JPH05331123A - Curable imide oligomer - Google Patents

Abstract

PURPOSE:To obtain a curable imide oligomer capable of providing a cured product having high heat resistance, further, having excellent mechanical strength, dimensional stability and moisture resistance and capable of providing a polyimide hardly producing void or crack in the molded product. CONSTITUTION:A curable imide oligomer of formula I [Ar1 is a tatravalent aromatic group; Ar2 is a divalent aromatic group; X is a trivalent bond style selected from formula II to formula IV; n is 0-15; R is reactive substituent group]. The compound is obtained by dissolving an acid dianhydride derivative of formula V or acid dianhydride derivative of formula VI (Y1 to Y4 are H or 1-5C alkyl) in a inert gas atmosphere in a polar organic solvent, adding the formula H2N-Ar2-NH2 and/or an organic diamine compound of formula VII (Ar3 is a divalent organic group) to the solution to afford a telechelic oligomer whose both ends are amine groups and then adding an acid anhydride of formula VIII thereto and reacting the oligomer with the acid anhydride of formula VIII to terminate the oligomer ends and thermally cyclizing and dehydrating the resultant oligoamic acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel curable oligomer. More specifically, the present invention relates to an imide oligomer having excellent heat resistance, good solubility in an organic solvent, and a polyimide having reactivity suitable for lamination and molding.

[0002]

2. Description of the Related Art Thermosetting resins are used for various electrical insulating materials such as casting, impregnation, lamination, and molding materials.
It is used as a structural material. In recent years, the usage conditions of materials have become more and more severe in each of these uses, and in particular, the heat resistance of materials has become an important characteristic. Thermosetting polyimide resins and heat resistant epoxy resins have been conventionally used for applications requiring heat resistance. Among them, as the thermosetting polyimide resin, kelimide containing a combination of a bismaleimide compound and diaminodiphenylmethane as a main component is used [Matsuo Fujisawa, Plastics, Vol. 34, No. 7, p. 75, 1983].

Recently, for example, a thermosetting polyimide in which 3-aminophenylacetylene is used as a primary amine and the terminal is terminated is put on the market as thermid (Hughes Aircraft, JP-A-50-5348, etc.). Several methods for the synthesis of 3-aminophenylacetylene used herein (eg USP 4,125,563)
However, all of them have the problems that the synthetic route is long and the synthetic reagents are expensive. Also,
A thermosetting polyimide in which the end is terminated using propargylamine as a primary amine has also been proposed (Ube Industries, Ltd., JP-A-2-284923, JP-A-3-174).
427). However, it is known that the thermal reaction initiation temperature of the propargyl group is as high as 250 ° C., and the imide oligomer using this as a reactive group also has a high curing temperature and is inferior in terms of processability [“Polymer Engineering Science”]. (Polym. Eng. Sci.) ", 22 (1),
9-14 (1982)]. Further, generally, polyimide resins have poor moisture absorption resistance, and it has been pointed out that dimensional stability in the processing step is a problem.

[0004]

SUMMARY OF THE INVENTION The present inventors have arrived at the present invention as a result of intensive investigations in order to solve these technical problems in view of the above circumstances. That is, the present invention has the general formula (1)

[0005]

[Chemical 7]

(In the formula, Ar ₁ is a tetravalent aromatic group, Ar ₂
Represents a divalent aromatic group. Ar ₁ and Ar ₂ may be the same or different. Also, in the formula,
X is a trivalent bonding mode below

[0007]

[Chemical 8]

[0008] It is selected from among the same kind or different kinds. n is selected from 0 to 15. R is a curable imide oligomer represented by a substituent having reactivity).

First, the method for producing the curable oligomer of the present invention will be described. In an atmosphere of an inert gas such as argon or nitrogen in which the reaction tank is sufficiently dried, the general formula (2)

[0010]

[Chemical 9]

An acid dianhydride represented by the formula (wherein Ar ₁ is 4
Valent aromatic group. ) Or general formula (3)

[0012]

[Chemical 10]

An acid dianhydride derivative represented by the formula
Y ₁ , Y ₂ , Y ₃ , and Y ₄ are hydrogen, an alkyl group selected from C1 to 5, and Ar ₁ is a tetravalent aromatic group. ) Is dissolved in a polar organic solvent, and the organic diamine compound represented by the general formula (4) is dissolved in the solution.

H ₂ N--Ar ₂ --NH ₂ (4)

(Wherein Ar ₂ is a divalent organic group) and /
Or general formula (5)

[0016]

[Chemical 11]

(Wherein Ar ₃ is a divalent organic group) is dissolved in the same polar solvent as described above, or is added as a powder while paying attention to heat generation and thickening, and both ends are acid anhydrides. A base telechelic oligomer is obtained. The reaction temperature at this time is preferably in the range of -15 to 120 ° C, preferably -15 to 100 ° C, and more preferably -5 to 50 ° C. The reaction time is preferably about 1 to 5 hours. An acid anhydride having a thermosetting group represented by the general formula (6) is added to this reaction solution.

[0018]

[Chemical 12]

(In the formula, R is a reactive substituent.) Is added to terminate the above oligomer terminal to obtain an oligoamic acid solution which is a precursor of a reactive imide oligomer. The reaction temperature at this time is preferably 0 to 120 ° C, preferably 0 to 100 ° C, and more preferably 40 to 100 ° C. The reaction time is preferably about 1 to 5 hours. After that, the polyamic acid solution is thermally closed.
After adding a non-solvent for dehydration, it is converted to polyimide under reflux and azeotropy. As the non-solvent used here, aromatic hydrocarbons such as xylene and toluene can be used, but toluene is preferably used. In the reaction, azeotropically distilled water is refluxed using a Dean-Stark reflux device until a theoretical amount of water is collected. The dehydration ring closure reaction to this imide structure can also use the chemical ring closure method together. After the reaction, the polyimide solution is poured into water or an alcohol solvent with vigorous stirring to precipitate the polyimide as a powder. The powder is collected by filtration and then dried at 80 ° C. under reduced pressure for 48 hours.

As the organic tetracarboxylic dianhydride used in the present invention, organic tetracarboxylic dianhydrides having any structure can be used, and the above-mentioned general formula (2),
Those represented by (3) are preferable, and the Ar ₁ group is a tetravalent organic group, and preferably an aromatic group. This Ar
Specific examples of _one group include the following.

[0021]

[Chemical 13]

[0022]

[Chemical 14]

Preferably, at least one of the following is selected.

[0024]

[Chemical 15]

The diamine represented by the general formula (5) used in the present invention can be synthesized, for example, by the following reaction.

[0026]

[Chemical 16]

That is, the general formula (7) corresponding to nitrobenzoic acid or derivative

HO-Ar ₃ --OH (7)

A diol represented by the formula (wherein Ar ₃ represents a divalent aromatic group) is obtained in the presence of a tertiary amine catalyst to obtain a dinitro compound, and then the nitro group is converted to an amino group by a reduction catalyst. It is obtained by doing. Ar ₃ of the diol of the general formula (7) used here is essentially any divalent organic group, but specifically,

[0030]

[Chemical 17]

[0031]

[Chemical 18]

Can be illustrated. An aromatic group is particularly desirable, and specifically,

[0033]

[Chemical 19]

It is preferable to use at least one of the above as a main component. Further, in the present invention, a diamine component having another structure can be used at the same time. Ar _{2 of the} diamine compound represented by the general formula (4) can be essentially any divalent organic group, but specifically,

[0035]

[Chemical 20]

[0036]

[Chemical 21]

Can be illustrated. In particular, an aromatic group is desirable and specifically,

[0038]

[Chemical formula 22]

It is preferable that at least one of the above is used as a main component. As an example of the reactive functional group R represented by the general formula (6) used in the present invention for terminal termination,

[0040]

[Chemical formula 23]

From the viewpoint of cost and handling, it is preferable that

[0042]

[Chemical formula 24]

It is Examples of the organic solvent used in the reaction for producing a polyamic acid solution include, for example, dimethyl sulfoxide, sulfoxide-based solvents such as diethyl sulfoxide,
Examples thereof include formamide solvents such as N, N′-dimethylformamide and N, N′-diethylformamide, acetamide solvents such as N, N′-dimethylacetamide and N, N′-diethylacetamide. These may be used alone or as a mixed solvent of two or more kinds. Further, it can be used as a mixed solvent with a non-solvent of polyamic acid such as methanol, ethanol, isopropanol, benzenemethylcellosolve, etc. together with these polar solvents.

The oligomer of the present invention may be used in combination with so-called B-stage formation, if necessary. B-stage conversion is 100 ° C. or higher, preferably 15
0 ° C or higher, more preferably 200 ° C or higher, 1 minute or longer,
It is preferable that the heating is performed for 5 minutes or more under hot air circulation or under vacuum.

Although the mechanism for the highly heat-resistant polyimide having reactivity according to the present invention is not clear, formation of a benzene skeleton by thermosetting acetylene / acetylene or [3,3] sigmatropy of propargyl ether. It is said that the effect is due to the formation of a chromene skeleton by transition / polymerization by ring-opening thermosetting [eg, 3rd International Samppi Electric Conference (3rd. Int.SAMPE Elect. Conf.) 169, 1989. , Dow Chemical., JP-A-2-8527
5]. In addition, the number average degree of polymerization (Principles of Polymer Chemistr
y) page 91, 1953], the degree of polymerization n is 0 to 30, preferably 0 to 20, and more preferably 1 to 15. When it is more than that, solubility in organic solvent is lowered, and when it is less than that, there arises a problem in mechanical strength.

In obtaining a thermosetting resin from the curable oligomer of the present invention, if necessary, an epoxy resin or epoxy resin curing agent, a curing accelerator, a filler, a flame retardant, a reinforcing agent,
Surface treatment agents, pigments, various elastomers alone or 2
One or more species can be used in combination. These curable resins are
There is no limitation on the usage, and it can be applied in various modes. Among them, it is also possible to use it as a matrix resin for a laminated board for electricity, so-called PWB (printed wiring board). When used for PWS applications, various fillers and reinforcing agents can be used.
Examples of the filler include aluminum hydroxide, antimony trioxide, red phosphorus and the like. As the reinforcing material, carbon fiber, glass fiber, aramid fiber, liquid crystal polyester fiber such as Vectra, polybenzothiazole (PBT) fiber,
Examples thereof include woven fabrics, non-woven fabrics, mats, papers (paper) made of alumina fibers and the like, or a combination thereof.

[0047]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples, and the present invention is within the scope of the invention. The present invention can be implemented with various modifications and improvements based on the knowledge of those skilled in the art.

Reference Example 1 3-Propargyloxyphthalic Anhydride 12.5 g (0.051 mol) bromophthalic acid (Bromchemy) and 8.0 g (0.2 mol) sodium hydroxide were added to 200 ml of water in a reactor. It was dissolved in and prepared. 6.
After adding 45 g (0.2 mol) of tetra-n-butylbutylammonium bromide, 2.79 g (0.050 mol) of propargyl alcohol was added from a dropping funnel over about 30 minutes and then reacted at 80 ° C. for 4 hours. After that, stirring was continued overnight at room temperature. The precipitated crystals were separated by filtration and recrystallized from toluene to give 10.5 g (yield:
94.2%) of propargyl ether was obtained. The obtained crystals were placed in a reactor substituted with nitrogen together with 100 ml of o-toluene and refluxed for 12 hours. The precipitated crystals were collected by filtration while hot and purified by sublimation. 5.8 g
To obtain 3-propargyloxyphthalic anhydride.

[Elemental analysis value] Calculated value: C; 65.35, H; 2.99. Found: C; 64.99, H; 3.12. [Spectral Data] IR (neat, cm ⁻¹ ) ν = 3000, 2950, 16
20, 1600, 1580, 1495, 1450, 13
50, 1220, 1160, 990, 905, 860,
780,690. ¹ H-NMR (chloroform-d, ppm) δ = 3.
5 (d., J = 2.4 Hz, 1H), 5.15 (d.,
J = 2.4 Hz, 2H), 6.7 (m., 3H)

Reference Example 2 2,2-bis (4-nitrobenzoyloxyphenyl)
Propane reflux condenser, thermometer, stirrer, dropping funnel attached 1
In a 4-liter 4-neck flask, 360 ml of dry pyridine, 3
71 g (2 mol) of p-nitrobenzoyl chloride and 457 g (2 mol) of bisphenol A were charged, and the atmosphere was replaced with nitrogen. The mixture was reacted under heating under reflux for 3 hours. The reaction solution was poured into 2 liters of ice water, and the precipitated solid was filtered and dried. Recrystallized from toluene to give 697 g (89.6).
%) 2,2-bis (4-nitrobenzoyloxyphenyl) propane was obtained. [Elemental analysis value] Calculated value: C; 65.37, H; 4.28, N; 5.4
5. Found: C; 65.05, H; 4.38, N; 5.6.
5.

Reference Example 3 2,2-bis (4-aminobenzoyloxyphenyl)
Propane reflux condenser, thermometer, stirrer, dropping funnel attached 1
To a liter 4-necked flask, 500 ml of ethanol was added, and 148.4 (0.25 mol) of the dinitro compound obtained in Reference Example 2 was dispersed, and 10% by weight of supported palladium-activated carbon (2.5 g) was added. 66g from dropping funnel
(1.05 mol) of hydrazine was added over 30 minutes while paying attention to rapid reflux, and then reflux was continued for 3 hours. After the reaction, the precipitate was removed by filtration, the filtrate was concentrated with an evaporator, and recrystallized from ethanol. 111.5 g (yield 86.7%) of 2,2-bis (4-aminobenzoyloxyphenyl) propane was obtained. [Elemental analysis value] Calculated value: C; 74.01, H; 5.73, N; 6.1
7. Found: C; 73.84, H; 5.83, N; 6.5.
1.

[0052]

Example 1 A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock, and a seal gap, and dried under reduced pressure.
The atmosphere was replaced with argon. 3.22 g (0.02005 mol)
Of benzophenone tetracarboxylic acid dianhydride was charged into the reactor, and then 150 ml of dimethylformamide (DM
F) was added. 1.46 g (0.005 mol) of 1,3
-Bis (3-aminophenoxy) benzene and 2.23
g (0.005 mol) of 2,2-bis (4-aminobenzoyloxyphenyl) propane obtained in Reference Example 3
After dissolving in 0 ml of DMF, it was introduced into the reactor through a dropping funnel. After stirring at 80 ° C for 2 hours, 1.57 g
(0.01 mol) of 3-propargyloxyphthalic anhydride obtained in Reference Example 1 was dissolved in 20 ml of DMF and added. After the reaction temperature of the obtained oligoamic acid was returned to room temperature, 11 ml of acetic anhydride and 10 ml of pyridine were added, and the mixture was chemically dehydrated and cyclized to obtain an imide oligomer having the following structure.

[0054]

[Chemical 25]

After the reaction, the reaction solution was poured into 1 liter of methanol to precipitate the produced imide oligomer. Filter under reduced pressure with an aspirator, in vacuum at 80 ° C
When dried for 48 hours at 7.95 g (yield; 91.
The oligomer was obtained as a pale yellow powder (5%).

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3000, 2950, 17
80, 1750, 1700, 1620, 1600, 15
80, 1495, 1450, 1350, 1295, 12
20, 1160, 990, 905, 860, 780, 7
35,690.

When the oligomer was B-staged by melting and defoaming in a vacuum oven at 220 ° C., it became a reddish brown powder. Using 6.8 g of B-staged imide oligomer, 220 ° C. for 20 minutes, 250 ° C. for 30 minutes
Min., 270 ° C., 1 hour, pressed under contact pressure, having a density of 1.39 g / cm ³ 12 mm (width) × 12 cm (length)
A cast plate of x 3.2 mm (thickness) was obtained. This casting plate has 4
A flexural strength of 2.6 kg / mm ^2, and the flexural modulus of 315 kg / mm ^2, and impact strength of 35Kg · cm / cm ^2, was a resin having a glass transition temperature of 253 ℃ (Tg). The moisture absorption rate was 0.25% (C-96 / 20/65).

Example 2 Instead of 1.46 g (0.005 mol) of 1,3-bis (3-aminophenoxy) benzene, 1.06 g (0.
An imide oligomer having the following structure was obtained in the same manner as in Example 1 except that 005 mol) of diaminobenzophenone was used.

[0059]

[Chemical formula 26]

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3000, 2950, 17
80, 1750, 1700, 1620, 1600, 15
80, 1495, 1450, 1350, 1295, 12
20, 1160, 990, 905, 860, 780, 7
35,690.

When the oligomer was B-staged by melting and defoaming in a vacuum oven at 220 ° C., it became a reddish brown powder. Using 8.9 g of B-staged imide oligomer, 220 ° C. for 20 minutes, 250 ° C. for 30 minutes
Min., 270 ° C., 1 hour, pressed under contact pressure, having a density of 1.36 g / cm ³ 12 mm (width) × 12 cm (length)
A cast plate of × 3.8 mm (thickness) was obtained. This casting plate has 4
A flexural strength of 5.1 kg / mm ^2, and the flexural modulus of 315 kg / mm ^2, and impact strength of 36Kg · cm / cm ^2, was a resin having a glass transition temperature of 239 ℃ (Tg). The moisture absorption rate was 0.34% (C-96 / 20/65).

Example 3 Instead of 1.46 g (0.005 mol) of 1,3-bis (3-aminophenoxy) benzene, 0.54 g (0.
An imide oligomer having the following structure was obtained in the same manner as in Example 1 except that 005 mol) of metaphenylenediamine was used.

[0063]

[Chemical 27]

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3000, 2950, 17
75, 1750, 1700, 1625, 1600, 15
80, 1485, 1450, 1350, 1295, 12
20, 1160, 990, 905, 860, 780, 7
35,690.

When the oligomer was B-staged by melting and defoaming in a vacuum oven at 220 ° C., it became a reddish brown powder. Using 7.5 g of B-staged imide oligomer, 220 ° C. for 20 minutes, 250 ° C. for 30 minutes
Min., 270 ° C, 1 hour, pressed under contact pressure, having a density of 1.37 g / cm ³ 12 mm (width) x 12 cm (length)
A cast plate of x 3.2 mm (thickness) was obtained. This casting plate has 4
A flexural strength of 9.8 kg / mm ^2, and the flexural modulus of 345 kg / mm ^2, and impact strength of 26Kg · cm / cm ^2, was a resin having a glass transition temperature of 248 ℃ (Tg). The moisture absorption rate was 0.27% (C-96 / 20/65).

Comparative Example Using 9.2 g of a commercially available imide type thermosetting oligomer, 220 ° C. for 20 minutes, 250 ° C. for 30 minutes, 270 ° C.
Pressed under contact pressure for 1 hour, density 1.35g / cm ³
12mm (width) × 12cm (length) × 3.5mm (thickness)
To obtain a casting plate. The cast plate has a flexural strength of 38.2Kg / mm ^2, and a flexural modulus 261Kg / mm ^2, 18Kg · cm
/ Cm ² impact strength and glass transition temperature (T
g)). Moisture absorption rate is 0.75% (C-
96/20/65).

[0067]

INDUSTRIAL APPLICABILITY The curable oligomer having reactivity according to the present invention can provide a cured product having excellent processing characteristics and extremely high heat resistance which has never been obtained. Furthermore,
The curable oligomer having reactivity according to the present invention has excellent mechanical strength, dimensional stability, electrical characteristics, etc.,
It is possible to provide a polyimide in which voids and cracks are less likely to occur in a molded product. As described above, since the reactive oligomer of the present invention has many characteristics, it has a very high industrial value in a wide range of applications such as laminates, heat resistant coatings, polymer materials for electronic devices and molding materials. Can be provided, and its usefulness is extremely large.

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[Submission date] July 7, 1992

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Claims (5)

[Claims] 1. A compound represented by the general formula (1): (In the formula, Ar ₁ represents a tetravalent aromatic group and Ar ₂ represents a divalent aromatic group. Ar ₁ and Ar ₂ may be the same or different. In the formula, X is a trivalent bond, and is shown below. And may be the same or different. n is selected from 0 to 15. R is a reactive substituent. ) The curable imide oligomer represented by. 2. The imide oligomer according to claim 1, wherein Ar ₁ is at least one selected from the following. [Chemical 3] 3. At least 2 mol% or more of Ar ₂ has the following structure: The imide oligomer according to claim 1, having Ar ₃ (wherein Ar ₃ represents a divalent aromatic group). 4. The imide oligomer according to claim 3, wherein Ar ₃ is at least one selected from the following. [Chemical 5] 5. The imide oligomer according to claim 1, wherein R is at least one selected from the following. [Chemical 6]