KR20100105182A - Process for making imide and aramid function containing novel polymer and application - Google Patents

Abstract

PURPOSE: A manufacturing method of a polymer and an application using thereof are provided to improve the workability of the polymer by dissolving into an organic solvent, and to apply the polymer to an LCD when being formed in a film. CONSTITUTION: A manufacturing method of a polymer containing an imide group and an aramid group at a polymer chain marked with chemical formula 1. The manufacturing method of the polymer comprises the following steps: forming a mixed solution by dissolving a diamine compound to a polymerization solvent; forming a prepolymer-A by adding dianhydride to the mixed solution; forming another mixed solution by dissolving aromatic diamine to the polymerization solvent; forming a prepolymer-B by adding an aromatic dicarbonyl compound to the mixed solution; and mixing the prepolymers, a diamine compound as a chain extender, the dianhydride, and a diisocyanate compound.

Description

Process for making new polymer having imide group and aramid group and application using the same {Process for Making Imide and Aramid function containing Novel Polymer and Application}

The present invention relates to a method for preparing a new polymer having an imide group and an aramid group having excellent transparency and processability, and an application using the same. More specifically, brown or yellow color is compared with polyimide and aramid having excellent properties. Eggplant is lighter or more transparent than polyimide, and when compared with aramid, it relates to a method of preparing a new polymer (imide: abbreviation) improved in processability by dissolving in a general organic solvent, not sulfuric acid, and an application using the same.

Polyimide, which is widely used as a conventional heat resistant film, refers to a high heat resistant resin prepared by condensation polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate followed by imidization. In order to prepare a polyimide resin, pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), or the like is used as an aromatic dianhydride component, and oxydianiline (ODA) or p is used as an aromatic diamine component. -Phenylene diamine (p-PDA) and the like are used. In addition to excellent heat resistance, polyimide resins have excellent properties in mechanical properties, flame retardancy, chemical resistance, low dielectric constant, etc., and therefore have a wide range of uses in coating materials, molding materials, and composite materials. However, polyimide resins have a brown or yellow color due to high aromatic ring density, and thus have a low transmittance in the visible light region, which makes it difficult to use them as optical materials. In order to solve this problem, a method of polymerizing the monomer and the solvent by high purity has been attempted, but the improvement of the transmittance is not large. U.S. Patent No. 553480480 describes a method of using an aliphatic ring-based dianhydride component instead of an aromatic dianhydride. When compared to the purification method, there was an improvement in transparency and color when in solution or film formation. 2009-0021591 also has a limitation in the improvement of the permeability, the high permeability was not satisfied, and also resulted in the degradation of the thermal and mechanical properties. Also, U.S. Pat.Nos. 4,595,548,460,306,464,464,4895972,509,3453,52,18083,52,18077,53,383,826,53,670,595936,6232428 and Republic of Korea Patent Publication No. 2003-0009437 discloses an aromatic dianhydride dianhydride having a linking group, such as -O-, -SO2-, CH2-, and a bent structure linked to the m-position instead of the p-position, or a substituent such as -CF3; Although there have been reports of a novel polyimide structure having improved transmittance and color transparency using aromatic diamine monomers, while the thermal properties are not significantly degraded, the mechanical properties, yellowness and visible light transmittance are not limited to semiconductor insulating films and flexible materials. It was insufficient to use it as a display substrate.

  Aromatic polyamide fibers, commonly referred to as aramid fibers used as the existing high strength fibers, include para-aramid fibers and meta-aramid fibers having a structure in which benzene rings are linearly connected through an amide group (CONH). The wholly aromatic aramid fiber has excellent properties such as thermal stability, insulation, abrasion resistance, chemical resistance, high melting temperature, and is used as a high performance material such as high strength high modulus fiber and a high functional material such as an electro-optic structural material. In addition, it is used for body armor, optical cables, tire cords, conveyor belt reinforcements, ropes, cords, and bulletproof equipment requiring high strength and high breaking energy.It is also used as a fiber reinforcement material for aerospace composites requiring high rigidity and light weight. In addition, due to its excellent chemical resistance, it is widely used as a gas filtration material, and thus its use is being widely expanded. These aramid fibers are required to have a high strength and high modulus of elasticity, which must be dissolved in concentrated sulfuric acid and produced spinning dope with high concentration. Such a process has a high process cost and has a high concentration in concentrated sulfuric acid compared to a spinning process using a general organic solvent, which makes it difficult to control the process.

  In order to overcome the shortcomings of polyimide and aramid having excellent characteristics as described above, the necessity of a new material is extremely demanded, and in order to satisfy such demand, a new structure of imamide polymer has been synthesized and applied.

The present invention was derived to solve the above problems, an object of the present invention is to provide a method for producing a new polymer with improved transparency and processability.

Another object of the present invention is to provide a method for producing a film, an adhesive, a metal laminate, and a fiber by using a polymer having improved transparency and improved processability.

In order to achieve the above object, the present inventors have found that by synthesizing a new polymer having an imide group and an aramid group in the polymer chain at the same time, it is possible to overcome the color problem of the existing polyimide and the dissolution and processability of the aramid. It was confirmed that the polymer is excellent in transparency and processability and completed the present invention.

 The present invention is a method for synthesizing a random copolymer by dissolving and reacting a diamine compound, dianhydride dianhydride, aromatic diamine, aromatic dicarbonyl compound in a polymerization solvent to prepare an imamide polymer and a diamine compound in a polymerization solvent. To prepare a mixed solution; Preparing prepolymer-A by adding dianhydride dianhydride to the mixed solution; Dissolving the aromatic diamine to prepare a mixed solution; Preparing a prepolymer-B by adding an aromatic dicarbonyl compound to the mixed solution; And mixing the prepolymers A and B and adding a chain extender to the block copolymer to synthesize the block copolymer to simultaneously have an imide group and an aromatic amide (aramid) group in the polymer.

  In another aspect, the present invention is to prepare a fiber by dissolving a polymer (imide) having an imide group and an aramid group at the same time in a spinning solvent to form a spinning dope to spin through a spinneret to produce a fiber It is dissolved in a film-forming solvent, cast on a support and dried to produce a film and to prepare an adhesive or a metal laminate in a state dissolved in a solvent.

As described above, the present invention was able to synthesize a new polymer having improved transparency and improved processability, and when it was made into a film, it could be applied to LCD, and also semiconductor insulating film, TFT-LCD insulating film, passivation film, liquid crystal alignment film, and optical communication material. It can be used in various fields such as solar cell protective film, flexible display board, etc., and it can be used as body armor, optical cable, pulp, staple yarn, spinning yarn, protective suit, reinforcing material, etc. It can be used as an adhesive layer or a metal laminate.

 Hereinafter, an embodiment of a method for preparing a new polymer (imide) having an imide group and an aramid group of the present invention, and a method for producing a film or fiber using the same will be described in detail.

  In order to achieve the above object, the present invention synthesized a new polymer having an imide group and an aramid group as a block copolymer and a random copolymer.

About block copolymer

a) dissolving a diamine compound in a polymerization solvent to prepare a mixed solution,

b) preparing a prepolymer-A by adding dianhydride dianhydride to the mixed solution, and

c) dissolving aromatic diamine in a polymerization solvent to prepare a mixed solution,

d) preparing a prepolymer-B by adding an aromatic dicarbonyl compound to the mixed solution, and

e) mixing the prepolymers A and B and further adding a chain extender to the reaction to provide a polymer manufacturing method comprising synthesizing the block copolymer.

  The method also provides a polymer manufacturing method comprising synthesizing a random copolymer by dissolving and reacting a diamine compound, a dianhydride dianhydride, an aromatic diamine, and an aromatic dicarbonyl compound in a polymerization solvent with respect to the random copolymer. do.

  In the present invention, a) is a step of preparing a mixed solution by dissolving a diamine compound in a polymerization solvent. B) is a step of preparing a prepolymer-A by adding dianhydride dianhydride to the mixed solution of a). The prepolymer-A may be prepared by a method known in the art using a dianhydride dianhydride represented by the following Chemical Formula 2 and a diamine compound represented by the following Chemical Formula 3, respectively.

(Formula 2)

In Formula 2, R ₁

At least one selected from the group consisting of,

Y1 and Y2 are each independently or simultaneously a direct bond, -O-, -CO-, -S-, -SO _2- , -C (CH ₃ ) 2-, -CONH,-(CH2) n1-,- O (CH2) n2O-, -COO ( CH2) group of n3OCO-, a group substituted with a hydrogen of the alkyl group as a crowd fluorine (F); is selected from (for example, -C (CF ₃₎ 2-), where , n1, n2 and n3 are each independently an integer of 1 to 5.

(Formula 3)

In Formula 3, R2

At least one selected from the group consisting of,

Hydrogen of the benzene in the structure may be substituted with CF3, OH, Y1 and Y2 are each independently or simultaneously a direct bond, -O-, -CO-, -S-, -SO 2-, -C (CH3) 2-,-CONH,-(CH2) n1-, -O (CH2) n2O-, -COO (CH2) n3OCO-, the group in which the hydrogen of the above alkyl group is substituted with fluorine (F) (e.g.- C (CF ₃ ) 2-), wherein n1, n2 and n3 are each independently an integer from 1 to 5.

  Specifically, the method for preparing the prepolymer-A dissolves at least one of the diamine compounds represented by Formula 3 in a polymerization solvent, and adds at least one of the dianhydride dianhydrides represented by Formula 2 to the solution. Can be prepared by reacting.

  The reaction of the diamine compound and dianhydride dianhydride is preferably carried out at 0 to 10 to 24 hours. At this time, it is preferable to mix dianhydride dianhydride and a diamine compound in the molar ratio of 1: 0.9-1: 1.1. When the molar ratio of the diamine compound to the dianhydride dianhydride is less than 0.9 or more than 1.1, it is difficult to prepare a polymer having a low molecular weight and excellent mechanical properties, and a viscosity may be difficult to coat and various processes.

  Specifically, the dianhydride dianhydride includes PMDA (pyromellitic dianhydride), BPDA (3,3'4,4'biphenyltetracarboxylic dianhydride), TDA (3,3'4,4 '). Benzophenonetetracarboxylic dianhydride), ODPA (4,4'oxydiphthalic anhydride), BPADA (4,4 '-(4,4'anhydride), 6FDA (2,2'-bis One or more selected from the group consisting of-(3,4-dicarboxylphenyl) hexafluoropropane dianhydride) and TMEG (ethylene glycol bis (anhydro- trimellitate) may be used, but the present invention is not limited thereto. no.

  Examples of the diamine compound include TFDB (bis trifluoromethyl benzidine), p-PDA (p-phenylenediamine), m-PDA (m-phenylenediamine), and 4,4'-ODA (4,4'-jade. Cidianiline), 3,4'ODA (3,4'-oxydianiline), BAPP (2,2-bis (4- [4-aminophenoxy] -phenyl) propane), 4BDAF (bis amino phenoxy phenyl Hexafluoropropane), TPE-R (1,3-bis (4-aminophenoxy) benzene) and m-BAPS (2,2-bis (4- [3-aminophenoxy] phenyl) sulfone) One or more selected from the group consisting of may be used, but is not limited thereto.

  As the solvent, a conventional organic solvent can be used without limitation, and specifically N-methylpyrrolidinone (NMP), N, N-dimethylacetamide (DMAc), tetrahydrofuran (tetrahydrofuran; THF), N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), cyclohexane, acetonitrile and mixtures thereof One or more selected from may be used, but is not limited thereto.

  C) is a step of preparing a mixed solution by dissolving the aromatic diamine in the polymerization solvent. In step d), a prepolymer-B is prepared by adding an aromatic dicarbonyl compound to the mixed solution of c). The prepolymer-B may be prepared by a method known in the art using an aromatic diamine represented by the following general formula (4) and an aromatic dicarbonyl compound represented by the following general formula (5).

(Formula 4)

In Formula 4, R ₃

At least one selected from the group consisting of,

Y1 and Y2 are each independently or simultaneously a direct bond, -O-, -CO-, -S-, -SO _2- , -C (CH ₃ ) 2-, -CONH,-(CH2) n1-,- O (CH2) n2O-, -COO ( CH2) group of n3OCO-, a group substituted with a hydrogen of the alkyl group as a crowd fluorine (F); is selected from (for example, -C (CF ₃₎ 2-), where , n1, n2 and n3 are each independently an integer of 1 to 5.

(Formula 5)

In Formula 5,

X1 and X2 are selected from the group of Cl, OH, OCH3

R4 is

Y 1 is independently or simultaneously directly bonded, -O-, -CO-, -S-, -SO _2- , -C (CH ₃ ) 2-, -CONH,-(CH2) n1-, -O (CH2 ) n2O-, -COO (CH2) n3OCO-, wherein n1, n2 and n3 are each independently integers of 1-5.

Specifically, in the method for preparing the prepolymer-B, at least one of the aromatic diamines represented by Formula 4 is dissolved in a polymerization solvent, and at least one of the aromatic dicarbonyl compounds represented by Formula 5 is added to this solution. Can be prepared by reacting.

The reaction of the aromatic diamine and the aromatic dicarbonyl compound is carried out at a low temperature, preferably 0 to 50, maintaining the reaction temperature, and instead of giving sufficient polymerization time of about 2 to 60 minutes, to increase the molecular weight in two steps It can superpose | polymerize. In addition, in order to increase the molecular weight, an inorganic salt may be polymerized into a polymerization solvent, and specific examples thereof include halogenated alkali metal salts or halogenated alkaline earth metal salts such as LiCl, LiBr, CaCl ₂ , NaCl, KCl, and KBr. These inorganic salts may be added alone or in the form of a mixture of two or more thereof. At this time, it is preferable to mix the aromatic dicarbonyl compound and the aromatic diamine in a molar ratio of 1: 0.9 to 1: 1.1. When the molar ratio of the aromatic diamine to the aromatic dicarbonyl compound is less than 0.9 or more than 1.1, it may be difficult to prepare a polymer having a low molecular weight and excellent mechanical properties, and may have a low viscosity, thus making coating and various processes difficult.

Specifically, the aromatic dicarbonyl compound is terephthalic acid, dimethyl terephthalate, terephthaloyl dichloride, 4,4'-benzoyl dichloride, 2,6-naphthalenedicarboxylic acid dichloride or 1,5-naphthalenedicarboxylic acid Dichloride, but is not necessarily limited thereto.

The aromatic diamine is selected from the group consisting of para-phenylenediamine, 4,4'-diaminobiphenyl, 2,6-naphthalenediamine, 1,5-naphthalenediamine, 4,4'-diaminobenzanilide, and the like. One or more selected may be used, but is not limited thereto.

  In the present invention, e) is a step of synthesizing the block copolymer by mixing the prepolymer-A and B and further adding a chain extender thereto. After the prepolymer-A and prepolymer-B manufacturing process is completed, the temperature is lowered to a temperature of 0 to 50 ° C., and the prepolymer is mixed. A diamine compound, dianhydride dianhydride, and a diisocyanate compound are further added to the chain extender. The final polymer may be prepared by reacting and removing the polymerization solvent and depending on the application and drying to form a precursor containing amic acid or imidization.

  As an imidation method applied at this time, it can be applied in combination with thermal imidation, chemical imidation, or thermal imidation and compound imidation. Chemical imidization involves the use of acid anhydrides such as acetic anhydride, isoquinoline, β-picolin, pyridine, azole, phosphine, malononitrile, 1,4-diazabicyclo [2,2, 2] octane, 2,6-dimethylpiperidine, triethylamine, N, N, N, N'-tetramethylethylenediamine, triphenylphosphine, 4-dimethylaminopyridine, tripropylamine, tributylamine, tri It is a method of injecting an imidation catalyst represented by octylamine, N, N-dimedylbenzylamine, 1,2,4-triazole, triisobutylamine, or the like. When thermal imidation or thermal imidation is used in combination with chemical imidization, the heating conditions of the precursor solution containing amic acid may vary depending on the type of precursor solution and the field to be applied. In the case of using thermal imidization and chemical imidization together, the final polymer resin will be described in more detail. For example, a dehydrating agent and an imidization catalyst are added to a precursor solution containing amic acid. Partial imidation by heating at 80-180 ° C to activate the dehydrating agent and imidization catalyst, further imidation by heating at 200-400 ° C for 5-400 seconds, heating at 200-400 ° C for 30 minutes or more, 90% or more It can be imidized.

  Unlike block copolymers, random copolymers do not synthesize prepolymers A and B, but dissolve diamine compounds, dianhydride dianhydrides, aromatic diamines, and aromatic dicarbonyl compounds in a polymerization solvent and lower the temperature to 0 to 50 ° C. The reaction can be made into precursors containing amic acid or imidized to produce the final polymer, the monomer used being the same as the block copolymer.

  When preparing a new polymer (imide) having the imide group and the aramid group at the same time, the mole number of the diamine compound including aromatic diamine is such that the mole ratio of dianhydride dianhydride and aromatic dicarbonyl compound is almost 1: 1. Decide However, one or more small amounts of diamine compounds containing aromatic diamines, dianhydride dianhydrides, and aromatic dicarbonyl compounds may be added to adjust the terminal of the polymer or depending on the application.

  The final polymer or precursor thereof having the imide group and the aramid group obtained at the same time may be formed into a film, a spinning, a slime according to the use, and may be produced as a film, a metal laminate, an adhesive, a fiber, or the like.

The precursor is finally imidized after application depending on the use to have a structure having an imide group and an aramid group at the same time.

  When the film is prepared, the final polymer or its precursor may be brought into solution and cast on a support to obtain a film.

  When imidating the said precursor solution, it can apply in combination with thermal imidation, chemical imidation, or thermal imidation and chemical imidation similarly to the above-mentioned. Examples of specific imidization in the case of using both thermal imidization and chemical imidization, can be imidized by adding a dehydrating agent and an imidization catalyst to the obtained polyamic acid solution and heating at 20 to 180 ° C. for 1 to 12 hours. In this case, the solid content of the precursor solution is preferably 5 ~ 30 wt%. Thereafter, the film is gradually heated in a temperature range of 40 to 400 ° C. for 1 minute to 8 hours, thereby obtaining a new film having an imide group and an aramid group having excellent transparency compared to the existing brown polyimide film.

  In the present invention, the film obtained as described above may be subjected to a heat treatment step once more. The temperature of the additional heat treatment step is preferably 100 ~ 500 ℃, the heat treatment time is preferably 1 minute to 30 minutes.

The residual volatile content of the film after heat treatment is 5% or less, and preferably 3% or less.

  Although the thickness of the obtained imide film is not specifically limited, It is preferable that it is the range of 10-250 micrometers, More preferably, it is 25-150 micrometers.

  When the fiber is prepared, the final polymer or its precursor is prepared in solution to prepare spinning dope. The organic solvent used herein is selected according to the degree of imidization, the ratio of imide group and aramid group, and 1,3- Dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidone (NMP), m-cresol, dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), Hexamethylphosphoamide (HMPA), N, N, N ', N'-tetramethyl urea (TMU) or mixtures thereof can be used.

The polymer concentration in the spinning dope is preferably 10 to 30 wt% for the fiber properties. As the concentration of the polymer increases, the intrinsic viscosity of the spinning dope also increases, but if it exceeds the critical concentration, the viscosity of the spinning dope can be drastically reduced, so that the viscosity of the spinning dope becomes too low when the concentration is too large.

  The spinneret has a plurality of capillaries having a diameter of 0.1 mm or less and preferably a plurality of capillaries having a diameter of 0.08 mm or less. If the diameter of the capillary formed in the spinneret exceeds 0.1 mm, the molecular orientation of the resulting filament is poor, resulting in a decrease in the strength of the filament.

  After spinning the spinning dope using a spinneret, the solvent is evaporated through a drying unit to form a filament. The drying unit may also use an air layer or an inert gas layer, and may control the solvent content of the filament by adjusting the residence time or the temperature in the drying unit. The temperature in the drying section is composed of two or more stages up to 150 ~ 300 ℃, and the residence time of each stage is suitable for 30 seconds to 5 minutes. The drying section is preferably heated by a predetermined means to maintain the temperature, and the drying section is preferably at least partially surrounded by the heat shield means in order to prevent excessive heat from being released and generating heat loss. Subsequently, the dried filament is wound on a branch pipe. The spin winding speed is 200 to 3,000 m / min.

  Application to metal laminates and adhesives can be applied in the same manner as general applications known in the art, except that a polymer having an imide group and an aramid group of the present invention is used.

  Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. However, the following examples are only intended to help the understanding of the present invention, and the scope of the present invention is not limited thereto.

(1) measuring the strength of the film

  The strength, initial modulus and elongation at break of the prepared films were measured using an Instron tensile tester (model Instron-5564). The strength of the film was obtained from the average value after testing five samples.

(2) measuring the strength of the fiber

  The strength of the sample was determined by measuring the strength (g) when a 25 cm long sample was broken in an Instron tester (Instron Engineering Corp, Canton, Mass) and dividing it by the denier of the sample. At this time, the tensile speed was 300mm / min, the super-load was fineness × 1 / 30g. The strength of the fiber was obtained from the average of five samples after testing.

(3) Yellow Index measurement of film

  Yellowing degree was measured by ASTM E313 standard.

≪ Example 1 >

  Bistrifluoromethyl benzidine (TFDB) in 190 ml of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor. 16.012 g was dissolved to prepare a mixed solution. To the mixed solution was added 21.768 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and stirred to prepare Prepolymer-A. At the same time, 5.407 g of meta-phenylenediamine (MPD) was dissolved in 100 ml in N-methyl-2-pyrrolidone (NMP) to prepare a mixed solution. 9.948 g of isophthaloyl dichloride (IPC) was added to the mixed solution, followed by stirring to prepare a prepolymer-B. Prepolymer-A and B prepared above were mixed and 0.888 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) was added to N-methyl-2-pyrrolidone (NMP). It was dissolved in 10 ml, added further, and reacted to obtain a precursor solution with amic acid having a solid concentration of 15 wt%.

  The precursor solution was stirred at room temperature for 8 hours, and gradually poured into a container containing 2 L of water, followed by precipitation. The precipitated solid was filtered and pulverized and dried at 80 ° C. for 6 hours under vacuum to obtain a solid powder. It was dissolved in N, N-dimethylacetaamide (DMAc) to make a solution of 25wt%.

In order to use thermal imidization and chemical imidization together, 20.418 g of acetic anhydride is first added to the precursor solution and then reacted with stirring at 150 ° C. for 3 hours.

After the reaction was completed, the obtained solution was applied to a stainless plate, then cast at about 400 μm, dried for 1 hour with hot air at 150 ° C., and the film was peeled off from the stainless plate to fix the pin to the frame.

The film on which the film was fixed was put in a vacuum oven and heated slowly at 100 ° C. to 300 ° C. for 2 hours, and then slowly cooled to separate the film from the frame. Thereafter, as a final heat treatment process, heat treatment was again performed at 300 ° C. for 30 minutes to obtain a film having a thickness of 100 μm.

<Example 2>

  The precursor solution was synthesized and thermally imidized in the same manner as in Example 1, except that the solution obtained after imidization was spun through spinneret, the solvent was removed through a drying unit, and finally a fiber having both imide and aramid groups was obtained. And chemical imidization.

<Example 3>

  Diamine was added to oxydianiline (ODA) in 97 ml of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor. g was dissolved to prepare a mixed solution. Prepolymer-A was prepared by adding and stirring 10.688 g of pyromellitic dianhydride (1,2,4,5-benzene tetracarboxylic dianhydride (PMDA)) to the mixed solution. At the same time, 5.407 g of para-phenylenediamine (PPD) was dissolved in 100 ml in N-methyl-2-pyrrolidone (NMP) to prepare a mixed solution. Prepolymer-B was prepared by adding 9.948 g of terephthaloyl dichloride (TPC) to the mixed solution and stirring the mixture. The prepolymer-A and B prepared above were mixed, 0.436 g of pyromellitic acid dianhydride (PMDA) was dissolved in 5 ml of N-methyl-2-pyrrolidone (NMP), and further added and reacted to obtain a solid content of 15 wt%. A precursor solution with phosphorous amic acid was obtained.

  The precursor solution was stirred at room temperature for 8 hours, and gradually poured into a container containing 2 L of water, followed by precipitation. The precipitated solid was filtered and pulverized, and then dried under vacuum at 80 ° C. for 6 hours to obtain a solid powder. It was dissolved in, N-dimethylacetaamide (DMAc) to make a solution of 25wt%.

In order to use thermal imidization and chemical imidization together, 20.418 g (0.2 mol) of acetic anhydride is first added to the precursor solution, followed by reaction with stirring at 150 ° C. for 3 hours.

After the reaction was completed, the obtained solution was applied to a stainless plate, then cast at about 400 μm, dried for 1 hour with hot air at 150 ° C., and the film was peeled off from the stainless plate to fix the pin to the frame.

The film on which the film was fixed was put in a vacuum oven and heated slowly at 100 ° C. to 300 ° C. for 2 hours, and then slowly cooled to separate from the frame to obtain a film. Thereafter, the film was heat-treated again at 300 ° C. for 30 minutes as a final heat treatment process to obtain a film having a thickness of 100 μm.

<Example 4>

  The precursor solution was synthesized and thermally imidized in the same manner as in Example 3 except that the solution obtained after imidization was spun through a spinneret, the solvent was removed through a drying part, and finally a fiber having an imide group and an aramid group was obtained. And chemical imidization.

Comparative Example 1

  After filling 116 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler as a reactor, the temperature of the reactor was 25 ° C. Diamine dissolved 10.012 g of oxydianiline (ODA) to maintain this solution at 25 ° C. To this was added 10.906 g of pyromellitic dianhydride (1,2,4,5-benzene tetracarboxylic dianhydride, PMDA) and stirred for 1 hour to completely remove pyromellitic dianhydride (PMDA). After dissolving, a polyamic acid solution having a solid content of about 15 wt% was obtained and formed into a film in the same manner as in Example 1 to prepare a general polyimide film.

Comparative Example 2

A mixed solution was prepared by dissolving 5.41 g of para-phenylenediamine (PPD) in 100 ml of a polymerization solvent in which 7.5 wt% of CaCl _{2 was} added to N-methyl-2-pyrrolidone (NMP). 4.06 g of terephthaloyl dichloride (TPC) was added to the mixed solution, followed by stirring to prepare a prepolymer. 6.09 g of terephthaloyl dichloride (TPC) was further added to the prepolymer thus prepared and reacted to prepare a final polymer, poly (paraphenylene terephthalamide: PPTA).

  A spinning dope was prepared by taking 18 g of the poly (paraphenylene terephthalamide: PPTA) and dissolving it in 100 ml of 100% sulfuric acid to spin aramid fiber.

 The Yellow Index and the strength measured for the film and the fiber having the imide group and the aramid group obtained by the above Examples and Comparative Examples are shown in Table 1 below.

<Table 1>

division Product form Processing solvent Y.I. burglar Example One film DMAc 4.9 225 Mpa 3 film DMAc 65.3 239 Mpa Comparative example One film DMAc 91.7 210 Mpa Example 2 fiber DMAc - 23 g / d 4 fiber DMAc - 24 g / d Comparative example 2 fiber Sulfuric acid - 22 g / d

Claims (11)

A block copolymer or a random copolymer having an imide group and an aramid (aromatic amide) group together in a polymer chain represented by the following formula (1)

The method according to claim 1, Block copolymer a) dissolving a diamine compound in a polymerization solvent to prepare a mixed solution, b) preparing prepolymer-A by adding dianhydride dianhydride to the mixed solution; c) dissolving aromatic diamine in a polymerization solvent to prepare a mixed solution, d) preparing a prepolymer-B by adding an aromatic dicarbonyl compound to the mixed solution, e) mixing the prepolymer-A and B and synthesizing the block copolymer by further adding a diamine compound, dianhydride dianhydride and a diisocyanate compound with a chain extender and reacting the prepolymer-A. Is an amine or anhydride terminal and the prepolymer-B is an amine or carbonyl compound terminal, Random copolymer Method for producing a polymer of block copolymers and random copolymers characterized in that a random copolymer is synthesized by dissolving and reacting a diamine compound, dianhydride dianhydride, aromatic diamine, and aromatic dicarbonyl compound in a polymerization solvent. The molar content of dianhydride dianhydride used is A and the molar content of the aromatic dicarbonyl compound is B. A method for producing a polymer, characterized in that the relative amounts of dianhydride dianhydride and aromatic dicarbonyl compound are adjusted to satisfy either 0 <A ≤ B or 0 <B ≤ A The method of claim 2, wherein the dianhydride dianhydride is represented by the following Chemical Formula 2.

In Formula 2, R ₁

At least one selected from the group consisting of, Y1 and Y2 are each independently or simultaneously a direct bond, -O-, -CO-, -S-, -SO _2- , -C (CH ₃ ) 2-, -CONH,-(CH2) n1-,- O (CH2) n2O-, -COO ( CH2) group of n3OCO-, a group substituted with a hydrogen of the alkyl group as a crowd fluorine (F); is selected from (for example, -C (CF ₃₎ 2-), where , n1, n2 and n3 are each independently an integer of 1 to 5. The method of claim 2, wherein the diamine compound is represented by the following Chemical Formula 3.

In Formula 3, R2

At least one selected from the group consisting of, Hydrogen of the benzene in the structure may be substituted with CF3, OH, Y1 and Y2 are each independently or simultaneously a direct bond, -O-, -CO-, -S-, -SO2-, -C (CH3) 2 -, -CONH,-(CH2) n1-, -O (CH2) n2O-, -COO (CH2) n3OCO-, the group in which the hydrogen of the above alkyl group is substituted with fluorine (F) (e.g. -C (CF ₃ ) 2-), wherein n1, n2 and n3 are each independently an integer from 1 to 5. The method according to claim 2, wherein the aromatic diamine used is represented by the following formula (4).

In Formula 4, R ₃

At least one selected from the group consisting of, Y1 and Y2 are each independently or simultaneously a direct bond, -O-, -CO-, -S-, -SO _2- , -C (CH ₃ ) 2-, -CONH,-(CH2) n1-,- O (CH2) n2O-, -COO ( CH2) group of n3OCO-, a group substituted with a hydrogen of the alkyl group as a crowd fluorine (F); is selected from (for example, -C (CF ₃₎ 2-), where , n1, n2 and n3 are each independently an integer of 1 to 5. The method of claim 2, wherein the aromatic dicarbonyl compound is represented by the following Formula (5).

In Formula 5, X1 and X2 are selected from the group of Cl, OH, OCH3 R4 is

Y 1 is each independently or simultaneously a direct bond, -O-, -CO-, -S-, -SO _2- , -C (CH ₃ ) 2-, -CONH,-(CH2) n1-, -O ( CH 2) n 2 O—, —COO (CH 2) n 3 OCO—, wherein n 1, n 2 and n 3 are each independently an integer from 1 to 5. The method of claim 2, wherein the solvent is 1,3-dimethyl-2-imidazolidinone (DMI), N-methylpyrrolidinone (NMP), N, N-dimethylacetamide (N, N- dimethylacetamide (DMAc), tetrahydrofuran (THF), N, N-dimethylformamide (NMF), dimethylsulfoxide (DMSO), cyclohexane, acetonitrile and Method for producing a polymer that is one or more selected from the group consisting of a mixture thereof. The method of claim 1, wherein the imide is an acid anhydride such as acetic anhydride, isoquinoline, β-picolin, pyridine, azole, phosphine, malononitrile, 1,4-dia Xavicyclo [2,2,2] octane, 2,6-dimethylpiperidine, triethylamine, N, N, N, N'-tetramethylethylenediamine, triphenylphosphine, 4-dimethylaminopyridine, tripropyl Of polymers characterized by imidization using amines, tributylamines, trioctylamines, N, N-dimedylbenzylamines, 1,2,4-triazoles and triisobutylamines Manufacturing method. 1,4-diazabicyclo [2,2,2] octane, 2,6-dimethylpiperidine, triethylamine, N, N, N, N'-tetramethylethylenediamine, triphenyl, as used in claim 9 Phosphine, 4-dimethylaminopyridine, tripropylamine, tributylamine, trioctylamine, N, N-dimedylbenzylamine, 1,2,4-triazole and triisobutylamine for the stabilization of aromatic diamines A method for producing a polymer having an imide group and an aromatic amide group using the aromatic diamine, which can be put in transportation and storage after preparation of the aromatic diamine. Polymer film, adhesive, metal laminate, fibers having the structure of claim 1