JPS58113223A - Preparation of aromatic polymer solution - Google Patents

Abstract

PURPOSE:To obtain titled solution of high stability, with fine carbon particles uniformly dispersed, suitable for forming operation, by dispersing fine carbon particles in a dispersion containing a specific amount of an aromatic polymer followed by further dissolving the above polymer. CONSTITUTION:(A) An aromatic polymer (e.g. aromatic polyamide) is dissolved in (B) a solvent (e.g. dimethylamide) to prepare a solution of a component A content of 0.1-10wt%. Following that, (C) fine carbon particles are dispersed in the above solution preferably under a stirring condition so as to be subject to high shear force to prepare a dispersion containing both components A and C. Furthermore, the component A is additionally dissolved in the above dispersion to obtain the objective solution. It is preferable that the concentration of the component A in the final solution would be 12-15wt%. EFFECT:Clogging of nozzle and/or net in manufacturing formed products is inhibited, thus permitting the products to have excellent conductivity through well-known processes.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an aromatic polymer melt containing carbon mold particles suitable for molding.

Furthermore, we have developed a carbon mold particle company that has uniform and stable dispersion of carbon fine particles, which is useful for producing the aromatic polymer Yuken Crystal, which is highly rated as having excellent I1 chicken resistance and has good electrical conductivity. The present invention relates to a method for producing an aromatic polymer 1lIl case.

Molding and molding of aromatic polymers containing an appropriate amount of carbon mold particles, in addition to the excellent heat resistance and chemical resistance inherent in aromatic polymers, they also have electrical conductivity. It is possible to suppress outbreak 1.

For example, Baka 9 is not only useful as a heat-resistant antistatic fiber, but also useful as an electrical component material utilizing its conductivity.

In order to produce such an aromatic polymer molded article containing fine carbon particles, it is necessary to perform wet or dry molding from a polymer solution in which the carbon fine particles are uniformly and stably dispersed. However, the process of dispersing carbon particles that requires shear force, such as dispersing carbon particles in a solvent under high shear force and then dissolving the polymer to form a molding solution, is not possible in a system where no polymer is present. In the method in which carbon particles are added to a viscous polymer solution in which the polymer has already been dissolved to a degree suitable for molding, the dispersion of carbon particles is uneven. And unstable aromatic polymer 11[L] cannot be produced, and such S*
The net clogging occurs when the molding starts.

There is a problem with extremely poor operability due to nozzle clogging, etc. Moreover, when a large amount of carbon particles are dispersed in a solvent to increase conductivity, the dispersion becomes muddy and the mobility deteriorates, which makes it difficult to obtain a uniform dispersion or a stable dispersion. Therefore, the amount of carbon fine particles must be dispersed to such an extent that such a phenomenon does not occur.

There is also the problem that it is not possible to obtain molded articles having sufficiently satisfactory conductivity from such dispersions.

As a result of extensive research aimed at providing a method for producing an aromatic polymer solution containing carbon mold particles that is stable and suitable for molding, we have found that a system containing a specific amount of aromatic polymer has been developed. After fully dispersing the carbon particles, an aromatic polymer is added to the dispersion to form an all! ni′
The present invention has been achieved by discovering that the above object can be achieved by additionally dissolving the mixture until the amount reaches .

That is, in the present invention, when producing a carbon fine particle-containing aromatic polymer solution consisting of an aromatic polymer, a solvent, and carbon fine particles, the aromatic polymer is contained in an amount of 11 to 10% by weight based on 0 dispersion. A carbon suitable for molding, characterized by dispersing carbon fine particles in a dispersion liquid to obtain a dispersion liquid containing an aromatic polymer and carbon fine particles, and then additionally dissolving the aromatic polymer in a scissors dispersion moat. This is a method for producing a fine particle-containing aromatic polymer 1IIIll.

In the present invention, the aromatic polymer refers to a soluble aromatic polymer, and specific examples include aromatic polyamide, aromatic polyamide-imide, aromatic boria-based hydrazide, aromatic polyimide, aromatic polyamide-based dazole, Aromatic polyoxadiazole, aromatic polythiazole, polyparabanic acid.

Examples include polyhydantoin and polybenzimidazole. Such aromatic polymers include dimethylformamide, dimethylacetamide, M-methylpyrrolidone, and tetramethylurea.

It can be dissolved in solvents such as hexamethylphosphoramide, tetramethylenesulfono, and methylsulfone. Among these aromatic polymers, aromatic polyamides and aromatic polyamideimides are particularly popular in terms of raw materials.
It is also a suitable polymer in that a high concentration polymer *t can be obtained. The type of carbon fine particles that can be used in the present invention is not particularly limited, and commonly used carbon particles such as acetylene black, furnace black, and channel black can be used. The amount of carbon fine particles added varies depending on the type and required properties, but it is preferably Fll based on the total amount of polymer, including the polymer that will be added subsequently.
It is 0 to 50 weight ginseng.

In order to produce a polymer solution according to the present invention, carbon fine particles are first dispersed in a dispersion liquid containing an aromatic polymer of α1 to 10% by weight to contain the aromatic polymer and carbon fine particles. It is necessary to obtain a dispersion. Such dispersions can be amped even to the d order. First, dissolve the aromatic polymer in a solvent and add 11 to 10% by weight to the dispersion.
Obtain a solution containing an amount of aromatic polymer such that
By dispersing carbon fine particles in this solution, a dispersion containing an aromatic polymer and carbon fine particles can be prepared. K for dissolving the aromatic polymer in a solvent can be prepared using a known method and apparatus. If the aromatic polymer content is less than 11% by weight, the effect of the present invention will not be substantially recognized, while if it exceeds 10% by weight, S*
The content of the aromatic polymer should be α1 to 10% by weight, preferably α5 to 5% by weight, since the viscosity of the aromatic polymer is too high and it becomes difficult to uniformly disperse the carbon particles in the subsequent process. is necessary. Preferably, a method is employed in which the KFi solution is stirred under high shear force, and the carbon particles are added thereto for dispersion. Preferred stirring devices used for such stirring include so-called homogenizers such as pipeline mixers and homomixers. Further, when the amount of carbon fine particles used is relatively small, the dispersion liquid can be purified as follows, for example. That is, carbon fine particles are added to the melt under stirring under high shear force and dispersed, and then the polymer is added to the dispersion liquid [11 to 10].
A dispersion can also be prepared by adding and dissolving the ingredients so as to give a weight of -1, and then continuing stirring under high shear force for dispersion.

In the present invention, it is then necessary to add an aromatic polymer to the dispersion obtained as described above. This results in a solution having a polymer degree suitable for molding, i.e. preferably a polymer solution [12 to 25
It is possible to obtain fIIIi[ containing - by weight of aromatic polymer. To additionally dissolve the aromatic polymer, it is preferable to use an apparatus equipped with stirring blades suitable for stirring highly viscous liquids, such as helical ribbon blades or anchor-shaped blades.

The aromatic polymer can be added as an isolated polymer or as a high-strength polymer solution. Highly concentrated polymer solution #Lf: Although it is possible to add it to the above dispersion in a tank batchwise, it is also possible to adopt a continuous method in which both are mixed using a pipeline mixer or static mixer. You can also do it.

According to the present invention, carbon fine particles are uniformly distributed at a high concentration.
Moreover, a stably dispersed aromatic polymer solution suitable for molding can be obtained. Since the polymer solution obtained by the present invention is less prone to nozzle clogging and net clogging during the production of molded products, it can be molded into molded products such as fibers, films, pulp particles, etc. by known methods. The molded article thus obtained has excellent electrical conductivity.

The present invention will be explained in more detail below with reference to Examples.

Implementation IN) By polymerizing phenylenediamine and isophthalic acid chloride using a conventional method, and then isolating and purifying it! 096
9 g of polymetaphenylene isophthalamide having an intrinsic viscosity of 1.54 when scooped out in sulfuric acid was obtained.

On the other hand, dimethylacetamide 45Kyt-pipeline mixer [Tokushu Kika Kogyo Co., Ltd. #! ] While circulating and stirring, first add IKf of Tokuyu polymer and calcium chloride dihydrate a.
, 5Kp were gradually added and stirring was continued for 1 hour after the addition to complete the dissolution.

While continuing to stir, add Ketjenbrak 1. .

(@ diameter 30 it) 2 Kft was gradually added and stirring was continued for 2 hours after the addition to obtain a dispersion. The entire amount of this dispersion was transferred to a 1101 universal mixer (manufactured by Hinayo Kogyo Co., Ltd.), and while stirring, 11x of Tokutomo Polymer was first added and stirred for 5 hours to achieve a polymer concentration of 1'. 18 weight -, the concentration of carbon fine particles is 16.7 with respect to the polymer
A solution of weight - was obtained.

When the solution obtained by K as described above was subjected to wet spinning using polyethylene glycol as a coagulation bath, the spinning condition was good and the strength was 1.7y/11. A fiber having an elongation of 40-2 and an electrical resistance of 1 x 101 j/ was obtained.

Comparative Example 1 Calcium chloride dihydrate asxy was gradually added to 45[y] of dimethylacetamide with circulation stirring using the same pipeline mixer as in Example 1. Dissolved calcium. The only difference from Example 1 was that polymer 1q was not added.

While continuing to stir this solution, Ketjenbrak C, was gradually added to this solution.

At 9 points after adding 1 and 2 Kf, the entire solution became muddy and lost its properties, making it impossible to perform circulation stirring and making it impossible to add and disperse Ketjenblack E and C any further. Ta.

Reference Example 1.2 45 Kft of dimethylacetate, doamide (polymer 1 obtained in Example 1 with circulation stirring using the same pipeline mixer as in Example 1) and 8.5 kg of calcium chloride dihydrate
1.1 Kf of Ketjen Black 1.0 was added to the solution containing Kf and stirred for 2 hours to obtain a dispersion (Dispersion A).

On the other hand, a dispersion liquid (dispersion liquid B) was obtained in the same manner as in the above case except that 0 polymer I Kft was not added.

10- Let each dispersion stand still for 5 hours. C was deposited on the bottom, but no deposit of Ketjen Black 3.0 was observed in the 1 dispersion liquid.

Comparative Example 2 Dimethylacetamide 45! Polymer 12 obtained in Example 1 was dissolved in a 1101 universal mixer to obtain a solution with a polymer concentration of 1 and 3 by weight.

Continue stirring and add Ketjenblack '1B and 02Kfl.
was gradually added over about 1 hour, and then stirring was continued for 10 hours to obtain a polymer solution containing fine carbon particles. When this solution was subjected to wet spinning in the same manner as in Example 1, there were frequent net clogging and nozzle clogging, resulting in poor operability.
That's extremely bad, my friend.

Example 3 Trimellitic anhydride and 4,4'-diphenylmethane diisocyanate were polymerized and isolated by a conventional method.

Polyamideimide was obtained by purification. N-methylpyrrolidone 45Kf! Add and dissolve the previously obtained polymer 1.5 into the system that is being circulated and stirred in the ft pipeline, then add it to Ketjen Black IC-02, 21ft Xu7, and continue stirring for 2 hours after addition. A dispersion liquid was obtained. The entire amount of this dispersion was transferred to a 110-sized universal mixer, and while stirring, 1α5!1 of the above polymer was added,
A molding solution was obtained by further stirring for 5 hours.

When this solution was extruded into a coagulation bath mainly containing an aqueous calcium chloride solution and wet-spun, the spinning condition was 1, strength 1.
．． 6y/d, elongation 42%, electrical resistance value 1.2X10Ω/
A fiber with IM performance was obtained.

Patent applicant: Unitika Co., Ltd. 1

Claims (1)

[Claims] (When producing a carbon mold-containing aromatic polymer solution consisting of an aromatic polymer, carbon particles, and carbon particles, α1 to 10 weight of aromatic polymer is A dispersion liquid containing an aromatic polymer and carbon fine particles is obtained by dispersing carbon fine particles in a dispersion liquid containing the aromatic polymer, and then an IEK aromatic polymer dispersed with scissors is further dissolved. A method for producing an aromatic polymer containing carbon mold particles.