.46 (theoretical value 83.56), H: 7.52 (theoretical value 7.43), and N: 5.71 (theoretical value 5.74). The IR spectrum is shown in FIG. 15 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 1240 cm ⁻¹ : Ether C-O-C antisymmetric stretching vibration 910, 990 cm ^-1 : out-of-plane bending vibration of allyl group C-H 1240 cm ^-1 : ether C-O-C antisymmetric stretching vibration 720 cm ^-1 : cis of norbornene ring C-H bending vibration based on -2-substituted alkene structure

Example 9 17.8 g (0.
12 mol) of AN-Ald and 5.4 g (0.05 mol) of p-PD were added and heated with stirring at 100 ° C for 1 hour. Then, under reduced pressure of 2-3 mmHg, 80-90 ° C
When the water and unreacted substances generated by the treatment with were removed, 19.2 g of a semi-solid substance at room temperature was obtained. It was found from the results of IR, NMR, mass spectrometry and elemental analysis that this substance was the compound shown in Table 1. The yield based on diamine was 96%.

The molecular weight of this substance by mass spectrometry is 39.
6 (theoretical value 396.27), elemental analysis value (wt%) is C:
The values were 84.71 (theoretical value 84.79), H: 8.30 (theoretical value 8.14), and N: 7.07 (theoretical value 7.07). The IR spectrum is shown in FIG. 17 and the ¹ H-NMR spectrum is shown in FIG.

The main absorptions in the IR spectrum are as follows. 3050 cm ⁻¹ : Alken C—H stretching vibration 3000 to 2850 cm ⁻¹ : Alkane C—H stretching vibration 1640 cm ⁻¹ : C = N stretching vibration 1500 cm ⁻¹ : Aromatic ring stretching vibration 910, 990 cm ⁻¹ : Out-of-plane bending vibration of allyl group C—H 720 cm ⁻¹ : CH bending vibration based on cis-2-substituted alkene structure of norbornene ring

[0047]

[Table 1]

Example 10 100 g of the azomethine group-containing norbornene derivative obtained in Example 1 was heated at 120 ° C. for 10 hours under reduced pressure of 2-3 mmHg.
After the time treatment, 99 g of an oligomer having a melting point of 97 to 105 ° C. was obtained.

Example 11 The polymer obtained by heat-treating the azomethine group-containing norbornene derivative obtained in Example 1 under reduced pressure of 3 mmHg at 160 to 170 ° C. for 1 hour and then at 190 to 200 ° C. for 1 hour was obtained. Further, it was post-cured at 250 ° C. for 6 hours under atmospheric pressure to be completely cured.

The cured product was insoluble in various solvents and exhibited a glossy black color, and its specific gravity was 1.158. Further, when a thermal analysis test was conducted on this product, the following results were obtained.

Thermal loss onset temperature of fine powder: 298 ° C. Glass transition temperature (Tg): 281 ° C. Thermal expansion coefficient (25 ° C. to Tg): 1.10 × 10 ⁻⁴ (1 /
℃)

It is considered that the polymer obtained by this reaction was not obtained by simply reacting only the norbornene ring, but was also obtained by reacting the double bond of the azomethine group in the polymerization raw material. That is, the IR of the polymer obtained in this Example
This is also supported by the weaker absorption based on C = N at 1640 cm ^{−1 in} the spectrum as compared with FIG. 1, which is the IR spectrum of the polymerization raw material. Example 12 A cured product obtained by heat-treating under exactly the same conditions as in Example 11 except that the post-cure conditions were changed as follows was subjected to the same thermal analysis test, and the following results were obtained. Was obtained.

[0053]

[Table 2]

Example 13 The azomethine group-containing norbornene derivative obtained in Example 2 was heat-treated at 180 ° C. for 5 hours under normal pressure, and then 200
It was post-cured at 24 ° C. for 24 hours to be completely cured. The cured product was insoluble in various solvents and exhibited a glossy black color. When a thermal analysis test was conducted, the decomposition start temperature was 300 ° C.

Example 14 In Example 13, the post cure conditions were 250 ° C. and 5
When the same heat treatment was performed except that the time was changed, the obtained cured product was insoluble in various solvents and exhibited a glossy black color. When a thermal analysis test was performed, the decomposition start temperature was 308 ° C.

Example 15 The azomethine group-containing norbornene derivative obtained in Example 3 was subjected to the same heat treatment and post cure as in Example 13 to completely cure it. The cured product is insoluble in various solvents,
When it showed a glossy black color and was subjected to a thermal analysis test, the decomposition initiation temperature was 338 ° C.

Example 16 The azomethine group-containing norbornene derivative obtained in Example 4 was subjected to the same heat treatment and post cure as in Example 13 to completely cure it. The cured product is insoluble in various solvents,
It showed a glossy black color and was subjected to a thermal analysis test to find that the decomposition initiation temperature was 252 ° C.

Example 17 In Example 16, the post cure conditions were 250 ° C. and 8 ° C.
When the same heat treatment was performed except that the time was changed, the obtained cured product was insoluble in various solvents and exhibited a glossy black color. When a thermal decomposition test was performed, the decomposition start temperature was 266 ° C. Example 18 The azomethine group-containing norbornene derivative obtained in Example 5 was subjected to the same heat treatment and post cure as in Example 13 to be completely cured. The cured product is insoluble in various solvents,
When it showed a glossy black color and was subjected to a thermal analysis test, the decomposition initiation temperature was 273 ° C.

Example 19 The azomethine group-containing norbornene derivative obtained in Example 6 was subjected to the same heat treatment and post cure as in Example 13 to completely cure it. The cured product is insoluble in various solvents,
When it showed a glossy black color and was subjected to a thermal analysis test, the decomposition start temperature was 281 ° C.

Example 20 The azomethine group-containing norbornene derivative obtained in Example 7 was subjected to the same heat treatment and post cure as in Example 13 to completely cure it. The cured product is insoluble in various solvents,
It showed a glossy black color and was subjected to a thermal analysis test to find that the decomposition start temperature was 317 ° C.

Example 21 In Example 20, the post cure conditions were 250 ° C. and 8 ° C.
When the same heat treatment was performed except that the time was changed, the obtained cured product was insoluble in various solvents and exhibited a glossy black color. When a thermal analysis test was performed, the decomposition start temperature was 328 ° C. Example 22 The azomethine group-containing norbornene derivative obtained in Example 8 was subjected to the same heat treatment and post cure as in Example 13 to be completely cured. The cured product is insoluble in various solvents,
When it showed a glossy black color and was subjected to a thermal analysis test, the decomposition start temperature was 337 ° C.

Example 23 The azomethine group-containing norbornene derivative oligomer obtained in Example 10 was heat-treated at 180 ° C. for 5 hours under atmospheric pressure, and postcured at 210 ° C. for 20 hours under atmospheric pressure to obtain a black cured product. Got This cured product had a glass transition temperature (Tg) of 277 ° C and a thermal decomposition initiation temperature of 296 ° C.

[0063]

The azomethine group-containing norbornene derivative of the present invention has a low melting point and is soluble in various solvents, so that it is easy to handle. Further, since harsh polymerization conditions are not required, polymerization molding can be easily performed by molding methods such as cast molding, injection molding and compression molding. Further, since the molded product is excellent in heat resistance, flame retardancy, etc., it is useful as a structural member, a material for electric and electronic parts.

[0064]

Claims (8)

[Claims] 1. The following general formula [1]: (However, R is hydrogen, a C ₁ -C ₃ alkyl group or C ₂
To C ₅ alkenyl group, and X represents a C _{6 to} C ₁₈ aromatic residue. ) An azomethine group-containing norbornene derivative represented by 2. The azomethine group-containing norbornene derivative according to claim 1, wherein R in the general formula [1] is hydrogen, a methyl group or an allyl group. 3. In the general formula [1], X is o-, m.
-, Or p-phenylene group, or general formula [2]-
pPh-Y-pPh- (where PPH is a p- phenylene group, Y is _{-CH 2 -, - O -,} - CO -, -
Represents SO ₂ −. The azomethine group-containing norbornene derivative according to claim 1, which is an aromatic residue represented by 4. In the general formula [2], Y is —CH ₂ —,
The azomethine group-containing norbornene derivative according to claim 3, which is -O-. 5. The following general formula [3]: (However, R is hydrogen, a C ₁ -C ₃ alkyl group or C ₂
An alkenyl group of ~C _5. ) And a general formula [4] H ₂ N—X—
An aromatic diamine represented by NH ₂ (where X represents a C _{6 to} C ₁₈ aromatic residue) is used at room temperature to 180 ° C.
The method for producing an azomethine group-containing norbornene derivative according to claim 1, which comprises heating at ° C. 6. The azomethine group-containing norbornene derivative according to claim 1 at 0.5 to 3 at 120 to 250 ° C.
A method for producing a polymer of an azomethine group-containing norbornene derivative, which comprises heating for 0 hour. 7. The azomethine group-containing norbornene derivative according to claim 1 is heat-treated at a temperature of 80 to 150 ° C. for 0.1 to 20 hours and then at 120 to 250 ° C.
A method for producing a polymer of an azomethine group-containing norbornene derivative, which comprises heating for 5 to 30 hours. 8. The azomethine group-containing norbornene derivative according to claim 1, wherein R in the general formula [1] is hydrogen, a methyl group,
Or an allyl group and X is o-, m- or p-
Phenylene group, -pPh-CH ₂ -pPh- or -
The method for producing a polymer of an azomethine group-containing norbornene derivative according to claim 6 or 7, which is pPh-O-pPh- (where pPh represents a p-phenylene group).