KR20030048669A - Manufacturing method of poly(amideimide) - Google Patents

Abstract

PURPOSE: A process for preparing polyamideimides is provided to obtain polyamideimide having high viscosity and strength, excellent moldability and uniform physical properties. CONSTITUTION: The process for preparing polyamideimides comprises the steps of: (a) polymerizing 4-trimellitoyl anhydride halide, 0.9 to 1.5 equivalents of an aromatic diamine based on 1 equivalent of 4-trimellitoyl anhydride halide, 0.01 to 0.1 equivalents of acetic anhydride based on 1 equivalent of 4-trimellitoyl anhydride halide in the presence of an organic solvent to obtain polyamide amic acid; and (b) carrying out imidation of the polyamide amic acid. The polyamideimide obtained by the process can be used as heat resistant materials, insulation coating materials, rigid plastic materials and metal substitutes.

Description

Manufacturing method of polyamideimide {MANUFACTURING METHOD OF POLY (AMIDEIMIDE)}

The present invention relates to a method for producing polyamideimide, and more particularly, to a method for producing polyamideimide having high viscosity and strength, excellent moldability, and uniform physical properties.

Since polyamideimide has excellent heat resistance and mechanical strength, polyamideimide homopolymers as well as polyamideimide copolymers and their precursor polymers are used for parts requiring properties such as abrasion resistance, flame retardancy, radiation resistance, and creep resistance. It is widely used as an industrial material. For example, molding polyamideimide is one of the representative thermoplastics used for producing moldings, having a heat deformation temperature of 278 ° C and a long service temperature of 200 ° C or higher.

As an example of a method of making polyamideimide, US Pat. No. 4,016,140 discloses a method of reacting a polycarboxylic acid anhydride derivative with a primary diamine to form a polymer. In addition, U.S. Patent No. 4,136,085 discloses polyamides by adding 4-trimellitoyl anyhydride halide and at least one aromatic diamine to trimellitic acid anhydride to react in an organic solvent. Disclosed is a method of making a mead. However, there is a problem that the polyimideamide prepared according to the above production methods does not have uniform physical properties.

The present invention has been made to solve the above problems, and an object thereof is to provide a method for producing a polyamideimide having high viscosity and strength.

In addition, another object of the present invention is to provide a method for producing polyamideimide having excellent moldability and uniform physical properties.

In order to achieve the above object, the present invention

a) 4-trimellitoylanhydride halide in an organic solvent, aromatic diamine having a ratio of 0.9 to 1.5 equivalents relative to 1 equivalent of 4-trimellitoylanhydride halide, and 4-trimelili Polymerizing acetic anhydride having a ratio of 0.01 to 0.1 equivalents to 1 equivalent of tonanhydride halide to prepare a polyamideamic acid;

b) a method for producing a polyamideimide comprising the step of imidating the polyamide amic acid.

Hereinafter, the present invention will be described in detail.

In the step a), 4-trimellitoylanhydride halide, 4-trimellitoylanhydride halide, aromatic diamine, and acetic anhydride are polymerized according to the above equivalent ratio to prepare polyamideamic acid, which is a precursor of polyamideimide.

To this end, first, diamine is dissolved in an organic solvent, and then 4-trimelytoyl anhydride halide is added dropwise. Since the heat of reaction is generated when the 4-trimelyltoyl hydride halide is added dropwise, it is added dropwise while continuing to cool the reaction. Acetic anhydride is added for the purpose of controlling the molecular weight of the polyamideimide, and is added with diamine at the beginning of the reaction, or added dropwise to the diamine with 4-trimelytoylanhydride halide, or 4-trimelytoylanhydride The halide can be added dropwise to the diamine followed by reaction.

The aromatic diamine is preferably added in an equivalent ratio of 1: 0.9 to 1.5, more preferably in an equivalent ratio of 1: 0.9 to 1.1 with respect to the 4-trimelyltoylanhydride halide.

The acetic anhydride is preferably added in an equivalent ratio of 1: 0.01 to 0.1, more preferably 1: 0.01 to 0.05, relative to the 4-trimelyltoyl anhydride halide.

Since the polyamideimide of the present invention is produced according to the composition ratio described above, it is excellent in viscosity, strength and moldability, and can be obtained reproducibly at a constant molecular weight, thereby ensuring uniform physical properties.

The polyamide-amic acid preparation reaction of step a) is preferably polymerized at -10 to 120 ℃ for 0.5 to 12 hours while mixing the diamine, 4- trimellitoyl anhydride halide, and acetic anhydride. More preferably, the reactants are polymerized at 20-60 ° C. for 2-4 hours.

As 4- trimellitoyl anhydride halide, 4- trimellitoyl anhydride chloride, 4- trimellitoyl anhydride bromide, or 4- trimellitoyl anhydride iodide may be used. For example, 4- trimellitoyl anhydride chloride can be used.

Examples of the aromatic diamine include metaphenylenediamine, paraphenylenediamine, p, p'-oxybisaniline, p, p'-methylenebisaniline, p, p'-oxyvinylaniline, p, p'-oxydianiline Or p, p'-sulfonylbisaniline (p-aninophenyl) sulfone, or mixtures thereof, may be used, but is not limited thereto.

As the organic solvent, N-methylpyrrolidone, N, N'-dimethylacetamide, and N, N'-dimethylformamide, which are generally non-reactive polar solvents containing nitrogen, are used. It is also possible to use phenols such as o, m, p-cresol and xenol and phenols substituted with alkyl groups.

In the reaction for producing the polyamide amic acid, a non-solvent may be added in addition to the solvents in order to lower the viscosity during the polyamide amic acid polymerization. The moisture content remaining in the non-solvent is 0.01 It is preferable that it is -1000 ppm, and it is preferable that it is 0.01-400 ppm. If the water content remaining in the solvent is outside the above range, the physical properties of the product may be lowered because water may escape during transport or storage.

In addition, in step b), the polyamide-amic acid prepared in step a) is imidized to prepare polyamideimide.

As a method of imidizing the polyamide-amic acid, a method of increasing the reaction temperature under the same reaction conditions as when polyamide-amic acid is prepared or imidizing the polyamide-amic acid dissolved in an organic solvent in a non-solvent The method of imidizing through neutralization, drying, and aging can be used.

When imidating the polyamide-amic acid produced by heating up in the imidation process of the said polyamide-amic acid, it is preferable to heat up to 50-60 degreeC, and it is more preferable to heat up to 50-55 degreeC.

In the case where the polyamideamic acid is imidized by precipitation, neutralization, drying, and aging in a non-solvent, as a non-solvent that can be used, a non-solvent generally used such as water, ethanol, methanol, or acetone may be used. Preferably, the polyamide-amic acid solution and pure water having 5 kW / cm 3 or more are used in an equivalent ratio of 1: 3 to 10. When using pure water of 5 kPa / cm 3 or more, metal ions in water are adsorbed on the precipitate to further improve the physical properties of the final product. In the precipitation step, the polyamide-amic acid solution is required to be precipitated in the non-solvent, and the precipitate is pulverized and stirred. Therefore, an apparatus such as a homomixer is used. After precipitating the polyamideamic acid, the precipitate precipitated in the non-solvent is neutralized by filtering and washing with pure water having a resistance of 5 kW / cm 3 or more. The precipitate is filtered and neutralized until the precipitate has a pH above 3.5. After neutralizing the precipitate, the neutralizer is put in a drying oven using an aspirator, and dried at a temperature of 60 to 150 ° C. for 0.5 to 12 hours. Then, the dried neutralized product is placed in a hot air oven at 200 to 240 ° C., and aged for 0.5 to 4 hours to prepare a polyamideimide powder.

The imidation ratio of the polyamideimide can be adjusted in the imidization step of the polyamideamic acid according to the use of the polyamideimide to be produced. In general, it is preferable to adjust the imidation ratio to 95 to 100% in order to manufacture the polyamideimide for molding, and to adjust the imidation ratio to 0 to 70% in order to prepare the polyamide for coating. The process of preparing polyamideimide by precipitating, neutralizing, drying and aging the polyamideamic acid in a non-solvent is preferably used when partially imidating the polyamideamic acid.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, an Example is for illustrating this invention and this invention is not limited only to these.

(Example 1)

2.39 g (0.0406 mol) of metaphenylenediamine, 32.36 g (0.163 mol) of p, p'-oxydianiline, and 0.842 g (0.0061) in a 2 L reactor equipped with a stirrer, nitrogen purge, thermometer, and chiller Mole) and then N-methylpyrrolidone having a water content of 350 ppm was added. To the mixture was added 41.5 g (0.197 mol) of 4-trimelyloyl anhydride chloride in several portions under 50 ° C. for 1 hour. 4-trimelyloyl anhydride chloride was added, and then the mixture was stirred for 3 hours to prepare polyamideamic acid. Next, the intrinsic viscosity of the polyamideamic acid prepared at 25 ° C. was measured with a Brunner viscometer. The intrinsic viscosity of the polyamide-amic acid according to Example 1 was 12500 cps.

The precipitate was slowly poured into 1000 ml of ultrapure water to obtain a precipitate. After filtering the precipitate, the filtered precipitate was added to 1000 mL ultrapure water again and stirred for 30 minutes to neutralize. After repeated precipitation and stirring five times, the pH of the neutralized product was 3.9. The neutralized product was dried in a 60 ° C. drying oven for 12 hours. The intrinsic viscosity of the dried neutralized material was measured and aged in a 220 ° C. hot air oven for 4 hours to obtain a polyamideimide powder. Subsequently, the intrinsic viscosity of the aged polyamideimide was measured, and then a specimen was prepared by applying the polyamideimide powder to a pressure of 350 kg / cm 2 at a temperature of 350 ° C. using an extruder. The intrinsic viscosity of the polyamideimide of Example 1 measured after the aging was 0.53 dl / g.

(Example 2)

Instead of 0.842 g (0.0061 mole) of acetic anhydride and 41.5 g (0.197 mole) of 4-trimelytoyl anhydride chloride, 1.408 g (0.0102 mole) of acetic anhydride, 40.648 g (0.193 mole) of 4-trimelitoyl anhydride chloride It carried out similarly to Example 1 except having added mole). The intrinsic viscosity of the polyamide-amic acid of the present Example 2 measured by the Brunner viscometer at 25 degreeC was 8100 cps, and the intrinsic viscosity of the polyamide-imide powder of this example 2 measured after aging was 0.50 dl / g.

(Comparative Example 1)

4.39 g (0.0406 mole) of metaphenylenediamine, 32.36 g (0.163 mole) of p, p'-oxydianiline, 0.842 g (0.0061 mole) of acetic anhydride, and 41.5 g (0.197 mole) of 4-trimelitoylanhydride chloride ), 4.758 g (0.044 mol) of metaphenylenediamine, 35.241 g (0.176 mol) of p, p'-oxydianiline, and 42.11 g of 4-trimelitoyl anhydride chloride, without adding acetic anhydride The same procedure as in Example 1 was carried out except that (0.20 mol) was added. The intrinsic viscosity value of the polyamide-amic acid of this comparative example 1 measured by the Bruckner viscometer at 25 degreeC was 6500 cps, and the intrinsic viscosity of the polyamide-imide of this comparative example 1 measured after aging was 0.41 dl / g.

(Comparative Example 2)

4.39 g (0.0406 mole) of metaphenylenediamine, 32.36 g (0.163 mole) of p, p'-oxydianiline, 0.842 g (0.0061 mole) of acetic anhydride, and 41.5 g (0.197 mole) of 4-trimelitoylanhydride chloride 4.325 g (0.04 mol) of metaphenylenediamine, 32.037 g (0.16 mol) of p, p'-oxydianiline, and 45.27 g of 4-trimelitoyl anhydride chloride, without adding acetic anhydride, instead of The same procedure as in Example 1 was carried out except that (0.215 mol) was added. The intrinsic viscosity of the polyamide amic acid of Comparative Example 2 measured at 25 ° C. was 7700 cps, and the intrinsic viscosity of the polyamideimide of Comparative Example 2 measured after aging was 0.44 dl / g.

The physical properties of the polyamideimide according to the Examples and Comparative Examples of the present invention were measured according to the following evaluation items, and are shown in Table 1 below.

(Evaluation item)

1) Intrinsic Viscosity: 0.1 g of the polyamideimide powder of this example and the comparative example was dissolved in 10 ml of N, N'-dimethylacetamide, and measured by a Ubbelohde viscometer in a thermostat maintained at 30 ° C.

2) Solution Viscosity: The viscosities of the polyamide-amic acid solutions of this example and the comparative example were measured by a Bruckner viscometer at 25 ° C.

3) Elongation at Break and Tensile Strength: The elongation at break and tensile strength of the polyamideimide of this Example and Comparative Example were measured by the ASTM D1708 method.

4) Water content: The water content of the polyamideimide powder of this example and the comparative example was measured by Karl-Fischer moisture meter.

In addition, TMAc, AA, ODA, and m-PDA shown in Table 1 are abbreviations of 4-trimelitoyl anhydride chloride, acetic anhydride, p, p'-oxydianiline, and metaphenylenediamine, respectively. .

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Input molar number of each reactant TMAc 0.197 0.193 0.20 0.215 AA 0.0061 0.0102 0 0 ODA 0.163 0.163 0.176 0.16 m-PDA 0.0406 0.0406 0.044 0.04 Intrinsic viscosity of polyamideamic acid (cps) (measured by Bruckner viscometer) 12500 8100 6,500 7700 Intrinsic viscosity of polyamideimide (㎗ / g) 0.53 0.50 0.41 0.44 Tensile Strength (kg / ㎠) 1160 950 550 760 Elongation at Break (%) 11 12 3.1 4.2 Water content (%) 0.02 0.01 0.02 0.02

As shown in Table 1, the polyamideimide of Examples 1 to 2 of the present invention showed a maximum tensile strength of at least 2 times and an elongation at break of up to 4 times as compared with Comparative Examples 1 and 2. Therefore, it can be confirmed that the strength and workability are improved compared to the polyamideimide prepared by the conventional manufacturing method.

The polyamideimide production method of the present invention can produce a polyamideimide for molding having a high viscosity and strength, excellent moldability and uniform physical properties.

In addition, the polyamideimide prepared according to the production method of the present invention can be used as a replacement for rigid plastic materials and metals through heat-resistant coating material, insulating coating material, and compression molding or injection molding.

Claims (5)

a) 4-trimellitoylanhydride halide in an organic solvent, aromatic diamine having a ratio of 0.9 to 1.5 equivalents relative to 1 equivalent of 4-trimellitoylanhydride halide, and 4-trimelili Polymerizing acetic anhydride having a ratio of 0.01 to 0.1 equivalents to 1 equivalent of tonanhydride halide to prepare a polyamideamic acid; b) A method for producing a polyamideimide comprising the step of imidating the polyamide amic acid. The method of claim 1, wherein the 4-trimmellitoyl-anhydride halide is 4-trimelytoyl-anhydride chloride, 4-trimelytoyl-anhydride bromide, or 4-trimelitoyl-anhydride iodide bromide Process for the production of phosphorus polyamideimide. The method of claim 1, wherein the aromatic diamine is metaphenylenediamine, paraphenylenediamine, p, p'-oxybisaniline, p, p'-methylenebisaniline, p, p'-oxyvinylaniline, p, p A method for producing a polyamideimide selected from the group consisting of '-oxydianiline and p, p'-sulfonylbisaniline (p-aninophenyl) sulfone. The method of claim 1, wherein the imidization is Precipitating the polyamideamic acid in the nonsolvent; Neutralizing the precipitate with pure water; Drying the neutralized product at a temperature of 60 to 150 ° C. for 0.5 to 12 hours; And Aging the dried product at a temperature of 200 to 240 ℃ for 0.5 to 4 hours Method of producing a polyamideimide that is carried out. The method of claim 1, wherein the imidization is Method for producing a polyamideimide is carried out by heating the polyamide amic acid to 50 to 60 ℃.