JPS60215025A - Injection-moldable aromatic polyamide-imide copolymer - Google Patents

Abstract

PURPOSE:The titled copolymer excellent in melt flow and mechanical properties, obtained by polycondensing an aromatic diamine (derivative) with an aromatic tricarboxylic acid (derivative) and an aromatic aminocarboxylic acid (devirative). CONSTITUTION:An aromatic diamine (derivative) is polycondensed with an aromatic tricarboxylic acid (derivative) and an aromatic aminocarboxlic acid (derivative) to obtain an injection-moldable aromatic polyamide-imide copolymer comprising 90-30mol% repeating units of formula I (wherein Ar1 is a bivalent aromatic residue and Ar2 is a trivalent aromatic residue in which two of the three valences are on two adjacent carbons) and 10-70mol% repeating units of formula II (wherein Ar3 is Ar1) and having a reduced viscosity of 0.3- 1.0dl/g when measured in an N-methylpyrrolidone solution of a concentration of 0.5g/dl at 25 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aromatic polyamide-imide resin, and more particularly to an aromatic polyamide-imide copolymer having a characteristic composition, which can be injection molded, and has excellent heat resistance.

Aromatic polyamide-imide resin is a useful resin material that has high heat resistance, excellent chemical resistance, and mechanical properties similar to aromatic polyimide resin, but it generally has poor melt flowability and cannot be used by melt molding methods such as injection molding. difficult to do.

In an attempt to improve the drawbacks of aromatic polyamide-imide resins, polyamide-imide copolymers consisting of trimellitic acid residues and multi-component diamine residues have been proposed (for example, U.S. Pat. No. 3,748 , No. 304, JP-A-4
7-8093, JP-A-56-112933, etc.).

However, these copolymers that have been proposed so far have problems such as low viscosity stability during melting, and are not necessarily satisfactory as injection molding materials.

Under such circumstances, the inventors of the present invention conducted intensive studies to establish an aromatic polyamideimide resin that can be injection molded and does not have the above-mentioned drawbacks. The present invention was completed after discovering that a copolymer containing three components, a group and an aromatic aminocarboxylic acid residue, in a specific ratio and having a molecular weight within a specific range has both excellent melt fluidity and excellent mechanical properties. I ended up doing it.

That is, the present invention is based on the formula % formula % (wherein Ar z and Ar 3 are divalent aromatic residues, A
r 2 is a trivalent aromatic residue in which the divalents are on adjacent carbon atoms. ), and has a molar composition ratio ^)/Y) of approximately 90/10 to 30/70,
0.5y/dl! The reduced viscosity measured at a concentration of N-methylpyrrolidone solution at a temperature of 25°C is approximately 0.3 to 1.0.
dl! The present invention provides an injection moldable aromatic polyamide-imide copolymer characterized in that: /g.

Ar of the component constituting the unit of formula ^) in the present invention
z is a divalent aromatic residue, and specific examples thereof (Xosha,
(Xotsu, 04℃.

(X), S building.

X-Shi Toda, Kon et al. and their nuclear substitution products can be listed. Among these, preferable Arz is [D
', +θ is now and now @, and particularly preferably +-0-.

These residues Ar□ are introduced into the inner unit from the corresponding aromatic diamine.

The component Ar2 is a trivalent aromatic residue with one divalent on the adjacent carbon atom that should be bonded to the two carbonyl groups participating in the imide ring formation. It is possible to list the substitutions.

These residues Ar 2 are introduced into the Bumon unit from the corresponding aromatic tricarboxylic acids or derivatives thereof.

The unit represented by the above formula (A) may contain an amic acid portion which is not ring-closed to an imide, a portion having a head-to-head bond structure, etc. in a proportion of about 30 mole or less.

Ar3 of the component constituting the Bumon unit in the present invention is 2
This is an aromatic residue with a specific value.

These residues Ar3 are introduced into the unit of the above formula from the corresponding aromatic aminocarboxylic acid.

The aromatic polyamide-imide copolymer of the present invention, which has both excellent melt flowability and excellent mechanical properties, contains the units of the above formula 4 and Bumon units in a specific ratio, and has a narrow molecular weight and a specific This is achieved only when the ratio is within the range, and one of the necessary conditions, the ratio between the two, is on a molar basis ^/(Bl-90/10 to 30/70, preferably 80
/20 to 50150. (c) The value of l/(B) is 9
If it is larger than 0/10, the melt fluidity is poor and injection molding is substantially difficult, and (A) /
(If the value of 81 is less than 30/70, it is not preferred because it has low melt fluidity and does not exhibit the high heat resistance and excellent mechanical properties characteristic of aromatic polyamide-imide resins.

The other necessary condition, the molecular weight, is approximately 0.3 to 1, Od//f, preferably 0 as a reduced viscosity value measured in an N-methylpyrrolidone solution with a concentration of 0.5 f/dr at a temperature of 25°C. .4 to 0.8 dl/f. A low molecular weight copolymer with a reduced viscosity value of less than about 0.3 dl/9 is undesirable because only a brittle molded product can be obtained.
Furthermore, copolymers having a high molecular weight greater than 1. Od//f are not preferred because they have low melt fluidity and are virtually impossible to injection mold.

The aromatic polyamide-imide copolymer of the present invention is an aromatic diamine or a derivative thereof giving the above-mentioned Ar
aromatic tricarboxylic acid or its derivative giving x,
And, it can be produced from aromatic aminocarboxylic acids or derivatives thereof which provide Ar3 by various production methods applicable to aromatic polyamideimides or aromatic polyamides. Examples of these production methods include a method of polycondensing aromatic diamine and an acyl halide of an aromatic polycarboxylic acid (Japanese Patent Publication No. 15637/1983, Japanese Patent Publication No. 10863/1983, Japanese Patent Publication No. 10863/1989,
98 Publication, etc.), Yoshi.

Method of polycondensing aromatic diamine with aromatic polycarboxylic acid or phenyl ester of aromatic aminocarboxylic acid (JP-A-48-34297, JP-A-52-8)
No. 2996, etc.), a method of heating an aromatic diamine and an aromatic tricarboxylic anhydride in the presence of a dehydration catalyst in an organic polar solvent (Buddhist Patent No. 1,515,06),
6, JP-A-56-112933, etc.). Among these production methods, the method of causing an aromatic diamine and an aromatic tricarboxylic acid anhydride to undergo a thermal reaction is an economical method and is preferably employed.

In the various production methods mentioned above, polycondensation reactions are performed in the presence of monofunctional carboxylic acids, carboxylic acid anhydrides, carboxylic acid halides, amines, etc. for modification of terminal groups, or post-treatment with these. etc. are possible arbitrarily.

That is, the aromatic polyamideimide copolymer of the present invention has -N
HCO-@), NHCOCH3° optionally included. In addition, the above formula (A
) may contain repeating units other than the units represented by Bumon. Specific examples of these other repeating units include -fHN-A r-NHCO-A'r -CQ-)-.

Here, Ar and Nr represent a divalent aromatic residue, and r represents a tetravalent aromatic residue.

The aromatic polyamide-imide copolymer of the present invention contains a small amount of a reinforcing agent, an abrasion resistance improver, a flame retardance improver, an electrical property improver,
There is no problem in adding additives such as acid resistance improvers and stabilizers, fillers, or blending other resins.

Thus, the aromatic polyamide-imide copolymer of the present invention can be processed by various melt molding methods including injection molding, and can easily give various molded products having excellent physical properties. These molded products can be used in a variety of applications such as automobile parts, electrical and electronic parts, etc. by taking advantage of their excellent heat resistance, mechanical properties, electrical properties, chemical resistance, etc.
Its industrial value is enormous.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The scope of the present invention is not limited by these examples.

In addition, ηs p/C in the examples is 0.59/di
This is the reduced viscosity measured at 25°C for an N-methylpyrrolidone solution with a concentration of 400ff/Cal. 1m in diameter under the conditions of
This is calculated from the outflow velocity of the resin extruded from the nozzle.

In addition, the term "strand" refers to the linear molded resin extruded at this time.

Reference Example This reference example is one of the methods for producing the aromatic polyamide-imide copolymer of the present invention, and shows the general method used for producing the aromatic polyamide-imide copolymer of the following Examples and Comparative Examples. It is something that

500- equipped with temperature needle, nitrogen inlet tube, distillation port, and stirrer
In a separable flask, a predetermined amount of a mixture consisting of an aromatic tricarboxylic acid derivative, an aromatic diamine and an aromatic aminocarboxylic acid, 0.2 mol, benzoic acid 0.005 mol,
0.005 mol of phosphorous acid and 180 mZ of sulfolane
The mixture was stirred while blowing nitrogen into the mixture, and the stirring was continued for about 3 hours to substantially complete the polycondensation reaction. During this time, the produced water was distilled off together with some sulfolane and continuously taken out of the reaction system. After the reaction operation was completed, the reaction mixture obtained as a viscous solution was vigorously stirred with a mixer. Pour in ion-exchanged water,
The resulting aromatic polyamide-imide copolymer was precipitated.

The copolymer was delivered to each house, washed with 500 g of boiled acetone, and then dried under reduced pressure at 180°C for 24 hours.

In this way, the aromatic polyamide-imide copolymer of the present invention was obtained in a yield of 96 to 98 cm. The production of copolymers with different ηsp/C values was achieved by adjusting the amount of benzoic acid used and the reaction time.

Example 1 Trimethic anhydride 26°88F (0.14 mol) as aromatic tricarboxylic acid derivative, 4,4'-diaminodiphenyl ether 28.00 f as aromatic diamine
An aromatic polyamide-imide copolymer was produced by the method of the reference example using m-aminobenzoic acid (0.14 mol) and m-aminobenzoic acid (8.22M, 0.06 mol) as the aromatic aminocarboxylic acid. The obtained copolymer has a concentration of 0.604 dl/l
It was confirmed that it was polyamide-imide from the infrared absorption spectrum showing the characteristic absorption of an imide group at 1775 ox and 1715C11 and that of an amide group at 1665CII-1. Furthermore, the elemental analysis results of the copolymer showed good agreement with the theoretical values calculated using the structural formula, as shown below.

Elemental analysis results of the aromatic polyamide-imide copolymer at 290°C and 310°C
The apparent melt viscosities at °C were 6 x 106 poise and 3 x 10' poise, respectively, and had sufficient practical melt fluidity to withstand injection molding. Further, the strand was strong enough to not break even when bent by 18°.

Examples 2 to 4, Comparative Examples 1 to 3 Repeating units shown in Table 1 obtained in the same manner as Example 1 and η
The temperature at which the apparent melt viscosity of an aromatic polyamideimide copolymer having an sp/C value becomes 1XIO3 poise (referred to as flow point) and the strength of the strand were measured. The results are shown in Table 1. It is clear from this that the aromatic polyamide-imide copolymer of the present invention is a useful resin having both high melt fluidity and excellent mechanical properties.

Claims (1)

[Claims] (1) Formula % Formula % (wherein A r and Ar 3 are divalent aromatic residues,
Ar z is a trivalent aromatic residue in which the divalents are on adjacent carbon atoms. ), and the composition ratio (A)/(B) on a molar basis is approximately 90/10 to 30/70.
and 0. ．． N-methylpyrrolidone solution with a concentration of 5f//di, the reduced viscosity measured at a temperature of 25°C is approximately 0.
．． An injection-moldable aromatic polyamide-imide copolymer having a molecular weight of 3 to 1.0 dl/f. (2) The injection moldable aromatic polyamide-imide copolymer according to claim 1, characterized in that the composition ratio is 80/20 to 50/50. +31 The injection moldable aromatic polyamide-imide copolymer according to claim 1, characterized in that the reduced viscosity is 0.4 to 0.8 dl/9. (4) Ar 2 in the repeating unit represented by formula 4 is a divalent aromatic residue containing 80 moles or more of Ar 4+ 2. The injection moldable aromatic polyamide-imide copolymer according to claim 1. (Formula 51 (Injection moldable aromatic polyamide-imide copolymer according to claim 1, characterized in that Ar 3 represented by Bl is ゝ[S'). Argon machining in the repeating unit is (
3. The injection moldable aromatic polyamide-imide copolymer according to claim 2, wherein Arta is 疋 and Ars in the repeating unit represented by Bumon is 竩r. (7) The injection moldable aromatic polyamide-imide copolymer according to claim 6, which has a reduced viscosity of 0.4 to 0.8 dl/1/.