WO2016032299A1

WO2016032299A1 - Polyimide preparation method using monomer salt

Info

Publication number: WO2016032299A1
Application number: PCT/KR2015/009102
Authority: WO
Inventors: 정찬문; 유환철; 이재희
Original assignee: 연세대학교 원주산학협력단
Priority date: 2014-08-29
Filing date: 2015-08-29
Publication date: 2016-03-03

Abstract

The present invention relates to a polyimide preparation method and a polyimide prepared thereby, the method comprising the steps of: a) preparing a monomer salt mixture by putting a dianhydride monomer and a diamine monomer into water; b) recovering a monomer salt by filtering and drying the monomer salt mixture or evaporating water; and c) preparing a polyimide by heating the monomer salt. According to the present invention, preparation of a polyimide, a polyimide copolymer or a polyimide composite is carried out under moderate conditions, the preparation process is simple and economical and is environmental friendly by not using organic solvents, and the polyimide has a high molecular weight, excellent mechanical properties and high thermal characteristics compared with a polyimide prepared by a conventional method.

Description

Method for producing polyimide using monomer salt

The present invention relates to a method for producing polyimide using a monomer salt.

High heat-resistant polymer materials such as polyimide are essential materials for miniaturization, high performance, and high reliability of products according to the development of advanced technology. In the form of film, molded products, fibers, paints, adhesives and composites, aerospace, aviation, electricity It is used in a wide range of industries such as electronics, automotive and precision equipment.

Polyimide (PI) of the high heat resistant polymer material has excellent mechanical strength, chemical resistance, weather resistance, and heat resistance based on the chemical stability of the imide ring. In addition, it is easy to synthesize, can be made into a thin film, has the advantage of not needing a cross-linking group for curing, and due to its excellent electrical properties, it has been spotlighted as a high functional polymer material from microelectronics to optical.

Meanwhile, due to the growth of the high-tech industry, many studies have been conducted to increase the performance of the polyimide material itself or to replace the previously used polymer material. These studies attempted to obtain the above characteristics by dispersing organic or inorganic materials in polyimide itself or materials prepared by modifying them in polymers. The polyimide composite material produced by this method may show higher mechanical and thermal properties, and also high transmittance or high dielectric constant depending on the dispersing material. The polyimide composite thus prepared can be used in new fields such as organic thin film transistors, which were not used at low dielectric constants in addition to those in which polyimide was used.

In the present invention, the synthesis step is greatly reduced, the reaction proceeds under mild conditions during the preparation of the monomer salt, and a method for preparing a polyimide, polyimide copolymer or polyimide composite using the prepared monomer salt, and It is intended to provide a polyimide, polyimide copolymer or polyimide composite.

In one embodiment of the present invention for achieving the above object, a) preparing a monomer salt mixture by putting a dianhydride monomer and a diamine monomer in water; b) recovering the monomer salts by filtration and drying the monomer salt mixture or by evaporating water; And c) heating the monomer salt to prepare a polyimide.

In another embodiment of the present invention, a polyimide having a number average molecular weight of 5,000 to 1,000,000 is provided as a polyimide prepared according to the above method.

In another embodiment of the present invention, a polyimide having a number average molecular weight of 50,000 to 2,000,000 as a polyimide in the form of a composite prepared according to the above method is provided.

In another embodiment of the present invention, at the same time as the imidization of the step c), film processing, including melt processing, hollow processing, calender processing and sintering method; Molded article processing including casting, lamination, compression molding, injection molding, blow molding, rotational molding, thermoforming and slush molding; And it provides a method for producing a polyimide molded article further comprising the step of processing by one or more processing methods selected from the group consisting of fiber spinning, including wet spinning, dry spinning and melt spinning.

In another embodiment of the present invention, a polyimide molded article manufactured according to the above method, a polyimide film, a high heat resistance engineering plastic, an adhesive, a tape, a fiber, a liquid crystal alignment film, an interlayer insulator, a coating film resin, a printed circuit board, and a flexible display Provided is a polyimide molded article for use in one or more applications selected from the group consisting of substrates.

According to the present invention, the production of polyimide, polyimide copolymer or polyimide composite proceeds under mild conditions, the manufacturing process is simple and economical, and it is environmentally friendly because no organic solvent is used.

The polyimide, polyimide copolymer or polyimide composite prepared according to the present invention has higher molecular weight, better mechanical properties and higher thermal properties than the polyimide prepared according to the conventional method.

Figure 1 shows the FT-IR spectrum of the polyimide prepared according to Example 1-1 of the present invention.

Figure 2 shows the FT-IR spectrum of the polyimide prepared according to Examples 1-2 of the present invention.

Figure 3 shows the FT-IR spectrum of the polyimide prepared according to Examples 1-3 of the present invention.

Figure 4 shows the FT-IR spectrum of the polyimide prepared according to Examples 1-4 of the present invention.

Figure 5 shows the FT-IR spectrum of the material prepared according to Comparative Example 1-1 of the present invention.

Figure 6 shows the FT-IR spectrum of the material prepared according to Comparative Example 1-2 of the present invention.

Figure 7 shows the FT-IR spectrum of the polyimide according to Comparative Examples 1-3 of the present invention.

8 shows the FT-IR spectrum of the polyimide according to Comparative Example 1-4 of the present invention.

Figure 9 shows the FT-IR spectrum of the monomer salt according to Example 2-1 of the present invention.

10 shows the FT-IR spectrum of the polyimide obtained by heating the monomer salt according to Example 2-1 of the present invention.

11 shows the FT-IR spectrum of monomer salts according to Examples 2-4 of the present invention.

12 shows the FT-IR spectrum of the polyimide obtained by heating the monomer salt according to Examples 2-4 of the present invention.

Figure 13 shows a photograph of a polyimide composite film obtained by heating a composition of polyamic acid and graphene oxide according to Comparative Example 2-3 of the present invention.

Figure 14 shows a photograph of a polyimide composite film obtained by heating the composition of polyamic acid and graphene oxide according to Comparative Example 2-4 of the present invention.

Figure 15 shows a photo of the polyimide composite film obtained by heating the composition of the monomer salt and graphene oxide according to Example 2-3 of the present invention.

Figure 16 shows a photo of the polyimide composite film obtained by heating the composition of the graphene oxide dispersed in the monomer salt and water according to Example 2-4 of the present invention.

17 shows the FT-IR spectrum of the polyimide composite according to Example 3-1 of the present invention.

18 shows the FT-IR spectrum of the polyimide composite according to Example 3-3 of the present invention.

19 shows the FT-IR spectrum of the polyimide composite according to Examples 3-4 of the present invention.

20 shows the FT-IR spectrum of the polyimide composite according to Examples 3-5 of the present invention.

Figure 21 shows the FT-IR spectrum of the polyimide composite according to Examples 3-6 of the present invention.

22 shows the FT-IR spectrum of the polyimide copolymer according to Example 4-1 of the present invention.

Figure 23 shows the FT-IR spectrum of the polyimide copolymer according to Example 4-2 of the present invention.

24 shows the FT-IR spectrum of the polyimide copolymer according to Example 4-3 of the present invention.

25 shows the FT-IR spectrum of the polyimide copolymer according to Examples 4-4 of the present invention.

26 shows the FT-IR spectrum of the polyimide copolymer according to Example 4-5 of the present invention.

27 shows the FT-IR spectrum of the polyimide copolymer according to Examples 4-6 of the present invention.

The present invention relates to a process for preparing monomer salts from monomers and for preparing polyimides using the monomer salts prepared above.

According to the present invention, the production of polyimide, polyimide copolymer or polyimide composite proceeds under mild conditions, the manufacturing process is simple and economical, and it is environmentally friendly because no organic solvent is used. In addition, the polyimide, polyimide copolymer or polyimide composite prepared according to the present invention has higher molecular weight, excellent mechanical properties and higher thermal properties than the polyimide prepared according to the conventional method.

Hereinafter, the present invention will be described in more detail.

Process for preparing polyimide, polyimide copolymer or polyimide composite

Polyimide manufacturing method according to an embodiment for achieving the object of the present invention comprises the steps of: a) preparing a monomer salt mixture by putting a dianhydride monomer and a diamine monomer in water; b) recovering the monomer salt by filtration and drying the monomer salt mixture or by evaporating water; And c) heating the monomer salt to produce a polyimide.

First, a dianhydride monomer and a diamine monomer are added to water to prepare a monomer salt mixture (step a).

In one embodiment of the invention, the dianhydride may be one or more dianhydrides, the dianhydride may be aromatic or aliphatic. On the other hand, when the dianhydride is used in two or more types, a polyimide in the form of a copolymer may be prepared.

Meanwhile, in one embodiment of the present invention, the dianhydride may include a compound of Formula 1 below.

(In Formula 1 R ₁ is the chemical structure of

It is selected from the group consisting of.)

In one embodiment of the invention, the diamine may be one or more diamines, the diamine may be aromatic or aliphatic. On the other hand, when the diamine is used in two or more types, a polyimide in the form of a copolymer may be prepared.

Meanwhile, in one embodiment of the present invention, the diamine may include a compound of Formula 2 below.

(In Formula 2 R ₂ is the chemical structure of

It is selected from the group consisting of. On the other hand, x is an integer satisfying 1≤x≤50, n is a natural number in the range of 1 to 20, W, X, Y are each an alkyl group or an aryl group having 1 to 30 carbon atoms, Z is an ester group , Amide group, imide group and ether group.)

On the other hand, the molar ratio of the diamine to dianhydride in step a) may be 0.5 to 2 equivalents. The molar ratio may be specifically 0.8 to 1.5 equivalents. When the molar ratio is less than 0.5 equivalents or more than 2 equivalents, the molecular weight of the finally formed polyimide becomes very small, and thus there may be a problem that the physical and chemical properties of the polyimide are very low.

On the other hand, step a) may be carried out in a variety of ways, for example, by dispersing each monomer in water, and then putting it in the reaction vessel, as another method, the water in the reaction vessel It may also be carried out by the method of adding the first monomer and then adding each monomer. In addition, each monomer may be first added to the reaction vessel and then water may be added thereto, or a combination of the above methods may be performed.

On the other hand, in one embodiment of the present invention, when the monomer salt mixture of step a) is prepared, it may comprise the step of adding a dispersing material.

The dispersion material used may be at least one material selected from the group consisting of organic materials and inorganic materials. On the other hand, the organic material or inorganic material may be processed by one or more methods selected from chemical methods that react with chemicals and physical methods including immersion in water to disperse or pulverize.

In one embodiment of the present invention, the organic material may be at least one material selected from the group consisting of polyether ether ketone and polypropylene sulfide.

Meanwhile, in one embodiment of the present invention, the inorganic material may be at least one material selected from the group consisting of graphite, zinc oxide, silicate, kaolinite, smectite, graphene oxide, zirconium dioxide and carbon nanotubes.

On the other hand, the dispersion material may be one or two or more materials selected from the group consisting of particulate matter, plate-like material, fibrous material. If the dispersion is particulate, it can give additional benefits such as thermal stability, increased density, stiffness or texture in the composition and final product, and in the case of a plate, the dispersion spreads well and By reducing thermal expansion, reducing gas permeability, and treating the surface of the dispersing material with various functional groups, it is possible to give such properties as adhesion.In the case of fibrous materials, it is possible to reduce the coefficient of thermal expansion or improve mechanical strength such as elastic modulus and bending strength. It can give the advantage of.

On the other hand, when the dispersion material is further added, the dispersion material may be included in 1 to 90wt% of the total weight of the mixture in the monomer salt mixture and may be included in detail from 1 to 50wt%. When the content of the dispersion material is less than 1wt% of the total weight of the mixture, it is difficult to express the inherent characteristics of the dispersion material in the polyimide of the composite form to be produced, and when it is more than 90wt%, the mechanical properties of the polyimide of the composite form to be produced are greatly increased. May decrease.

On the other hand, when preparing the monomer salt mixture, it may further include one or more additives selected from the group consisting of dispersants and thickeners.

In one embodiment of the present invention, the dispersant may be one or more dispersants selected from the group consisting of surfactants of cations, anions and nonions.

In one embodiment of the invention, the thickener is hydroxypropyl cellulose, hydroxypropylmethyl cellulose, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate, polyvinyl alcohol and polyvinylpyrrolidone It may be one or more thickeners selected from the group consisting of.

The amount of the additive may be 0.1 to 10 wt% based on the total weight of the monomer and the dispersion material in the monomer salt mixture. If the content of the additive is less than 0.1wt%, the effect of the additive may be insignificant, and if it is more than 10wt%, the mechanical properties of the resulting polyimide may be greatly reduced.

On the other hand, when the monomer salt composition is prepared, the dispersion may be performed by one or more methods selected from the group consisting of stirrer dispersion, homogenizer dispersion, ultrahigh pressure dispersion, and ultrasonic dispersion, and may also undergo agitation process.

On the other hand, step a) may be carried out in the temperature range of 5 to 55 ℃ ℃, in detail may be carried out in the temperature range of 10 to 35 ℃. If the step a) is carried out below 5 ° C, the stirring and dispersion process may not proceed smoothly, and when carried out above 55 ° C, a separate heat source supply device or a cooling condensation device may be required.

On the other hand, step a) may be performed for 1 hour to 5 days, in detail it may be performed for 3 hours to 1 day. If the step a) is performed for less than 1 hour, the added dispersing material may not be uniformly dispersed, and if the process is performed for more than 5 days, the cost may be excessively increased according to the process.

Next, the monomer salt mixture is filtered and dried, or water is evaporated to recover the monomer salts of dianhydride and diamine (step b). On the other hand, in the case of the obtained monomer salt, if the dispersion material is added in step a) may be present in the form of a mixture of the dispersion material and the monomer salt.

In one embodiment of the present invention, filtering the mixture may yield a solid, and the obtained solid may be dried to prepare a salt. On the other hand, a salt may be further obtained by evaporating the filtrate obtained in the said filtration process.

In another embodiment of the present invention, salts may be prepared by evaporating the water in the mixture. On the other hand, the water vapor generated by the evaporation may be cooled and condensed to recover the water and reuse.

In one embodiment of the present invention, the filtration is carried out by one or two or more combinations selected from the group consisting of gravity filtration, vacuum filtration, pressure filtration, compression filtration, centrifugal filtration, microfiltration, ultrafiltration and reverse osmosis method. It may be.

In one embodiment of the present invention, the drying is one selected from the group consisting of natural drying, pressure drying, hot air drying, spray drying, film drying, vacuum drying, freeze drying, spray freeze drying, electromagnetic wave drying and flash drying method or It may be performed by a combination of two or more.

In one embodiment of the invention, the evaporation is to be carried out by one or two or more combinations selected from the group consisting of natural evaporation, membrane evaporation, thermal evaporation, pervaporation, vacuum evaporation, co-vacuum evaporation and rotary concentrated evaporation method. Can be.

On the other hand, the drying or evaporation may be performed under conditions of 1 atm or less. In addition, the drying or evaporation may be carried out in a temperature range of -60 to 200 ℃. When the drying or evaporation is carried out at a temperature of less than -60 ℃ may not occur smoothly drying or evaporation, there may be a problem that discoloration occurs when carried out at a temperature of more than 200 ℃.

Next, when the monomer salt obtained through the above process is heated, imidization proceeds to prepare a polyimide (step c).

In one embodiment of the present invention, step c) may be carried out in a temperature range of 150 to 450 ℃. Specifically, it may be performed within a temperature range of 180 to 400 ° C. If the step c) is carried out at a temperature of less than 150 ℃ imidization may not proceed, when carried out at a temperature of more than 450 ℃ may cause thermal decomposition of the monomer or polymer itself.

In one embodiment of the present invention, the step c) may be performed for 10 minutes to 3 days, in detail may be performed for 30 minutes to 2 days, more specifically 1 hour to 1 day Can be. If step c) is performed in less than 10 minutes, imidization may not be performed, and if it is performed for more than 3 days, thermal decomposition of the polymer itself may occur.

Meanwhile, the heating in step c) may be performed by one or more combinations selected from the group consisting of heat treatment, hot air treatment, corona treatment, high frequency treatment, ultraviolet treatment, infrared treatment, and laser treatment.

On the other hand, step c) may be carried out at atmospheric pressure, pressure, reduced pressure or vacuum conditions, for example, the pressure or reduced pressure conditions may be to pressurized or reduced pressure to more than 0 to 1000 bar conditions. On the other hand, when the reaction pressure is more than 1000 bar, damage to the reaction vessel may be caused.

On the other hand, step c) may be performed in an atmosphere or inert gas atmosphere. In one embodiment of the present invention, the inert gas may be one or a combination of two or more selected from the group consisting of nitrogen, argon, helium, neon, krypton and xenon.

On the other hand, when step c) is carried out under pressurized conditions, one or more combinations selected from the group consisting of a method of forming a water vapor pressure inside the pressure vessel, injecting an inert gas into the pressure vessel, or compressing the pressure vessel It may be to be performed by. The inert gas may be one or a combination of two or more selected from the group consisting of nitrogen, argon, helium, neon, cropton and xenon.

The polyimide or polyimide copolymer prepared through the series of processes may be a fully aromatic, partially aliphatic or fully aliphatic polyimide, and the number average molecular weight of the polyimide is 5,000 to 1,000,000.

In addition, the polyimide of the composite form prepared through the series of processes has a form in which the dispersing material (organic or inorganic) is uniformly dispersed in the polyimide, the polyimide is fully aromatic, partially aliphatic ( It may be a partially aliphatic or fully aliphatic polyimide, and the molecular weight of the polyimide in the complex form may be 50,000 to 2,000,000.

The molecular weight of the polyimide, polyimide copolymer or polyimide composite is significantly higher than the polyimide prepared according to the conventional polyimide production method, and thus has excellent mechanical and high thermal properties.

In particular, the polyimide in the form of a composite prepared according to one embodiment of the present invention may have a Young's modulus of 2.0 to 8.0 GPa, more specifically 6.2 to 8.0 GPa. On the other hand, the tensile strength of the polyimide of the composite form prepared according to an embodiment of the present invention may be 100 to 300MPa, more specifically may have a range of 182 to 210MPa. This is a marked improvement over the mechanical strength of polyimides prepared according to conventional methods.

Accordingly, the polyimide, polyimide copolymer or polyimide composite prepared according to the present invention may be used in space, aviation, electrical / electronics, semiconductors, transparent / flexible displays, liquid crystal alignment films, automobiles, precision instruments, packaging, medical materials, separators, It is highly useful in a wide range of industries such as fuel cells and secondary batteries.

Polyimide Manufacturing Method Using Mechanical Grinding Method

On the other hand, the monomer salts prepared from the dianhydride monomer and the diamine monomer may be mixed with the dispersion material and then ground to prepare a composition in powder form, and then heated to imidize to prepare a polyimide composite.

The monomer salt used here is as described above, the dispersion material is also as described above.

On the other hand, the grinding process may be carried out using a heavy mill capable of grinding the raw material of 6 to 50 mm in size 3 to 10 mm or a fine grinding machine capable of grinding the raw material of 3 to 10 mm or less to 150 ㎛, Roll crushers, edge runners, hammer crushers and disc crushers can be used as heavy mills, and ball mills, jet mills, port mills, turbo mills, supermicron mills, roller mills, raymond mills and tube mills can be used as grinding mills. . On the other hand, the grinding process may be performed by a grinder.

On the other hand, the powder particle size included in the composition through the grinding process may have a range of 100nm to 10mm. Meanwhile, in one embodiment of the present invention, the fine powder particles may be included in the composition through the grinding process, and the size of the fine powder particles may be in the range of 100 nm to 150 μm.

Meanwhile, as a monomer salt prepared from the dianhydride monomer and the diamine monomer, two or more different kinds of monomer salts are mixed and pulverized to prepare a powder, followed by heating and imidization to prepare a polyimide copolymer. You may.

The monomer salt used here is as described above, the dispersion material is also as described above. On the other hand, the grinding process is also the same as described above.

Polyimide molded article manufacturing method

On the other hand, when the imidization of the step c) is carried out in a molding apparatus, the molding proceeds simultaneously with the imidization, thereby producing a polyimide molded article.

In the step c), the monomer salt is heated in a molding apparatus to advance the imide reaction, and at the same time, film processing including melt processing, hollow processing, calender processing, and sintering method; Molded article processing including casting, lamination, compression molding, injection molding, blow molding, rotational molding, thermoforming and slush molding; And fiber processing including wet spinning, dry spinning and melt spinning; by processing by one or more processing methods selected from the group consisting of, a polyimide molded article can be produced immediately.

Meanwhile, the manufactured polyimide molded article corresponds to a polyimide copolymer molded article when two or more dianhydrides or two or more diamines are used in step a), and when the dispersion material is further added in step a), Corresponds to the mid composite molded article.

Meanwhile, the polyimide molded article manufactured according to the above method is one selected from the group consisting of polyimide film, high heat resistant engineering plastic, adhesive, tape, fiber, liquid crystal alignment film, interlayer insulator, coating film resin, printed circuit board, and flexible display substrate. It can be used for the above uses.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are intended to help the understanding of the present invention and are not intended to limit the scope of the present invention thereto.

Example

Example 1-1 Preparation of Whole Aromatic Polyimide

Into a 100-mL 1-neck round bottom flask with nitrogen gas, add 60 mL of water, and 3.102 g (0.01 mol) of 4,4'-oxydiphthalic anhydride and 2,2-bis (3-amino-4-hydride. 3.663 g (0.01 mol) of loxylphenyl) hexafluoropropane was added at once, followed by stirring at 20 ° C. for 12 hours. Next, the mixture was gravity filtered to obtain a solid, followed by vacuum drying for 1 day to prepare a monomer salt.

Next, the monomer salt was heated at 350 ° C. for 6 hours using an electric furnace to synthesize a wholly aromatic polyimide. In the infrared absorption spectrum of the synthesized polymer 1786cm ^- ¹ and 1719cm ^-1 C = O absorption band of the already deugi, already CN absorption band at 1380cm ^-1 in the deugi was observed (Fig. 1).

Example 1-2 Preparation of Partial Aliphatic Polyimides

50 mL of water was added to a 100-mL one-neck round bottom flask substituted with nitrogen gas, and 3.222 g (0.01 mol) of 3,3 ', 4,4'-benzophenone-tetracarboxylic dianhydride and 4,4'-methylene 2.384 g (0.01 mol) of bis (2-methylcyclohexamine) was added at once, followed by stirring at 20 ° C. for 12 hours. Next, the mixture was gravity filtered to obtain a solid, followed by vacuum drying for 1 day to prepare a monomer salt.

Next, the monomer salt was heated at 350 ° C. for 6 hours using an electric furnace to synthesize a partial aliphatic polyimide. In the infrared absorption spectrum of the synthesized polymer 1770cm ^- it is already in the CN absorption band of deugi ¹ and 1706cm ^-1 C = O absorption band of the already deugi, 1381cm ^-1 in was observed (Fig. 2).

Example 1-3 Preparation of Partial Aliphatic Polyimides

Two 50-mL one-neck round-bottom flasks replaced with nitrogen gas: 1.961 g (0.01 mol) of cyclobutane-1,2,3,4-tetracarboxylic dianhydride and 2.002 g of 4,4'-oxydianiline (0.01 mol) was added to each flask, and 10 mL water was added to each flask for dispersion. Each obtained mixture was put into a 100-mL 1-neck round bottom flask substituted with nitrogen gas, and 15 mL of water was added thereto, followed by stirring at 25 ° C for 18 hours. Next, the mixture was gravity filtered to obtain a solid, followed by vacuum drying for 1 day to prepare a monomer salt.

Next, the monomer salt was heated at 300 ° C. for 8 hours using an electric furnace to synthesize a partial aliphatic polyimide. In the infrared absorption spectrum of the synthesized polymer 1774cm ^- ¹ and 1710cm ^-1 C = O absorption band of the already deugi, already CN absorption band at 1381cm ^-1 in the deugi was observed (Fig. 3).

Example 1-4 Preparation of Whole Aliphatic Polyimide

2.242g (0.01mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 4,4'-methylenebis (cyclohexyl) in two 50-mL 1-neck round bottom flasks substituted with nitrogen gas 2.104 g (0.01 mol) of amine) was added to the flask, and 10 mL of water was added to each flask for dispersion. Each obtained mixture was put into a 100-mL 1-neck round bottom flask substituted with nitrogen gas, and 20 mL of water was added thereto, followed by stirring at 30 ° C. for 18 hours. Next, the mixture was gravity filtered to obtain a solid, followed by vacuum drying for 1 day to prepare a monomer salt.

Next, the monomer salt was heated at 300 ° C. for 8 hours using an electric furnace to synthesize all aliphatic polyimide. In the infrared absorption spectrum of the synthesized polymer 1782cm ^- it was already deugi the C = O absorption band, already CN absorption band at 1374cm ^-1 for deugi observed at ¹ and 1714cm ^-1 (Fig. 4).

Comparative Example 1-1: Preparation of Whole Aliphatic Polyimide

40 mL of water was added to a 100-mL 1-neck round bottom flask substituted with nitrogen gas, and 2.242 g (0.01 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 4,4'-methylenebis ( 2.104 g (0.01 mol) of cyclohexylamine) was added at a time and stirred at 25 ° C. for 12 hours. Next, the mixture was gravity filtered to obtain a solid, followed by vacuum drying for 1 day to prepare a monomer salt.

Next, the monomer salt was heated at 80 ° C. for 24 hours using an electric furnace, but it was not possible to synthesize all aliphatic polyimide. In the infrared absorption spectrum of the synthesized polymer, no C═O absorption band of the imide group at 1785 cm ⁻¹ , which can be seen in the typical polyimide, was observed (FIG. 5).

Comparative Example 1-2: Preparation of Whole Aliphatic Polyimide

Next, the monomer salt was heated at 180 ° C. for 1 minute using an electric furnace, but it was not possible to synthesize all aliphatic polyimide. In the infrared absorption spectrum of the synthesized polymer, no C═O absorption band of the imide group at 1785 cm ⁻¹ , which can be seen in the typical polyimide, was observed (FIG. 6).

Comparative Example 1-3: Preparation of Whole Aromatic Polyimide

45 mL of N-methyl-2-pyrrolidone was added to a 100-mL two-necked round-bottom flask substituted with nitrogen gas, and 3.102 g (0.01 mol) of 4,4'-oxydiphthalic anhydride and 4,4 'were added. -Oxydianiline 2.002g (0.01mol) was added and reacted at 25 ° C for 18 hours to synthesize a monomer salt. Next, the mixture was reprecipitated using water. After gravity filtration, the resultant was washed with 100 mL of water and 100 mL of methanol and dried in vacuo to obtain a dried polyamic acid.

5 mL of acetic anhydride and 3 mL of pyridine were added to the solution by chemical imidization, and the mixture was refluxed at 170 ° C. for 5 hours, cooled to room temperature, and reprecipitated using excess ice water. Then, the mixture was washed with 100 mL of water and 100 mL of methyl alcohol, followed by vacuum drying to synthesize all aromatic polyimides. (The thermal imidization method heated the synthesized polyamic acid solution stepwise in an oven or a hot plate at 250 to 300 ° C. and heated it for 12 hours. Polyimide can be obtained). In the infrared absorption spectrum of the synthesized polymer 1783cm ^- ¹ and 1713cm ^-1 C = O absorption band of the already deugi, already CN absorption band at 1385cm ^-1 in the deugi was observed (Fig. 7).

Comparative Example 1-4: Preparation of Whole Aliphatic Polyimide

2.242g (0.01mol) of 1,2,4,5-cyclocyclotetracarboxylic dianhydride was added to 40 mL of N-methyl-2-pyrrolidone in a 100-mL two-necked round-bottom flask substituted with nitrogen gas. And 2.002g (0.01mol) of 4,4'-methylenebis (cyclohexylamine) were added and reacted at 25 ° C for 18 hours to synthesize a polyamic acid solution. Next, the mixture was reprecipitated using water. After gravity filtration, washed with 100 mL of water and 100 mL of methanol and dried in vacuo to obtain a dried polyamic acid.

5 mL of acetic anhydride and 3 mL of pyridine were added to the solution by chemical imidization, and the mixture was refluxed at 170 ° C. for 5 hours, cooled to room temperature, and reprecipitated using excess ice water. After washing with 100 mL of water and 100 mL of methyl alcohol and drying in vacuo, all aliphatic polyimides were synthesized (by thermal imidization, the synthesized polyamic acid solution was heated to 250-300 ° C. step by step in an oven or hot plate and heated for 12 hours. Polyimide can be obtained). In the infrared absorption spectrum of the synthesized polymer 1774cm ^- ¹ and 1711cm ^-1 C = O absorption band of the already deugi, already CN absorption band at 1380cm ^-1 in the deugi was observed (Fig. 8).

Example 2-1 Preparation of Whole Aromatic Polyimide Composite Film

Pyromellitic dianhydride (10.906 g), 4,4'-oxydianiline (10.012 g), and graphene oxide (5.00 g) were added to the water at 5 wt% based on the total weight of the composition, followed by 24 hours at 25 ° C. The monomer salt composition was prepared by dispersing with a stirrer.

Next, the composition was spun onto a glass plate and then heated to a temperature of about 7 hours at atmospheric pressure using a heater until the final temperature reached 250 ° C., and then maintained for 1 hour to prepare a polyimide composite film (FIGS. 9 and FIG. 10).

Example 2-2 Preparation of Partial Aliphatic Polyimide Composite Film

A pyromellitic dianhydride (10.906 g), hexamethylene diamine (5.810 g) and mica (mica) (5.00 g) were added and then dispersed in a stirrer at 25 ° C. for 24 hours to prepare a monomer salt composition.

Next, the composition was spun onto a glass plate and heated to a temperature slowly until the final temperature reached 250 ° C. for 7 hours at atmospheric pressure using a heater to prepare a polyimide composite film.

Example 2-3 Preparation of Partial Aliphatic Polyimide Composite Film

4,4'-oxydiphthalic dianhydride (15.510g), hexamethylene diamine (5.810g) and graphene oxide (5.00g) were added and dispersed in a stirrer at 25 ℃ for 24 hours to monomer salt composition Was prepared.

Next, the composition was spun on a glass plate and heated to a temperature slowly until the final temperature reached 250 ° C. for 7 hours at atmospheric pressure using a heater to prepare a polyimide composite film (FIG. 15).

Example 2-4 Preparation of Whole Aliphatic Polyimide Composite Film

1,2,4,5-cyclohexanetetracarboxylic dianhydride (11.208g) and hexamethylene diamine (5.810g) and graphene oxide mixture (5.00g) previously dispersed in water at 1wt% were added. The monomer salt composition was prepared by dispersing at 25 ° C. for 24 hours with a stirrer.

Next, the composition was spun on a glass plate and heated to a temperature gradually until the final temperature reached 250 ° C. for 7 hours at atmospheric pressure using a heater to prepare the polyimide composite film (FIG. 11, 12 and 16)

Example 2-5 Preparation of Whole Aliphatic Polyimide Composite Films

1,2,3,4-cyclobutanetetracarboxylic dianhydride (9.805g), 4,4'-methylenebis (2-methylcyclohexylamine) (11.920g) and mica (mica) (5.00g) After addition, the monomer salt composition was prepared by dispersing with a stirrer at 25 ° C. for 24 hours.

Example 2-6 Preparation of Whole Aliphatic Polyimide Composite Films

1,2,3,4-cyclopentanetetracarboxylic dianhydride (10.507g), 4,4'-methylenebis (cyclohexylamine) (10.518g) and carbon nanotubes (5.00g) were added. The monomer salt composition was prepared by dispersing with a stirrer at 占 폚 for 24 hours.

Comparative Example 2-1: Preparation of Whole Aromatic Polyimide Composite Film

N-methyl-2-pyrrolidone was added to a 100-mL two-necked round-bottom flask substituted with nitrogen gas, pyromellitic dianhydride (6.543 g) and 4,4'-oxydianiline (6.072 g). After reacting at 25 ℃ for 18 hours to synthesize a 10wt% polyamic acid solution.

Next, graphene oxide (5.00 g) was added to the solution, and the composition was prepared by dispersing with a stirrer at 25 ° C. for 18 hours.

Next, the composition was spun onto a glass plate and heated to a temperature slowly until the final temperature reached 300 ° C. for 11 hours at atmospheric pressure using a heater to prepare a polyimide composite film.

Comparative Example 2-2: Preparation of Partially Aliphatic Polyimide Composite Film

N-methyl-2-pyrrolidone was added to a 100-mL two-necked round bottom flask substituted with nitrogen gas, pyromellitic dianhydride (7.634 g) and hexamethylene diamine (4.067 g) were added. After reacting for 18 hours, a 10 wt% polyamic acid solution was synthesized.

Comparative Example 2-3: Preparation of Partially Aliphatic Polyimide Composite Film

N-methyl-2-pyrrolidone was added to a 100-mL two-necked round-bottom flask substituted with nitrogen gas, and 4,4'-oxydiphthalic dianhydride (9.306g) and hexamethylene diamine (3.486g) were added. After the reaction was carried out at 25 ℃ 18 hours to synthesize a 10wt% polyamic acid solution.

Next, the composition was spun onto a glass plate and heated to a temperature slowly until the final temperature reached 300 ° C. for 11 hours at atmospheric pressure using a heater to prepare a polyimide composite film (FIG. 13).

Comparative Example 2-4: Preparation of Total Aliphatic Polyimide Composite Film

N, N-dimethylacetamide was added to a 100-mL two-necked round bottom flask substituted with nitrogen gas, and 1,2,4,5-cyclocyclotetracarboxylic dianhydride (7.845 g) and hexamethylene diamine ( 4.067 g) was reacted at 25 ° C. for 18 hours to synthesize a 10 wt% polyamic acid solution.

Next, the composition was spun onto a glass plate and heated to a temperature slowly until the final temperature reached 300 ° C. for 11 hours at atmospheric pressure using a heater to prepare a polyimide composite film (FIG. 14).

As can be seen in Table 1, in Examples 1-1 to 1-4, the monomer salt preparation process was performed in a range of 12 to 24 hours at a temperature range of 20 to 30 ° C. using water, and the monomer salt was 180 to 350. It was confirmed that the polyimide obtained by heat treatment for 6 to 24 hours in the temperature range of ℃ having a high molecular weight.

On the other hand, in Comparative Example 1-1 and Comparative Example 1-2, the prepared monomer salt was heat-treated at a temperature of less than 160 ℃, or less than 5 minutes, it was confirmed that the polyimide can not be obtained by the above method. . In Comparative Examples 1-3 and Comparative Examples 1-4, a polyimide was obtained by performing a conventional method of preparing a polyimide by synthesizing a polyamic acid precursor using an organic solvent, but the obtained polyimide was obtained in Example 1-. It was confirmed that the molecular weight of the low level compared to the polyimide obtained in 1 to 1-4.

On the other hand, as can be seen in Table 2, according to Examples 2-1 to 2-6, after the synthesized monomer salt composition prepared by rotating the solution on a glass plate to increase the temperature slowly from room temperature to 250 ℃ for 8 hours It was heat-treated to obtain a polyimide composite film. The polyimide composite film was confirmed to have improved mechanical and thermal properties compared to the polyimide composite film produced by a general polyimide film production method.

In particular, referring to Figures 15 and 16, it was confirmed that the dispersion material is evenly spread in the polyimide composite film prepared by dispersing the dispersion material at the same time as the monomer salt synthesis.

On the other hand, the polyimide composite film prepared in Comparative Examples 2-1 to 2-3 can be confirmed that the dispersion material is not dispersed well in the organic solvent when the conventional polyimide composite film is prepared, which is agglomerated, as shown in FIGS. 13 and 14. Could. In particular, in Comparative Example 2-4, mechanical properties could not be confirmed due to cracks in the film. The prepared polyimide composite film was not well dispersed in the dispersion material was confirmed that the mechanical properties and thermal properties are low.

Example 3-1 Preparation of Whole Aromatic Polyimide Composite

2.18 g of pyromellitic dianhydride, 2.00 g of 4,4'-oxydianiline and 100 ml of distilled water were added to a round bottom flask to prepare a monomer salt at room temperature.

Next, 0.01 g of montmorillonite was added to the obtained 0.10 g of the monomer salt, and then milled for 1 hour using a ball mill to prepare a fine powder composition.

Next, the fine powder composition was heated at 200 ° C. for 6 hours using a heater to prepare a wholly aromatic polyimide composite.

Example 3-2 Preparation of Whole Aromatic Polyimide Composites

3.10 g of 4,4'-oxydiphthalic anhydride, 2.00 g of 4,4'-oxydianiline and 100 ml of distilled water were added to a round bottom flask to prepare a monomer salt at room temperature.

Next, 0.01 g of graphene oxide was added to the obtained 0.10 g of the monomer salt, and then milled for 1 hour using a ball mill to prepare a fine powder composition.

Example 3-3 Preparation of Subaliphatic Polyimide Composites

2.18 g of pyromellitic dianhydride, 2.10 g of 4,4'-methylenebis (cyclohexylamine) and 100 ml of distilled water were added to a round bottom flask to prepare a monomer salt at room temperature.

Next, 0.01 g of bentonite was added to the obtained 0.10 g of the monomer salt, and then milled for 1 hour using a ball mill to prepare a fine powder composition.

Next, the fine powder composition was heated at 200 ° C. for 6 hours using a heater to prepare a aliphatic polyimide composite.

Example 3-4 Preparation of Subaliphatic Polyimide Composites

3.10 g of 4,4'-oxydiphthalic anhydride, 1.16 g of hexamethylene diamine and 100 ml of distilled water were added to a round bottom flask to prepare a monomer salt at room temperature.

Example 3-5 Preparation of Full Aliphatic Polyimide Composites

2.24 g of 1,2,4,5-cyclocyclotetracarboxylic dianhydride, 2.10 g of 4,4'-methylenebis (cyclohexylamine) and 100 ml of distilled water were added to a round bottom flask to prepare monomer salts at room temperature. It was.

Next, the fine powder composition was heated at 200 ° C. for 6 hours at atmospheric pressure using a heater to prepare an aliphatic polyimide composite.

Example 3-6 Preparation of Full Aliphatic Polyimide Composites

2.24 g of 1,2,4,5-cyclocyclotetracarboxylic dianhydride, 1.16 g of hexamethylene diamine and 100 ml of distilled water were added to a round bottom flask to prepare monomer salts at room temperature.

Comparative Example 3-1: Preparation of Whole Aromatic Polyimide Composite

Next, 9.90 g of montmorillonite was added to the obtained 0.10 g of the monomer salt in an amount of 99 wt% based on the total weight of the composition, and then milled for 1 hour using a ball mill to prepare a fine powder composition.

Comparative Example 3-2: Preparation of Full Aliphatic Polyimide Composite

Next, 0.01 g of bentonite was added to the obtained 0.10 g of the monomer salt, followed by heating at 200 ° C. for 6 hours using a heater without a separate milling process, thereby preparing an aliphatic polyimide composite.

Comparative Example 3-3: Preparation of Whole Aromatic Polyimide Composite

N-methyl-2-pyrrolidone was added to a 100-mL two-necked round bottom flask substituted with nitrogen gas, and 3.10 g of 4,4'-oxydiphthalic anhydride and 2.00 g of 4,4'-oxy were added. After adding dianiline and reacting at 25 ° C. for 24 hours, a 10 wt% polyamic acid solution was synthesized.

Next, 0.51 g of graphene oxide was added to the solution, and the composition was prepared by dispersing with a stirrer at 25 ° C. for 18 hours.

Comparative Example 3-4: Preparation of Whole Aromatic Polyimide Composite

N-methyl-2-pyrrolidone was added to a 100-mL two-necked round-bottom flask substituted with nitrogen gas, followed by 2.18 g of pyromellitic dianhydride and 2.00 g of 4,4'-oxydianiline. The reaction was carried out at 24 ° C. for 24 hours to synthesize a 10 wt% polyamic acid solution.

Next, 0.42 g of montmorillonite was added to the solution and dispersed at 25 ° C. for 18 hours using a stirrer to prepare a composition.

Comparative Example 3-5: Preparation of Battery-Arm Polyimide Composite

N-methyl-2-pyrrolidone was added to a 100-mL two-necked round bottom flask substituted with nitrogen gas, and 2.24 g of 1,2,4,5-cyclocyclohexanetetracarboxylic dianhydride and 2.10 g of 4, 4'-methylenebis (cyclohexylamine) was added thereto and reacted at 25 ° C. for 24 hours to synthesize a 10 wt% polyamic acid solution.

Next, 0.43 g of montmorillonite was added to the solution, and the composition was dispersed by stirring at 25 ° C. for 18 hours.

Comparative Example 3-6: Preparation of Full Aliphatic Polyimide Composite

N-methyl-2-pyrrolidone was added to a 100-mL two-necked round bottom flask substituted with nitrogen gas, and 2.24 g of 1,2,4,5-cyclocyclohexanetetracarboxylic dianhydride and 1.16 g of hexamethylene After diamine was added and reacted at 25 ° C. for 24 hours, a 10 wt% polyamic acid solution was synthesized.

Next, 0.34 g of bentonite was added to the solution, followed by dispersion at 25 ° C. for 18 hours to prepare a composition.

Comparative Example 3-7: Preparation of Whole Aromatic Polyimide Composite

A solid obtained by reprecipitating the polyamic acid synthesized in Comparative Example 3 to clean distilled water was dried to prepare a polyamic acid solid.

Next, 0.01 g of graphene oxide was added to the 0.10 g of polyamic acid, and then milled for 1 hour using a ball mill to prepare a fine powder composition.

Comparative Example 3-8: Preparation of Whole Aromatic Polyimide Composite

The solid obtained by reprecipitating the polyamic acid synthesized in Comparative Example 4 in clean distilled water was dried to prepare a polyamic acid solid.

Next, 0.01 g of montmorillonite was added to the 0.10 g of polyamic acid, and then milled for 1 hour using a ball mill to prepare a fine powder composition.

Comparative Example 3-9: Preparation of Full Aliphatic Polyimide Composite

A solid obtained by reprecipitating the polyamic acid synthesized in Comparative Example 5 to clean distilled water was dried to prepare a polyamic acid solid.

Comparative Example 3-10: Preparation of Battery Aliphatic Polyimide Composite

A solid obtained by reprecipitation of the polyamic acid synthesized in Comparative Example 6 in clean distilled water was dried to prepare a polyamic acid solid.

Next, 0.01 g of bentonite was milled in 0.10 g of polyamic acid for 1 hour using a ball mill to prepare a fine powder composition.

As can be seen in Table 3, the polyimide composite was obtained by mixing, grinding and heating the dispersion material in the monomer salt according to Examples 3-1 to 3-6. The polyimide composite was confirmed to have improved mechanical and thermal properties compared to the polyimide composite prepared by a general polyimide composite manufacturing method.

On the other hand, as shown in Table 4, the polyimide composite prepared by mixing the dispersion material in the monomer salt synthesized in Comparative Example 3-1 at 99wt% of the total composition significantly reduced mechanical and thermal properties, Comparative Example 3-2 The polyimide composites prepared without the addition of dispersions to the monomer salts synthesized at and without milling were significantly reduced in mechanical and thermal properties. Polyimide composite prepared by adding a dispersion and a solvent to the polyamic acid synthesized in Comparative Examples 3-3 to 3-6 was able to confirm the improved results compared to the mechanical and thermal properties of the general polyimide Example 3 The results were lower than those of the polyimide composites synthesized in 1 to 3-6, and the polyimide composites prepared by adding the dispersion to the solid polyamic acid synthesized in Comparative Examples 3-7 to 3-10 did not disperse the dispersion well. As a result, the polyimide and the dispersion were separated from each other, and the mechanical and thermal properties were greatly reduced.

Example 4-1 Preparation of Whole Aromatic and Subaliphatic Polyimide Copolymers

2.18 g of pyromellitic dianhydride (2.18 g), 2.00 g of 4,4'-oxydianiline and distilled water were added to a 100 ml round bottom flask to prepare monomer salt A at room temperature. Also, 3.10 g of 4,4'-oxydiphthalic anhydride, 1.16 g of hexamethylene diamine, and distilled water were added to a 100 ml round bottom flask to prepare monomer salt B at room temperature.

Next, 1.00 g of the monomer salts A and B were mixed, and then milled for 1 hour using a ball mill to prepare a fine powder.

Next, the fine powder was heated at 200 ° C. for 6 hours using a heater to prepare a wholly aromatic and partially aliphatic polyimide copolymer.

Example 4-2 Preparation of Whole Aromatic and Fully Aromatic Polyimide Copolymers

2.18 g of pyromellitic dianhydride, 2.00 g of 4,4'-oxydianiline and distilled water were added to a 100 ml round bottom flask to prepare monomer salt A at room temperature. Also, add 2.24 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2.10 g of 4,4'-methylenebis (cyclohexylamine) and distilled water in a 100 ml round bottom flask to add monomer salt B at room temperature. Was prepared.

Next, the fine powder was heated at 200 ° C. for 6 hours using a heater to prepare the wholly aromatic and all-aliphatic polyimide copolymer.

Example 4-3 Preparation of Whole Aromatic and Fully Aromatic Polyimide Copolymers

2.18 g of pyromellitic dianhydride, 2.00 g of 4,4'-oxydianiline and distilled water were added to a 100 ml round bottom flask to prepare monomer salt A at room temperature. Also, monomer salt B was prepared at room temperature by adding 2.24 g of 1,2,4,5-cyclocyclotetracarboxylic dianhydride, 1.16 g of hexamethylene diamine and distilled water to a 100 ml round bottom flask.

Example 4-4 Preparation of Whole Aromatic and Subaliphatic Polyimide Copolymers

3.10 g of 4,4'-oxydiphthalic anhydride, 2.00 g of 4,4'-oxydianiline and distilled water were added to a 100 ml round bottom flask to prepare monomer salt A at room temperature. Also, 2.18 g of pyromellitic dianhydride, 2.10 g of 4,4'-methylenebis (cyclohexylamine) and distilled water were added to a 100 ml round bottom flask to prepare monomer salt B at room temperature.

Example 4-5 Preparation of Whole Aromatic and Fully Aromatic Polyimide Copolymers

3.10 g of 4,4'-oxydiphthalic anhydride, 2.00 g of 4,4'-oxydianiline and distilled water were added to a 100 ml round bottom flask to prepare monomer salt A at room temperature. Also, add 2.24 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2.10 g of 4,4'-methylenebis (cyclohexylamine) and distilled water in a 100 ml round bottom flask to add monomer salt B at room temperature. Was prepared.

Example 4-6 Preparation of Whole Aromatic and Whole Aromatic Polyimide Copolymers

3.10 g of 4,4'-oxydiphthalic anhydride, 2.00 g of 4,4'-oxydianiline and distilled water were added to a 100 ml round bottom flask to prepare monomer salt A at room temperature. Also, monomer salt B was prepared at room temperature by adding 2.24 g of 1,2,4,5-cyclocyclotetracarboxylic dianhydride, 1.16 g of hexamethylene diamine and distilled water to a 100 ml round bottom flask.

Comparative Example 4-1: Preparation of Whole-aromatic and All-Aromatic Polyimide Copolymers

Next, 1.00 g of the monomer salts A and B were mixed, and the mixture was heated at 200 ° C. for 6 hours at atmospheric pressure using a heater to prepare the wholly aromatic and all-aliphatic polyimide copolymer.

Comparative Example 4-2: Preparation of Whole-aromatic and All-Aromatic Polyimide Copolymers

Comparative Example 4-3 Preparation of Fully Aromatic and Fully Aromatic Polyimide Copolymer

N-methyl-2-pyrrolidone was added to a 100-mL two-necked round-bottom flask substituted with nitrogen gas, followed by 2.18 g of pyromellitic dianhydride and 2.00 g of 4,4'-oxydianiline. The reaction was carried out at 24 ° C. for 24 hours to synthesize 10 wt% polyamic acid solution A. In addition, N-methyl-2-pyrrolidone was added to a 100-mL two-necked round bottom flask substituted with nitrogen gas, and 2.24 g of 1,2,4,5-cyclocyclohexanetetracarboxylic dianhydride and 1.16 g of hexa were added. Methylene diamine was added and reacted at 25 ° C. for 24 hours to synthesize 10 wt% polyamic acid solution B.

Next, the solution A and B were added to the reaction vessel and mixed for 3 hours to prepare a polyamic acid solution.

Next, the polyamic acid solution was rotated on a glass plate, and the temperature was gradually raised until the final temperature reached 300 ° C. for 11 hours at atmospheric pressure using a heater, and then maintained for 1 hour to form a wholly aromatic and all-aliphatic polyimide copolymer. Prepared.

Comparative Example 4-4: Preparation of Whole Aromatic and Fully Aromatic Polyimide Copolymer

N-methyl-2-pyrrolidone was added to a 100-mL two-necked round bottom flask substituted with nitrogen gas, and 3.10 g of 4,4'-oxydiphthalic anhydride and 2.00 g of 4,4'-oxy were added. After adding dianiline and reacting at 25 ° C. for 24 hours, 10 wt% polyamic acid solution A was synthesized. In addition, N-methyl-2-pyrrolidone was added to a 100-mL two-necked round bottom flask substituted with nitrogen gas, and 2.24 g of 1,2,4,5-cyclocyclohexanetetracarboxylic dianhydride and 2.10 g of 4 were added. After adding 4'-methylenebis (cyclohexylamine) and reacting at 25 ° C. for 24 hours, 10 wt% polyamic acid solution B was synthesized.

Comparative Example 4-5: Preparation of Whole-aromatic and All-Aromatic Polyimide Copolymer

N-methyl-2-pyrrolidone was added to a 100-mL two-necked round-bottom flask substituted with nitrogen gas, followed by 2.18 g of pyromellitic dianhydride and 2.00 g of 4,4'-oxydianiline. The reaction was carried out at 24 ° C. for 24 hours to synthesize a 10 wt% polyamic acid solution. The polyamic acid solution was reprecipitated in clean distilled water and dried to prepare polyamic acid A.

Next, N-methyl-2-pyrrolidone was added to a 100-mL two-necked round bottom flask substituted with nitrogen gas, and 2.24 g of 1,2,4,5-cyclocyclotetracarboxylic dianhydride and 2.10 g of 4,4'-methylenebis (cyclohexylamine) was added thereto, and reacted at 25 ° C. for 24 hours to synthesize a 10 wt% polyamic acid solution. The polyamic acid solution was reprecipitated in clean distilled water and dried to prepare polyamic acid B.

Next, 1.00 g of each of the polyamic acids A and B were mixed, and then milled for 1 hour using a ball mill to prepare a fine powder.

Comparative Example 4-6: Preparation of Whole Aromatic and Whole Aromatic Copolymer Polyimide

N-methyl-2-pyrrolidone was added to a 100-mL two-necked round bottom flask substituted with nitrogen gas, and 3.10 g of 4,4'-oxydiphthalic anhydride and 2.00 g of 4,4'-oxy were added. After adding dianiline and reacting at 25 ° C. for 24 hours, a 10 wt% polyamic acid solution was synthesized. The polyamic acid solution was reprecipitated in clean distilled water and dried to prepare polyamic acid A.

As can be seen in Table 5, according to Examples 4-1 to 4-6, a polyimide copolymer was obtained by mixing, pulverizing and heating the prepared two monomer salts. The polyimide copolymer was confirmed to have improved thermal properties and molecular weight as compared to the polyimide copolymer prepared by the general polyimide copolymer production method.

On the other hand, as can be seen in Table 6, according to Comparative Examples 4-1 to 4-2 it was confirmed that the polyimide composition prepared by mixing two prepared monomer salts did not form a polyimide copolymer because it does not undergo a grinding process, This could be confirmed in molecular weight and thermal properties. According to Comparative Examples 4-3 to 4-4, the polyimide copolymer prepared by mixing the synthesized polyamic acid solution has a well formed polyimide copolymer but has a lower molecular weight than the polyimide copolymer prepared according to the embodiment of the present invention. I could confirm that. In addition, according to Comparative Examples 4-5 to 4-6, it was confirmed that the polyimide composition prepared by mixing the synthesized polyamic acid did not form a polyimide copolymer.

In the present invention, the synthesis step is greatly reduced, the reaction proceeds under mild conditions during the preparation of the monomer salt, and a method for preparing a polyimide, polyimide copolymer or polyimide composite using the prepared monomer salt, and Polyimide, polyimide copolymers or polyimide composites are provided.

Claims

a) adding a dianhydride monomer and a diamine monomer into water to prepare a monomer salt mixture;

b) recovering the monomer salts by filtration and drying the monomer salt mixture or by evaporating water; And

c) heating the monomer salt to prepare a polyimide.
The method of claim 1,

Wherein said dianhydride is at least one dianhydride and said diamine is at least one diamine.
The method of claim 1,

Method for producing a polyimide comprising the step of further adding a dispersing material when preparing the monomer salt mixture of step a).
The method of claim 1,

Wherein said dianhydride is an aromatic or aliphatic dianhydride.
The method of claim 1,

The dianhydride is a polyimide manufacturing method of the dianhydride of the formula (1).

<Formula 1>

(In Formula 1 R 1 is the chemical structure of

It is selected from the group consisting of.)
The method of claim 1,

Wherein said diamine is an aromatic or aliphatic diamine.
The method of claim 1,

The diamine is a polyimide production method of the diamine of the formula (2).

<Formula 2>

(In Formula 2 R 2 is the chemical structure of

It is selected from the group consisting of. On the other hand, x is an integer satisfying 1≤x≤50, n is a natural number in the range of 1 to 20, W, X, Y are each an alkyl group or an aryl group having 1 to 30 carbon atoms, Z is an ester group , Amide group, imide group and ether group.)
The method of claim 3, wherein

The dispersion material is a polyimide manufacturing method of at least one material selected from the group consisting of organic materials and inorganic materials.
The method of claim 8,

Wherein said organic material is at least one selected from the group consisting of polyether ether ketone and polypropylene sulfide.
The method of claim 8,

The inorganic material is polyimide manufacturing method of at least one selected from the group consisting of graphite, zinc oxide, silicate, kaolinite, smectite, graphene oxide, zirconium dioxide and carbon nanotubes.
The method of claim 1,

The step a) is a polyimide manufacturing method carried out in the temperature range of 5 to 55 ℃.
The method of claim 1,

Step a) is a method for producing polyimide is carried out for 1 hour to 5 days.
The method of claim 1,

The method for producing a polyimide further comprising the step of further evaporating water from the filtrate obtained by filtration in step b).
The method of claim 1,

And b) recovering the solvent by cooling and condensing the water vapor generated by evaporation in step b).
The method of claim 1,

Wherein c) step is carried out in a temperature range of 150 to 450 ℃.
The method of claim 1,

C) step is performed for 10 minutes to 3 days.
The polyimide prepared according to claim 1 has a number average molecular weight of 5,000 to 1,000,000.
Polyimide in the form of a composite prepared according to claim 3 has a number average molecular weight of 50,000 to 2,000,000.
The method of claim 1,

Simultaneously with the imidization of step c), film processing including melt processing, hollow processing, calendering and sintering; Molded article processing including casting, lamination, compression molding, injection molding, blow molding, rotational molding, thermoforming and slush molding; And processing the fiber by at least one processing method selected from the group consisting of wet spinning, dry spinning and melt spinning.
The polyimide molded article manufactured according to claim 19 is at least one selected from the group consisting of polyimide films, high heat resistant engineering plastics, adhesives, tapes, fibers, liquid crystal alignment films, interlayer insulators, coating film resins, printed circuit boards and flexible display substrates. Polyimide molded articles for use.