JPH05339371A - Poly@(3754/24)azole-imide) - Google Patents

Abstract

PURPOSE:To obtain a polymer excellent in heat resistance and mechanical characteristics and improved in solubility by selecting a polymer comprising specific repeating units having thiazole rings and imide rings directly included in the main chain and by specifying the wt. decrease temp. CONSTITUTION:A poly(azole-imide) comprises repeating units of formula I, has a reduced specific viscosity (measured at 25 deg.C in 0.5% sulfuric acid soln.) of 0.1 or higher, and does not have the wt. decrease temp. below 300 deg.C. In formula I, Ar<1> and Ar<2> are each an arom. group of formula II, III, or IV provided that when Ar<2> is a group of formula VI, then Ar<1> is not a group of formula V nor VI; X is -O- or -S-; and the arrow indicates that X and N may be replaced with each other. In formula III, Y is -O-, -CO-, -SO2-, -CH2-C(CH3)2-, -C(CF3)2-, or a group of formula VI; and m is 0 or 1, while in formula IV, n is 0 or 1.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel poly (azole-
Imide). More specifically, it has an azole ring and an imide ring directly bonded to the main chain skeleton and has a reduced specific viscosity of 0.1.
The present invention relates to a novel poly (azole-imide) which does not have a weight reduction temperature below 300 ° C. The polymer according to the present invention is excellent in heat resistance and mechanical properties, and has remarkably improved solubility, so that it is used as a film, a sheet, a coating agent or an adhesive agent as well as a fiber. Therefore, it is suitably used not only for clothing and industrial materials but also in various fields such as the electric and electronic industries as well as the automobile and aircraft industries.

[0002]

2. Description of the Related Art Polyimide is a useful material used in numerous industrial fields because of its excellent heat resistance, mechanical properties, and various physical properties such as good electrical and optical properties. As is well known. In general, heat-resistant polymers such as polyimide are often insoluble and infusible in spite of their excellent physical properties, and are usually poor in moldability. However, polyimide is attractive because polyamic acid as a precursor has good solubility, and a method of imidizing after processing by solution molding with a general-purpose solvent in this polyamic acid state is possible. It is used as a material in more industrial fields.

However, during imidization from the polyamic acid precursor, problems such as generation of voids and pinholes and warpage due to strain occur, and it cannot be said that the molding method is sufficiently satisfactory. In order to solve this problem, many thermal imidization conditions and chemical imidization conditions have been studied and proposed.
The current situation is that none of them has been satisfied.

In order to solve this problem, development of soluble polyimide has been vigorously carried out. Attempts have been made to introduce many bulky substituents and flexible bonds to impart solubility to the polyimide (see, for example, J. Pol.
ym. Lett. 13. 5 . 283 (1975)). However, in order to impart sufficient solubility, it is necessary to copolymerize a large amount of these bulky substituents and very flexible bonds, which significantly impairs various excellent properties of polyimide. I will end up.

On the other hand, poly (p-phenylenebenzobisoxazole) (PBO) and poly (p-) are polymers having excellent physical properties including heat resistance comparable to that of polyimide.
(Phenylenebenzobisthiazole) (PBT) and poly (p-phenylenebenzobisimidazole) (PBI)
The polybenzbisazole (hereinafter abbreviated as PBZ), which is typified by, has been paid attention and has been vigorously researched and developed. For example, Wolfe et al., SRI International (US Pat. No. 4,533,692 1985, US Pat.
3,724 1985 and US Pat. No. 4,533,6
93 1985 and Macromorecules
Volume 14, page 909 1981, same magazine 14 volumes 9
There are many reports such as page 15, 1981). These PBZs are dissolved in general organic solvents such as concentrated sulfuric acid and methanesulfonic acid, and there is no problem as with the above polyimide.

However, these PBZs generally require the use of a strong acid such as polyphosphoric acid as a polymerization solvent, which requires troublesome consideration for acid corrosion in the polymerization process. In order to solve this problem, a new polymerization method has been studied, but it can only be applied to PBZ having a limited chemical structure.

On the other hand, polythiazole imides containing a thiazole ring and an imide ring have been proposed to solve the above-mentioned problems (J. Polym. Sci .; Part.
A: Polym. Chem. , 27 , 738 (198
9)), a very rigid tetracarboxylic acid anhydride is used, and sufficient moldability including film forming ability is not expressed.

As described above, materials having good physical properties including heat resistance generally have low moldability, and this trade-off is an unavoidable problem in pursuit of polymer performance. However, as described above, at present, it is difficult to obtain a polymer which does not require a troublesome polymerization step, has excellent physical properties such as heat resistance and mechanical properties, and has good moldability. If a polymer that solves these problems is obtained,
The fiber is very useful as a film, sheet, coating agent, or adhesive agent from the base, and is useful in all industrial fields including the electric, electronic, automobile and aircraft industries.

[0009]

Here, the present inventors do not require a troublesome polymerization step, have improved solubility, and have moldability which is excellent in mechanical properties and heat resistance. Based on the recognition that the development of a good polymer of (1) is extremely important, it has become urgent to solve the above-mentioned drawbacks of the conventional method.

[0010]

[Means for Solving the Problems] As a result of intensive research and study by the present inventors in order to solve the above-mentioned problems, the present invention has finally been completed. That is, the present invention has the following general formula 7 as a repeating unit and has a reduced specific viscosity of 0.1 or more measured in a 0.5% sulfuric acid solution at 25 ° C. and a weight reduction temperature of 300 ° C. or less. Is a poly (azole-imide).

[0011]

[Chemical 7](However, in the general formula 7,¹And Ar²Is the following
An aromatic group represented by the general formulas 2, 3, and 4
R, Ar²When is a group represented by Chemical formula 12, Ar is ¹Haka
11 and 12 are absent. X is -O-, -S
-, And the arrow in chemical formula 7 may switch X and N.
Indicates that. )

[0012]

[Chemical 8]

[0013]

[Chemical 9](In the chemical formula 9, Y is -O-, -CO-, -SO.₂-,-
CH₂-, -C (CH ₃)₂, -C (CF₃)₂-And
And m is O or 1. )

[0014]

[Chemical 10] (In Chemical formula 10, n is 0 or 1.)

[0015]

[Chemical 11]

[0016]

[Chemical formula 12]

The present invention will be described in detail below. The polymer of the present invention is produced by a combination of monomers selected from two types of monomer groups. As the first monomer group,
It is an aromatic diamine compound having 6 or more and 24 or less carbon atoms, and specific examples thereof include compounds represented by the following general formulas 13 to 30.

[0018]

[Chemical 13]

[0019]

[Chemical 14]

[0020]

[Chemical 15]

[0021]

[Chemical 16]

[0022]

[Chemical 17]

[0023]

[Chemical 18]

[0024]

[Chemical 19]

[0025]

[Chemical 20]

[0026]

[Chemical 21]

[0027]

[Chemical formula 22]

[0028]

[Chemical formula 23]

[0029]

[Chemical formula 24]

[0030]

[Chemical 25]

[0031]

[Chemical formula 26]

[0032]

[Chemical 27]

[0033]

[Chemical 28]

[0034]

[Chemical 29]

[0035]

[Chemical 30]

Examples of the diamine compound containing no azole ring include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,
By partially copolymerizing 4'-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-diominodiphenyl, etc. It does not matter at all.

The second monomer group is an aromatic tetracarboxylic acid anhydride having a carbon number of 6 or more and 24 or less, and specific examples thereof include compounds represented by the following general formula 31.

[0038]

[Chemical 31]

As the method for obtaining the poly (azole-imide) of the present invention, all the conventionally known polymerization methods for polyimide, for example, low temperature solution polymerization, heat medium polymerization or melt polymerization can be used for synthesis. ..

The polymer of the present invention obtained as described above is
The reduced specific viscosity measured at 25 ° C. in a 0.5% sulfuric acid solution is 0.
Must be 1 or greater. When it is less than 0.1, the degree of polymerization is not sufficient, and it is not enough to exhibit excellent physical properties as a polymer including heat resistance.

The poly (azole-imide) of the present invention may optionally contain an ultraviolet absorber, various pigments, a fibrous reinforcing material such as glass fiber or carbon fiber, a non-fibrous reinforcing material such as clay, a matting agent, or In some cases, antioxidants may be added appropriately,
No problem whatsoever.

The present invention will be specifically described below with reference to examples, but the present invention is not limited by these. The measuring methods used in the examples are as follows. Reduced specific viscosity: In the case of poly (azole-imide): 0.50 g of polymer in 100 m of solvent using concentrated sulfuric acid as a solvent
It melt | dissolved in 1 and measured in the 25 degreeC thermostat. In the case of poly (azole-amic acid): Using N-methylpyrrolidone (NMP) as a solvent, 0.50 g of a polymer was dissolved in 100 ml of the solvent and measured in a thermostat at 25 ° C. Setting of thermogravimetric reduction start temperature: Sample 5 by thermobalance
Using mg, the temperature was measured under a nitrogen stream of 40 ml / min at a room temperature of 10 ° C./min to obtain the temperature at which weight loss started.

Reference Example 1 Synthesis of 2,6-diaminobenzobisthiazole J. Wolfe et al.'S method (Macromolecules
14, page 909, 1981) to synthesize the crude product. That is, p-phenylenediamine and ammonium thiocyanate were refluxed in an aqueous solution to synthesize p-phenylenebisthiourea, and then reacted with bromine in chloroform. The reaction product was recrystallized twice from acetic acid to obtain a pale yellow crude product. The crude product was recrystallized from N, N-dimethylacetamide to obtain a colorless target product.

Example 1 100 ml of 3 equipped with stirrer, thermometer and gas inlet tube
In a two-necked flask, 2.1 g of 2,6-diaminobenzobisthiazole and 45 m of N-methylpyrrolidone (NMP) were added.
I was prepared. To this solution was added 4.20 g of 2,2-bis (3,4-dicarboxyphenyl) perfluoropropane anhydride under stirring at room temperature, and the mixture was reacted under a nitrogen stream for 24 hours. The reduced specific viscosity of the obtained polyamic acid was 0.36.
It was 9 dl / g. Next, the NMP solution of the obtained polymer was cast on a glass plate and dried to form a film. This film was heat-treated under reduced pressure at 240 ° C. for 4 hours to obtain poly (thiazole-imide). The reduced specific viscosity of the obtained poly (thiazole-imide) was 0.659.
It was dl / g. The chemical structure of the polymer was confirmed by infrared absorption spectrum (Fig. 1). The thermogravimetric reduction temperature of this polymer was 505 ° C., which showed very good heat resistance.

Example 2 100 parts of the NMP solution of the polyamic acid obtained in Example 1 was added.
ml acetic acid / pyridine mixed solution (mixing volume ratio 70/3
0) was added and the mixture was refluxed for 4 hours to obtain poly (thiazole-imide). The reduced specific viscosity of the obtained poly (thiazole-imide) was 0.494 dl / g. Also, the chemical structure of the polymer was confirmed to be the same as that of the polymer of Example 1 by infrared absorption spectrum.

Examples 3 to 9 In the same manner as in Examples 1 and 2, polymers were synthesized from the monomers shown in Table 1. Table 1 shows the reduced specific viscosity and the thermogravimetric reduction temperature of the obtained polymer. In addition, Examples 3 to 5
2 to 4 show infrared absorption spectra of the polymer obtained in
Shown in.

[0047]

[Table 1] In Table 1, the upper part of the reduced specific viscosity of poly (azole-imide) represents the polymer after thermal cyclization, and the lower part represents the viscosity of the polymer after chemical cyclization. Further, as the monomers used, (a) to (f) are compounds represented by the following general formula 32.

[0048]

[Chemical 32]

Comparative Example 1 100 ml of 3 equipped with a stirrer, thermometer and gas inlet tube
In a two-necked flask, 3.0 g of 2,6-diaminobenzobisthiazole and 45 m of N-methylpyrrolidone (NMP)
I was prepared. To this solution, 2.94 g of pyromellitic dianhydride was added with stirring at room temperature, and the mixture was reacted under a nitrogen stream for 24 hours. The reduced specific viscosity of the obtained polyamic acid was 0.581.
It was 1 / g. Poly (thiazole-imide) was obtained in the same manner as in Examples 2 and 3, but was insoluble in concentrated sulfuric acid.

Comparative Example 2 Poly (thiazole-amic acid) was synthesized in the same manner as in Example 1 except that the reaction temperature was 100 ° C., and poly (thiazole-imide) was obtained. The reduced specific viscosity of the obtained polymer was 0.0811 / g. The thermal weight loss of this polymer started around 200 ° C., and it could not be said that the polymer had good heat resistance.

[0051]

The present invention has an azole ring and an imide ring directly bonded to the main chain skeleton, and a flexible bond.
Moldability based on the solubility of the intended polymer is significantly improved, and various physical properties such as heat resistance of the polymer are not impaired, so the range of applications is significantly expanded and it contributes to the industrial world. Is.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of poly (azole-imide) obtained in Example 1 of the present invention.

FIG. 2 is an infrared absorption spectrum of poly (azole-imide) obtained in Example 3 of the present invention.

FIG. 3 is an infrared absorption spectrum of the poly (azole-imide) obtained in Example 4 of the present invention.

FIG. 4 is an infrared absorption spectrum of the poly (azole-imide) obtained in Example 5 of the present invention.

Claims (1)

[Claims] 1. The following general formula 1 is used as a repeating unit,
The reduced specific viscosity measured at 25 ° C. in a 0.5% sulfuric acid solution is 0.
1 or more and a weight reduction temperature of 300 ° C or less
Not having poly (azole-imid)
De). [Chemical 1](However, in the general formula 1, Ar¹And Ar²Is the following
An aromatic group represented by the general formulas 2, 3, and 4
R, Ar²Is a group represented by Chemical formula 6, Ar¹Haka 5
And chemical formula 6 do not exist. X is -O- or -S-.
In the formula 1, the arrow indicates that X and N may be interchanged.
Show. ) [Chemical 2][Chemical 3](In chemical formula 3, Y is -O-, -CO-, -SO.₂-,-
CH₂-, -C (CH ₃)₂-, -C (CF₃)₂-O
And Chemical formula 6, and m is 0 or 1. ) [Chemical 4](In the chemical formula 4, n is 0 or 1.)[Chemical 6]