JPS60158222A - Production of polyether-imide-amide - Google Patents

Abstract

PURPOSE:To obtain a polyether-imide-amide excellent in mechanical properties and heat resistance, by polycondensing a polyamide forming monomer with an amino-terminated polyoxyalkylene and an acid anhydride. CONSTITUTION:A polyamide-forming monomer (A) is polycondensed with an amino-terminated polyoxyalkylene (B) of formula I (wherein R<1> and R<2> are each a 3C or higher alkylene, and n is 2-60) and an acid anhydride (C) of formula II(wherein R is an aromatic hydrocarbon residue). Examples of monomers (A) include omega-lactams, omega-aminocarboxylic acids and salts between diamines and dicarboxylic acids. The amount of component A used is preferably 40-90wt% based on the total components. Component B or both of component B and a diamine (D) are used preferably in such amounts that the equivalent ratio of the amino groups to the total of the carboxyl groups and acid anhydride groups of component C is 0.9-1.1.

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 component into polyamide, good flexibility and 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 polyether diol or polyether diamine is polycondensed with the polyamide component using an equivalent amount of dicarboxylic acid 9, for example, an aliphatic dicarboxylic acid as a chain extender. Obtaining ether amide. In either case, a large amount of polyether component is required to obtain a polymer that provides low temperature impact resistant fabrics with good flexibility. However, as the proportion of the polyether component in the Schiff polymer increases, flexibility and low-temperature properties increase, but there are disadvantages in that rigidity, heat resistance, etc. decrease. In addition, when the molecular weight of the polyether component among the ingredients increases, the compatibility with the polyamide-forming monomer 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. It has the disadvantage of That is, 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) Polyamide-forming monomer (B) Formula H2N -R' -0+R20 AyuR'-NH2
(In the formula, R1 and R2 are each an alkylene group having 5 or more carbon atoms, and n is 2 to 60.) and (In the formula, R is an aromatic hydrocarbon residue. Provided is a method for producing polyetherimide amide, which is characterized by carrying out double condensation of acid anhydrides represented by the following groups.

The present invention has the advantage that since an acid anhydride is used, a single 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.

Examples of the polyamide-forming monomer (A) include ω-lactams, ω-aminocarboxylic acids, and salts of diamines and dicarboxylic acids. As a specific example of ω-lactam,
Mention may be made of 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 ethylene diamine, trimethylene cyanide, tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, and dodecamethylene diamine.

2.2.4-72,4.4-)limethylhexamethylenediamine, 113-/1,4-bis(aminomethyl)cyclohexane, bis(4,4,'-aminocyclohexyl)methane + m/p- With diamines such as xylylene diamine, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, dodecanoic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid. Examples include salts with such dicarboxylic acids.

Terminal amine polyoxyalkylene (B) has linear or branched oxyalkylene repeating units having 6 or more carbon atoms in one molecular chain, and has amine groups at both ends of the molecular chain.2For example, propylene It can be synthesized by introducing an amine 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. The terminal amine polyoxyalkylene (B) encapsulates a polymer having at most 50 moles of oxyethylene repeating units in its main chain. A specific example is Toshiso.

Examples include polyoxypropylene amine and bis(o-aminopropyl) polytetrahydrofuran.

In addition, in the present invention, the terminal amine polyoxyalkylene (B) described above and a diamine (D) selected from aliphatic diamines, alicyclic diamines, and aromatic diamines may be used in combination to improve heat resistance. .

Specific examples of diamine (D) include ethylenediamine,
Trimethylene diamine, tetramethylene diamine, hexamethylene cyanide, undecamethylene diamine, dodecamethylene diamine, dimer diamine (oleic acid,
Dimeric aminated products of unsaturated fatty acids such as linoleic acid and lylunic acid).

2.2.4-72,4.4- Aliphatic diamines such as trimethylhexamethylene diamine; 1,1-71,
4-bis(aminomethyl)/chlorohexane, bis(4,
Examples include alicyclic diamines such as 4'-aminocyclohexyl)methane, and aromatic cyabane such as p-xylylene cyabane. 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-
) Ricarboxylic acid-1,8 anhydride, naphthalene 7-1.4
．． 5-) +) Carboxylic acid-4,5 anhydride.

In the present invention, each of the above components (A), (B) and (C).

Alternatively, add component (D) to this to cause polycondensation.

Manufactures 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), component (B) and diamine (D
) The ratio of the amount of diamine (D) used to the total amount of is.

It is preferably within 70% by weight, particularly within 50 parts by weight. Component (B) or component (B) and diamine (D)
It is preferable to use the amine group in an amount of 0.9 to 1.1 equivalents based on the total of the carboxyl group and acid anhydride group of component (C).

Polycondensation is carried out by known methods. For example, 150-65
Melt polycondensation is carried out at a temperature of 0°C, preferably 200-300°C. When using a lactam or a salt consisting of a diamine and a dicarboxylic acid as component (A), polycondensation is started in a pressurized container under a pressure of about 1 to xoK9/- in the presence of an appropriate amount of water, and then the pressure is released. Depending on the situation, the pressure may be reduced to complete the heating polycondensation. When ω-aminocarboxylic acid is used as component (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 is.

During or after the polycondensation, additives such as antioxidants, light and heat stabilizers, flame retardants, pigments, fillers, and glass fibers can be included.

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 products include injection molded products, pipes, and hoses.

Examples include extruded products such as 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 resins, and when used in a blend with polyamide resins, 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) was 0.5 wt/v at 25°C in metacresol.
Measured at a1%. Melting point (Tm) and glass transition point (T
, ) were measured by DSC. The polymer was formed into a film by hot pressing, and the tensile properties of the bone-dry film were measured at 24°C and a relative humidity of 65°C. or.

Thermal stability was measured using a differential thermal balance (heating rate: 10° C./min).

Example 1 Is, o o parts of ω-aminododecanoic acid, 8.392 parts of polyoxypropylene amine (manufactured by Jefferne Chemical Co., Ltd., Jeffermine D-400) and 3.608 parts of trimellitic anhydride were mixed with a stirrer. It was charged into a reaction vessel. 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, 6.081 parts of polyoxypropylene amine (Jeffamine D-400, manufactured by Jefferson Chemical Company), and 2,919 parts of trimellitic anhydride were charged into a reaction vessel equipped with a stirring device. is. 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 50.000 parts of ω-amine dodecanoic acid, 45.620 parts of polyoxypropylene amine (Jeffamine D-2000, manufactured by Jefferson Chemical Company), and 4.380 parts of trimellitic anhydride were charged into a reaction vessel equipped with a stirring device. is.

This was subjected to polycondensation under the same conditions as in Example 2 to obtain a slightly yellow, flexible and tough polymer.

Example 4 30.000 parts of ω-aminododecanoic acid, 18.416 parts of polyoxypropylene amine (manufactured by Jefferne Chemical Co., Ltd., Jeffermine D-2000), and 1.584 parts of trimellitic anhydride were placed in a reaction vessel equipped with a stirring device. I prepared it.

This was subjected to polycondensation under the same conditions as in Example 2 to obtain a slightly yellow, flexible and tough polymer.

Example 5 21.000 parts of ω-aminododecanoic acid, 8.212 parts of polyquine propylene amine (Jeffamine D-2000, manufactured by Jefferson Chemical Company), and 0.788 parts of trimellitic anhydride were charged into a reaction vessel equipped with a stirring device. is. This was polycondensed under the same conditions as in Example 2 to obtain a slightly yellow and tough polymer.

Example 6 ω-Aε nododecanoic acid 18.0 Oo parts, His(3-
abanozolovir) polytetrahydrofuran (BAS F
Co., Ltd., average molecular weight: approximately 750) and 2.446 parts of trimellitic anhydride were charged into a reaction vessel equipped with a stirring device. 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-abanododecanoic acid, 11.975 parts of polyoxypropylene amine (Jeffamine D-2000, manufactured by Jefferson Chemical Company), 5.130 parts of dimer diamine [Henkel Nippon ■g], and anhydrous triamine 2.897 parts of mellitic acid was 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 (polymerized products) obtained in each of the above Examples.

Claims (1)

[Claims] (A) Polyamide-forming monomer (B) 2H2N-R'-0-(-R20R'-NH
2 (wherein R1 and R2 are each an alkylene group having 3 or more carbon atoms, and n is 2 to 60), and (C) a terminal amine polyoxyalkylene represented by the formula HOOC-R>. A method for producing sulpolyetherimide amide, comprising condensing nine acid anhydrides represented by O (wherein R is an aromatic hydrocarbon residue).