KR20190118409A - The method of the aromatic polyamide resin - Google Patents

Abstract

The present invention relates to a manufacturing method for providing an aromatic polyamide resin having colorless transparent and excellent mechanical properties. According to the present invention, the aromatic polyamide resin having homogeneous physical/chemical properties while providing excellent optical properties and high mechanical properties can be provided.

Description

The manufacturing method of aromatic polyamide resin {THE METHOD OF THE AROMATIC POLYAMIDE RESIN}

The present invention relates to a method for producing an aromatic polyamide resin.

Aromatic polyimide resins are mostly polymers having an amorphous structure and exhibit excellent heat resistance, chemical resistance, electrical properties, and dimensional stability due to their rigid chain structure. Such polyimide resins are widely used as electrical / electronic materials. However, polyimide resins have many limitations in use because they have a dark brown limitation due to CTC (charge transfer complex) formation of π electrons present in the imide chain.

A method of limiting the transfer of π electrons by removing a strong electron attracting group such as a trifluoromethyl (-CF ₃ ) group to remove the above limitation and obtain a colorless transparent polyimide resin; A method of reducing the formation of the CTC by introducing a sulfone (-SO _2- ) group, an ether (-O-) group, or the like into a main chain to form a curved structure; Alternatively, a method of introducing an aliphatic ring compound to inhibit resonance structure formation of π electrons has been proposed.

However, the polyimide resin according to the above proposals is difficult to exhibit sufficient heat resistance by the bent structure or aliphatic ring compound, and the film produced using the same still has limitations showing poor mechanical properties.

On the other hand, in recent years, in order to improve the scratch resistance of polyimide, the polyamide copolymer which introduce | transduced the polyamide unit structure is developed.

However, the polyamide copolymer has a high haze value when the coating is formed to form a film due to the high crystallinity, the yellow index is high, in particular, such a phenomenon, the thicker the thickness of the film is a problem that is more severely expressed, the improvement There is a need for a solution.

The polyamide unit structure imparts great crystallinity to the copolymer, thereby enabling the expression of scratch resistance that can replace glass as a material for the display and window cover of various electronic devices.

However, the polymerization reaction forming the polyamide unit structure has a very high reactivity, so the reaction rate is high, and the product easily gels due to the influence of a salt (for example, HCl, etc.) generated during the reaction. And, due to the gelation, the unreacted monomers are easily trapped in the gel, which causes a problem that the physical property variation of the copolymer is increased.

In addition, since the gelled product does not dissociate well even after being left for a long time and can be dissociated only by diluting the product thinly, it also has a great influence on the polymerization scale for producing the copolymer.

Therefore, there is still a need for development of a method for producing an aromatic polyamide resin having excellent mechanical and optical properties without easily gelling during polyamide polymerization.

The present invention provides an aromatic polyamide resin having homogeneous physical and chemical properties while preventing gelation from occurring in the reactants or products at the time of the polymerization reaction process and the kind of reaction, while achieving excellent optical and high mechanical properties. It is to provide a method that can be produced.

According to the present invention, there is provided a process for producing an aromatic polyamide resin, comprising reacting an aromatic diamine monomer and an aromatic dicarbonyl monomer in the presence of a chloride of a metal.

Hereinafter, a method for preparing an aromatic polyamide resin according to specific embodiments of the present invention will be described in detail.

Unless expressly stated herein, the terminology is merely for reference to particular embodiments and is not intended to limit the invention.

As used herein, the singular forms “a”, “an” and “the” include plural forms as well, unless the phrases clearly indicate the opposite.

As used herein, the meaning of "comprising" embodies a particular property, region, integer, step, operation, element, and / or component, and other specific properties, region, integer, step, operation, element, component, and / or group. It does not exclude the presence or addition of.

According to one embodiment of the invention, there can be provided a method for producing an aromatic polyamide resin, comprising the step of reacting an aromatic diamine monomer and an aromatic dicarbonyl monomer in the presence of a chloride of a metal.

The present inventors, when carrying out the reaction of the aromatic diamine monomer and aromatic dicarbonyl monomer in the presence of a chloride of the metal, can prevent the gelation phenomenon in the reactant or the resultant at the time of the polymerization reaction and the kind of reaction, while being colorless Experiments confirmed that the present invention can provide an aromatic polyamide resin having high mechanical properties along with transparent and excellent optical properties.

In the process of reacting the aromatic diamine monomer and the aromatic dicarbonyl monomer, the chloride of the metal is present, it is possible to remove the salt generated in the reaction process or to minimize the generation of the salt. Specifically, the chloride of the metal may increase the polymerization solids concentration and may have an excellent effect on improving the polymerization uniformity and the final high molecular weight. Accordingly, the reaction between the aromatic diamine monomer and the aromatic dicarbonyl monomer may occur more efficiently and homogeneously, and the final aromatic polyamide resin may also have excellent physical and chemical properties while achieving excellent optical and high mechanical properties. Can be.

The chloride of the metal may be a chloride of an alkali metal or a chloride of an alkali metal, more specifically lithium chloride (LiCl), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), sodium chloride (NaCl), potassium chloride (KCl) or mixtures thereof.

The chloride of the metal may be appropriately adjusted in consideration of physical properties of the aromatic polyamide resin to be finally prepared or conditions of reacting the aromatic diamine monomer and the aromatic dicarbonyl monomer, and specifically, the chloride of the metal may be selected from the aromatic diamine. 5 wt% to 200 wt%, or 5 wt% to 150 wt%, or 5 wt% to 100 wt% based on the total weight of the monomer and the aromatic dicarbonyl monomer.

The chloride of the metal may be ineffective when used in an excessive amount relative to the total weight of the aromatic diamine monomer and the aromatic dicarbonyl monomer, and the chloride of the metal is excessive to the total weight of the aromatic diamine monomer and the aromatic dicarbonyl monomer. When used in amounts, hydrophilicity can be technically disadvantageous, either by inhibiting the degree of polymerization or by lowering the polymerization and final redissolution viscosity and by the inability to precipitate.

On the other hand, as described above, it is possible to prevent the gelation of the reactants or the resulting product appearing in the polymerization process or the end point in accordance with the use of the chloride of the metal, the chloride of the metal is used together with an organic anhydride having 2 to 10 carbon atoms Better effects can be achieved. That is, in the method for preparing the aromatic polyamide resin of the above embodiment, the method may include reacting the aromatic diamine monomer and the aromatic dicarbonyl monomer in addition to the chloride of the metal and in the presence of an organic acid anhydride having 2 to 10 carbon atoms. .

Specifically, the chloride of the metal has a low solubility or compatibility with the reactant or the solution containing the reactant, and may be used together with an organic anhydride having 2 to 10 carbon atoms to have higher solubility or compatibility. Therefore, it is possible to more smoothly and effectively participate in the reaction between the aromatic diamine monomer and the aromatic dicarbonyl monomer, and thus the mechanical or optical properties of the aromatic polyamide resin to be produced can be improved and the homogeneity of its physical and chemical properties can be improved. Can also be high.

The organic acid anhydride having 2 to 10 carbon atoms may be an anhydride of a carboxylic acid or dicarboxylic acid having 2 to 10 carbon atoms, and more specific examples thereof include acetic anhydride. These acetic anhydrides can effectively contribute to the contribution of existing polymerization solids and degree of polymerization due to the property of improving the solubility of chlorides of metals such as calcium chloride.

The organic acid anhydrides having 2 to 10 carbon atoms may be appropriately adjusted in consideration of physical properties of the aromatic polyamide resin to be finally prepared, conditions for reacting the aromatic diamine monomer and the aromatic dicarbonyl monomer, and specifically, 2 to 10 carbon atoms. The organic acid anhydride of may be used in 10wt% to 300wt%, or 10wt% to 250wt%, or 10wt% to 200wt% relative to the total weight of the aromatic diamine monomer and aromatic dicarbonyl monomer.

The organic acid anhydrides having 2 to 10 carbon atoms may have an insignificant effect when used in an excessive amount relative to the total weight of the aromatic diamine monomers and aromatic dicarbonyl monomers. When used in an excessive amount relative to the total weight of the dicarbonyl monomer, it may be technically disadvantageous due to hydrophilicity, which inhibits the degree of polymerization, lowers the polymerization and final re-dissolution viscosity, and facilitates precipitation.

On the other hand, as described above, according to the production method of the embodiment, it is possible to prevent the gelation phenomenon in the reactant or the resultant at the time of the polymerization reaction process and the kind of reaction, so that the reaction Enable reduction

On the other hand, the gelation phenomenon in the reaction product or the resultant at the time of the polymerization reaction process and the reaction type is the reaction is uniform within 24 hours when the polymerization reaction is stirred at 50 rpm or more while passing nitrogen through a 500 mL 4-neck round flask (reactor) It may be confirmed that it is released in a liquid phase, not released, is isolated, or exists as a solid.

In the production method of the above embodiment, the gelation of the product may not substantially occur. Here, the gelation of the product "substantially does not occur" means that the proportion of the gelled product in the product is less than 1.0% by volume or less than 1.0% by volume. For example, the product obtained through the reaction may have a degree of gelation of 1% by volume or less as defined by Equation 1 below.

 [Equation 1]

Degree of gelation (% by volume) = [Vb / Va] * 100

In Formula 1,

Va is the total volume of the product,

Vb is the volume of the gel product contained in the product.

The Vb may be measured by differential thermal analysis (DSC), ultrasonic analysis, or the like.

On the other hand, the step of reacting the aromatic diamine monomer and aromatic dicarbonyl monomer may be carried out in a temperature range of -25 ℃ to 50 ℃, or -15 ℃ to 25 ℃.

For example, in an inert gas atmosphere and a temperature range of -25 ° C to 50 ° C, in the presence of chlorides of metals and organic acid anhydrides having 2 to 10 carbon atoms, the aromatic diamine monomer is dissolved in a predetermined solvent, and then aromatic dica is added thereto. The polymerization reaction proceeds by adding the carbonyl monomer.

Examples of the solvent that can dissolve the aromatic diamine monomer are not limited, and for example, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetone, N-methyl-2-pyrroli Don, tetrahydrofuran, chloroform, gamma-butyrolactone and the like can be used.

Meanwhile, specific examples of the aromatic diamine monomer include 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine), 4,4'-diaminodiphenyl sulfone, 4,4 '-(9-fluorenylidene) dianiline (4,4'-(9-fluorenylidene) dianiline), bis (4- (4-aminophenoxy) phenyl) sulfone (bis (4- (4-aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'-tetrachlorobenzidine (2,2', 5,5 '-tetrachlorobenzidine), 2,7-diaminofluorene, 4,4-diaminooctafluorobiphenyl, m-phenylenediamine, p-phenylenediamine, 4,4'-oxydianiline, 2,2'-dimethyl-4,4'-diaminobiphenyl (2,2'- dimethyl-4,4'-diaminobiphenyl), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (2,2-bis [4- (4-aminophenoxy) phenyl] propane), 1,3 -Bis (4-aminophenoxy) benzene (1,3-bis (4-aminophenoxy) benzene), and 4,4'-di One or more compounds selected from the group consisting of aminobenzanilides (4,4'-diaminobenzanilide) can be used.

Among these, it is preferable to use 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine) as the aromatic diamine monomer. It is preferable in terms of improving hardness and maintaining a low yellowness index.

As a specific example of the aromatic dicarbonyl monomer, one or more compounds selected from the group consisting of benzene-1,3-dicarbonyl monomer and benzene-1,4-dicarbonyl monomer may be used, and preferably 4,4'- One or more compounds selected from the group consisting of 4,4'-biphenyldicarbonyl chloride, isophthaloyl chloride and terephthaloyl chloride can be used.

More preferably, the aromatic dicarbonyl monomer may be used together with isophthaloyl chloride and terephthaloyl chloride, and isophthaloyl chloride and terephthaloyl chloride are each meta or para relative to the central phenylene group. It is a compound in which two carbonyl groups are bonded to a position.

Therefore, by applying isophthaloyl chloride and terephthaloyl chloride together as the aromatic dicarbonyl monomer, it is possible to exhibit an advantageous effect on the improvement of processability due to meta-bonds in the copolymer and mechanical properties due to para-bonds. have.

In addition, the aromatic dicarbonyl monomer is benzene-1,3-dicarbonyl halogen (benzene-1,3-dicarbonyl halogen) and benzene-1,4-dicarbonyl (benzene-1,4-dicarbonyl halogen) from 5: 100 to 25: 100, or 10: 100 to 25: 100, or 15: 100 to 25: 100.

That is, isophthaloyl chloride and terephthaloyl chloride constituting the aromatic dicarbonyl monomer enable improvement of processability and mechanical properties of the copolymer at the molar ratio, and at the same time, high hardness and low haze expression Make it possible.

Preferably, the isophthaloyl chloride is at least 10 mol%, alternatively at least 12 mol%, alternatively at least 15 mol% relative to the total moles of the aromatic dicarbonyl monomers; And 20 mol% or less, or 19 mol% or less, or 18 mol% or less. And preferably, terephthaloyl chloride is at least 80 mol%, or at least 81 mol%, or at least 82 mol% relative to the total moles of the aromatic dicarbonyl monomers; And 90 mol% or less, or 88 mol% or less, or 85 mol% or less.

In addition, the aromatic diamine monomer and the aromatic dicarbonyl monomer may be included in a molar ratio of 1: 0.95 to 1: 1.05.

Meanwhile, in the step of reacting the aromatic diamine monomer and the aromatic dicarbonyl monomer, the aromatic dicarbonyl monomer may react with the aromatic diamine monomer in a liquid phase, and the aromatic dicarbonyl monomer is recrystallized after liquefaction. It can react with an aromatic diamine monomer in (solid state).

When the aromatic dicarbonyl monomer is reacted with an aromatic diamine monomer in a liquid phase, or when the solid aromatic dicarbonyl monomer is made into a liquid phase and recrystallized and reacted with an aromatic diamine monomer in a powder-type solid phase, Mechanical and optical properties can be further improved.

When the aromatic dicarbonyl monomer is reacted with the aromatic diamine monomer in a solid phase that is not recrystallized after liquefaction, loss of the material itself generated during the grinding of the solid phase may occur or randomization of particles may be difficult.

In the process for producing the aromatic polyamide resin of the above embodiment, in order to react the aromatic dicarbonyl monomer with the aromatic diamine monomer in the liquid phase or in the recrystallized state (solid state) after liquefaction, the aromatic diamine monomer and the aromatic dicarbonyl The method may further include liquefying the aromatic dicarbonyl monomer prior to the step of reacting the monomer.

Specifically, the method for producing the aromatic polyamide resin is, before the step of reacting the aromatic diamine monomer and aromatic dicarbonyl monomer, the aromatic dicarbonyl monomer is at least 70 ℃, or at least 80 ℃, or at least 85 ℃, or 70 Melting to 100 to 100 ℃ may further comprise the step of liquefaction. In this case, it is preferable to melt and liquefy at 80 degreeC or more, More preferably, 85 degreeC or more.

In addition, in detail, the method for preparing the aromatic polyamide resin may further include dissolving the aromatic dicarbonyl monomer in an organic solvent before reacting the aromatic diamine monomer and the aromatic dicarbonyl monomer.

The organic solvent used to dissolve the aromatic dicarbonyl monomer may be an aprotic polar solvent, more specifically, 1,4-dioxane, tetrahydrofuran (THF), dichloromethane (DCM), One or more selected from the group consisting of dichloroethane (DCE), acetone, acetonitrile (MeCN), dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) can be used.

The aromatic polyamide resin provided according to the embodiment may have a weight average molecular weight of 10,000 to 700,000 g / mol, or 50,000 to 700,000 g / mol, or 100,000 to 600,000 g / mol, or 300,000 to 600,000 g / mol. .

In this specification, a weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by the GPC method. In the process of measuring the weight average molecular weight of polystyrene conversion measured by the GPC method, it is possible to use a detector and an analytical column, such as a conventionally known analytical device, a differential index detector, and the like. Conditions, solvents and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30 ° C., a chloroform solvent and a flow rate of 1 mL / min.

The aromatic polyamide resin was measured according to ASTM D1003 at a pencil hardness of at least 3H measured according to ASTM D3363, a yellow index (YI) of 3.0 or less measured according to ASTM E313, and a thickness of 30 μm. Less than 1.0% haze.

According to the present invention, an aromatic polyamide resin having homogeneous physical / chemical properties while achieving excellent optical properties and high mechanical properties while preventing gelation of reactants or products at the time of polymerization and reaction type can be prevented. May be provided.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

Examples and Comparative Examples: Preparation of Polyamide Resin

Example 1

While passing nitrogen through a 500 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller, and a cooler, the temperature of the reactor was adjusted to 25 ° C., 180 g of N, N-dimethylacetamide (DMAc). And after filling 16.2g of calcium chloride (CaCl ₂ ) and stirred for a certain time.

12.053 g (0.037638 mol) of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (TFDB) was added to the reactor and dissolved to maintain the solution at 25 ° C.

After cooling the reaction solution to -10 ° C, 1.4519 g (0.007151 mol) of isophthaloyl chloride (IPC) and 6.4952 g (0.03199 mol) of terephthaloyl chloride (TPC) were liquefied at a temperature of 90 ° C. or higher. One melt was added and stirred inside the reactor.

N, N-dimethylacetamide was added to the polyamic acid solution obtained through the reaction to dilute the concentration of solids to 5% by weight, and the solids were precipitated with 1 L of methanol. The precipitated solid was filtered and dried in vacuo at 100 ° C. for at least 6 hours to obtain an aromatic polyamide resin in the form of a solid (weight average molecular weight about 421,785 g / mol).

Example 2

While passing nitrogen through a 500 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller, and a cooler, the temperature of the reactor was adjusted to 25 ° C., 180 g of N, N-dimethylacetamide (DMAc). After filling with 16.2 g of calcium chloride (CaCl ₂ ) and 18 g of acetic anhydride, the mixture was stirred for a while.

12.053 g (0.037638 mol) of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (TFDB) was added to the reactor and dissolved to maintain the solution at 25 ° C.

After cooling the reaction solution to -10 ° C, 1.4519 g (0.007151 mol) of isophthaloyl chloride (IPC) and 6.4952 g (0.03199 mol) of terephthaloyl chloride (TPC) were liquefied at a temperature of 90 ° C. or higher. One melt was added and stirred inside the reactor.

N, N-dimethylacetamide was added to the polyamic acid solution obtained through the reaction to dilute the concentration of solids to 5% by weight, and the solids were precipitated with 1 L of methanol. The precipitated solid was filtered and dried in vacuo at 100 ° C. for at least 6 hours to obtain an aromatic polyamide resin in the form of a solid (weight average molecular weight about 451,332 g / mol).

Example 3

176 g of N, N-dimethylacetamide (DMAc) after adjusting the temperature of the reactor to 25 ° C. while passing nitrogen through a 500 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler. After filling with 16.2 g of calcium chloride (CaCl ₂ ) and 35.2 g of acetic anhydride, the mixture was stirred for a while.

14.4636 g (0.0451662 mol) of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (TFDB) was added to the reactor and dissolved to maintain the solution at 25 ° C.

After cooling the reaction solution to −10 ° C., 1.7422 g (0.008581 mol) of isophthaloyl chloride (IPC) and 7.7942 g (0.038391 mol) of terephthaloyl chloride (TPC) were liquefied at a temperature of 90 ° C. or higher. One melt was added and stirred inside the reactor.

N, N-dimethylacetamide was added to the polyamic acid solution obtained through the reaction to dilute the concentration of solids to 5% by weight, and the solids were precipitated with 1 L of methanol. The precipitated solid was filtered and dried in vacuo at 100 ° C. for at least 6 hours to obtain an aromatic polyamide resin in solid form (weight average molecular weight about 492,518 g / mol).

Example 4

While passing nitrogen through a 500 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller, and a cooler, the temperature of the reactor was adjusted to 25 ° C., 180 g of N, N-dimethylacetamide (DMAc). And after filling 16.2g of calcium chloride (CaCl ₂ ) and stirred for a certain time.

12.053 g (0.037638 mol) of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (TFDB) was added to the reactor and dissolved to maintain the solution at 25 ° C.

After cooling the reaction solution to -10 ° C, 1.4519 g (0.007151 mol) of isophthaloyl chloride (IPC) and 6.4952 g (0.03199 mol) of terephthaloyl chloride (TPC) were liquefied at a temperature of 90 ° C. or higher. The melt was recrystallized and added and stirred in the form of a solid powder.

N, N-dimethylacetamide was added to the polyamic acid solution obtained through the reaction to dilute the concentration of solids to 5% by weight, and the solids were precipitated with 1 L of methanol. The precipitated solid was filtered and dried in vacuo at 100 ° C. for at least 6 hours to obtain an aromatic polyamide resin in the form of a solid (weight average molecular weight about 389,152 g / mol).

Comparative Example 1

While passing nitrogen through a 500 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller, and a cooler, the temperature of the reactor was adjusted to 25 ° C., 180 g of N, N-dimethylacetamide (DMAc). And after filling 16.2g of calcium chloride (CaCl ₂ ) and stirred for a certain time.

12.053 g (0.037638 mol) of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (TFDB) was added to the reactor and dissolved to maintain the solution at 25 ° C.

After cooling the temperature of the reaction solution to −10 ° C., 1.4519 g (0.007151 mol) of isophthaloyl chloride (IPC) and 6.4952 g (0.03199 mol) of terephthaloyl chloride (TPC) were converted into a solid powder. It was added and stirred inside.

N, N-dimethylacetamide was added to the polyamic acid solution obtained through the reaction to dilute the concentration of solids to 5% by weight, and the solids were precipitated with 1 L of methanol. The precipitated solid was filtered and dried in vacuo at 100 ° C. for at least 6 hours to obtain an aromatic polyamide resin in the form of a solid (weight average molecular weight about 430,201 g / mol).

Comparative Example 2

Polymerization was carried out in the same manner as in Example 1, but no calcium chloride was added.

N, N-dimethylacetamide was added to the polyamic acid solution obtained through the reaction to dilute the concentration of solids to 5% by weight, and the solids were precipitated with 1 L of methanol. The precipitated solid was filtered and dried in vacuo at 100 ° C. for at least 6 hours to obtain an aromatic polyamide resin in the form of a solid (weight average molecular weight about 415,271 g / mol).

Comparative Example 3

The polymerization was carried out in the same manner as in Comparative Example 2, but the molten liquid obtained by liquefying TPC / IPC at a temperature of 90 ° C. or higher was recrystallized, and stirred in the reactor in the form of a solid powder.

N, N-dimethylacetamide was added to the polyamic acid solution obtained through the reaction to dilute the concentration of solids to 5% by weight, and the solids were precipitated with 1 L of methanol. The precipitated solid was filtered and dried in vacuo at 100 ° C. for at least 6 hours to obtain an aromatic polyamide resin in solid form (weight average molecular weight about 401,118 g / mol).

Each reagent content and dosage form used to prepare the aromatic polyamide resins of the Examples and Comparative Examples are summarized in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 DMAc (g) 180 180 176 180 180 180 180 CaCl ₂ (g) 16.2 16.2 16.2 16.2 16.2 - - Acetic acid
Anhydride (g) - 18.0 35.2 - - - - TFDB (g) 12.053 12.053 14.464 12.053 12.053 12.053 12.053 IPC (g) 1.4519 1.4519 1.7422 1.4519 1.4519 1.4519 1.4519 TPC (g) 6.4952 6.4952 7.7942 6.4952 6.4952 6.4952 6.4952 IPC and TPC phase Liquid Liquid Liquid elegance elegance Liquid elegance IPC and TPC melted or not ○ ○ ○ ○ Ⅹ ○ ○

DMAc: N, N-dimethylacetamide * TFDB: 2, 2'-bis (trifluoromethyl) -4,4'-biphenyldiamine

* IPC: isophthaloyl chloride

* TPC: terephthaloyl chloride

Test Example

The following characteristics were measured or evaluated for the aromatic polyamide resins according to the Examples and Comparative Examples, and the results are summarized in Table 2 below. In this case, when the measurement target is a polymer film, a film was prepared as follows.

Preparation Example: Production of Polyamide Resin Film

Each of the polyamide resins obtained in Examples and Comparative Examples was dissolved in N, N-dimethylacetamide to prepare a polymer solution of about 12% (w / V). The polymer solution was applied on a plastic substrate (UPILEX-75s, UBE), uniformly adjusted in thickness using a film applicator and dried in a Matiz oven at 80 ° C. for 15 minutes, and then flowed under nitrogen at 30 ° C. at 30 ° C. Curing for minutes gave a polyamide resin film having a thickness of 50 μm.

(1) Yellow index (Y.I.): The yellow index (Y.I.) of the film was measured using a COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES) according to the measuring method of ASTM E313.

(2) Haze (Hazines): Haze value of the film was measured using the COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES) according to the measuring method of ASTM D1003.

(3) Pencil Hardness: The pencil hardness of the film was measured using a Pencil Hardness Tester according to the measuring method of ASTM D3363. Specifically, after fixing the pencil of varying hardness to the tester and scratching the film, the degree of scratches on the film was observed by naked eye or microscope, and when the scratch was not more than 70% of the total number of scratches, the hardness of the pencil The corresponding values were evaluated for the pencil path of the film. Table 2 below shows the number of times the film was scratched (5 times in total) and the number of scratches therein with the pencil of the corresponding hardness in the test.

(4) polydispersity index (PDI):

The polydispersity index is a value obtained by dividing the weight average molecular weight (Mw: Weight Average Molecular Weight) of each polymer obtained in Examples and Comparative Examples by the number average molecular weight (Mn: Number Average Molecular Weight) of the polymer (Mw / Mn). And the weight average molecular weight and the number average molecular weight were measured by GPC (Gel Permeation Chromatograph) [temperature of 30 ° C., chloroform solvent and flow rate of 1 mL / min].

(5) Confirmation of gel formation after polymerization process or completion

The gelation phenomenon of the reactant or the resultant at the time of the polymerization reaction process and the kind of reaction of the examples and comparative examples is within 24 hours when the polymerization reaction is stirred at 50 rpm or more while passing nitrogen through a 500 mL 4-neck round flask (reactor). It was confirmed whether the gel was formed after the completion of the polymerization reaction or the completion of the reaction by uncoupling the reactant into a homogeneous liquid phase and being isolated or present as a solid phase.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Thickness (㎛) 50.0 50.0 50.0 50.0 50.0 50.0 50.0 Solid content
(weight%) 10 10 12 10 10 10 10 Gel formation Ｘ Ｘ Ｘ Ｘ ○ ○ ○ Y.I. 2.72 2.75 2.81 2.79 5.41 6.28 5.18 Haze 0.54 0.53 0.58 0.52 2.34 1.54 1.87 Pencil hardness 3H 3H 3H 3H 2H 2H 2H PDI 1.89 1.88 1.91 1.88 2.23 2.38 2.04

As shown in Table 2, in the above example, no gel was formed at the end of the polymerization reaction and the end of the polymerization forming the polyamide unit structure, and an aromatic polyamide resin having a high solids content of 10% by weight was prepared. Confirmed.

In addition, the aromatic polyamide resins obtained in the Examples were confirmed to have excellent mechanical properties such as high pencil hardness while having excellent optical properties such as low haze and low yellowness index. It was confirmed that the polydispersity is less than the example.

Claims (16)

Reacting an aromatic diamine monomer and an aromatic dicarbonyl monomer in the presence of a chloride of a metal.
The method of claim 1,
The chloride of the metal is aromatic, including at least one compound selected from the group consisting of lithium chloride (LiCl), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), sodium chloride (NaCl) and potassium chloride (KCl) Method for producing a polyamide resin.
The method of claim 1,
Reacting the aromatic diamine monomer and aromatic dicarbonyl monomer
A method for producing a polyamide resin, wherein an organic anhydride having 2 to 10 carbon atoms is additionally used together with the chloride of the metal.
The method of claim 3,
The organic acid anhydride having 2 to 10 carbon atoms includes acetic anhydride.
The method of claim 1,
The step of reacting the aromatic diamine monomer and aromatic dicarbonyl monomer is carried out at a temperature range of -25 ℃ to 50 ℃, a method for producing an aromatic polyamide resin.
The method of claim 1,
The aromatic diamine monomer is 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine), 4,4'- Diaminodiphenyl sulfone (4,4'-diaminodiphenyl sulfone), 4,4 '-(9-fluorenylidene) dianiline (4,4'-(9-fluorenylidene) dianiline), bis (4- (4 -Aminophenoxy) phenyl) sulfone (bis (4- (4-aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'-tetrachlorobenzidine (2,2', 5,5'-tetrachlorobenzidine), 2,7-diaminofluorene, 4,4-diaminooctafluorobiphenyl, m-phenylenediamine, p-phenylenediamine (p-phenylenediamine), 4,4'-oxydianiline, 2,2'-dimethyl-4,4'-diaminobiphenyl (2,2'-dimethyl-4,4 '-diaminobiphenyl), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (2,2-bis [4- (4-aminophenoxy) phenyl] propane), 1,3-bis (4- Aminophenoxy) benzene (1,3-bis (4-aminophenoxy) benzene), and 4,4'-diaminobenzanilide ( 4,4'-diaminobenzanilide) comprising at least one member selected from the group consisting of.
The method of claim 1,
The aromatic dicarbonyl monomer comprises at least one member selected from the group consisting of benzene-1,3-dicarbonyl monomers and benzene-1,4-dicarbonyl monomers.
The method of claim 1,
The aromatic dicarbonyl monomer is a benzene-1,3-dicarbonyl halogen (benzene-1,3-dicarbonyl halogen) and benzene-1,4-dicarbonyl (benzene-1,4-dicarbonyl halogen) 5: 100 to 25 The manufacturing method of aromatic polyamide resin containing in molar ratio of: 100.
The method according to any one of claims 1, 7, and 8,
The aromatic dicarbonyl monomer reacts with the aromatic diamine monomer in a liquid phase, or
The aromatic dicarbonyl monomer is reacted with the aromatic diamine monomer in a recrystallized state after liquefaction, a method for producing an aromatic polyamide resin.
The method of claim 1,
Prior to reacting the aromatic diamine monomer and the aromatic dicarbonyl monomer,
Melting the aromatic dicarbonyl monomer at a temperature of 70 ℃ or more further comprising the step of producing an aromatic polyamide resin.
The method of claim 1,
Prior to reacting the aromatic diamine monomer and the aromatic dicarbonyl monomer,
Further comprising the step of dissolving the aromatic dicarbonyl monomer in an organic solvent, a method for producing an aromatic polyamide resin.
The method of claim 11,
The organic solvent is 1,4-dioxane, tetrahydrofuran (THF), dichloromethane (DCM), dichloroethane (DCE), acetone, acetonitrile (MeCN), dimethylformamide (DMF) and dimethyl sulfoxide (DMSO Method for producing an aromatic polyamide resin comprising at least one member selected from the group consisting of).
The method of claim 1,
The chloride of the metal is used at 5wt% to 200wt% relative to the total weight of the aromatic diamine monomer and aromatic dicarbonyl monomer.
The method of claim 3,
The organic acid anhydride having 2 to 10 carbon atoms is used in an amount of 10wt% to 300wt% based on the total weight of the aromatic diamine monomer and aromatic dicarbonyl monomer.
The method of claim 1,
The aromatic polyamide resin has a weight average molecular weight of 10,000 to 700,000 g / mol, a method for producing an aromatic polyamide resin.
The method of claim 1,
The aromatic polyamide resin was measured according to ASTM D1003 at a pencil hardness (Pencil Hardness) of at least 3H measured according to ASTM D3363, a yellowness index (YI) of 3.0 or less and a thickness of 30 μm measured according to ASTM E313. A process for producing an aromatic polyamide resin having a haze of less than 1.0%.