KR100948137B1 - Polyamideimide resin having improved dimensional stability - Google Patents

Abstract

The present invention relates to a polyamideimide resin having improved dimensional stability, wherein, in a polyamideimide resin prepared from a diamine compound and an unhydride, a diamino aromatic carboxyl azide is further added from 1: 0.001 to 1 with respect to the diamine compound. The polyamide-imide resin, which is manufactured by further including: 0.01 equivalent ratio, has excellent dimensional stability and durability, and can be used as a precision industrial part.

Dimensional Stability * Polyamideimide *

Description

Polyamideimide resin having improved dimensional stability

The present invention relates to a polyamideimide resin having excellent dimensional stability, and more particularly, to further improve the dimensional stability of a conventional polyamideimide resin, by further adding a diamino aromatic carboxyl azide, The present invention relates to a polyamideimide resin having greatly improved dimensional stability usable in molded parts for transporters.

The polyamideimide resin has a heat deformation temperature of 278 ° C. and a long service temperature of 200 ° C. or more, and has excellent heat resistance and excellent mechanical strength. In addition, it is widely used in parts requiring properties such as wear resistance, flame resistance, radiation resistance, creep resistance, and the like.

As such, homopolymers, polyamideimide copolymers, and precursor polymers thereof of polyamideimide have been used for various purposes due to their excellent physical properties.

However, polyamideimide having improved processability of polyimide has excellent processability, while its dimensional stability is weaker than that of polyimide, and polyimide has poor workability and thus has limited use range despite excellent dimensional stability.

Conventional techniques for such polyamideimide resins are disclosed in US Pat. Nos. 4,016,140 and 4,136,085. According to these patents, the equivalent ratio of two or more aromatic diamines and 4-trimelytoylanhydrchloride is controlled by controlling the equivalent ratio. Techniques for producing polyamideimide resins are known.

However, polyamideimide resins prepared from these patents have a disadvantage of insufficient dimensional stability. Therefore, if the dimensional stability of such a conventional polyamideimide is improved, the stability after processing will be improved and its use range such as the precision product field will be greatly increased.

Accordingly, the present inventors have been working to prepare a polyamideimide resin having excellent dimensional stability as described above, and in addition to the conventional polyamideimide resin prepared from a diamine compound and an hydride, the diamino aromatic carboxyl azide As a result of preparing a polyamideimide resin by further including the diamine compound in a ratio of 1: 0.001 to 1: 0.01, the dimensional stability was improved, and it was found that it can be used in various fields of precision parts for electronic parts. It became.

Accordingly, an object of the present invention is to provide a polyamideimide resin with improved dimensional stability.                         

The polyamideimide resin having improved dimensional stability of the present invention is a polyamide imide resin prepared from a diamine compound and an unhydride, and further, diamino aromatic carboxyl azide is 1: 0.001 to 1 with respect to the diamine compound. It is characterized by that it is further contained in a: 0.01 equivalence ratio.

Hereinafter, the present invention will be described in detail.

The present invention relates to a polyamideimide resin, in which a polyamideimide resin prepared from a conventional diamine compound and an hydride, further contains a diamino aromatic carboxy azide to improve water resistance.

Although the diamine compound used for superposition | polymerization of such polyamideimide of this invention is not specifically limited, Aromatic diamine compound is preferable, For example, metaphenyl diamine, paraphenyl diamine, p, p'- methylene bis aniline, p, p'-sulfonylbisaniline (p-aninophenyl) sulfone, 4,4'-oxydianiline and the like are used alone or in combination.

In addition, in the present invention, in order to improve the dimensional stability of the polyamideimide resin, diamino aromatic carboxy azide is further included in the ratio of 1: 0.001 to 1: 0.01 equivalents to the diamine compound.

Such diamino aromatic carboxy azide is at least one selected from the group of 3,5-diamino benzoic azide and 2,4-diamino benzoic azide, and particularly preferred is aromatic diamino benzoic azide.

When the diamino aromatic carboxy azide and the diamine compound of the present invention are added so as to deviate from the equivalent ratio, it is preferable that the diamino aromatic carboxy azide and the diamine compound are added in the molar ratio because a problem of greatly reducing the toughness and impact resistance of the product occurs.

The aromatic diamino benzoic azide of the present invention is prepared from diamino benzoic acid, the specific method of preparation is as follows. Diamino benzoic acid is dissolved in an organic solvent in a weight ratio of 15%, and then 2 to 6 equivalents of triethyl amine is added to diamino benzoic acid. After stirring the solution for 10 minutes, trivalent butoxycarbonyl anhydride is added in 3 to 8 equivalents to the diamino benzoic acid for the purpose of blocking the diamine group. The reaction is preferably reacted at 20 ^° C. at 60 ^° C. for 1 to 3 hours. The solution is extracted with other organic solvents under 1 molar concentration of potassium hydrogen sulfate to separate the organic layer, and the solvent is vaporized to obtain diaminobutoxy carbonyl benzoic acid in which diamine is blocked with trivalent butoxy carbonyl.

The blocked benzoic acid is dissolved in THF at 10% by weight, and then 1 to 2 equivalents of triethylamine are added to the benzoic acid. Ethylchloroformate and sodium azide are added to the solution in the amounts of 1-2 equivalents and 2-3 equivalents to benzoic acid, respectively. It is preferable to react the said reaction at -10-40 degreeC for 4 to 8 hours. The solution was extracted under water and diethyl ether to separate the organic layer, and then vaporized diethyl ether at low pressure to give a white solid in which benzoic acid was converted to benzoic azide. The two reactions blocked the diamine and changed the benzoic acid to benzoic azide. Acetic acid is dissolved in methylene chloride equivalent to 10% by weight of the two solutes with a solid obtained through the reaction and trifluoro corresponding to 25% by weight of the solid. The solution is left at room temperature for 24 to 36 hours. The oil layer is separated, washed with water, and then dissolved in methylene chloride to evaporate the solvent at low pressure, thereby obtaining a yellow solid from which trivalent butoxy carbonyl, which blocks diamine, is removed. The solid obtained in the reaction is diamino benzoic azide.

On the other hand, the organic solvent used for the polymerization of the polyamideimide resin of the present invention is N-methylpyrrolidone, N, N'-dimethylacetamide, N, N'-dimethylformamide, which is a non-reactive polar solvent containing nitrogen. And the like are generally used. In addition, phenols and phenols substituted with alkyl groups may also be used. For example, mixed solvents such as o-, m-, p-cresol and xylene are used.

Examples of the unhydride polymerized with the diamine compound include 4-trimelitoyl anhydride chloride, and in addition to 4-trimelitoyl anhydride bromide, 4-trimelitoyl anhydride iodide, and the like. Can be used.

The diamine compound and the unhydride of the present invention is preferably polymerized in an equivalent ratio of 1: 0.9 to 1: 1.1. If out of this range, the molecular weight of the polymerized resin is less than the appropriate level, there is a problem in the physical properties such as toughness, impact resistance and modulus during processing.

The method for producing a polyamideimide resin excellent in the dimensional stability of the present invention from the above compounds is explained as follows.

This polyamideimide resin of the present invention is carried out by dividing into two steps, first step is to add a diamino benzoic azide to the diamine mixture in an organic solvent, and 4-trimelytoyl anhydride, which is an unhydride Adding a chloride chloride to prepare a polyamide amic acid precursor of the polyamideimide.

The polyamide amic acid of the first stage is polymerized at a polymerization temperature of 10 to 60 ° C, preferably 20 to 60 ° C, 0.5 to 12 hours, preferably 2 to 4 hours. In addition, in the one-step reaction, the water content remaining in the solvent is preferably 1000 ppm or less in terms of preventing physical property degradation, and more preferably 300 ppm or less.

Next, in step 2, the polyamide-amic acid produced in step 1 is precipitated in distilled water to imide and crosslink in a powder state to prepare polyamideimide. Precipitation process is a process of precipitating the polyamide-amic acid solution in water. Since it must be possible to grind and stir at the same time as precipitation, a device such as a homomixer should be used. In this case, it is preferable to use ultrapure water having a resistance value of 5 MΩ / cm 3 or more. This is to prevent metal ions in the water from being adsorbed on the precipitate and affecting the properties of the final product. At this time, the volume ratio of the polyamide-amic-acid solution and ultrapure water used is 1: 3-1: 10.

After filtering the prepared powder, the powder is neutralized with ultrapure water having a resistance of 5 MΩ / cm 3 or more, and the filter and pure water washing are repeated until the acidity is 4 or more. The powder thus washed is dried for 12 hours in a vacuum drying oven at 60 ℃ using a vacuum pump. The intrinsic viscosity of the obtained polyamide-amic acid is 0.2-0.6 dl / g.

The imidization and crosslinking are performed by imidization reaction and crosslinking at 150 to 270 ° C. high temperature for 2 to 10 hours to prepare polyamideimide. In the imidization reaction, since water is synthesized as a product, it is preferable to stir to prevent agglomeration. The intrinsic viscosity of the polyamideimide thus obtained is 0.5 to 1.2 dl / g.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Example 1

3,5 in a mixture of 7.57 g (0.07 mol) of metaphenyldiamine and 26.03 g (0.13 mol) of 4,4'-oxydianiline (manufactured by Wakayama) in a 2 L reactor equipped with a stirrer, nitrogen purifier, thermometer, and chiller 0.18 g (0.001 mol) of diamino benzoic azide was added. To the mixture was added 142 g (32% by weight) of N-methylpyrrolidone having a water content of 300 ppm as a solvent, and then 40.43 g (0.192 mol) of 4-trimelitoyl anhydride chloride (Twinlake) The addition was carried out several times over one hour within the range not exceeding 55 ° C. Stirring was continued for 2 hours after the addition of 4- trimellitoylanhydride chloride was complete. The viscosity of this solution measured by a Brookfield viscometer at 25 ° C. was 51,800 cps.

After the reaction was completed, the reaction solution was run homomix and slowly poured into 1000 ml of ultrapure water to obtain a precipitate. After filtering the precipitate, the precipitate was added to 1000 ml of ultrapure water and stirred for 30 minutes. When precipitation and stirring were repeated five times and the measured pH reached 4.3, the neutralized polyamide-amic acid was dried in a 60 ° C. vacuum oven for 12 hours. The intrinsic viscosity of the dry powder was 0.30 dl / g. The polyamideimide resin was obtained by imidization and crosslinking the dry powder at 245 ° C. for 4 hours in a hot air oven under a nitrogen atmosphere, and the inherent viscosity of the film was 0.72 dl / g.

The physical properties of the resin thus obtained were measured as follows, and the results are shown in Table 1 below.

(1) intrinsic viscosity

0.1 g of polyamideimide powder is dissolved in 10 ml of N, N'-dimethylacetamide and measured with a Uberod viscometer in a thermostat maintained at 30 ° C.

(2) solution viscosity

Measured with a Bruckner viscometer at 25 ° C.

(3) Dimensional stability

The plate was manufactured by a compression molding machine, and then made into a 10 × 10 × 10 cube, and thermal expansion was measured by TMA.

Example 2

3,5-Diaminobenzoate in a mixture of 7.57 g (0.07 mol) of metaphenyldiamine and 26.03 g (0.13 mol) of 4,4'-oxydianiline in a 2 L reactor equipped with a stirrer, nitrogen purifier, thermometer and chiller Addition of 0.035 g (0.0002 mol) of azide was added. To the mixture was added 142 g (32% by weight) of N-methylpyrrolidone having a water content of 300 ppm as a solvent, and then 40.43 g (0.192 mol) of 4-trimelitoyl-anhydride chloride was kept at a temperature not exceeding 55 ° C. It was added in several portions over 1 hour within the range. Stirring was continued for 2 hours after the addition of 4- trimellitoylanhydride chloride was complete. The viscosity value which measured this solution with the Brookfield viscometer at 25 degreeC was 50000cps.

After the reaction was completed, the reaction solution was run homomix and slowly poured into 1000 ml of ultrapure water to obtain a precipitate. After filtering this precipitate, it added to 1000 ml ultrapure water and stirred for 30 minutes. When precipitation and stirring were repeated five times and the measured pH reached 4.3, the neutralized polyamide-amic acid was dried in a vacuum drying oven at 60 ° C. for 12 hours. The intrinsic viscosity of the dry powder was 0.29 dl / g. The dried powder was imidized and crosslinked at 245 ° C. for 4 hours in a hot air oven under a nitrogen atmosphere to obtain a polyamideimide resin, which had an inherent viscosity of 0.68 dl / g.

The physical properties of the resin thus prepared were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Comparative Example 1

300 ml of water content as a solvent in a mixture of 7.57 g (0.07 mol) of metaphenyldiamine and 26.03 g (0.13 mol) of 4,4'-oxydianiline in a 2 L reactor equipped with a stirrer, a nitrogen purifier, a thermometer and a chiller -142 g (32% by weight) of methylpyrrolidone was added and 40.43 g (0.192 mol) of 4-trimelytoyl anhydride chloride were added several times over an hour within a temperature not exceeding 55 ° C. Stirring was continued for 2 hours after the addition of 4- trimellitoylanhydride chloride was complete. The viscosity of this solution at 25 ° C. on a Brookfield viscometer was 51,000 cps.

After the reaction was completed, the reaction solution was started by homomixing and slowly poured into 1000 ml of ultrapure water to obtain a precipitate. The precipitate was filtered and then added to 1000 ml of ultrapure water and stirred for 30 minutes. When precipitation and stirring were repeated five times and the measured pH reached 4.3, the neutralized polyamide-amic acid was dried in a vacuum drying oven at 60 ° C. for 12 hours. The intrinsic viscosity of the dry powder was 0.31 dl / g. The dried powder was imidized and crosslinked for 4 hours at 245 ° C. under a nitrogen atmosphere in a hot air oven to obtain a polyamideimide resin, which had an inherent viscosity of 0.56 dl / g.

The physical properties of the resin thus prepared were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Comparative Example 2

3,5-diamino benzoic in a mixture of 7.57 g (0.07 mol) of metaphenyldiamine and 26.03 g (0.13 mol) of 4,4'-oxydianiline in a 2 L reactor equipped with a stirrer, nitrogen purifier, thermometer and chiller 0.7 g (0.004 mol) of azide was added. To the mixture was added 142 g (32% by weight) of N-methylpyrrolidone having a water content of 300 ppm as a solvent, and then 40.43 g (0.192 mol) of 4-trimelitoyl-anhydride chloride was kept at a temperature not exceeding 55 ° C. Add in several portions over 1 hour within the range. Stirring was continued for 2 hours after the addition of 4- trimellitoylanhydride chloride was complete. The viscosity value of this solution measured by the Brookfield viscometer at 25 degreeC was 54000 cps.

After the reaction was completed, the reaction solution was run homomix and slowly poured into 1000 ml of ultrapure water to obtain a precipitate. After filtering this precipitate, it added to 1000 ml ultrapure water and stirred for 30 minutes. When precipitation and stirring were repeated five times and the measured pH reached 4.3, the neutralized polyamide-amic acid was dried in a vacuum drying oven at 60 ° C. for 12 hours. The intrinsic viscosity of the dry powder was 0.30 dl / g. The dried powder was imidized and crosslinked in a hot air oven at 245 ° C. for 4 hours under a nitrogen atmosphere to obtain a polyamideimide resin, which had an inherent viscosity of 0.81 dl / g. However, the resin obtained in Comparative Example 2 had a problem that partial cracking occurred during molding.

The physical properties of the resin thus prepared were measured in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Input molar ratio of diamine compound / diamino benzoic azide ⁽¹⁾ 0.2 / 0.001 0.2 / 0.0002 0.2 / 0 0.2 / 0.004 Viscosity (cps) 51,800 50,000 51,000 54,000 Intrinsic viscosity (dl / g) 0.72 0.68 0.56 0.81 Thermal expansion coefficient (cm / cm ℃) 14 x 10 ^-5 15 x 10 ^-5 17 x 10 ^-5 - (Note) (1) The diamine compound is a mixture of 4,4'-oxydianiline and metaphenylenediamine.

As shown in the results of Table 1, in order to improve the dimensional stability of the polyamide-imide resin as described in the present invention, polyamideimide resin prepared by further adding a certain amount of diamino aromatic carboxy azide in a certain amount is excellent in dimensional stability As can be seen, the polyamideimide obtained in Comparative Example 2 in which the content of diamino aromatic carboxy azide deviates from the content of the present invention has a problem that partial cracking occurs during molding under the same conditions, so that the coefficient of thermal expansion cannot be measured. Therefore, its use as a resin is insufficient.

As described above in detail, according to the present invention, the polyamideimide resin prepared by adding diamino aromatic carboxy azide in a constant equivalent ratio to the diamine compound according to the present invention is greatly improved in dimensional stability and thus mechanically Excellent in physical properties, it can be applied to electrical and electronic parts and industrial molded parts.

Claims (4)

In a polyamideimide resin prepared by polymerizing a diamine compound, an hydride and a diamino aromatic carboxyl azide, The diamine compound may be metaphenyldiamine, paraphenyldiamine, p, p'-methylenebisaniline, p, p'-sulfonylbisaniline (p-aninophenyl) sulfone, 4,4'-oxydianiline and their Any one selected from the group consisting of a combination, The diamino aromatic carboxy azide is an aromatic diamino benzoic azide, The unhydride is any one selected from the group consisting of 4- trimellitoyl anhydride chloride, 4- trimellitoyl anhydride bromide, 4- trimellitoyl anhydride iodide, and combinations thereof, Wherein said diamino aromatic carboxyl azide is included in a ratio of 1: 0.001 to 1: 0.01 equivalents relative to said diamine compound. The method of claim 1, The aromatic diamino benzoic azide is polyamideimide resin, characterized in that any one selected from the group consisting of 3,5-diamino benzoic azide, 2,4-diamino benzoic azide and combinations thereof . The polyamideimide resin according to claim 1, wherein the diamine compound and the unhydride are reacted in an equivalent ratio of 1: 0.9 to 1: 1.1. a) diamine compounds under organic solvents, Diamino aromatic carboxyl azide in a ratio of 1: 0.001 to 1: 0.01 equivalents relative to the diamine compound and Anhydride in an amount ratio of 1: 0.9 to 1: 1.1, based on the diamine compound A first step of preparing a polyamide amic acid by polymerizing b) a second step of imidizing and crosslinking the polyamideamic acid to prepare a polyamideimide Method for producing a polyamideimide resin comprising a.