KR940000285B1 - Method of preparation for aromatic polyamide pulp - Google Patents

Abstract

The method for preparing the pulp in homo or copolymer type, having the repeat unit of (I) or (II), comprises: making a polymerization solvent by adding sulphonic compound and tert-amine to the amide-based organic solvent, urea-based organic solvent or their mixed organic solvent; adding aromatic diamine and aromatic diacidchloride to the mixed solvent to obtain an anisotropic liquid crystal polymer solution before gelation; leaving alone the solution at a specific temp. for a specific time; separating the polymerization solvent from the polymer by steeping the solution into water or basic aqueous solution; crushing the polymer with a pulping apparatus and drying.

Description

Process for producing aromatic polyamide pulp

The present invention relates to a method for producing an aromatic polyamide pulp, and more particularly, to an amide solvent, a urea polymerization solvent or a mixed solvent thereof, by adding a sulfone compound and a tertiary amine, or an inorganic salt together with them. After dissolving, the present invention relates to a method for producing an aromatic polyamide pulp having a high degree of polymerization by reacting an aromatic diamine with an aromatic dieside chloride.

Conventionally, US Pat. No. 4,511,623 is known as a technique for producing aromatic polyamide pulp. In this patent, a method of producing aromatic polyamide pulp using a mixed organic solvent obtained by adding an inorganic salt and a tertiary amine to an amide solvent is proposed. However, in the case of producing a high degree of polymerization of polyaromatic polyamides by the above method, the polymerization proceeds at a rapid rate due to the influence of the tertiary amine added in excess, and gelation occurs within a few seconds, making it almost impossible to control the process. In addition, since the molecular chains exhibit an isotropic orientation without gelation when gelling, there is a problem in that fibril is developed for 5 hours or more in order to prepare high molecular weight pulp. In addition, according to the above method, the reaction rate is too fast, and the reproducibility of producing pulp is also poor. Furthermore, in the above method, in order to prepare a polymer having a fractional weight, an expensive tertiary amine-based compound has to be used, which is not only economically disadvantageous but also has low solubility of the polymer, thereby making it impossible to increase the polymer content in the polymerization solvent. There is this.

In addition, Japanese Unexamined Patent Publication No. 59-47694 proposes a method of preparing pulp particles by reacting monomers in an amide polymerization solvent to prepare a polymer solution, and then directly immersing and pulverizing them in water or alcohol. In the low intrinsic viscosity, the polymer solution before gelation is pulverized in water or alcohol, so the intrinsic viscosity of the final product is about 2.0 to 3.5, as well as the low intrinsic viscosity has a disadvantage in that the physical properties are lowered.

In addition, U.S. Patent No. 4,876,040 discloses a technique for preparing short fibers or pulp by simultaneously extruding a liquid crystal prepolymer polymerized in an amide-based polymerization solvent containing an inorganic salt with a tertiary amine in a pulping apparatus. In the method, the excessive use of expensive tertiary amines has the disadvantage of increasing the manufacturing cost as well as pollution problems due to tertiary amines.

Therefore, the present invention solves the problems of the prior art as described above, the gelation time is increased and the solubility of the polymer in the polymerization solvent is also increased than when using the conventional method can further stabilize the process and also the polymer solution and 3 The purpose is to provide a process for producing pulp, since the process of completing the polymerization can be eliminated by using a tertiary amine.

In order to achieve the above object, the present invention,

A) preparing a polymerization solvent by adding a sulfone compound and a tertiary amine to an amide organic solvent, a urea organic solvent or a mixed organic solvent thereof;

B) dissolve the aromatic diamine therein, add aromatic dieside chloride and react until it becomes an anisotropic liquid crystalline polymer solution before gelation.

C) After leaving the polymer solution for a certain time under a predetermined temperature condition,

D) separating the polymer by immersion in water or basic aqueous solution,

E) Provided is a method for producing an aromatic polyamide pulp in the form of a homopolymer or copolymer having a repeating unit represented by the following structural formula (I) or (II), which is pulverized and dried with a pulping apparatus.

(Wherein R ₁ , R ₂ and R ₃ are each

Is any one aromatic group selected from X, X is H, Cl, Br, I or an alkyl or alkoxy group having 1 to 4 carbon atoms, Y is to be.)

In addition, an inorganic salt may be further added and mixed with the said polymerization solvent, and may be used.

Referring to each manufacturing process according to the method of the present invention in more detail as follows.

A) Preparation of polymerization solvent:

In the present invention, an amide organic solvent, a urea organic solvent, or a mixed organic solvent thereof is used as a basic polymerization solvent in the production of polyamide.

As the organic solvent, all organic solvents of amide or urea can be used, but in particular, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), hexamethyl phosphoamide ( Preference is given to using HMPA), N, N, N, N-tetramethylurea (TMU), N, N-dimethyl formamide (DMF), dimethyl sulfoxide (DMOS) or mixtures thereof.

In addition, in this invention, a sulfone type compound is further added and used for the said polymerization solvent.

Representative examples of such sulfone compounds include dimethyl sulfone and diphenyl sulfone.

The sulfone-based compound is preferably added and mixed in the range of 0.1 to 30% by weight based on the total amount of the organic solvent.

When the addition amount of the sulfone-based compound is less than 0.1% by weight relative to the total amount of the organic solvent, it is difficult to expect the effect of increasing the solubility and molecular weight of the final polymer, and when the addition amount exceeds 30% by weight, further solubility and Since the effect of increasing the molecular weight is not obtained, it becomes uneconomical.

Moreover, tertiary amine is further added and used for the polymerization solvent used for this invention.

Representative examples of such tertiary amines include pyridine, triethylamine, quinoline, t-butylamine, pyrroline, pyrimidine, pyrazine, quinoxaline, quinuclidin and diethyl methylamine.

It is preferable that the addition amount of tertiary amine is 0.01 to 5 weight% with respect to polymerization solvent whole quantity. If the added amount of the tertiary amine exceeds 5% by weight, it becomes uneconomical due to the increase in manufacturing cost.

In addition, an inorganic salt may be further added to the polymerization solvent used in the present invention as needed.

Representative examples of such inorganic salts include halogenated alkali metal salts or halogenated alkaline earth metal salts such as CaCl ₂ , LiCl, NaCl, KCl, LiBr, KBr, and the like. These inorganic salts may be added alone or in the form of a mixture of two or more kinds.

It is preferable that the addition amount of an inorganic salt is 20 weight% or less with respect to the polymerization solvent whole quantity. If the added amount of the inorganic salt exceeds 20% by weight, no further increase in effect can be expected and it becomes uneconomical.

In preparing a polymerization solvent using the organic solvents, sulfone compounds, and tertiary amines described above, first, an amide solvent or a urea solvent is used alone, or a mixture thereof is prepared to prepare a basic polymerization solvent. , Tertiary amine is added together with these inorganic salts to completely dissolve to prepare the desired polymerization solvent.

B) preparation of solutions of liquid crystal polymers:

Subsequently, after aromatic diamine is dissolved in the polymerization solvent, aromatic dieside chloride is added to react. It is preferable that the temperature of the reaction liquid at the time of adding aromatic dietary chloride is 0-50 degreeC. When the temperature of the reaction solution is less than 0 ℃, the reaction is less likely to occur and the solubility is also lowered. If the temperature exceeds 50 ℃, the reaction rate is too fast, it is difficult to control the end of the reaction.

It is preferable to add the said reactant so that content of the polymer in the polymer solution obtained may become 3 to 25weight% of a range with respect to a pure polymerization solvent. If the content of the intermediate is less than 3% by weight, there is an advantage that a high molecular weight polyamide pulp can be obtained, but it is uneconomical because the amount of solvent used is too high, and if the content exceeds 25% by weight, the high molecular weight polyamide A problem arises that makes pulp difficult to manufacture.

The reaction proceeds by polymerization until the aromatic diamine and the aromatic dieside chloride react with each other to form an anisotropic liquid crystal polymer solution before gelation having an intrinsic viscosity of 1.0 to 3.0.

When the reaction is terminated in the isotropic solution state before the liquid crystal polymer solution, a problem occurs that the shape and physical properties of the final polyamide pulp are lowered.

C) Aging of the liquid crystal polymer solution:

The anisotropic liquid crystalline polymer solution thus obtained before gelation is left to mature under predetermined conditions. It is preferable to leave to stand for 0.5 hours or more at the temperature of 25-100 degreeC of the polymer solution. The longer the leaving time, the higher the maturity of the liquid crystal polymer solution, but if it exceeds 5 hours, the effect of increasing the maturation time due to the increase of the leaving time is significantly lower than that of the maturing time within 5 hours. In consideration of this, the leaving time is preferably in the range of 0.5 to 5 hours.

If the leaving temperature is less than 25 ℃ takes too long to mature the polymer solution is uneconomical, if the leaving temperature exceeds 100 ℃, the intrinsic viscosity of the polyamide polymer is lowered, causing a problem of deterioration of physical properties.

D) separation of polymers:

Next, the polymer and the polymerization solvent are separated from the polymer solution which is left as described above and aged. Separation of the polymer is performed by immersing the polymer solution described above in water or a basic aqueous solution and extracting the polymerization solvent from the polymer.

Examples of the basic aqueous solution usable in the present invention include NaOH, KOH, Na ₂ CO ₃ , K ₂ CO ₃ , NaHCO ₃ , Ca (OH) ₂ , CaO aqueous solution, and the like. It is preferable that the density | concentration of these aqueous solutions is 0.1-20 weight%.

When the concentration of the aqueous solution is less than 0.1% by weight, the concentration of the aqueous solution is too cloudy, so it is difficult to expect an effect of about the same as water, and when the concentration is more than 20% by weight, the effect of acid neutralization and intrinsic viscosity is no longer It is not expected.

E) Preparation of Polyamide Pulp:

The aromatic polyamide polymer obtained as described above is pulverized with a known pulping apparatus and dried to produce a desired polyamide pulp.

Since the pulping apparatus used in the present invention is a known apparatus, a detailed description thereof will be omitted.

In this way, aromatic polyamide pulp in the form of a homopolymer or copolymer having a repeating unit represented by the following structural formula (I) or (II) can be prepared.

(Wherein R ₁ , R ₂ and R ₃ are each

Is any one aromatic group selected from X, X is H, Cl, Br, I or an alkyl or alkoxy group having 1 to 4 carbon atoms, Y is to be.)

The pulp thus produced has an intrinsic viscosity of 6.0 or more.

The most important effects of the present invention, the sulfone-based compounds such as diphenyl sulfone, diphenyl sulfone and the like are halogenated alkali metal salts such as CaCl ₂ , LiCl, NaCl, KCl, LiBr, KBr and the like and pyridine, triethyl amine, quinoline Use of a polymerization solvent made by addition to an amide-based and / or ureage organic solvent, with tertiary amines such as t-butylamine, picoline, pyrimidine, pyrazine, quinoxaline quinoxaline quinuclidin, diethyl methyl amine, etc. As a result, the gelation time is increased and the solubility of the polymer in the polymerization solvent is increased, compared to the conventional method, thereby further stabilizing the process, and the intrinsic viscosity of the polymer is increased to 7.0. Therefore, the process of completing the polymerization using the polymer solution and the tertiary amine can be eliminated as in the conventional method, thereby reducing the manufacturing cost.

In addition, according to the present invention, high molecular weight pulp having good orientation can be easily produced even without imparting special shear force or orientation during the polymer solution manufacturing process. It is thought that it is the effect of a phone type compound.

The intrinsic viscosity (I.V.) of the polymer prepared in the present invention is obtained by the following relationship.

IV (dl / g) = IN (η _rel ) / C

Where C is the concentration of the polymer solution (the solution of 0.5 g of the polymer dissolved in 100 ml of 95-98% sulfuric acid), and the relative viscosity η _rel is the flow time ratio between the solvent and the solution measured by a capillary viscometer at a temperature of 30 ° C. Is 95-98% concentrated sulfuric acid.

Next, preferred examples and comparative examples of the present invention are described. However, these examples are merely provided to more easily understand the present invention, the present invention is not limited to these examples.

Example 1

After completely purifying the 20 L reactor with nitrogen to completely remove moisture, 400 ml of N-methyl-2-pyrrolidone (NMP) was taken, and then 20 g of CaCl ₂ 10.0 g dimethyl sulfone and 15 g of pyridine were added and mixed to prepare a primary polymerization solvent. After the preparation, the temperature was raised to 70 ° C to completely dissolve, and then 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The temperature of the solution was raised to 50 ° C., left for 2 hours, and then immersed in water to extract a polymer solvent from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 6.3 when the intrinsic viscosity of the obtained pulp was measured.

Example 2

After completely purifying the 20-l reactor with nitrogen to completely remove moisture, 400 ml of N-methyl-2-pyrrolidone (NMP) was taken, and then 25 g of CaCl ₂ 15.0 g dimethyl sulfone and 10 g of pyridine were added and mixed to prepare a primary polymerization solvent. After preparing, 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The solution was heated to 50 ° C. and left for 3 hours, and then immersed in 5% aqueous NaOH solution to extract a polymer solvent from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 6.5 when the intrinsic viscosity of the obtained pulp was measured.

Example 3

After completely purifying the 20 L reactor with nitrogen to completely remove moisture, 500 ml of N-methyl-2-pyrrolidone (NMP) was taken, and then 20 g of LiCl ₂ 15.0 g dimethyl sulfone and 10 g of pyridine were added and mixed to prepare a primary polymerization solvent. After the preparation, the temperature was raised to 70 ° C to completely dissolve, and then 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The temperature of the solution was raised to 60 ° C. and left to stand for 1 hour, followed by immersion in water to extract a polymer solvent from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 6.3 when the intrinsic viscosity of the obtained pulp was measured.

Example 4

After purifying 20 L reactor thoroughly with nitrogen to completely remove moisture, 400 ml of N-methyl-2-pyrrolidone (NMP) was taken, and then 20 g of CaCl ₂ 10.0 g dimethyl sulfone and 10 g of pyridine were added and mixed to prepare a primary polymerization solvent. After the preparation, the temperature was raised to 70 ° C to completely dissolve, and then 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The solution was heated to 50 ° C. and left for 3 hours, and then immersed in 15% aqueous NaOH solution to extract a polymer solvent from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 6.0 when the intrinsic viscosity of the obtained pulp was measured.

Example 5

After purifying 20 L reactor thoroughly with nitrogen to completely remove water, 500 ml of N-methyl-2-pyrrolidone (NMP) was taken, and then 40 g of CaCl ₂ 20.0 g dimethyl sulfone and 20 g of pyridine were added and mixed to prepare a primary polymerization solvent. After the preparation, the temperature was raised to 70 ° C to completely dissolve, and then 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The temperature of the solution was raised to 50 ° C., left for 2 hours, and then immersed in 5% aqueous KOH solution to extract the polymerization solvent from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 6.8 when the intrinsic viscosity of the obtained pulp was measured.

Example 6

After purifying 20 L reactor thoroughly with nitrogen to completely remove moisture, 400 ml of N-methyl-2-pyrrolidone (NMP) was taken, and then 30 g of CaCl ₂ 25.0 g dimethyl sulfone and 10 g of pyridine were added and mixed to prepare a primary polymerization solvent. After the preparation, the temperature was raised to 70 ° C to completely dissolve, and then 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The temperature of the solution was raised to 60 ° C., left for 2 hours, and then immersed in water to extract a polymer solvent from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 6.5 when the intrinsic viscosity of the obtained pulp was measured.

Example 7

21 After purifying the reactor sufficiently with nitrogen to completely remove moisture, 400 ml of N-methyl-2-pyrrolidone (NMP) was taken, and then 30 g of CaCl ₂ 20.0 g dimethyl sulfone and 10 g of pyridine were added and mixed to prepare a primary polymerization solvent. After the preparation, the temperature was raised to 70 ° C to completely dissolve, and then 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The temperature of the solution was raised to 50 ° C., left for 3 hours, and then immersed in a 10% NaOH aqueous solution to extract a polymer solvent from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 6.0 when the intrinsic viscosity of the obtained pulp was measured.

Example 8

21 After fully purifying the reactor with nitrogen to completely remove moisture, 500 ml of N-methyl-2-pyrrolidone (NMP) was taken, and 40 g of CaCl ₂ 30.0 g dimethyl sulfone and 20 g of pyridine were added and mixed to prepare a primary polymerization solvent. After the preparation, the temperature was raised to 70 ° C to completely dissolve, and then 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The temperature of the solution was raised to 60 ° C., left for 3 hours, and then immersed in water to extract a polymer solvent from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 7.0 when the intrinsic viscosity of the obtained pulp was measured and viewed.

Example 9

21 After purifying the reactor sufficiently with nitrogen to completely remove moisture, 400 ml of N-methyl-2-pyrrolidone (NMP) was taken, and 30 g of LiCl ₂ 20.0 g dimethyl sulfone and 10 g of pyridine were added and mixed to prepare a primary polymerization solvent. After the preparation, the temperature was raised to 70 ° C to completely dissolve, and then 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The temperature of the solution was raised to 60 ° C., left for 2 hours, and then immersed in water to extract a polymer solvent from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 6.4 when the intrinsic viscosity of the obtained pulp was measured.

Example 10

21 After completely purifying the reactor with nitrogen to completely remove moisture, 500 ml of N-methyl-2-pyrrolidone (NMP) was taken, and then 40 g of CaCl ₂ 20.0 g dimethyl sulfone and 10 g of pyridine were added and mixed to prepare a primary polymerization solvent. After the preparation, the temperature was raised to 70 ° C to completely dissolve, and then 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The temperature of the solution was raised to 60 ° C., left for 3 hours, and then immersed in water to extract a polymer solvent from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 7.2 when the intrinsic viscosity of the obtained pulp was measured.

Example 11

21 After fully purifying the reactor with nitrogen to completely remove moisture, 300 ml of N-methyl-2-pyrrolidone (NMP) was taken, and then 20 g of CaCl ₂ 15.0 g dimenyl sulfone and 5 g of pyridine were added and mixed to prepare a primary polymerization solvent. After the preparation, the temperature was raised to 70 ° C. to completely dissolve it, and then 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The solution was heated to 50 ° C., left for 3 hours, immersed in water, and a polymer solvent was extracted from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 6.5 when the intrinsic viscosity of the obtained pulp was measured.

Example 12

21 After fully purifying the reactor with nitrogen to completely remove moisture, 200 ml of N-methyl-2-pyrrolidone (NMP) was taken, and then 20 g of CaCl ₂ 10.0 g diphenyl sulfone and 5 g of pyridine were added and mixed with the primary polymerization solvent. After the preparation, the temperature was raised to 70 ° C. to completely dissolve it, and then 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was maintained for 10 minutes, cooled with water and ice, lowered to 10 ° C., 45.95 g of terephthaloyl chloride was added thereto, and stirred and polymerized to prepare a liquid crystal polymer solution before gelation. The temperature of the solution was raised to 40 ° C., left for 3 hours, and then immersed in water to extract a polymer solvent from the polymer to separate the polymer. The separated polymer was ground and dried in a pulping apparatus to prepare pulp. It was 6.0 when the intrinsic viscosity of the obtained pulp was measured.

Comparative Example 1

21 Completely purify the reactor with nitrogen to completely remove the moisture, and then take 300 ml of N-methyl-2-pyrrolidone (NMP), add 20.0 g of CaCl ₂ and 10 g of pyridine, and dissolve completely by raising the temperature to 70 ° C. 1 After preparing a secondary polymerization solvent, 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The above solution was cooled with water and ice, lowered to 10 ° C., and then stirred and polymerized by adding 45.95 g of terephthaloyl chloride to form an isotropic gel. The polymer was immersed in water to form a polymer solvent. Was extracted to separate the polymer. The separated polymer was pulverized and dried in a pulping apparatus to give a L / D-free powder form that was not pulp.

Comparative Example 3

21 After fully purifying the reactor with nitrogen to completely remove moisture, take 500 ml of N-methyl-2-pyrrolidone (NMP), add 30 g of CaCl ₂ and 40 g of pyridine, and raise the temperature to 70 ° C. to completely dissolve it. After preparing a polymerization solvent, 24.5 g of 1,4-phenylene diamine was added to dissolve it.

The solution was cooled with water and ice, lowered to 0 ° C., and stirred and polymerized by adding 45.95 g of terephthaloyl chloride to form an isotropic gel. The polymer was immersed in a 10% NaOH aqueous solution to remove the polymer. The polymer solvent was extracted to separate the polymer. The separated polymer was pulverized and dried in a pulping apparatus to give a L / D free powder form that was not pulp.

The following table summarizes the polymerization solvent, sulfone-based compound, inorganic salt, tertiary amine, polymerization temperature, standing conditions, immersion solution, intrinsic viscosity of the obtained pulp, and the like used in Examples 1 to 12 and Comparative Examples 1 to 2. 1 is shown.

TABLE 1

As can be seen from the results of Table 1, according to the present invention, high molecular weight aromatic polyamide pulp can be produced through easy process control without using an expensive tertiary amine as in the conventional method. have.

Claims (14)

A) Sulfonated compounds and tertiary amines are added to an amide organic solvent, a urea organic solvent or a mixed organic solvent to prepare a polymerization solvent, and b) an aromatic diamine is dissolved therein and an aromatic dieside chloride is added. And react until it becomes an anisotropic liquid crystalline polymer solution before gelation. (C) The polymer solution is allowed to stand for a certain time under predetermined temperature conditions. D) The polymer is separated by immersion in water or basic aqueous solution. And e) a method for producing polyamide pulp in the form of a homopolymer or copolymer having a repeating unit represented by the following structural formula (I) or (II), which is ground and dried by a pulping apparatus. (Wherein R ₁ , R ₂ and R ₃ are each Is any one aromatic group selected from X, X is H, Cl, Br, I or an alkyl or alkoxy group having 1 to 4 carbon atoms, Y is to be,) The method for producing an aromatic polyamide pulp according to claim 1, wherein an inorganic salt is further added and mixed with the polymerization solvent. The organic solvent according to claim 1 or 2, wherein the organic solvent is N-methyl-2-pyrrolidone, N, N-dimeltyl acetamide, hexamethylphosphoamide, N, N, N ', N'. Tetramethylurea, N, N-dimethylformamide, dimethylsulfoxide or a mixture thereof. The method for producing an aromatic polyamide pulp according to claim 1 or 2, wherein the sulfone-based compound is selected from dimethyl sulfone and diphenyl sulfone. The method of claim 4, wherein the sulfone-based compound is added and mixed in the range of 0.1 to 30% by weight based on the total amount of the organic solvent. The method of claim 1 or 2, wherein the tertiary amine is selected from pyridine, triethylamine, quinoline, t-butylamine, picoline, pyrimidine, pyrazine, quinoxaline, quinuclidin, diethylmethyl amine Process for producing an aromatic polyamide pulp, characterized in that. The method according to claim 6, wherein the tertiary amine is added to and mixed in the range of 0.01 to 5% by weight based on the total amount of the organic solvent. The method of claim 2, wherein the inorganic salt is selected from CaCl ₂ , LiCl, NaCl, KCl, LiBr, and KBr. The method for producing an aromatic polyamide pulp according to claim 2, wherein the amount of the inorganic salt added is 0 to 20% by weight based on the total amount of the organic solvent. The method for producing an aromatic polyamide pulp according to claim 1 or 2, wherein the liquid crystal polymer solution is left at a temperature of 25 to 100 ° C. for at least 0.5 hours. The method for producing an aromatic polyamide pulp according to claim 10, wherein the liquid crystal polymer solution is left at a temperature of 25 to 100 ° C for 0.5 to 5 hours. The aromatic polyamide according to claim 1 or 2, wherein the basic aqueous solution is selected from NaOH, KOH, Na ₂ CO ₃ , K ₂ CO ₃ , NaHCO ₃ , Ca (OH) ₂ and CaO aqueous solution. Method for producing pulp. 12. The method of claim 11, wherein the concentration of the basic aqueous solution is 0.1 to 20% by weight. The method of claim 1 or 2, wherein the content of the polymer in the polymer solution is 3 to 25% by weight based on the organic solvent.