KR20220103618A - New compound, polyamide-based polymer using same - Google Patents

Abstract

The present invention relates to a novel compound used in the preparation of a polyamide-based polymer, and more specifically, to a compound represented by following chemical formula 1, and a polyamide-based polymer using the same. In chemical formula 1, n is 1 or 2.

Description

New compound and polyamide-based polymer using same {NEW COMPOUND, POLYAMIDE-BASED POLYMER USING SAME}

It relates to a novel compound useful for the production of a polyamide-based polymer and a polyamide-based polymer using the same.

The thin display device is implemented in the form of a touch screen panel, and is used in various smart devices ranging from smart phones, tablet PCs, and various wearable devices. .

Display devices using such a touch screen panel are provided with a window cover including a tempered glass or plastic film on the display panel to protect the display panel from scratches or external impact.

Since such a window cover is a configuration formed at the outermost part of the display device, heat resistance, mechanical properties, and optical properties must be satisfied. In particular, display quality is high, mura phenomenon, and image distortion are satisfied. It is important that light distortion does not occur.

Polyimide-based resin is used as a polymer material applied to such a window cover film, and in order to be applicable to a foldable display, it is required to improve transparent and mechanical properties.

One embodiment provides novel compounds useful for the preparation of polyamide-based polymers.

Another embodiment provides a polyamide comprising a repeating unit of a novel structure.

Another embodiment provides a polyamide-based polymer having excellent optical and mechanical properties prepared using the compound and a polyamide-based film using the same.

According to one embodiment, there is provided a compound represented by the following formula (1).

[Formula 1]

In Formula 1, n is an integer of 1 to 10.

The compound represented by Formula 1 may be specifically represented by Formula 2 below.

[Formula 2]

In Formula 2, n is an integer of 1 to 10.

In Formulas 1 and 2, n may be an integer of 1 to 5, more specifically, an integer of 1 or 2.

According to another embodiment, a polyamide having a repeating unit represented by the following Chemical Formula 3 is provided.

[Formula 3]

In Formula 3, m is an integer selected from 3 to 5,000.

In Formula 3, m may be an integer selected from 10 to 5,000.

The polyamide may be endcapped with units derived from terephthaloyl dichloride or isophthaloyl dichloride at one or more ends.

The polyamide may be end-capped at both ends with a unit derived from a compound represented by the following formula (4).

[Formula 4]

According to another embodiment, a polymer obtained by using the compound is provided.

According to another embodiment, there is provided a polymer obtained by using the polyamide.

It is possible to secure excellent optical properties and excellent mechanical properties.

Hereinafter, the present invention will be described in more detail. However, the following specific examples or examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention.

Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise.

Also, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Hereinafter, unless there is a special definition in the present specification, the term "compound" is a concept including all of a single molecule, an oligomer, and a polymer.

Hereinafter, unless otherwise defined in the present specification, the term "polymer" includes both oligomers and polymers. The oligomer means a range having a weight average molecular weight of 1000 to 10,000 g/mol, and the polymer may have a weight average molecular weight of 10,000 g/mol or more, more specifically 10,000 to 500,000 g/mol.

Unless otherwise defined herein, polymer includes homopolymers and copolymers, and the copolymer includes alternating polymers, block copolymers, random copolymers, branched copolymers, crosslinked copolymers, or both.

In the present specification, “*” means a moiety connected to the same or different atoms or chemical formulas.

Hereinafter, unless there is a specific definition in the present specification, the polyamide-based polymer refers to a resin including a structural unit having an amide bond, and a resin including a structural unit having an amide bond and a structural unit having an imide bond, that is, A polyamideimide resin may also be included.

Conventionally, in order to increase the mechanical properties of the polyamide-based film, a polyamide-based polymer including a structural unit derived from a compound having a rigid structure is used. However, due to this, the density between the resins is increased, and the retardation (R _th ) in the thickness direction increases during film formation, which causes distortion when applied to a display, etc. There was a problem with this deterioration. Accordingly, there is a need for a polyamide-based polymer capable of imparting excellent mechanical properties while maintaining optical properties.

According to one embodiment, by using a diamine compound containing an amide bond (-CONH-) in a molecule obtained by reacting an aromatic diamine with an aromatic diacid dichloride and a polyamide-based polymer using the same, excellent mechanical properties while maintaining optical properties properties can be given.

Specifically, the compound may be represented by the following Chemical Formula 1:

[Formula 1]

In Formula 1, n may be an integer of 1 to 10, but is not limited thereto.

Without wishing to be bound by a particular theory, the compound represented by Formula 1 includes a plurality of amide bonds in the molecule and also contains amine groups at both ends, so that when the polyamide-based polymer is prepared by reacting it with a dianhydride, amide bonds Intra-molecular and/or intermolecular interactions of

In addition, although not wishing to be bound by a particular theory, the compound represented by Formula 1 includes an aromatic ring, for example, a benzene ring, so that the carbon content of the resin increases, and the resin has a more rigid structure. can Accordingly, it is possible to provide a polyamide-based polymer having superior mechanical properties and sufficient optical properties and a polyamide-based film using the same.

For example, the compound represented by Formula 1 is obtained by reacting a compound represented by Formula 4 (hereinafter referred to as AB-TFMB) with terephthaloyl dichloride (TPC) or isophthaloyl dichloride (IPC). may be, but is not necessarily limited thereto.

[Formula 4]

As an example, it may be obtained by reacting the AB-TFMB and TPC or IPC in a molar ratio of 1 to 3:1, more specifically 1.5 to 2:1, but is not necessarily limited thereto.

More specifically, the compound may be a compound represented by the following formula (2).

[Formula 2]

In Formula 2, n may be an integer of 1 to 10, but is not limited thereto.

For example, n may be an integer of 1 to 5, for example, may be an integer of 1 to 3, for example, may be 1 or 2, but is not necessarily limited thereto.

For example, the compound represented by Formula 2 may be obtained by reacting the compound represented by Formula 4 (hereinafter, also referred to as AB-TFMB) with terephthaloyl dichloride (TPC), but is not necessarily limited thereto not.

For example, the compound represented by Formula 1 or Formula 2 may be applied as a diamine monomer for preparing a polyamide-based polymer. The polyamide-based polymer prepared including the compound represented by Chemical Formula 1 or Chemical Formula 2 and a film using the same have improved mechanical properties while maintaining optical properties as compared to a film not containing the compound. can be given

Hereinafter, the compound represented by Formula 1 or Formula 2 may be a first aromatic diamine monomer, and for example, the polyamide-based polymer may include a second aromatic diamine monomer different from the compound represented by Formula 1 or Formula 2 It may further include. As an example, the second aromatic diamine monomer may be a known diamine monomer commonly used in the art, and as long as the effect of the present invention is obtained, the type thereof is not limited, but a fluorine substituent may be introduced, and by using an aromatic diamine monomer into which a fluorine substituent is introduced, the polyamide-based polymer and a film using the same may provide more excellent optical properties.

Specifically, the second aromatic diamine monomer may include an aromatic ring substituted with one or two or more trifluoroalkyl groups, for example, the aromatic ring substituted with the trifluoroalkyl group is other than the trifluoroalkyl group. It may be further substituted or unsubstituted with a substituent, but is not limited thereto.

More specifically, the second aromatic diamine monomer may include 2,2'-bis(trifluoromethyl)-benzidine (hereinafter also referred to as TFMB), but is not limited thereto.

For example, when the polyamide-based polymer is prepared, the content of the compound represented by Formula 1 or Formula 2 is 0.1 to 99.9 mol%, more specifically 0.5 to 99.5 mol%, more specifically 1 to 99, based on the total content of the aromatic diamine. % by mole, more specifically, 2 to 98 mol% may be used, but is not necessarily limited thereto.

The polyamide-based polymer is an aromatic diamine using the compound represented by Formula 1 or Formula 2 alone, or by mixing the compound represented by Formula 1 or Formula 2 with a second aromatic diamine monomer of a different type. may be prepared by reacting with a known dianhydride.

The dianhydride may include any one or two or more selected from an aromatic dianhydride and a cycloaliphatic dianhydride, but is not necessarily limited thereto.

The aromatic dianhydride means a dianhydride comprising at least one aromatic ring, wherein the aromatic ring is a single ring; is a fused ring in which two or more aromatic rings are fused; At least two aromatic rings may be a single bond, a substituted or unsubstituted C1 to C5 alkylene group, an unfused ring connected by O or C(=O), but is not limited thereto.

Specifically, the aromatic dianhydride is a benzene ring, a non-fused ring in which two or more benzene rings are connected by a single bond, a non-fused ring in which two or more benzene rings are connected by a methylene group substituted with one or more trifluoromethyl groups, or their dianhydrides, including combinations, but are not necessarily limited thereto.

More specifically, the aromatic dianhydride is 2,2'-bis-(3,4-dicarboxylphenyl) hexafluoropropane dianhydride (6FDA), biphenyltetracarboxylic dianhydride (BPDA), 9 , 9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF), oxydiphthalic dianhydride (ODPA), sulfonyl diphthalic anhydride (SO2DPA), (isopropylidenediphenoxy) ) Bis (phthalic anhydride) (6HDBA), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxyl Ricdianhydride (TDA), 1,2,4,5-benzene tetracarboxylic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), bis(carboxyphenyl) dimethyl silane dianhydride lide (SiDA), bis (dicarboxyphenoxy) diphenyl sulfide dianhydride (BDSDA), or a combination thereof.

More specifically, the aromatic dianhydride is 2,2'-bis-(3,4-dicarboxylphenyl) hexafluoropropane dianhydride (6FDA), biphenyltetracarboxylic dianhydride (BPDA), or Combinations thereof may include, for example, the aromatic dianhydride may include 2,2'-bis-(3,4-dicarboxylphenyl) hexafluoropropane dianhydride (6FDA), The present invention is not limited thereto, and may further include the above-described aromatic dianhydride if necessary, but is not necessarily limited thereto.

The cycloaliphatic dianhydride means a dianhydride comprising at least one substituted or unsubstituted C3 to C60 aliphatic ring, and the substituted or unsubstituted C3 to C60 aliphatic ring is a substituted or unsubstituted C3 to C60 cycloalkane. , a substituted or unsubstituted C3 to C60 cycloalkene, or a combination thereof, but is not limited thereto.

Specifically, the cycloaliphatic dianhydride is substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted cycloheptane, substituted or unsubstituted cyclooctane, substituted or dianhydrides comprising unsubstituted cyclobutene, substituted or unsubstituted cyclopentene, substituted or unsubstituted cyclohexene, substituted or unsubstituted cycloheptene, substituted or unsubstituted cyclooctene, or combinations thereof can, but is not necessarily limited thereto.

More specifically, the cycloaliphatic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 5-(2,5-dioxotetrahydrofuryl)-3-methylcyclohexene -1,2-dicarboxylic dianhydride (DOCDA), bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BTA), bicyclo Octene-2,3,5,6-tetracarboxylic dianhydride (BODA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA), 1,2,4,5- Cyclohexanetetracarboxylic dianhydride (CHDA), 1,2,4-tricarboxy-3-methylcarboxycyclopentane dianhydride (TMDA), 1,2,3,4-tetracarboxycyclopentane dianhydride (TCDA), or a combination thereof, but is not necessarily limited thereto.

As an example, the cycloaliphatic dianhydride may include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), but is not necessarily limited thereto. It may further include water.

For example, when preparing the polyamide-based polymer, the aromatic diamine and the dianhydride may be used in an equivalent ratio of 1:0.9 to 1.1, and more specifically, may be close to 1:1, but is not limited thereto.

According to another embodiment of the present invention, there is provided a polyamide having a repeating unit represented by the following formula (3). In this case, the polyamide includes an oligomer or a polymer.

[Formula 3]

In Formula 3, m may be an integer selected from 3 to 5,000, but is not limited thereto.

In Chemical Formula 3, the polyamide may be end-capped with a unit derived from terephthaloyl dichloride or isophthaloyl dichloride at one or more ends. Alternatively, both ends may be end-capped with a unit derived from a compound (AB-TFMB) represented by the following formula (4).

For example, m may be an integer selected from 5 to 5,000, for example, may be an integer selected from 10 to 5,000, but is not necessarily limited thereto.

[Formula 4]

The polyamide represented by Formula 3 is one obtained by reacting the compound represented by Formula 4 (hereinafter referred to as AB-TFMB) with terephthaloyl dichloride (TPC) or isophthaloyl dichloride (IPC). can In one embodiment, it may be obtained by reacting the AB-TFMB and TPC or IPC in a molar ratio of 1 to 10: 1, specifically, in a molar ratio of 1.01 to 8: 1, but is not limited thereto.

As an example, when describing the method for preparing the compounds represented by Chemical Formulas 1 to 3, the above-described AB-TFMB and TPC or IPC may be reacted in the presence of an organic solvent. The organic solvent may be used without limitation as long as it can dissolve the monomers. Specifically, for example, dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), methylsulfoxide (DMSO), ethylcellusolve, methylcellusolve, acetone, From the group consisting of ethyl acetate, m-cresol, gamma butyrolactone (GBL) and derivatives thereof It may be any one or two or more polar solvents selected, but is not necessarily limited thereto.

In addition, the reaction may be performed using a reaction catalyst such as pyridine.

In this case, depending on the molar ratio of the reaction between AB-TFMB and TPC or IPC, compounds selected from Formulas 1 to 3 may be obtained.

The reaction may be carried out at room temperature, specifically, it may be carried out at 20 to 30 °C, and the reaction may proceed in an inert atmosphere such as argon or nitrogen during the reaction, but is not necessarily limited thereto.

According to another embodiment of the present invention, there is provided a composition comprising the polyamide-based polymer including the above-described polyamide-based polymer and a solvent.

The composition including the polyamide-based polymer may further include an additive, if necessary, in addition to the above-described polyamide-based polymer. The additive may be for improving film formation, adhesion, optical properties, mechanical properties, etc., flame retardancy, etc., for example, a flame retardant, an adhesive strength enhancer, inorganic particles, antioxidants, UV inhibitors, and/or It may be a plasticizer, but is not necessarily limited thereto.

According to another embodiment of the present invention, there is provided a polyamide-based film including the above-described polyamide-based polymer.

For example, the polyamide-based film has a modulus of 6 GPa or more, a total light transmittance measured at 400 to 700 nm according to ASTM D1003 of 88% or more, a haze according to ASTM D1003 of 1.5% or less, and yellowness according to ASTM E313 A physical property of 6 or less may be simultaneously satisfied, but the present invention is not limited thereto.

More specifically, the polyamide-based film may have a modulus of 6 GPa or more, specifically 7 GPa or more, specifically 6 to 10 GPa, and a total light transmittance measured at 400 to 700 nm according to ASTM D1003 of 88% or more, specifically, it may be 89% or more, and the haze according to ASTM D1003 is 1.5% or less, specifically 1.0% or less, more specifically 0.5% or less, and the yellowness according to ASTM E313 is 6 or less, specifically 5 Hereinafter, more specifically, the physical properties of 4 or less may be simultaneously satisfied, but the present invention is not limited thereto.

For example, the polyamide-based film may have a thickness of 1 to 500 μm, for example, 10 to 250 μm, for example, 10 to 100 μm, but is not necessarily limited thereto.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are only examples for explaining the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

[Method of measuring physical properties]

(1) Weight average molecular weight

Measured by dissolving the film in DMAc eluent containing 0.05M LiCl. For GPC, Waters GPC system, Waters 1515 isocratic HPLC Pump, and Waters 2414 Reflective Index detector were used, and the column was connected to Olexis, Polypore and mixed D columns, and polymethyl methacrylate (PMMA STD) was used as a standard material, Analysis was performed at 35°C and a flow rate of 1 mL/min.

(2) modulus

The modulus (GPa) was measured according to ASTM D882 using Instron's UTM 3365 under the conditions of pulling a polyamide film having a length of 50 mm and a width of 10 mm at 25° C. at 50 mm/min.

Preparation of compounds

Synthesis example One

In a nitrogen environment, 250 ml of N,N-dimethylacetamide and 14.2 g (2 equivalents) of pyridine were added to 50 g of AB-TFMB and dissolved. Herein, a solution of 9.1 g (0.5 equivalents) of terephthaloyl chloride (TPC) in 100 ml of N,N-dimethylacetamide was added dropwise for 30 minutes.

After stirring at room temperature (25° C.) for 3 hours, the prepared reactant was added dropwise to 3.5 L of distilled water so that organic matter was precipitated. After filtration of the solid, it was filtered again with 1 L of distilled water and dried under nitrogen conditions to obtain 53 g of compound 1 . (yield 95%)

¹ H NMR (DMSO-d6, 500 MHz, ppm): 10.72 (brs, 2H), 10.58 (brs, 2H), 10.15 (brs, 2H), 8.38-8.31 (m, 4H), 8.17-8.00 (m, 16H) ), 7.78- 7.75 (m, 4H), 7.39- 7.29 (m, 4H), 7.65-6.62 (m, 4H), 5.83 (s, 4H).

At this time, AB-TFMB : TPC was used in a molar ratio of 2 : 1, and the reaction formula is as follows.

Synthesis example 2

In a nitrogen environment, 250 ml of N,N-dimethylacetamide and 14.2 g (2 equivalents) of pyridine were added to 50 g of AB-TFMB and dissolved. Here, a solution of 12.1 g (0.67 equivalent) of TPC (Terephthaloyl chloride) in 100 ml of N,N-dimethylacetamide was added dropwise for 30 minutes.

After stirring at room temperature (25° C.) for 3 hours, the prepared reactant was added dropwise to 3.5 L of distilled water so that organic matter was precipitated. After filtering the solid, it was filtered again with 1 L of distilled water and dried under nitrogen condition to obtain 55 g of compound 2 . (yield 95%)

¹ H NMR (DMSO-d6, 500 MHz, ppm): 10.72 (brs, 4H), 10.58 (brs, 4H), 10.15 (brs, 2H), 8.38-8.31 (m, 6H), 8.17-8.00 (m, 30H) ), 7.78- 7.75 (m, 4H), 7.39- 7.29 (m, 6H), 7.65-6.62 (m, 4H), 5.83 (s, 4H).

In this case, AB-TFMB:TPC was used in a molar ratio of 3:2, and the reaction formula is as follows.

Preparation of polyamide-based polymer

Example One

N,N-dimethylacetamide (DMAc, 290 g) and 2,2'-bis (trifluoromethyl)-benzidine (TFMB, 26 g) were put into a reactor under a nitrogen atmosphere and stirred sufficiently, and then terephthaloyl dichloride (TPC) , 11.8 g) was added and stirred for 6 hours to dissolve and react.

Thereafter, the reaction product obtained by precipitation and filtration using an excess of methanol was vacuum dried at 50° C. for 6 hours or more to obtain an oligomer.

Again in a reactor under a nitrogen atmosphere, N,N-dimethylacetamide (DMAc, 219.35 g), compound 1 (2.486 g) obtained in Synthesis Example 1 (2.486 g), the oligomer (15.634 g), AB-TFMB (0.014 g), and 2 ,2'-bis(trifluoromethyl)-benzidine (TFMB, 0.785 g,) was added. Here, 2,2'-bis-(3,4-dicarboxylphenyl) hexafluoropropane dianhydride (6FDA, 2.896 g), 3,3',4,4'-biphenyltetracarboxylic carboxylic A polyamide-based resin precursor composition was prepared by sequentially adding dianhydride (BPDA, 2.557 g) and dissolving and reacting the mixture with stirring at 40° C. for 12 hours. At this time, the solid content was adjusted to be 10% by weight, and the temperature of the reactor was maintained at 40 ℃.

Then, pyridine and acetic anhydride were sequentially added to the solution in an amount of 2.5 times the total dianhydride content, respectively, and stirred at 60° C. for 12 hours to prepare a composition containing a polyamide-based polymer. The weight average molecular weight of the polyamide-based polymer was 270,000 g/mol.

Example 2

N,N-dimethylacetamide (DMAc, 290 g) and 2,2'-bis (trifluoromethyl)-benzidine (TFMB, 26 g) were put into a reactor under a nitrogen atmosphere and stirred sufficiently, and then terephthaloyl dichloride (TPC) , 11.8 g) was added and stirred for 6 hours to dissolve and react.

Thereafter, the reaction product obtained by precipitation and filtration using an excess of methanol was vacuum dried at 50° C. for 6 hours or more to obtain an oligomer.

Again in a reactor under a nitrogen atmosphere, N,N-dimethylacetamide (DMAc, 226.74 g), compound 1 (10.043 g) obtained in Synthesis Example 1 (10.043 g), the oligomer (3.553 g), AB-TFMB (0.058 g), and 2 ,2'-bis(trifluoromethyl)-benzidine (TFMB, 4.978 g,) was added. Here, cyclobutanetetracarboxylic dianhydride (CBDA, 3.906 g), 2,2'-bis- (3,4-dicarboxylphenyl) hexafluoropropane dianhydride (6FDA, 2.654 g) were sequentially added A polyamide-based resin precursor composition was prepared by dissolving and reacting the mixture with stirring at 40° C. for 12 hours. At this time, the solid content was adjusted to be 10% by weight, and the temperature of the reactor was maintained at 40 ℃.

Then, pyridine and acetic anhydride were sequentially added to the solution in an amount of 2.5 times the total dianhydride content, respectively, and stirred at 60° C. for 12 hours to prepare a composition containing a polyamide-based polymer. The weight average molecular weight of the polyamide-based polymer was 330,000 g/mol.

Example 3

N,N-dimethylacetamide (DMAc, 290 g) and 2,2'-bis (trifluoromethyl)-benzidine (TFMB, 26 g) were put into a reactor under a nitrogen atmosphere and stirred sufficiently, and then terephthaloyl dichloride (TPC) , 11.8 g) was added and stirred for 6 hours to dissolve and react.

Thereafter, the reaction product obtained by precipitation and filtration using an excess of methanol was vacuum dried at 50° C. for 6 hours or more to obtain an oligomer.

Again in a reactor under a nitrogen atmosphere, N,N-dimethylacetamide (DMAc, 229.70 g), compound 2 (6.779 g) obtained in Synthesis Example 2 (6.779 g), the oligomer (2.558 g), AB-TFMB (3.064 g), and 2 ,2'-bis(trifluoromethyl)-benzidine (TFMB, 4.969 g,) was added. Here, cyclobutanetetracarboxylic dianhydride (CBDA, 3.375 g), 2,2'-bis- (3,4-dicarboxylphenyl) hexafluoropropane dianhydride (6FDA, 4.778 g) were sequentially added A polyamide-based resin precursor composition was prepared by dissolving and reacting the mixture with stirring at 40° C. for 12 hours. At this time, the solid content was adjusted to be 10% by weight, and the temperature of the reactor was maintained at 40 ℃.

Then, pyridine and acetic anhydride were sequentially added to the solution in an amount of 2.5 times the total dianhydride content, respectively, and stirred at 60° C. for 12 hours to prepare a composition containing a polyamide-based polymer. The weight average molecular weight of the polyamide-based polymer was 320,000 g/mol.

Example 4

In a nitrogen environment, 250 ml of N,N-dimethylacetamide and AB-TFMB were put into the reactor and sufficiently stirred. Thereafter, TPC (Terephthaloyl chloride) was added and stirred for 6 hours to dissolve and react to prepare a polyamide-based resin composition.

At this time, the amount of each monomer was adjusted to be 10 moles of AB-TFMB to 1 mole of TPC, and the solid content was adjusted to 4% by weight, and the temperature of the reactor was maintained at 30°C.

After completion of the reaction, it was confirmed that a polymer resin including an amide group was prepared.

comparative example One

N,N-dimethylacetamide (DMAc, 224.56 g) and 2,2'-bis (trifluoromethyl)-benzidine (TFMB, 11.208 g,) were placed in a reactor under a nitrogen atmosphere. Here, cyclobutanetetracarboxylic dianhydride (CBDA, 1.366g), 2,2'-bis-(3,4-dicarboxylphenyl) hexafluoropropane dianhydride (6FDA, 12.377g) were sequentially added A polyamide-based resin precursor composition was prepared by dissolving and reacting the mixture with stirring at 40° C. for 12 hours. At this time, the solid content was adjusted to be 10% by weight, and the temperature of the reactor was maintained at 40 ℃.

Then, pyridine and acetic anhydride were sequentially added to the solution in an amount of 2.5 times the total dianhydride content, respectively, and stirred at 60° C. for 12 hours to prepare a composition containing a polyamide-based polymer. The weight average molecular weight of the polyamide-based polymer was 290,000 g/mol.

comparative example 2

N,N-dimethylacetamide (DMAc, 236.85 g), AB-TFMB (19.547 g), and 2,2'-bis(trifluoromethyl)-benzidine (TFMB, 11.208 g) were placed in a reactor under a nitrogen atmosphere. . Here, cyclobutanetetracarboxylic dianhydride (CBDA, 2.732 g), 2,2'-bis- (3,4-dicarboxylphenyl) hexafluoropropane dianhydride (6FDA, 12.377 g) were sequentially added A polyamide-based resin precursor composition was prepared by dissolving and reacting the mixture with stirring at 40° C. for 12 hours. At this time, the solid content was adjusted to be 10% by weight, and the temperature of the reactor was maintained at 40 ℃.

Then, pyridine and acetic anhydride were sequentially added to the solution in an amount of 2.5 times the total dianhydride content, respectively, and stirred at 60° C. for 12 hours to prepare a composition containing a polyamide-based polymer. The weight average molecular weight of the polyamide-based polymer was 300,000 g/mol.

comparative example 3

N,N-dimethylacetamide (DMAc, 290 g) and 2,2'-bis (trifluoromethyl)-benzidine (TFMB, 26 g) were put into a reactor under a nitrogen atmosphere and stirred sufficiently, and then terephthaloyl dichloride (TPC) , 11.8 g) was added and stirred for 6 hours to dissolve and react.

Thereafter, the reaction product obtained by precipitation and filtration using an excess of methanol was vacuum dried at 50° C. for 6 hours or more to obtain an oligomer.

N,N-dimethylacetamide (DMAc, 232.19g), the oligomer (14.923g) and 2,2'-bis(trifluoromethyl)-benzidine (TFMB, 3.465g) were added to the reactor under a nitrogen atmosphere again. Here, 2,2'-bis-(3,4-dicarboxylphenyl) hexafluoropropane dianhydride (6FDA, 4.054 g), 3,3',4,4'-biphenyltetracarboxylic carboxylic A polyamide-based resin precursor composition was prepared by sequentially adding dianhydride (BPDA, 3.356 g) and dissolving and reacting the mixture with stirring at 40° C. for 12 hours. At this time, the solid content was adjusted to be 10% by weight, and the temperature of the reactor was maintained at 40 ℃.

Then, pyridine and acetic anhydride were sequentially added to the solution in an amount of 2.5 times the total dianhydride content, respectively, and stirred at 60° C. for 12 hours to prepare a composition containing a polyamide-based polymer. The weight average molecular weight of the polyamide-based polymer was 320,000 g/mol.

manufacture of film

Solution casting was performed on the polyamide-based resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 on a glass substrate using an applicator, respectively. Thereafter, after primary drying for 30 minutes at 90 °C using a convection oven, additional heat treatment was performed at 280 °C for 1 hour under nitrogen stream conditions, followed by cooling at room temperature. Thereafter, the film formed on the glass substrate was separated from the substrate to obtain a polyamide film.

The modulus of the prepared film was measured and shown in Table 1 below.

evaluation: modulus

division thickness
(μm) modulus
(GPa) Example 1 48 6.47 Example 2 47.8 9.08 Example 3 50 7.75 Comparative Example 1 48 4.03 Comparative Example 2 49 5.9 Comparative Example 3 51 5.8

Referring to Table 1, the polyamide-based polymers of Examples 1 to 3 were used. The prepared polyamide-based film was a polyamide-based polymer of Comparative Example. Since it has a higher modulus than the prepared polyamide-based film, it can be confirmed that it has excellent mechanical properties.

As described above, the present invention has been described by specific matters and limited examples, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the field to which the present invention belongs Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (10)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1, n is an integer of 1 to 10. According to claim 1,
The compound is a compound represented by the following formula 2:
[Formula 2]

In Formula 2, n is an integer of 1 to 10. According to claim 1,
wherein n is an integer of 1 to 5; According to claim 1,
wherein n is an integer of 1 or 2. A polyamide having a repeating unit represented by the following formula (3):
[Formula 3]

In Formula 3, m is an integer selected from 3 to 5,000. 6. The method of claim 5,
Wherein m is an integer selected from 10 to 5,000 polyamide. 6. The method of claim 5,
wherein the polyamide is endcapped with units derived from terephthaloyl dichloride or isophthaloyl dichloride at least one terminus. 6. The method of claim 5,
The polyamide is a polyamide in which both ends are end-capped with units derived from a compound represented by the following formula (4):
[Formula 4]

. A polymer obtained using the compound of any one of claims 1 to 4. A polymer obtained by using the polyamide according to any one of claims 5 to 8.