KR0163095B1 - Orientation apparatus of aromatic polyamide polymer - Google Patents

Abstract

The present invention relates to an alignment device for an aromatic polyamide polymer, and in an alignment device for an aromatic polyamide polymer composed of an alignment tank, a screw, and a screw shift, the ratio of the screw shaft diameter (D1) to the alignment tank inner diameter (D3) ( D3 / D1) is 1.5 to 5, and the ratio (P / D2) of the distance between the screw pitches (P) to the sum (D2) of the screw shaft diameter and the blade width is 0.7 or less. According to the present invention, pulp having excellent physical properties can be produced easily and inexpensively by a continuous manufacturing process without using expensive tertiary amines and maximizing molecular orientation.

Description

Aligner of aromatic polyamide polymer

1 is a flow chart of continuous polymerization.

2 is an enlarged view of one polymerization-orientator, wherein the impeller inside is an orientation impeller of the present invention.

* Explanation of symbols for main parts of the drawings

A: secondary aromatic dietary chloride

B: primary polymer solution C: secondary polymer solution

1: Continuous Mixer 2: Outlet

3: rotating shaft 4: cylindrical reaction vessel

5: screw type orientation impeller 6: reaction motor

D1: diameter of screw shaft (shaft) D2: diameter to screw blade

D3: Diameter of cylindrical reaction vessel W: Width of screw blade

P: Screw pitch interval H: Height of reaction vessel

The present invention relates to an alignment device for aromatic polyamide polymers, and more particularly, to an amide solvent, a urea polymerization solvent or a mixed solvent thereof, in which an inorganic salt alone or a mixture with a Lewis acid compound is added and dissolved, followed by dissolution of an aromatic diamine. The present invention relates to an aromatic polyamide polymer alignment apparatus for continuously producing an aromatic polyamide pulp having excellent physical properties by reacting with an aromatic dieside chloride.

Conventionally, as a technique for producing aromatic polyamide pulp, a method of producing aromatic polyamide pulp using a mixed solvent in which an inorganic salt and a tertiary amine are added to an amide solvent is known from US Patent No. 4,511,623.

In the above production method, aromatic diamine and aromatic dieside chloride are added to a polymerization solvent in which an inorganic salt and a tertiary amine are added to an amide solvent, and stirred by a general wing-type impeller as shown in the figure on the right. In the process, the polymerization reaction proceeds rapidly and gelation occurs in a few seconds due to the addition of excess tertiary amine and aromatic dieside chloride in one step. Process control is difficult even in the case of the (BATCH) type polymerization, and increasing the scale makes it difficult to evenly mix the polymer solution in the reaction vessel, and the fibril develops because the molecular chain exhibits weak aromaticity during gelation. To produce high molecular weight pulp, it is left for a long time at least 5 hours after polymerization Or there is a problem that needs to be aged.

In addition, U.S. Patent Nos. 5,106,560 and 5,028,372 have a method in which a polymer solution having a certain range and intrinsic viscosity is oriented through a die (DIE) with an alignment device and discharged to a slanted belt surface to give an orientation to the pulp continuously. Although a method of preparing a method has been described, the method has an excellent pulp property such as KEVLAR PULP due to the characteristics of the manufacturing method, which effectively limits the molecular orientation in one direction which has a significant effect on the physical properties of the pulp. Don't have

In order to solve all the problems of the prior art, the inventors of the present invention, in the orientation device of the aromatic polyamide pulp that is polymerized and orientated continuously using several screw type reactors, the screw as well as the transfer capacity of the material as well as the selection of the polymer solution It has been found that the mixture and the molecules can be designed to orient in one direction and this produces aromatic polyamide pulp of good physical properties.

Accordingly, the present invention aims to produce pulp having excellent physical properties by using an easy and inexpensive continuous manufacturing process without the use of expensive tertiary amines. The type | mold orientation impeller is used to perform superposition | polymerization and orientation continuously.

More specifically, according to the present invention, in the alignment device of the aromatic polyamide polymer composed of the alignment tank, the screw and the screw shift, the ratio (D3 / D1) of the screw shaft diameter (D1) to the alignment tank inner diameter (D3) is 1.5 to And an ratio (P / D2) of the distance between the screw pitches (P) to the sum (D2) of the screw shaft diameter and the wing width is 0.7 or less.

In general, a single screw has been used only for the transport of materials, but in the present invention it has the ability to transport materials as well as to evenly mix polymer solutions and orient molecules in one direction.

This characteristic is that in the case of the conventional single screw cylindrical container, the clearance between the end face of the screw blade and the inner surface of the tube (TUBE) is generally small for the transfer of material, but in this device, the orientation required for pulping is polymerized. In order to impart to the solution, this spacing, i.e. the ratio (D3 / D1) of the inner diameter (D3) of the vessel and the screw shaft diameter (D1) is 1-5, and the sum of the screw shaft diameter and the wing width (D2) If the ratio (P / D2) of the screw pitch (P) is set to 0.7 or less, the transfer capacity for mixing the upper and lower polymers in the reaction vessel as well as the maximum molecular orientation prior to gelation in the polymer solution are provided. This excellent pulp can be produced continuously.

In this device, if the D3 / D1 ratio is too small, the space in the reaction vessel becomes small, and the mixing of the polymer solution becomes uneven, so that the physical properties become uneven. If this ratio is too large, the polymer solution located on the outer wall of the container is well mixed. Since the orientation is also lower than the polymer near the screw, the orientation of the polymer may be uneven as a whole.

In addition, if the ratio (P / D2) of the distance between the screw pitches (P) to the sum (D2) of the screw shaft diameter and the wing width is too large, it is difficult to obtain a constant orientation because the moving angle of the polymer is too large. Poor development leads to the problem of increased Canadian freedom.

In particular, the advantage of this screw-type stirrer blade is that its shape and properties can give a SHEAR FORCE to the polymer solution in a reaction vessel, and also if a polymer solution is received in one polymerization-orientator for several minutes. As a result, the polymer solution received increases in viscosity even without artificial agitation over time. Thus, the first and second polymer solutions having different viscosities can be mixed evenly, thereby making it possible to produce pulp with uniform physical properties. .

However, it is difficult to mix the upper and lower polymer solutions evenly in the form of a general stirrer blade, and does not give a sufficient viscosity increase and orientation for pulping to the polymer solution at the lower viscosity when stirring for polymerization-orientation.

This is because the polymer solution at the bottom of the highly viscous reactor undergoes too much reaction and gels, the polymer is broken and the orientation is broken before the polymer solution at the top has sufficient viscosity rise and orientation necessary for pulping. This is because it is degraded.

Hereinafter, the present invention will be described in detail.

The present invention relates to an alignment apparatus for aromatic polyamide polymers applied to polymerization and alignment processes in a continuous production method of aromatic polyamide pulp.

In more detail with reference to the accompanying drawings, FIG. 1 shows a polymerization-orientation apparatus for the continuous production of a plurality of polyamide pulp, and one of them is shown in FIG. 2. The illustrated polymerization-aligner 4 is equipped with a screw-type orientation impeller 5 driven therein by a reaction motor 6.

In the polymerization-orientation device (4), the secondary polymer solution obtained by mixing the primary aromatic diacid chloride and the primary polymer solution in the continuous mixer (1) is agitated while increasing the intrinsic viscosity.

At this time, when the secondary polymer solution is received in one polymerization-orientator for more even mixing, the polymer is received while turning the stirrer so that the first and later received polymer solutions are evenly mixed. Stirring of the polymer solution is performed until the polymer solution is gelled, and the polymer before gelling is instantaneously gelled, and upon further stirring, the polymer is broken.

The polymer just before gelation is left until it is solidified enough to be discharged from the polymerization-orientator, where heat may be applied around the polymerization-orientator to facilitate the solidification and discharge of the polymer. The screw is rotated in the reverse direction to discharge the solidified polymer.

The discharged polymer is left to age or aged, cut into suitable sizes, left to age or aged under predetermined temperature conditions, and then immersed in water to extract the polymerization solvent. As described above, the polymer from which the polymerization solvent is extracted is poured with water in a pulping apparatus, pulverized, and dried to prepare a desired aromatic polyamide pulp.

According to the present invention as described above, a polymer having a high degree of polymerization and a high degree of orientation can be easily obtained by a continuous polymerization-orientation agent without using a tertiary amine which is expensive and harmful to the human body.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples.

Example 1

After the vessel containing 1,000 kg of N-methyl-2-pyrrolidone was adjusted to 80 ° C., 80 kg of CaCl ₂ was added and stirred to dissolve. 48.67 kg of p-phenylenediamine was added to the polymerization solvent, followed by stirring and dissolution. The aromatic diamine solution was adjusted to 5 ° C. using a metering feeder and a temperature controller, and then fed to the mixing device at 1128.67 g / min. Terephthaloyl chloride in a state of 27.41 g / min was fed and reacted to prepare a primary polymer solution.

The primary polymer solution was again adjusted to 5 ° C. using a temperature controller and fed to the continuous mixer at 1156.08 g / min using a metering feeder while simultaneously supplying 63.95 g / min of terephthaloyl chloride in solution. The mixture was mixed for 30 seconds (retention time of the polymer in the continuous mixer = 30 seconds). The polymer solution was polymerized-folded with a screw shaft diameter of 4 cm, a screw pitch of 5 cm, a screw blade width of 3 cm, an inner diameter of a cylindrical vessel of a reaction vessel of 20 cm, and a height of 40 cm of the vessel. After receiving the fragrance for 2 minutes, the screw was stirred at a rate of 300 RPM to polymerize and orient until gelation. After leaving it for 10 minutes at 30 ° C., the screw was rotated in the reverse direction to discharge the polymer, and the polymer was cut to a size of about 3 cm in the fiber length direction and a thickness of about 2 cm or less with a knife, and then aged at 80 ° C. for 2 hours. Subsequently, the mixture was immersed in a coagulating solution to remove the polymerization solvent, and then pulverized and dried with water in a pulping apparatus to prepare pulp.

The intrinsic viscosity of the pulp thus obtained was 3.9. The Canadian standard freedom was 490 ml and the specific surface area was 6.7 m3 / g.

Example 2

The vessel containing 1,000 kg of N-methyl-2-pyrrolidone was adjusted to 80 ° C., and then 80 kg of CaCl ₂ was added and stirred to dissolve. 48.67 kg of p-phenylenediamine was added to the polymerization solvent, followed by stirring and dissolution. The aromatic diamine solution was adjusted to 5 ° C. using a metering feeder and a temperature controller, and then fed to the mixing device at 1128.67 g / min. Terephthaloyl chloride in a state of 27.41 g / min was fed and reacted to prepare a primary polymer solution.

The primary polymer solution was again adjusted to 5 ° C. using a temperature controller and fed to the continuous mixer at 1156.08 g / min using a metering feeder while simultaneously supplying 63.95 g / min of terephthaloyl chloride in solution. The mixture was mixed for 30 seconds (retention time of the polymer in the continuous mixer = 30 seconds). The polymer solution was polymerized-folded with a screw shaft diameter of 6 cm, a screw pitch of 6 cm, a screw blade width of 3 cm, an inner diameter of a cylindrical vessel of a reaction vessel of 20 cm, and a height of 40 cm of the vessel. After receiving the fragrance for 2 minutes, the screw was stirred at a rate of 300 RPM to polymerize and orient until gelation. After leaving it for 10 minutes at 30 ° C., the screw was rotated in the reverse direction to discharge the polymer, and the polymer was cut to a size of about 3 cm in the fiber length direction and a thickness of about 2 cm or less with a knife, and then aged at 80 ° C. for 2 hours. Subsequently, the mixture was immersed in a coagulating solution to remove the polymerization solvent, and then pulverized and dried with water in a pulping apparatus to prepare pulp.

The intrinsic viscosity of the pulp thus obtained was 4.3, the Canadian standard freedom was 340 ml, and the specific surface area was 9.2 m 3 / g.

[Examples 3 to 6]

Other conditions were the same as in Example 2, and the experiments were changed only with the conditions as shown in the following table.

Claims (1)

In the alignment device of the aromatic polyamide polymer composed of the alignment tank, the screw and the screw shift, the ratio (D3 / D1) of the screw shaft diameter (D1) to the alignment tank inner diameter (D3) is 1.5 to 5, and the screw shaft diameter and The ratio (P / D2) of the distance between screw pitches (P) to the sum (D2) of the wing widths is 0.7 or less, wherein the aromatic polyamide polymer is oriented.