JPH02229827A - Wholly aromatic copolymer polyamide and molded article thereof - Google Patents

Abstract

PURPOSE:To obtain the title polyamide soluble in organic solvents having low toxicity to organisms, excellent spinning stability, high mechanical properties, heat resistance and flame retardance, comprising a specific repeating unit. CONSTITUTION:The aimed polyamide having a main repeating unit shown by formula I and comprising diamine components shown by formula II (X is halogen; m and n are <=4 integer) to formula IV. The diamine components are preferably in the range of C, D, E, F, G and H and an amine component shown by formula II is preferably chlorobenzidine group, especially 3,3'- dichlorobenzidine.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is directed to a novel wholly aromatic polyamide that has excellent mechanical properties such as strength and modulus, and is rich in heat resistance, flame retardance, and chemical resistance. (aramid). More specifically, it relates to a copolymerized aramid that is soluble in 81-positive solvents and has good 1-processability. [Prior art] Aramid has high strength. 4 is widely used in fibers, films, etc. due to its high modulus and high heat resistance.
In particular, boly p-phenylene terephthalamide (P }) 1゛A), which is a rose-shaped aramid, has become the mainstream aramid for industrial materials, protective equipment, etc., taking advantage of its characteristics. However, when looking at the production and spinning molding of PPT A, there are problems caused by the rigidity of the molecule, and M1 uses hexamethylphosphorotriamide, which is highly toxic to living organisms, as the polymerization reaction solvent. In addition, a liquid crystalline spinning dope must be made into pA using concentrated sulfuric acid, and so-called liquid crystal spinning must be performed. However, in order to neutralize this sulfuric acid, a large amount of neutralization is required, and =a ions from these neutralizing agents are mixed into the product, impairing the quality of the product. It is also disadvantageous in terms of process. On the other hand, an attempt has been made to simplify the process by preparing an isotropic spinning stock solution using a general organic polar solvent for polymerizing Fg. Specifically, a method of copolymerizing ether bonds into molecular chains to improve solubility (
tJ Epa, JP-A-51-76386, JP-A-51-1
No. 34743, JP-A-51-136916, Special [1st issue No. 61-252229, JP-A-62-27431,
JP-A-62-225530, JP-A-62-17702
No. 2, Japanese Unexamined Patent Publication No. 177023/1983, etc.), and many others have been proposed. Among these, copolymerized aramid, which is a copolymerization of P-phenylenediamine (PPDA) and 3,4°-diaminodiphenyl ether (3.4'DAPE), has excellent strength, rigidity, and chemical resistance. N-methyl pyrrolidone (N-IP), which is a polymer with ft, and is a general organic polar solvent, can be used as a polymerization reaction solvent, and the polymer solution after this polymerization reaction can be directly used. It can be used for spinning, etc., making it possible to significantly improve the process. Introducing ether bonds, which are flexible bonding species, into the polymer chain is an effective means in terms of the solubility propensity L, but as can be inferred from the primary structure of the polymer, heat resistance. It has not yet achieved sufficient performance in terms of physical properties such as rigidity and miscellaneous flammability. 6 When seeking even higher mechanical properties, heat resistance, and flame retardance, it is also soluble in organic solvents.
Currently, aramid, which can be manufactured using a simple manufacturing process, is not yet available. Furthermore, in recent years, flame retardancy and non-combustibility have been required more than ever from the viewpoint of safety, and this performance is especially necessary for safety protection equipment and materials for aircraft interiors. In this respect as well, existing aramids have inadequate flammability and non-combustibility properties, so the field of use is currently limited. +LObject of the Invention] The object of the present invention is to create an aramid that is soluble in organic solvents with low toxicity to living organisms, has excellent thread-making stability, and has high Rja physical properties, heat resistance, flame retardancy, and noncombustibility. The goal is to provide the following. [Achievement of the invention] Improved mechanical properties while maintaining solubility in organic solvents during the polymerization stage. As a result of intensive research on copolymerized aramid with chemical resistance and B flammability, PPDA, 3,4°-DAP
It was discovered that an aramid of diamine containing halogenated benzidine as a third component in addition to E and terephthalic acid halide (T' P C ) has good performance, leading to the present invention. That is, the present invention is a wholly aromatic copolyamide in which the main repeating unit is exposed, X is a halogen element, and l and n are integers of 4 or less. In the present invention, diamine component A,
B and C are essential components. Examples of the halogenated benchcine represented by component A include 3-chlorobenzidine. 3-promobenzidine, 3.3′-dibromobenzidine, 3,3°-dibromobenzidine, 3,
3゜-difluorobenzidine, 2,2゜-difluorobentizine, 2,2゛-difluorobenzidine, 3.3',
5,5°-tetrafluorbenzidine, 3,3°. 5,
Examples include 5°-dichlorobenzine, but 3.3°-dichlorobennadine is preferred from the viewpoint of ease of synthesis and production. The composition ratio of diamine components A, B, and C influences the solubility during the polymerization reaction. In the present invention, in which an organic solvent such as NMP is used, the area C D E F shown in FIG.
GH is preferred. Here, each point D to H indicates the following composition. With a composition within this range, a polymer with excellent solubility in the reaction solvent and a high degree of polymerization can be obtained. Furthermore, the performance of the obtained molded product is particularly poor, and its industrial value is also high. Especially flame retardant. In order to impart nonflammability, it is effective to increase the halogen in aramid;
The height should be 0.5% or more, preferably 1.0% or more. Methods for producing this aramid include melt polymerization, solid phase polymerization, interfacial polymerization, and solution polymerization, but solution polymerization is preferred. In addition, as a reaction solvent, dimethylformamide, which is generally known as an organic polar solvent,
Dimethylacetamide. N-methylpyrrolidone, N-
At least one selected from methylprolactam, dimethylsulfone, tetramethylurea, etc. can be used as the main component. In this case, before polymerization to increase solubility. in the middle. At the end of the process, an appropriate amount of a generally known salt-free salt may be added. Examples of such salts include lithium chloride and calcium chloride. In addition, although the ratio of the acid component and the diamine component is substantially equimolar, the reaction component can be used in excess in order to control the weight. , amino components, etc. may also be used. Furthermore, aliphatic and aromatic amines are used to capture acids such as hydrogen chloride produced by the reaction. Can be used in combination with quaternary ammonium salt. After the reaction is completed, a basic inorganic compound such as sodium hydroxide or potassium hydroxide may be added as necessary. Calcium hydroxide. Calcium oxide etc. are added to carry out a neutralization reaction. The drift of the polymer produced in a polymerization reaction with respect to the solvent is important. In order to obtain a homogeneous polymer with a high degree of polymerization, the concentration of the produced polymer is preferably 20% by weight or less. In particular, a range of from several % to 10% is convenient for obtaining a stable polymer.

Reactive staining requires no special restrictions. The reaction between an acid halide and a diamine is generally rapid, and the reaction temperature is, for example, -25°C to 100°C, preferably -10°C to 80°C. It goes without saying that foreign substances that inhibit the reaction, such as water, entering the reaction system must be avoided. The aramid obtained in this way can be poured into a non-solvent such as alcohol or water to precipitate it, and then recovered in the form of a bulb. This can be redissolved in another solvent and used for molding, but the solution obtained by the polymerization reaction can be used as it is as a molding solution. In particular, the aramid having the composition of the present invention has excellent solubility and does not precipitate polymers during the polymerization reaction, so it can be used directly as a forming solution for spinning, etc. Molding methods include first applying the pulp or powder and then compression molding, and casting. Examples include film formation from a polymer solution by the -'r Yast method, spinning by a wet method, and film formation. When molding from a solution, it is extruded into a coagulation bath, the molded product is once solidified, and then washed with water. Nobunaka: Fibers and films can be obtained by heat treatment. In this case, an organic polar surfactant/water system is preferably used as the coagulation bath. [Effects of the Invention] The aramid of the present invention has high solubility in solvents, strength,
Mechanical properties such as modulus, heat resistance, chemical resistance,
We provide molded products with high flame retardancy. [Examples] The present invention will be explained in more detail with reference to Examples below.
Needless to say, the present invention is not limited to this. Further, in the examples, parts refer to parts by weight, and the logarithmic viscosity ηinh, which is a guideline for the degree of polymerization, is 98.5% by weight. Concentration 0 in f4 sulfuric acid
．． Measurements were made using the usual method at 30°C for the 5t/8 waterfall melted in the old water. Example 1 N-
Methyl pyrrolidone (NMP) 1888.5 parts, 3,3'-dichlorobenzidine (DCB; component A)
33.534 parts, and p-phenylenediamine (PPD
A; Component B) 23.687 parts, 3,4°-diaminodiphenyl ether (3.4'-DAPE;
Component C) 17.545 parts were added at room temperature, dissolved in nitrogen, and then stirred to give T P O 88. 945
part was added. The viscosity gradually increased as the polymerization reaction progressed. When the reaction was finally carried out at 80°C for 60 minutes, a viscous polymer solution with excellent transparency was obtained. Next, 143.824 parts of NMP containing 22.5% by weight of rhusium hydroxide was added to this product to carry out a neutralization reaction. The viscosity, ηinh, measured for the polymer precipitated from the obtained polymer solution was 3.59.
Met. The aramid solution has a pore size of 0.1? Number of on holes: 25
The mixture was placed in a cylinder equipped with a cap of 1,000 ml, and was extruded into a coagulation bath containing a 30% by weight NMP aqueous solution while maintaining the temperature at 80°C. The spun fibers were washed with water, dried, and then stretched in two stages on a hot plate at 300°C and 460°C at a total draw ratio of 9.5 to obtain filaments with a total fineness of 37 de. The mechanical properties of this fiber are strength 23-8t/de. Nakajima 2.6%
, the modulus was 910g/dθ. Next, we focused 100 of these filaments and made a copper wire with a diameter of 1
I set it in a coil with 0 fins, kept it at 45 degrees, and observed the combustion condition by applying a flame from the bottom. No flame spread was observed, indicating that it was a nonflammable Im female. According to elemental analysis, the chlorine content in the polymer was 7.3%. For reference, a similar evaluation was performed on PPTA (bory ρ-phenylene terephthalamide) 1/a fiber, and the flame spread, and the 10011 test piece was completely burnt out after igniting four times. Example 2 DC850 mol%. PPDA 40 mol%, 3,4°-D
The diamine component was weighed and polymerized so that the APE content was 10 mol%. That is, D C 8 33.811 parts, P P D A
11.449 parts and 5.300 parts of 3,4°-DAPE were added to NMP 1932. After dissolving in 7 parts at room temperature, 53. 737 parts of TPO was added with stirring and polymerized for 60 minutes at room temperature, followed by 60 minutes at 80°C.
Although it became viscous as the 11th cup progressed, the reaction system had good transparency and no turbidity was observed. After the reaction is completed, NMP slurry i86 containing 22.5% by weight of hydroxide
．． 892 parts were gradually added to complete the neutralization reaction. The θinh measured for the polymer obtained by precipitation from the obtained polymer was 3.36. Using this polymer solution, the method shown in Example 1 was used for spinning and drawing (total draw ratio: 3.
2) A fiber with a total fineness of 73 denier was obtained. This fiber exhibited collapsed mechanical properties with a strength of 14.3 g/dG, a stiffness of 1.8%, and a modulus of 890 g/de. According to a simple evaluation of flammability (see Example 11), this polymer was also a nonflammable polymer. Also, chlorine in the polymer is
It was 11.17% by weight. Example 3 DC840 mol%. PPDA 30 mol%, 3.4'-D
The diamine component was weighed and polymerized so that APE was 30 mol%. i.e. D C 8 48.633 parts, PPDA 12.0
22 parts, 3.4'-DAPE 22.262 parts were dissolved in 1905.6 parts of NMP at room temperature, then 75.289 parts of TPO was added with stirring, and the mixture was heated at room temperature for 60 minutes. , followed by polymerization at 80°C for 60 minutes.
Although it became viscous as the polymerization progressed, the reaction system was transparent and no turbidity was observed. After the reaction, 121.7% of NMP slurry containing 22.5% by weight of hydroxide
8 parts were gradually added to complete the middle phase reaction. ηi measured for the polymer obtained by precipitation from the obtained polymer
nh was 2.30. Using this polymer solution, a fiber having a total fineness of 29 denier was obtained by stretching in two stages at 300°C and 460°C (total draw ratio 22.0) by the method shown in Example 1. This fiber has a strength of 12.5 g/de,
It exhibited excellent mechanical properties with a density of 2.0% and a modulus of 790 g/de. The amount of chlorine 3 in the polymer was 8.9% by weight, and the 1m fiber was crushed to be flame retardant. Example 4 DC860 mol%. PPDA 20 mol%, 3.4'-D
The diamine component was measured and polymerized so that the APE content was 20 mol%. That is, to increase solubility, the chloride force 19.374
Part of NMP 1937. Then, DC837.709 parts, PPDA 5.320 parts, 3.4'-DAPE 9.8! ) and dissolved at room temperature, then 49.944 parts of TPO was added with stirring and heated at room temperature for 00+ hours, then at 80° C.
Polymerized for 0 minutes. Does it become viscous as the polymerization progresses?
The final reaction product was a slightly cloudy yellow fin. After the reaction, N containing 22.5% by weight of hydroxide
80.759 parts of MP slurry i was gradually added to complete the neutralization reaction. The ηinh measured for the polymer precipitated from the obtained polymer was 3.83. Using this polymer solution, stretching was carried out in two stages at 300°C and 440°C according to the method shown in Example 1 (total stretching ratio 2.
50) A fiber with a total fineness of 90 denier was obtained. This fiber had a strength of 17.3 sr/de, a stiffness of 1.8%, and a modulus of 830 g/de, and had excellent mechanical performance. The chlorine content measured in the same manner was 11.2%, indicating that it was a nonflammable fiber. Example 5 DC 85 mol%, PPDA 45 mol%, 3,4°-DA
The diamine component was weighed and polymerized so that PE was 45 mol %, and a polymer with ηinh 3.56 was obtained. Next, as in Example 1, the total expansion ratio was 20 at 300°C and 490″C.
This fiber of 33de obtained as O has a strength of 23.5
+r/dB, elongation 3.9%, modulus 780t/de
It showed excellent mechanical properties. Simple flammability, tV value (
According to Example 1), the present polymer required 12 ignitions for combustion of 1G (up to). The chlorine content in the polymer was 1.3% by weight. Table 1 Examples 6 to 12 Comparative Examples 1 to 5 Next, the compositions were variously changed and the solubility of the polymer solutions was evaluated. The method of Example I was followed except that the composition was changed. Polymer solution turbidity is the initial stage of polymerization. If it becomes cloudy in the middle stage,
A solution that becomes turbid in the late stage of the reaction is indicated by Δ, and a solution that is not cloudy and has good transparency is indicated by ○. Both were determined visually. Note that the reference examples in Table 1 are cases where the composition is outside the scope of the present invention.

[Brief explanation of the drawing]

Claims (5)

[Claims] (1) The main repeating unit is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (A) However, X is a halogen element, m and n are integers of 4 or less ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...・(B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(C) A wholly aromatic copolymer polyamide consisting of. (2) Amine components A, B, and C are within the range CD shown in Figure 1.
The wholly aromatic copolyamide according to claim (1), which is EFGH. (3) The wholly aromatic copolyamide according to claim (1) or (2), wherein the amine component (A) is a chlorobenzidine group. (4) The wholly aromatic copolyamide according to any one of claims (1) to (3), wherein the amine component (A) is a 3,3'-dichlorobenzidine group. (5) A molded product made of the wholly aromatic copolyamide according to any one of claims (1) to (4).