KR20110010008A - Manufacturing method of a novel polymer, a novel polymer manufactured by thereof and film manufactured using said polymer - Google Patents

Abstract

PURPOSE: A method for manufacturing a polymer is provided to prepare a polymer with excellent thermal stability due to low thermal expansion coefficient and improved transparency. CONSTITUTION: A method for manufacturing a polymer comprises: a first prepolymer synthesis step for reacting a dianhydride compound in a solution in which a diamine compound is dissolved in a polymerization solvent; a second prepolymer synthesis step for reacting a aromatic dicarbonyl compound in a solution in which a diamine compound is dissolved in a polymerization solvent; a precursor solution preparation step for mixing the first prepolymer and the second prepolymer and adding a chain extender to the mixture; and an imidization step for adding a catalyst to the precursor solution and heating it.

Description

Manufacturing method of a novel polymer and a film produced by the polymer {manufacturing method of a novel polymer, a novel polymer manufactured by particular and film manufactured using said polymer}

The present invention relates to a novel polymer manufacturing method, a novel polymer produced thereby and a film made of the polymer, specifically a novel polymer manufacturing method improved thermal stability with improved transparency and low coefficient of thermal expansion, new novel produced thereby It relates to a polymer and a film made of the polymer.

In addition to heat resistance, polyimide resins have excellent mechanical properties, flame retardancy, chemical resistance, low dielectric constant, and have a wide range of applications such as 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. 5053480 discloses a method of using an aliphatic ring-based dianhydride component instead of an aromatic dianhydride, which has improved transparency and color when in solution or film compared to the purification method, but improves permeability. There was a limit to the results, which resulted in degradation of thermal and mechanical properties. Korean Patent Laid-Open Publication No. 2003-0009437 has a linking group such as -O-, -SO _2- , CH ₂ -and a monomer having a curved structure connected to the m-position instead of the p -position or a substituent such as -CF ₃ . A report has been made on the production of a novel polyimide with improved aromaticity and color transparency using aromatic dianhydride dianhydride and aromatic diamine monomers, provided that the thermal properties are not significantly reduced. The transmittance was insufficient to be used as a substrate for a semiconductor insulating film and a flexible display.

An object of the present invention to solve the above problems is to provide a novel polymer production method, a novel polymer produced by this and a film made of the polymer improved transparency and low thermal expansion coefficient improved thermal stability.

According to an aspect of the present invention,

A first pre-polymer synthesis step of adding and reacting a dianhydride compound to a mixed solution in which a diamine compound is dissolved in a polymerization solvent;

A second pre-polymer synthesis step of adding and reacting an aromatic dicarbonyl compound to a mixed solution prepared by dissolving an aromatic diamine compound in a polymerization solvent;

Preparing a precursor solution for reacting the first pre-polymer and the second pre-polymer by mixing and adding a chain extender; And

Provided is a novel polymer preparation method comprising an imidization step of adding a catalyst or heating to the precursor solution to form a final product.

The diamine compound may be at least one selected from compounds represented by the following general formula (1):

[Formula 1]

(In Chemical Formula 1,

R ₁ is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or a polycyclic compound group in which an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group is directly or connected by a crosslinking group.)

R ₁ in Formula 1 may be selected from the group consisting of:

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And

The dianhydride compound may be at least one selected from the compound represented by the following formula (2):

[Formula 2]

(In Chemical Formula 2,

R ₂ is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or a polycyclic compound group in which an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group is directly or connected by a crosslinking group.)

R ₂ in Formula 2 may be selected from the group consisting of:

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And

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The diamine compound and the diamine hydride compound may be reacted in a molar ratio of 1: 0.3 to 1: 2.0.

The polymerization solvent is 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidinone, N, N-dimethylacetamide, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, cyclohexane And acetonitrile may be a single or a mixture thereof selected from the group consisting of.

In the second pre-polymer synthesis step, the polymerization solvent may include an inorganic salt.

The inorganic salt may be a single or a mixture thereof selected from the group consisting of halogenated alkali metal salts and halogenated alkaline earth metal salts.

The aromatic diamine compound in the general formula 1 R ₁ Is an aromatic hydrocarbon group; Or a polycyclic compound group in which an aromatic hydrocarbon group is linked directly or by a crosslinking group.

The aromatic diamine compound may be para-phenylenediamine.

The aromatic dicarbonyl compound may be represented by the following Chemical Formula 3:

(3)

(In Chemical Formula 3,

R ₃ is a substituted or unsubstituted aromatic hydrocarbon group; Or a polycyclic compound group in which an aromatic hydrocarbon group is directly or connected by a crosslinking group,

X represents a halogen element.)

The aromatic dicarbonyl compound may be terephthaloyl dichloride.

The aromatic diamine compound and the aromatic dicarbonyl compound may be reacted in a molar ratio of 1: 0.3 to 1: 2.0.

The chain extender may be a single or a mixture thereof selected from the group consisting of diamine compounds, dianhydride compounds, terephthaloyl dichloride and diisocyanate.

The polymer may be a block copolymer having the structure of Formula 4 below:

[Formula 4]

(In Formula 4,

R ₁ and R ₂ are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or a polycyclic compound group in which an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group is directly or connected by a crosslinking group,

CE stands for chain extender,

n is an integer from 10 to 1000,

m is an integer from 10 to 1000.)

The ratio of the sum of the moles of the diamine compound and the aromatic diamine compound and the sum of the moles of the dianhydride compound and the aromatic dicarbonyl compound may be 1: 0.8 to 1: 1.2.

In order to achieve the other object of the present invention,

It provides a polymer production method comprising a polymerization step of dissolving and reacting a diamine compound, a dianhydride compound, an aromatic diamine compound, and an aromatic dicarbonyl compound in a polymerization solvent.

The aromatic diamine compound may be para-phenylenediamine.

The aromatic dicarbonyl compound may be terephthaloyl dichloride.

The polymer may be a random copolymer having the structure of Formula 5:

[Chemical Formula 5]

(In Chemical Formula 5,

R ₁ and R ₂ are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or a polycyclic compound group in which an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group is directly or connected by a crosslinking group,

z is an integer from 10 to 2000.)

In order to achieve another object of the present invention,

It provides a novel polymer produced by the above polymer production method.

In order to achieve another object of the present invention,

It provides a film made of the polymer.

In order to achieve another object of the present invention,

Imidizing the precursor solution produced in the precursor solution preparation step of the novel polymer production method;

It provides a film manufacturing method comprising the step of forming a film on the support by dissolving the imidized precursor solution in an organic solvent.

In addition, imidizing the precursor solution generated in the precursor solution manufacturing step of the novel polymer manufacturing method;

A precipitation step of precipitating the imidized precursor solution in a solvent having a lower polarity than a polymerization solvent used in the preparation of the precursor solution to obtain a solid content; And

It provides a film manufacturing method comprising the step of forming a film to dissolve the solid content in an organic solvent and cast on a support.

The polymer produced by the production method of the present invention is a polymer having a new structure and excellent in transparency.

The polymer produced by the production method of the present invention has a low thermal expansion coefficient and is excellent in thermal stability.

The polymer produced by the production method of the present invention is excellent in physical properties such as mechanical strength, impact resistance.

The film made of the polymer of the present invention can be applied to LCD, and can be applied to various fields such as semiconductor insulating film, TFT-LCD insulating film, passivation film, liquid crystal alignment film, optical communication material, solar cell protective film, and flexible display substrate. .

Hereinafter, the present invention will be described in detail so that those skilled in the art can easily practice.

The present invention comprises a first pre-polymer synthesis step; A second pre-polymer synthesis step; Preparing a precursor solution; And it provides a novel polymer manufacturing method comprising the imidization step. The method includes a pre-polymer preparation step, thereby allowing pre-polymers having different physical properties to react with each other to enable polymer synthesis of a novel structure having various excellent physical properties.

The first pre-polymer synthesis step is a step of reacting by adding a dianhydride compound to a mixed solution in which a diamine compound is dissolved in a polymerization solvent.

The diamine compound may be at least one selected from compounds represented by the following general formula (1):

[Formula 1]

In Formula 1, R ₁ is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group may be a polycyclic compound group directly or connected by a crosslinking group, Preferably, it may be selected from the group consisting of:

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And

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Specific examples of the diamine compound include bis amino phenoxy phenyl hexafluoropropane (DBOH), bis trifluoromethyl benzidine, p -phenylenediamine, m-phenylenediamine, bis (3-aminophenyl) sulfone, Bis (4-aminophenyl) sulfone, 4,4'-oxydianiline, 3,3'-oxydianiline, 2,2-bis (4- [4-aminophenoxy] -phenyl) propane, cyclohexane diamine And 2,2-bis (4- [3-aminophenoxy] phenyl) sulfone, but are not limited thereto.

The dianhydride compound may be at least one selected from the compound represented by the following formula (2):

[Formula 2]

In Formula 2, R ₂ is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group may be a polycyclic compound group connected directly or by a crosslinking group, and may be preferably selected from the group consisting of:

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And

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Specific examples of the dianhydride compound include pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3', 4,4 '-Benzophenonetetracarboxylic dianhydride (TDA), 4,4'-oxydiphthalic anhydride (ODPA), 2,2'-bis- (3,4-dicarboxylphenyl) hexafluoropropane Dianhydride (6FDA), cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) and cyclohexane dianhydride (CHDA), but are not limited thereto.

The polymerization solvent can be used without limitation, those known in the art as long as it can dissolve the diamine compound and dianhydride compound, preferably 1,3-dimethyl-2-imidazolidinone (1,3-dimethyl -2-imidazolidinone; DMI), N-methylpyrrolidinone (NMP), N, N-dimethylacetamide (DMAc), tetrahydrofuran (THF), N, N-dimethylformamide (NMF), dimethyl sulfoxide (DMSO), cyclohexane (cyclohexane) and acetonitrile (acetonitrile) may be used alone or a mixture thereof.

The reaction may be performed at 0 to 50 ° C. for 1 to 24 hours. In the above conditions, the reaction proceeds sufficiently to complete the reaction, and the reaction yield may be improved.

The dianhydride compound and the diamine compound may react in a molar ratio of 1: 0.3 to 1: 2.0, preferably in a molar ratio of 1: 0.4 to 1: 1.6. When the diamine compound is reacted with a molar ratio of less than 0.3 or more than 2.0 with respect to the dianhydride compound, it may be difficult to prepare a polymer having low molecular weight and excellent mechanical properties, and the viscosity of the polymer may be lowered.

The second pre-polymer synthesis step is a step of reacting by adding an aromatic dicarbonyl compound to a mixed solution prepared by dissolving the aromatic diamine compound in a polymerization solvent. Since the second pre-polymer is synthesized using the aromatic diamine compound and the dicarbonyl compound, the finally prepared polymer includes an aramid polymer, thereby improving dimensional stability and thermal stability.

The polymerization solvent is as described above. The polymerization solvent may comprise an inorganic salt, preferably may comprise an inorganic salt in the second pre-polymer synthesis step. By adding an inorganic salt, the molecular weight of the polymer can be increased. The inorganic salt may be a single or a mixture thereof selected from the group consisting of halogenated alkali metal salts and halogenated alkaline earth metal salts. Specifically, the inorganic salt may be used alone or a mixture thereof selected from the group consisting of LiCl, LiBr, CaCl ₂ , NaCl, KCl and KBr, but is not limited thereto.

The aromatic diamine compound may be an aromatic hydrocarbon group in which R ₁ is substituted or unsubstituted in Chemical Formula 1; Or a compound in which the aromatic hydrocarbon group is a polycyclic compound group connected directly or by a crosslinking group, It may be preferably p -phenylenediamine.

The aromatic dicarbonyl compound may be represented by the following Chemical Formula 3:

(3)

In Formula 3, R ₃ is a substituted or unsubstituted aromatic hydrocarbon group; Or a polycyclic compound group in which an aromatic hydrocarbon group is directly or connected by a crosslinking group, and X may be a halogen element. X may be specifically F, Cl, Br or I and the like. Preferably, the aromatic dicarbonyl compound may be terephthaloyl dichloride.

The reaction can be carried out for 2 to 60 minutes at a temperature of 0 to 50 ℃. When the reaction proceeds under the above conditions, polymerization is sufficiently performed to obtain a polymer having a high molecular weight, and the reaction efficiency is increased.

The aromatic dicarbonyl compound and the aromatic diamine compound may be reacted in a molar ratio of 1: 0.3 to 1: 2.0, preferably in a molar ratio of 1: 0.4 to 1: 1.6. When the aromatic diamine compound is reacted with the aromatic diamine compound in a molar ratio of less than 0.3 or more than 2.0, it may be difficult to prepare a polymer having a low molecular weight and excellent mechanical properties. It can be difficult.

The precursor solution preparation step is a step of reacting by mixing the first pre-polymer and the second pre-polymer and adding a chain extender.

The first pre-polymer and the second pre-polymer may be mixed and reacted by further adding a chain extender thereto to prepare a precursor solution including amic acid. In the precursor solution preparation step, it may be partially imidized. The reaction can be carried out at 0 to 50 ℃. The reaction proceeds smoothly within the temperature range, thereby preparing a precursor solution.

The chain extender serves to connect the first pre-polymer and the second pre-polymer and to strengthen the bond. The chain extender may be used without limitation those known in the art, but preferably, a single or a mixture thereof may be used selected from the group consisting of diamine compound, dianhydride compound, terephthaloyl dichloride and diisocyanate compound. have.

The imidization step is a step of adding a catalyst or heating the precursor solution to form the final product.

The imidation can be carried out by introducing a catalyst into the precursor solution containing the amic acid to advance chemical imidization. The catalyst can be used without limitation, those known in the art, specifically, anhydrides such as acetic anhydride, isoquinoline, β-picolin, pyridine, azole, phosphine, malononitrile, 2,6-dimethylpiper Ridine, triethylamine, N, N, N, N'-tetramethylethylenediamine, triphenylphosphine, 4-dimethylaminopyridine, tripropylamine, tributylamine, N, N-dimedylbenzylamine, 1, 2,4-triazole, triisobutylamine, etc. can be used.

The imidation can be carried out using a combination of chemical imidization and thermal imidization. Specifically, the precursor solution containing the amic acid may be partially imidized by adding a dehydrating agent and an imidization catalyst and heating to activate the dehydrating agent and the imidization catalyst. The imidation may proceed at 50 to 400 ° C., and may be imidized at least 90% by heating at 200 to 400 ° C. for at least 30 minutes.

The imidization catalyst may be added in a molar ratio of 1: 1 or more with respect to the amic acid, preferably in a molar ratio of 1: 3 or more. When the imidization catalyst is added in an excess mole than amic acid, the dehydration reaction can be effectively induced to facilitate the imidization well, and the change in color and heat due to the long time reaction at high temperature can be achieved by the imidization at a lower temperature. The deterioration of stability can be prevented.

The polymer prepared by the preparation method may be a block copolymer having a structure of Formula 4 below:

[Formula 4]

In Formula 4, R ₁ and R ₂ are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group is a polycyclic compound group connected directly or by a crosslinking group, CE is a chain extender, and n and m are each an integer of 10 to 1000. Wherein R ₁ is the same as R ₁ of a diamine compound, wherein R ₂ is the same as R ₂ of the dianhydride compound. The block copolymer has excellent stereoregularity in a structure connected by a chain extender (CE).

The ratio of the sum of the number of moles of the diamine compound and the aromatic diamine compound and the number of moles of the dianhydride compound and the aromatic dicarbonyl compound may be 1: 0.8 to 1: 1.2, preferably 1: 1. When reacting at a molar ratio, a polymer having a high molecular weight may be obtained, and when any one component is contained in a small amount or an excess of the molar range, it may be difficult to obtain a high molecular weight polymer. However, one or more small amounts of diamine compound, dianhydride dianhydride and terephthaloyl dichloride (TPC) may be added to adjust the terminal of the polymer or depending on the application.

The present invention also provides a method for preparing a polymer comprising dissolving and reacting a diamine compound, a dianhydride compound, an aromatic diamine compound, and an aromatic dicarbonyl compound in a polymerization solvent. The method does not go through the pre-polymer manufacturing step, it is possible to produce a polymer having excellent transparency and thermal stability in a simpler method.

The polymerization solvent, diamine compound, dianhydride compound, aromatic diamine compound and aromatic dicarbonyl compound are as described above. Preferably, the aromatic diamine compound may be para-phenylenediamine, and the aromatic dicarbonyl compound may be terephthaloyl dichloride.

The polymer prepared by the above method may be a random copolymer having a structure of Formula 5:

[Chemical Formula 5]

In Formula 5, R ₁ and R ₂ are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group is a polycyclic compound group directly or connected by a crosslinking group, and z is an integer of 10 to 2000.

The reaction may be performed at 0 to 50 ° C. to form a precursor solution including amic acid, or may be imidized to prepare a polymer as a final product.

The present invention provides a film formed of the polymer produced by the above method. The film is transparent and thermally stable and can be applied to LCD, and can be applied to various fields such as semiconductor insulating film, TFT-LCD insulating film, passivation film, liquid crystal alignment film, optical communication material, solar cell protective film, and flexible display substrate. have.

The film can be prepared by conventional methods known in the art. The film may be prepared from a precursor solution containing amic acid formed when preparing the polymer of the present invention. Specifically, the precursor solution including the amic acid may be cast on the support and imidized to prepare a film. In addition, additives or fillers known in the art may be added during the casting. The said imidation can use together thermal imidation, chemical imidation, or thermal imidation, and chemical imidation. Specifically, after the dehydrating agent and imidization catalyst are added to the precursor solution and cast, the film may be heated at room temperature to 150 ° C. for 1 to 12 hours. At this time, the precursor solution may be partially imidized to include a solid content, the solid content is preferably 5 to 30% by weight based on the total precursor solution. In addition, the precursor solution may be cast on a support and then thermally imidized by heating for 1 minute to 4 hours while gradually increasing the temperature at a temperature of 40 to 400 ° C.

In addition, the film is prepared by precipitating the precursor solution containing the amic acid in a solvent such as water, methanol or ethyl ether having a lower polarity than a polymerization solvent to obtain a solid content, which is dissolved in a solvent and cast on a support and imidized. can do. The solvent is 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidinone, N, N-dimethylacetamide, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, cyclohexane and Alone or a mixture thereof selected from the group consisting of acetonitrile can be used.

The film manufacturing method may further include a heat treatment step of heat treatment for 1 to 30 minutes at a temperature of 150 ~ 450 ℃ under a constant tension. When the thermal imidization is performed, the thermal stability of the final imide product may be lowered, thereby preventing the thermal stability from being lowered through the heat treatment process.

The film production method of the present invention includes an imidization step and a film forming step. Since the polymer of the present invention has an improved solubility in solvents than a conventional polymer and is easy to process, the film may be manufactured using a polymer that has already undergone imidation without undergoing imidization during the film forming process. The imidization step is to imidize the precursor solution produced in the precursor solution preparation step of the novel polymer production method of the present invention. In the film forming step, the imidized precursor solution is dissolved in an organic solvent and cast on a support.

In addition, the film production method of the present invention comprises an imidization step; Precipitation step; And a film forming step. The above-mentioned method also advances imidation before the film forming step, and does not require imidization in the film forming step. The imidization step is the same as described above, and the precipitation step is to obtain the solid content by precipitating the imidized precursor solution in an organic solvent having a lower polarity than the polymerization solvent used in the preparation of the precursor solution. . In the film forming step, the solid is dissolved in an organic solvent and cast on a support.

The organic solvent is 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidinone, N, N-dimethylacetamide, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, cyclohexane And acetonitrile may be used alone or in a mixture thereof.

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. This is for the purpose of illustrating the invention only, and thus the scope of the invention is not limited.

< Example  1> Synthesis of Block Copolymer and Film Made Therefrom

1-1. 2,2′-bis (3-aminophenyl) in 594.60 ml of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 1 liter reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler. 30.08 g of hexafluoropropane were dissolved to prepare a mixed solution. To the mixed solution was added 35.98 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and stirred to prepare a first pre-polymer. At the same time, 1.08 g of para-phenylenediamine (PPD) was dissolved in 17.45 ml of N-methyl-2-pyrrolidone (NMP) to prepare a mixed solution, and 1.83 g of terephthaloyl dichloride (TPC) was added thereto. Stirring gave a second pre-polymer. The first pre-polymer and the second pre-polymer were mixed and 4.44 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) was N-methyl-2-pi. The solution was dissolved in 44.42 ml of rolidone (NMP), further added, and reacted to obtain a precursor solution which was a block copolymer having an amic acid having a solid concentration of 10 wt%. The precursor solution was stirred at room temperature for 8 hours, and gradually poured into a container containing 4 liters of water, followed by precipitation. The precipitated solid was filtered and pulverized, and dried at 80 ° C. for 8 hours under vacuum to obtain a solid powder. It was dissolved in N, N-dimethylacetaamide (DMAc) to make a solution of 25 wt%. In order to use thermal imidization and chemical imidization together, 36.75 g of acetic anhydride was first added to the precursor solution, followed by stirring at 150 ° C. for 3 hours to obtain a polymer solution.

1-2. The imidized polymer solution synthesized in 1-1 was applied to a stainless plate, cast at about 400 μm, and dried for 1 hour with hot air at 150 ° C. to prepare a film. The film was peeled off the stainless plate and pinned to the frame. The film on which the film was fixed was put in a vacuum oven and slowly heated from 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  2> Synthesis of Block Copolymer and Film Made Therefrom

2,2′-bis (3-aminophenyl) in 462.47 ml of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 1 liter reactor equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler. 23.40 g of hexafluoropropane was dissolved to prepare a mixed solution. 27.99 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added to the mixed solution and stirred to prepare a first pre-polymer. At the same time, 3.24 g of para-phenylenediamine (PPD) was dissolved in 52.35 ml of N-methyl-2-pyrrolidone to prepare a mixed solution, and 5.48 g of terephthaloyl dichloride (TPC) was added to the mixed solution. Stirring gave a second pre-polymer. The first pre-polymer and the second pre-polymer prepared above were mixed, and 4.44 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was N-methyl-2-pyrrolidone. (NMP) was dissolved in 62.42 mL, further added and reacted to obtain a precursor solution which was a block copolymer with amic acid having a solid concentration of 10 wt%. Thereafter, the block copolymer and the film were prepared in the same manner as in Example 1.

< Example  3> Synthesis of Block Copolymer and Film Made Therefrom

2,2′-bis (3-aminophenyl) in 330.33 ml of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 1 liter reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler. 16.71 g of hexafluoropropane was dissolved to prepare a mixed solution. 19.99 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added to the mixed solution and stirred to prepare a first pre-polymer. At the same time, 5.41 g of para-phenylenediamine (PPD) was dissolved in 87.26 ml of N-methyl-2-pyrrolidone (NMP) to prepare a mixed solution, and terephthaloyl dichloride (TPC) was 9.14. g was added and stirred to prepare a second pre-polymer. The first pre-polymer and the second pre-polymer were mixed and 4.44 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added with N-methyl-2-pyrrolidone (NMP ) Was dissolved in 80.42 mL, further added, and reacted to obtain a precursor solution which was a block copolymer having an amic acid having a solid concentration of 10 wt%. After the process was the same as in Example 1 to obtain a block copolymer and a film.

< Example  4> Synthesis of Block Copolymers and Films Prepared therefrom

2,2'-bis (3-aminophenyl) hexafluoro in 198.20 ml of N-methyl-2-pyrrolidone with nitrogen passing through a 1 l reactor equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler 10.03 g of ropeophane was dissolved to prepare a mixed solution. 11.99 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added to the mixed solution and stirred to prepare a first pre-polymer. At the same time, 12.79 g of terephthaloyl dichloride was added and stirred to a mixed solution in which 7.57 g of para-phenylenediamine was dissolved in 122.16 ml of N-methyl-2-pyrrolidone to prepare a second pre-polymer. The first pre-polymer and the second pre-polymer were mixed and 4.44 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was 98.42 ml of N-methyl-2-pyrrolidone. It was dissolved in and further added and reacted to obtain a precursor solution which was a block copolymer with amic acid having a solid concentration of 10 wt%. Thereafter, polymers and films were prepared in the same manner as in Example 1.

< Example  5> Synthesis of block copolymers and films made therefrom

2,2′-bis (3-aminophenyl) hexafluoro in 66.07 mL of N-methyl-2-pyrrolidone with nitrogen passing through a 1 L reactor equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler 3.34 g of ropeophane was dissolved to prepare a mixed solution. 4.00 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added to the mixed solution and stirred to prepare a first pre-polymer. At the same time, 16.44 g of terephthaloyl dichloride was added to the mixed solution prepared by dissolving 9.73 g of para-phenylenediamine in 157.06 ml of N-methyl-2-pyrrolidone and stirred to prepare a second pre-polymer. The first pre-polymer and the second pre-polymer were mixed and 4.44 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 116.42 ml of N-methyl-2-pyrrolidone It was dissolved in and further added and reacted to obtain a precursor solution which was a block copolymer with amic acid having a solid concentration of 10 wt%. Thereafter, a block copolymer and a film were obtained in the same manner as in Example 1.

< Example  6> Preparation of random copolymers and films

2,2′-bis (3-aminophenyl) hexafluoro in 656.48 ml of N-methyl-2-pyrrolidone with nitrogen passing through a 1 liter reactor equipped with a stirrer, nitrogen injector, dropping funnel, thermostat and cooler 30.08 g of ropropane, 40.43 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1.08 g of para-phenylenediamine and 1.83 g of terephthaloyl dichloride are added and stirred, followed by reaction. To obtain a precursor solution which is a random copolymer having a solid content of 10 wt% and having an amic acid. Thereafter, a random copolymer and a film were obtained in the same manner as in Example 1.

< Comparative example  1> Preparation of Polyimide Film

376 g of N-methyl-2-pyrrolidone was charged with nitrogen through a 1 liter reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler, and then the temperature of the reactor was adjusted to 25 ° C. and oxydianiline 20.024 g were dissolved to maintain this solution at 25 ° C. 21.812 g of pyromellitic dianhydride (1,2,4,5-benzene tetracarboxylic dianhydride (PMDA)) was added thereto, followed by stirring for 1 hour to completely dissolve the pyromellitic dianhydride. A polyamic acid precursor solution having a concentration of solids of about 10 wt% was obtained and formed into a film in the same manner as in Example 1 to obtain a polyimide film.

< Experimental Example  1> Film strength measurement

The strength, initial modulus and elongation at break of the films prepared in Examples 1 to 6 and Comparative Example 1 were measured using an Instron tensile tester (model Instron-5564). The strength of the film was obtained by the average value after testing five samples, the results are shown in Table 1 below.

< Experimental Example  2> coefficient of thermal expansion ( coefficient thermal expansion , CTE )

TMA (Perkin Elmer, Diamond TMA) was used to measure the coefficient of thermal expansion at 50 to 200 ℃ over three times of first run, second run, and third run according to TMA-Method. That is, after increasing the temperature from 30 ℃ to 230 ℃ and lowered again to 30 ℃, it was measured while increasing again to 230 ℃ three times, the results are shown in Table 1 below.

< Experimental Example  3> film Yellow Index  Measure

The yellowing degree was measured by ASTM E313 standard, and the results are shown in Table 1 below.

According to Table 1, the polymer prepared in Example showed a low thermal expansion coefficient and excellent thermal stability, it can be seen that the transparency is improved by a low Yellow Index. Moreover, intensity | strength improved also than the polyimide film of a comparative example.

As described above, the polymer having a novel structure synthesized by the manufacturing method of the present invention is excellent in mechanical properties and transparency including amide and aramid, and is improved in thermal stability and applied to various fields. It is expected to be.

Claims (25)

A first pre-polymer synthesis step of adding and reacting a dianhydride compound to a mixed solution in which a diamine compound is dissolved in a polymerization solvent; A second pre-polymer synthesis step of adding and reacting an aromatic dicarbonyl compound to a mixed solution prepared by dissolving an aromatic diamine compound in a polymerization solvent; Preparing a precursor solution for mixing the first pre-polymer and the second pre-polymer and reacting by adding a chain extender (CE); And Adding a catalyst to the precursor solution or heating to form an imidization step to form a final product. The method of claim 1, Method for producing a new polymer, characterized in that the diamine compound is selected from one or more of the compounds represented by the following formula (1): [Formula 1]

(In Chemical Formula 1, R ₁ is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or a polycyclic compound group in which an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group is directly or connected by a crosslinking group.) The method of claim 2, Wherein R ₁ is selected from the group consisting of:

,

.

,

,

,

, ,

,

,

,

And

. The method of claim 1, The dianhydride compound is a method for producing a novel polymer, characterized in that at least one selected from the compound represented by the formula (2): [Formula 2]

(In Chemical Formula 2, R ₂ is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or a polycyclic compound group in which an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group is directly or connected by a crosslinking group.) The method of claim 4, wherein Wherein R ₂ is selected from the group consisting of:

,

,

,

,

,

And

. The method of claim 1, The diamine compound and the diamine hydride compound is a method for producing a novel polymer, characterized in that the reaction in a molar ratio of 1: 0.3 to 1: 2.0. The method of claim 1, The polymerization solvent is 1,3-dimethyl imidazolidinone, N-methylpyrrolidinone, N, N-dimethylacetamide, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, cyclohexane and acetonitrile Method of producing a novel polymer, characterized in that single or a mixture thereof selected from the group consisting of. The method of claim 1, And wherein said polymerization solvent of said second pre-polymer synthesis step comprises an inorganic salt. The method of claim 8, The inorganic salt is a novel polymer production method, characterized in that the alone or a mixture thereof selected from the group consisting of halogenated alkali metal salts and halogenated alkaline earth metal salts. The method of claim 1, The aromatic diamine compound may be an aromatic hydrocarbon group of R ₁ of Formula 1; Or a compound in which the aromatic hydrocarbon group is a polycyclic compound group connected directly or by a crosslinking group. The method of claim 1, And said aromatic diamine compound is para-phenylenediamine. The method of claim 1, Method for producing a novel polymer, wherein the aromatic dicarbonyl compound is represented by the following formula (3): (3)

(In Chemical Formula 3, R ₃ is a substituted or unsubstituted aromatic hydrocarbon group; Or a polycyclic compound group in which an aromatic hydrocarbon group is directly or connected by a crosslinking group, X is a halogen element.) The method of claim 1, And said aromatic dicarbonyl compound is terephthaloyl dichloride. The method of claim 1, The aromatic diamine compound and the aromatic dicarbonyl compound are reacted in a molar ratio of 1: 0.3 to 1: 2.0. The method of claim 1, The chain extender is a novel polymer production method, characterized in that the singly or a mixture thereof selected from the group consisting of diamine compound, dianhydride compound, terephthaloyl dichloride and diisocyanate. The method of claim 1, The ratio of the sum of the number of moles of the diamine compound and the aromatic diamine compound and the sum of the moles of the dianhydride compound and the aromatic dicarbonyl compound is 1: 0.8 to 1: 1.2. The method of claim 1, Method for producing a novel polymer, characterized in that the polymer is a block copolymer having a structure of formula (4): [Formula 4]

(In Formula 4, R ₁ and R ₂ are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or a polycyclic compound group in which an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group is directly or connected by a crosslinking group, CE is a chain extender, n is an integer from 10 to 1000, m is an integer from 10 to 1000.) And a polymerization step of dissolving and reacting a diamine compound, a dianhydride compound, an aromatic diamine compound, and an aromatic dicarbonyl compound in a polymerization solvent. The method of claim 18, And said aromatic diamine compound is para-phenylenediamine. The method of claim 18, And said aromatic dicarbonyl compound is terephthaloyl dichloride. The method of claim 18, Method for producing a new polymer, characterized in that the polymer is a random copolymer having a structure of formula (5): [Chemical Formula 5]

(In Chemical Formula 5, R ₁ and R ₂ are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms; Substituted or unsubstituted alicyclic hydrocarbon group; Substituted or unsubstituted aromatic hydrocarbon group; Substituted or unsubstituted heterocyclic group; Or a polycyclic compound group in which an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group is directly or connected by a crosslinking group, z is an integer from 10 to 2000.) A novel polymer produced by the method of any one of claims 1-21. A film made of the polymer of claim 22. An imidization step of imidizing the precursor solution of claim 1; And And forming a film on the support by dissolving the imidized precursor solution in an organic solvent. An imidization step of imidizing the precursor solution of claim 1; A precipitation step of precipitating the imidized precursor solution in a solvent having a lower polarity than a polymerization solvent used in the preparation of the precursor solution to obtain a solid content; And And forming a film on the support by dissolving the solid in an organic solvent.