JPH0374254B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing novel polyetherimide amides, in particular polyetherimideamides having excellent mechanical properties and heat resistance. Generally, by incorporating polyether components into polyamide, good flexibility, low temperature impact resistance,
Methods for obtaining polyamides having dyeability, hygroscopicity, antistatic properties, etc. are known. In the above method, polyether diol or polyether diamine is used as the polyether component, and an equivalent amount of dicarboxylic acid, such as an aliphatic dicarboxylic acid, is used as a chain extender and polycondensed with the polyamide component to form a polyether ester amide. Or polyether amide is obtained. In either case, a large amount of polyether component is required to obtain a polymer with good flexibility and low temperature impact resistance. However, when the proportion of the polyether component in the polymer increases, flexibility, low-temperature properties, etc. increase, but stiffness, heat resistance, etc. decrease. In addition, when the molecular weight of the polyether component among the charged components increases, the compatibility with the raw material component (A) decreases, and when dicarboxylic acid is used as a chain extender, the polymerization system becomes non-uniform and a high molecular weight product cannot be obtained. The disadvantage is that there is no In other words,
The molecular weight of the polyether component used is limited. The purpose of the present invention is to overcome the above-mentioned drawbacks while maintaining various properties such as flexibility, low-temperature impact resistance, dyeability, hygroscopicity, and antistatic property, and to have excellent mechanical properties and thermal stability. The object of the present invention is to provide a new method for producing polyetherimide amide. According to the invention, (A) a nylon salt of an ω-lactam and/or an ω-aminocarboxylic acid and/or a diamine and a dicarboxylic acid (B) formula H ₂ N−R ¹ −O−(R ² O−) _o R ¹ -NH ₂ (In the formula, R ¹ and R ² are each an alkylene group having 3 or more carbon atoms, and n is 2 to 60.)
Terminal aminopolyoxyalkylene represented by, and (C) formula A method for producing a polyetherimide amide is provided, which is characterized by polycondensing an acid anhydride represented by the formula (wherein R is an aromatic hydrocarbon residue). In the present invention, since an acid anhydride is used, there is an advantage that the polymerization system is uniform and a high molecular weight product can be obtained without being affected by the molecular weight of the terminal aminopolyoxyalkylene used. Specific examples of ω-lactams include caprolactam, enantlactam, decalactam, undecalactam, and dodecalactam. ω-
Specific examples of aminocarboxylic acids include 6-aminocaproic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Specific examples of salts of diamine and dicarboxylic acid include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-/2,4,4-trimethyl hexamethylene diamine, 1,3-/1,
4-bis(aminomethyl)cyclohexane, bis(4,4'-aminocyclohexyl)methane, m
-/p-xylylenediamine and diamines such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, and terephthalic acid. Examples include salts with acids and dicarboxylic acids such as isophthalic acid. Terminal amino polyoxyalkylene (B) has linear or branched oxyalkylene repeating units having 3 or more carbon atoms in the molecular chain and has amino groups at both ends of the molecular chain, such as propylene. It can be synthesized by introducing an amino group at the end of a polymer obtained by single or copolymerization of oxide or tetrahydrofuran. A preferable value of n in the above formula is 4 to 40. Note that the terminal aminopolyoxyalkylene (B) encapsulates a polymer having at most 50 mol% of oxyethylene repeating units in its main chain. Specific examples include polyoxypropylene amine and bis(3-aminopropyl) polytetrahydrofuran. Furthermore, in the present invention, the terminal aminopolyoxyalkylene (B) described above and a diamine (D) selected from aliphatic diamines, alicyclic diamines, and aromatic diamines can also be used in combination to improve heat resistance. . Specific examples of diamine (D) include ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, dimer diamine (unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid). dimeric aminated product),
Aliphatic diamines such as 2,2,4-/2,4,4-trimethylhexamethylene diamine; 1,3
Examples include alicyclic diamines such as -/1,4-bis(aminomethyl)cyclohexane and bis(4,4'-aminocyclohexyl)methane; and aromatic diamines such as m-/p-xylylene diamine. Among these diamines, dimer diamines are preferably used. Specific examples of the acid anhydride (C) include trimellitic anhydride, hemimellitic anhydride, naphthalene-1,
2,5-tricarboxylic acid-1,2 anhydride, naphthalene-1,3,8-tricarboxylic acid-1,8 anhydride, naphthalene-1,4,5-tricarboxylic acid-
Examples include 4,5 anhydride. In the present invention, each of the components (A), (B) and (C), or the component (D) is added thereto and polycondensed to produce polyetherimide amide. The ratio of component (A) used to all components is preferably 15 to 95% by weight, particularly 40 to 90% by weight. When using diamine (D), the usage ratio of diamine (D) to the total amount of component (B) and diamine (D) is 70% by weight.
It is preferably within 50% by weight, particularly within 50% by weight.
Component (B) or component (B) and diamine (D) can be used in such a way that the amino group thereof is 0.9 to 1.1 equivalent to the total of the carboxyl group and acid anhydride group of component (C). preferable. Polycondensation is carried out by known methods. For example, 150
Melt polycondensation is carried out at a temperature of ~350°C, preferably 200-300°C. When using a salt consisting of a lactam or a diamine and a dicarboxylic acid as component (A), polycondensation is initiated in a pressurized container under a pressure of about 1 to 30 kg/cm ² in the presence of an appropriate amount of water, and then the pressure is released and further Depending on the case, the pressure may be reduced to complete the heating polycondensation. component
When ω-aminocarboxylic acid is used as (A), polycondensation is started under normal pressure, and depending on the case, the pressure is reduced to complete heating polycondensation. The polyetherimide amide obtained in the present invention may contain additives such as antioxidants, light and heat stabilizers, flame retardants, pigments, fillers, and glass fibers during or after polycondensation. . The polyetherimide amide obtained by the present invention can be easily processed and provides molded products with excellent heat resistance, water resistance, flexibility, low-temperature impact resistance, rubber elasticity, etc. Such molded articles include injection molded articles, extruded articles such as tubes, hoses, profiles, sheets, monofilaments, and fibers. The polyetherimidoamides according to the invention can also be used as coating materials. Furthermore, the polyetherimide amide according to the present invention has good compatibility with polyamide resin,
When blended with polyamide resin, its impact resistance, flexibility, and elasticity can be significantly improved. The present invention will be explained below with reference to Examples. In addition,
In the Examples, "part" means "part by weight". Relative solution viscosity (ηr) in metacresol at 25°C;
Measured at 0.5wt/vol%. Melting point (Tm) and glass transition point (Tg) were measured by DSC. The polymer was heat-pressed into a film, and the tensile properties of the bone-dry film were measured at 24°C and 65% relative humidity. or,
Thermal stability was measured using a differential thermal balance (heating rate: 10°C/min). Example 1 18.000 parts of ω-aminododecanoic acid, polyoxypropylene amine (manufactured by Freuderson Chemical Co., Ltd.)
8.392 parts of Difurmine D-400) and 3.608 parts of trimellitic anhydride were placed in a reaction vessel equipped with a stirrer. This was polycondensed at 240°C under a nitrogen atmosphere for 10 hours, and then cooled to obtain a slightly yellow, flexible, and tough polymer. Example 2 21.000 parts of ω-aminododecanoic acid, polyoxypropylene amine (manufactured by Freuderson Chemical Co., Ltd.)
6.081 parts of Difurmine D-400) and 2.919 parts of trimellitic anhydride were charged into a reaction vessel equipped with a stirrer. This was polycondensed at 240°C under a nitrogen atmosphere for 8 hours, and then cooled to obtain a slightly yellow, flexible and tough polymer. Example 3 50.000 parts of ω-aminododecanoic acid, polyoxypropylene amine (manufactured by Freuderson Chemical Co., Ltd.)
45.620 parts of Difurmine D-2000) and 4.380 parts of trimellitic anhydride were charged into a reaction vessel equipped with a stirrer. This was subjected to polycondensation under the same conditions as in Example 2,
A slightly yellow, flexible and tough polymer was obtained. Example 4 30.000 parts of ω-aminododecanoic acid, polyoxypropylene amine (manufactured by Freuderson Chemical Co., Ltd.,
18.416 parts of Difurmine D-2000) and 1.584 parts of trimellitic anhydride were charged into a reaction vessel equipped with a stirrer. This was subjected to polycondensation under the same conditions as in Example 2,
A slightly yellow, flexible and tough polymer was obtained. Example 5 21.000 parts of ω-aminododecanoic acid, polyoxypropylene amine (manufactured by Freuderson Chemical Co., Ltd.)
8.212 parts of Difurmine D-2000) and 0.788 parts of trimellitic anhydride were placed in a reaction vessel equipped with a stirrer. This was polycondensed under the same conditions as in Example 2 to obtain a slightly yellow and tough polymer. Example 6 18.000 parts of ω-aminododecanoic acid, bis(3-aminopropyl)polytetrahydrofuran (BASF
Co., Ltd., average molecular weight: approximately 750) and 2.446 parts of trimellitic anhydride were charged into a reaction vessel equipped with a stirrer. This was polycondensed at 240°C for 6 hours and then cooled to obtain a pale yellow, flexible and tough polymer. Example 7 30.000 parts of ω-aminododecanoic acid, polyoxypropylene amine (manufactured by Freudson Chemical Co., Ltd.,
Dimer Diamine D-2000) 11.973 parts Dimer Diamine (manufactured by Henkel Nippon Co., Ltd.) 5.130 parts and trimellitic anhydride 2.897 parts were charged into a reaction vessel equipped with a stirring device. This was polycondensed under the same conditions as in Example 2 to obtain a pale yellow, flexible and tough polymer. Table 1 shows the physical properties of the polymers obtained in each of the above Examples. 【table】

Claims (1)

[Claims] 1 (A) Nylon salt of ω-lactam and/or ω-aminocarboxylic acid and/or diamine and dicarboxylic acid (B) Formula H ₂ N−R ¹ −O−(R ² O− ) _o R ¹ -NH ₂ (In the formula, R ¹ and R ² are each an alkylene group having 3 or more carbon atoms, and n is 2 to 60.)
Terminal aminopolyoxyalkylene represented by, and (C) formula A method for producing polyetherimide amide, which comprises polycondensing an acid anhydride represented by the formula (wherein R is an aromatic hydrocarbon residue).