WO2016032299A1 - Polyimide preparation method using monomer salt - Google Patents

Polyimide preparation method using monomer salt Download PDF

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WO2016032299A1
WO2016032299A1 PCT/KR2015/009102 KR2015009102W WO2016032299A1 WO 2016032299 A1 WO2016032299 A1 WO 2016032299A1 KR 2015009102 W KR2015009102 W KR 2015009102W WO 2016032299 A1 WO2016032299 A1 WO 2016032299A1
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polyimide
monomer
method
according
salt
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PCT/KR2015/009102
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French (fr)
Korean (ko)
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정찬문
유환철
이재희
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연세대학교 원주산학협력단
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions or lattices by other methods than by solution, emulsion or suspension polymerisation techniques
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/041Carbon nanotubes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K5/00Use of organic ingredients
    • C08K5/01Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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 of producing a polyimide using a monomer salt

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

Highly heat-resistant polymer material such as polyimide is small frivolous screen product according to the development of high technology, high performance, space as an essential material for highly reliable screen in the form of films, molded articles, fibers, coatings, adhesives and composite materials, aerospace, electrical / e, are used in a wide range of industries such as automotive and precision equipment.

The high heat resistance of the polyimide polymer material (polyimide, PI) is already have excellent mechanical strength, chemical resistance, weather resistance, heat resistance on the basis of the chemical stability of the DE loop. In addition, and also can make the synthesis is easy, and film-film, and has the advantage of no cross-linking group is required for curing, and because of the excellent electrical properties and, from such microelectronic field, optical field receiving attention as a functional polymeric material.

On the other hand, studies for up due to the growth of high-tech industries also attracted the performance of polyimide material itself or to replace the polymer materials have been used in the existing number were in progress. These studies are an organic material, or inorganic material, or those materials modified by preparing the polyimide itself were to win the above features are dispersed in a polymer. The polyimide composite material produced by such a method has also shows a higher mechanical and thermal properties in accordance with the dispersion material, and also shows a high permeability or a high dielectric constant. The thus produced polyimide composite is made possible to use the new areas, such as areas, etc. In addition it had been the conventional polyimide used is used as a low dielectric constant organic thin film transistor.

The invention of synthetic steps are greatly reduced, and the reaction proceeds under mild conditions when manufacturing the monomer salt, the method for producing a polyimide, a polyimide copolymer or a polyimide composite material using the above prepared monomer salt and prepared by this and to provide a polyimide, a polyimide or a polyimide copolymer complex.

In an embodiment of the present invention for achieving the problems as described above, a) to prepare a Diane hydride (dianhydride) and a diamine monomer (diamine) salt monomer mixture into a monomer in water; b) step of the monomer salt mixture recovered monomer salts Evaporation of the filtration and drying, or water; It provides a method for manufacturing a polyimide comprising a and c) preparing a polyimide by heating the monomer salt.

In another embodiment of the present invention, the number average molecular weight of a polyimide which is prepared according to the method provides a 5,000 to 1,000,000 polyimide.

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

In yet another one embodiment, the c) at the same time as the imidization step, film processing, including melt processing, the hollow processing, calendar processing, and sintering; Casting, lamination, compression molding, injection molding, blow molding, rotational molding, the molded product processing, including thermoforming and slush molding; And wet spinning, dry spinning, and melt-spun fiber comprising a processed; provides a process for producing a polyimide molded article further comprises the step of processing the at least one processing method selected from the group consisting of ways.

In another embodiment of the present invention, there is provided a polyimide molded article prepared according to the method polyimide film, a highly heat-resistant engineering plastics, adhesives, tapes, fibers, liquid crystal orientation film, an interlayer insulator, coating resin, and the printed circuit board and a flexible display It provides a polyimide molded article to be used with one or more purposes selected from the group consisting of a substrate.

In accordance with the invention takes place in a polyimide, a polyimide copolymer or a polyimide composite manufacture a mild condition, this manufacturing process is simple and cost-effective, and environmentally sound does not use an organic solvent.

Polyimide, polyimide copolymer or a polyimide composite prepared according to the present invention has a high molecular weight, excellent mechanical properties and high thermal properties compared to 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 Example 1-2 of the present invention.

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

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

Figure 5 shows the FT-IR spectrum of the material prepared according to Comparative Examples 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 the comparative example 1-3 of the present invention.

Figure 8 shows the FT-IR spectrum of the polyimide according to the comparative example 1-4 of the present invention.

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

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

Figure 11 shows the IR spectrum of the monomeric salt-FT Example 2-4 of the present invention.

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

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

Figure 14 shows a picture of a polyimide composite film obtained by heating the composition of polyamic acid of graphene oxide according to the comparative example 2-4 of the present invention.

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

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

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

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

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

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

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

Figure 22 shows the FT-IR spectrum of the polyimide copolymers according to Examples 4-1 of the present invention.

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

Figure 24 shows the FT-IR spectrum of the polyimide copolymers according to the embodiment 4-3 of the present invention.

Figure 25 shows the FT-IR spectrum of the polyimide copolymers according to the embodiment 4-4 of the present invention.

Figure 26 shows the FT-IR spectrum of the polyimide copolymers according to the embodiment 4-5 of the present invention.

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

The present invention relates to a process for preparing a salt from the monomer monomer, producing a polyimide using the above prepared monomer salt.

In accordance with the invention takes place in a polyimide, a polyimide copolymer or a polyimide composite manufacture a mild condition, this manufacturing process is simple and cost-effective, and environmentally sound does not use an organic solvent. In addition, a polyimide, a polyimide copolymer or a polyimide composite prepared according to the present invention has a high molecular weight, excellent mechanical properties and high thermal properties compared to the polyimide prepared according to the conventional method.

Will now be described in detail the invention.

Polyimide, polyimide copolymer or a polyimide composite production method

Polyimide manufacturing method according to an embodiment for achieving the object of the present invention comprising the steps of: a) preparing a Diane hydride (dianhydride) and a diamine monomer (diamine) salt monomer mixture into a monomer in water; b) step of the monomer salt mixture recovered monomer salts Evaporation of the filtration and drying, or water; And a and c) preparing a polyimide by heating the monomer salt.

First, put the Diane hydride (dianhydride) and a diamine monomer (diamine) monomer to water to prepare a monomer salt mixture (step a).

In one embodiment of the invention, the Diane hydride may be in one or more of Diane hydride, Diane the hydride may be aromatic or aliphatic. On the other hand, the polyimide of the copolymer form may be prepared if the Diane hydride is used as the two or more kinds.

On the other hand, the Diane hydride to in one embodiment of the present invention may comprise a compound of formula (I).

Figure PCTKR2015009102-appb-I000001

<Formula 1>

(R 1 in the formula 1 is the chemical structure:

Figure PCTKR2015009102-appb-I000002

Figure PCTKR2015009102-appb-I000003

Figure PCTKR2015009102-appb-I000004

Figure PCTKR2015009102-appb-I000005

It is selected from the group consisting of a.)

In one embodiment, the diamine may minil least one diamine, the diamine may be aromatic or aliphatic. On the other hand, the polyimide of the copolymer form may be prepared, used as the diaphragm Min of two or more.

On the other hand, the diamine in one embodiment of the present invention may comprise a compound of formula (2).

Figure PCTKR2015009102-appb-I000006

<Formula 2>

(R 2 is the chemical structure of the following in formula (2)

Figure PCTKR2015009102-appb-I000007

Figure PCTKR2015009102-appb-I000008

Figure PCTKR2015009102-appb-I000009

Figure PCTKR2015009102-appb-I000010

Figure PCTKR2015009102-appb-I000011

Figure PCTKR2015009102-appb-I000012

Figure PCTKR2015009102-appb-I000013

Figure PCTKR2015009102-appb-I000014

Figure PCTKR2015009102-appb-I000015

It is selected from the group consisting of. On the other hand, the x is an integer satisfying the 1≤x≤50, wherein n is a natural number ranging from 1 to 20, W, an alkyl group or an aryl group between the X, Y are each a carbon number of 1 to 30, Z is an ester group , an amide group, is already selected from the group consisting of an deugi and ether.)

On the other hand, the molar ratio of diamine to Diane hydride in the a) step may be from 0.5 to 2 equivalents. The molar ratio may be specifically from 0.8 to 1.5 equivalents. If the molar ratio exceeds the one to less than 0.5 equivalent or 2 equivalent is finally becomes extremely small, the molecular weight of the polyimide is formed in a, so that there can be a very less physical and chemical properties of the polyimide problems.

On the other hand, the step a) may take place in various ways, for example, can be carried out by a method to inject the respective dispersed, and then, this reaction vessel, the respective monomers in water, addition of water to the reaction vessel as another method a first input to the next can be carried out by a method to inject the respective monomers. Also may be carried out in a manner to inject water and then added to each monomer preferentially to the reaction vessel, it can be performed by a combination of the above methods.

On the other hand, it may include steps for loading in one embodiment of the present invention, further the step a) of the monomer salt mixture produced during the dispersion material.

It said dispersion material used may be one kind of substance selected from the group consisting of organic materials and inorganic materials. On the other hand, the organic material or inorganic material can be processed by one or more methods selected from physical methods including a method of dispersing or grinding by immersion in water and chemical methods of reacting with chemicals.

In one embodiment of the present invention, the organic material may be a polyether ether ketone, and one or more materials selected from the group consisting of poly propylene sulfide.

On the other hand, in one embodiment, the inorganic material may be one or more substances selected from the group consisting of graphite, zinc oxide, silicates, kaolinite, smectite, graphene oxide, zirconium dioxide, and carbon nanotubes.

On the other hand, the dispersion material can be a particulate, plate-like materials, alone or in combination of two or more materials selected from the group consisting of fibrous materials. If the dispersed material is particulate in the composition and the final product can be given additional benefits, such as thermal stability, increased density, stiffness (stiffness) or texture (texture), when the plate has spread well-dispersed material of the polymer material reducing the thermal expansion, it is possible to process the surface of the gas permeability decreases and the dispersion material in a variety of functional groups giving the following characteristics and adhesion, if the fiber is, the reduction of the thermal linear expansion coefficient, or modulus of elasticity, improvement of mechanical strength such as bending strength, etc. the can give an advantage.

On the other hand, the dispersion material when putting more the dispersion material may be included in the monomer mixture to the salt mixture as a whole compared to 1 to be included as 90wt%, and 1 to 50wt% are more detail by weight. When the content of the dispersed material is less than 1wt% total based on the weight of the mixture is difficult to express the unique properties of the dispersion material in the polyimide of the composite type is produced, in the case of 90wt% more than the mechanical properties of the composite type polyimide produced significant It can be reduced.

On the other hand, it may further include one or more additives selected from the group consisting of the monomer salt mixture during manufacturing, dispersing agents and thickening agents.

In one embodiment, the dispersant may be dispersed first at least one member selected from the group consisting of surfactants of cationic, anionic and nonionic.

In one embodiment of the present invention, the thickening agent is hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate, polyvinyl alcohol and polyvinyl pyrrolidone as it may be at least one thickening agent selected from the group consisting of.

The amount of the additive may be 0.1 to 10wt% compared to the combined weight of the monomer and a dispersed material within the monomer salt mixture. When the amount of the additive is less than 0.1wt%, the effect of the additive can be minimal, and may be the mechanical properties of the resulting polyimide greatly reduced if the excess of 10wt%.

On the other hand, the preparation of the monomer salt composition, and may undergo a process of dispersion by one or more selected from the group consisting of a stirrer dispersion, homogenizer dispersion, ultra-high pressure dispersion and ultrasonic dispersion, it may also be subjected to the process of stirring.

On the other hand, the a) step can be carried out in a can be performed within 5 to 55 ℃ temperature range and, particularly, from 10 to 35 ℃ temperature range. a) step is to be a need for such a separate heat source supply or cooling condenser, if performed in the agitation, more than 55 ℃ can be distributed process is not smoothly if carried out in less than 5 ℃.

On the other hand, the a) step can be carried out for, and may be performed during a day to 5 hours, particularly from 3 hours to 1 day. a) step and the number of the injected material is not distributed uniformly dispersed when performed in less than 1 hour, there may occur a problem that the cost of the process increases excessively when performed for more than 5 days.

Next, the monomer salt mixture by filtration and drying, or evaporation of the water is recovered Diane hydride and diamine monomer salt (step b). On the other hand, when the monomer is obtained if a salt if in step a) applying a dispersion material may be present in a mixed dispersion material and the monomer in salt form.

In one embodiment of the present invention, when the mixture was filtered and the obtained solid, it can be prepared by salt drying the resulting solid. On the other hand, the filtrate obtained from the filtration process may be obtained by adding the salt by evaporating.

In another embodiment of the present invention, when the evaporation of the water in the mixture can be made a salt. On the other hand, the water vapor generated by the evaporation may be re-used to recover by cooling and condensation water.

In one embodiment of the invention, the filtering is to be gravity filtration, vacuum filtration, pressure filtration, press filtration, centrifugal filtration, microfiltration, ultrafiltration and reverse osmosis method, performed by one or combination of two or more selected from the group consisting of It may be.

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

In one embodiment of the invention, the evaporation will be performed by natural evaporation, membrane evaporation, thermal evaporation, pervaporation, vacuum evaporation, simultaneous vacuum evaporation and rotation concentrated combinations evaporation method with at least one or two selected from the group consisting of can.

On the other hand, the drying or evaporation may be performed under conditions of less than atmospheric pressure. Further, the drying or evaporation may be performed within the temperature range -60 to 200 ℃. When the drying or evaporation is carried out at a temperature of less than -60 ℃ and a drying or evaporation may take place smoothly, it may be a problem with discoloration occurs when carried out at a temperature of more than 200 ℃.

Next, by heating the monomer salt obtained by the above process is already in progress de painter is producing the polyimide (step c).

In one embodiment of the invention, step c) may be carried out in a temperature range from 150 to 450 ℃. Specifically, it may be carried out in a temperature range of 180 to 400 ℃. It said step c) the case is carried out at a temperature of less than 150 ℃ may not imidization not proceed, a heat decomposition of the monomer or the polymer itself may experience when carried out at a temperature of more than 450 ℃.

In one embodiment of the invention, the step c) is between 10 minutes can be carried out for three days, or more specifically, may be performed for 30 minutes to 2 days, more specifically, it is carried out for 1 hour to 1 day can. If case step c) is carried out in less than 10 minutes it can not be carried out already de artist performing in excess of three days can result in thermal degradation of the polymer itself.

On the other hand, the heating in step c) may be performed by a heat treatment, hot air treatment, corona treatment, high frequency treatment, one or a combination of two or more selected from the group consisting of ultraviolet light treatment, infrared treatment, and laser treatment.

On the other hand, the step c) may be performed at atmospheric pressure, pressure, reduced pressure or vacuum conditions, for example, pressurized or reduced pressure condition may be to pressure or in a vacuum to from greater than 0 to 1000 bar condition. On the other hand, if the reaction pressure exceeds 1000bar there is damage to the reaction vessel may be caused.

On the other hand, the step c) may be performed in air or an inert gas atmosphere. In one embodiment of the 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, the step c) is, if carried out in a pressurized condition, or vapor pressure is formed inside the pressure vessel, one selected from the group consisting of a method of injecting or compressing the pressure vessel an inert gas inside the pressure vessel or in combination of two or more in may 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, and xenon crop tone.

A polyimide or a polyimide copolymer produced through the series of processes are wholly aromatic (fully aromatic), part of an aliphatic (partially aliphatic), or around the aliphatic (fully aliphatic) polyimide may be, number average molecular weight of the polyimide is 5,000 to 1,000,000 can be.

Moreover, having a form of dispersed substance in the polyimide poly complex form as prepared by the series of processes polyimide (organic or inorganic) are homogeneously dispersed, said polyimide wholly aromatic (fully aromatic), part of an aliphatic ( partially aliphatic) aliphatic or before (fully aliphatic) polyimide may be, the molecular weight of the polyimide of the composite form may be from 50,000 to 2,000,000.

The molecular weight of the polyimide, a polyimide or a polyimide copolymer complex is considerably higher compared to the polyimide prepared according to the method for producing a conventional polyimide, and has excellent mechanical properties and high thermal properties accordingly.

In particular, there is a Young's modulus of poly imide of a composite form made in accordance with one embodiment of the present invention may be from 2.0 to 8.0GPa, may be more particularly 6.2 to 8.0GPa. On the other hand, the tensile strength of the polyimide in a composite form made in accordance with one embodiment of the present invention may be in the 100 to 300MPa, and more details can range from 182 to 210MPa. This is significantly improved compared to the mechanical strength of the polyimide prepared according to conventional methods.

Thus, the polyimide, the polyimide copolymer or a polyimide composite prepared according to the present invention space, aerospace, electrical / electronic, semiconductor, transparent / flexible display, a liquid crystal alignment film, automobile, precision instruments, packaging, medical material, a separator, a fuel cell and a secondary battery including a wide range of industries, high utility value.

Method of producing a polyimide using a mechanical grinding method

On the other hand, after the monomer produced from the salt Diane anhydride monomer and a diamine monomer are mixed and dispersed material is ground to prepare a composition in powder form, and then, by heating them to imidization may be produced polyimide composite.

The monomer was the salt used is the same described above, it is as also described above dispersion material.

On the other hand, the grinding process can take place using the pulverizer grinding the raw material available at most 6 to 50 ㎜ possible crushing heavy chain group of 3 to 10㎜ size of a raw material of the sized or 3 to 10 ㎜ below 150㎛, heavy chain groups may be used a roll crusher, an edge runner, a hammer crusher and a disc crusher, pulverizer as may be used a ball mill, a jet mill, a pot mill, turbo mill, super micron mill, a roller mill, a Raymond mill, and tube mill . On the other hand, the grinding process can be carried out by using a crusher.

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

On the other hand, as the monomer salt prepared from the Diane anhydride monomer and a diamine monomer, and then pulverized by mixing two different monomers salt or more species produced in powder form and then to imidization by heating it preparing a polyimide copolymer You may.

The monomer was salts used are the same described above, are as also described above dispersion material. On the other hand, the grinding process is also the same as described above.

Polyimide molded article production method

On the other hand, the c) if carried out in the already forming the encoding device of the stage, the molding is already in progress at the same time as the encoding can be produced a polyimide molded article.

Wherein c) a monomeric salt in step and simultaneously proceeding the imidization reaction by heating in a forming device, film processing, including melt processing, the hollow processing, calendar processing, and sintering; Casting, lamination, compression molding, injection molding, blow molding, rotational molding, the molded product processing, including thermoforming and slush molding; And wet spinning, dry spinning and melt spinning the fiber modification comprising; when processed into at least one processing method selected from the group consisting of, it is possible to directly prepare a polyimide molded article.

On the other hand, a polyimide molded product in which the preparation a) in the case 2 with at least one Diane hydride or two or more kinds of diamine in step, and that the polyimide copolymer molded article, a) when inserted further the dispersion material in the step, polyimides It corresponds to the mid composite molded article.

On the other hand, one being a polyimide molded article prepared according to the method selected from the polyimide film, a highly heat-resistant engineering plastics, adhesives, tapes, fibers, liquid crystal orientation film, an interlayer insulator, coating resin, the group consisting of a printed circuit board and the flexible display substrate It can be used in more applications.

Will be described below in more detail the present invention by way of example and experimental example of the present invention. However, the following Examples and Experimental Examples are intended for better understanding of the present invention is not intended to limit the scope of the invention thereto.

Example

Examples 1-1: before the production of an aromatic polyimide

Into 60mL of water in a 100-mL 1-neck round bottom flask was replaced with nitrogen gas should 4,4' oxidase pipe Talic hydride 3.102g (0.01mol) and 2,2-bis (3-amino-4-hydroxy hydroxyl phenyl) and stirred for 12 hours at 20 ℃ after inserting the hexafluoropropane 3.663g (0.01mol) in one at a time. Then the monomer salt was vacuum dried for one day and then the mixture was gravity filtered, the obtained solid was prepared in the.

Then the wholly aromatic polyimide was prepared by heating at 350 ℃ for 6 hours using an electric furnace, the monomer salt. 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 an aliphatic polyimide parts

Into 50mL of water in a 100-mL 1-neck round bottom flask was replaced with nitrogen gas of 3,3 ', 4,4'-tetra-carboxylic Diane hydride 3.222g (0.01mol) and 4,4'-methylene bis (2-methyl bicyclo hexamine) after the 2.384g (0.01mol) loaded at a time and stirred for 12 hours at 20 ℃. Then the monomer salt was vacuum dried for one day and then the mixture was gravity filtered, the obtained solid was prepared in the.

Next, the monomer salt was prepared using portions aliphatic polyimide by heating at 350 ℃ for 6 hours using an electric furnace to. 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 an aliphatic polyimide parts

Nitrogen gas, the two 50-mL 1-neck round bottom flask cyclo-butane-1, & hydroxy carboxylic Diane substituted with fluoride 1.961g (0.01mol) and 4,4'-oxy-dimethyl aniline 2.002g after loading the (0.01mol), each followed by dispersion by the addition of 10mL of water to each flask. Each mixture thus obtained was placed in a 100-mL 1-neck round bottom flask was replaced by nitrogen gas followed by the addition of 15mL of water at 25 ℃ was stirred for 18 hours. Then the monomer salt was vacuum dried for one day and then the mixture was gravity filtered, the obtained solid was prepared in the.

Next, the monomer salt was prepared using portions aliphatic polyimide by heating at 300 ℃ for 8 hours using an electric furnace to. 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 an aliphatic polyimide before

In the two 50-mL 1-neck round bottom flask was replaced with nitrogen gas 1,2,4,5-tetramethyl cyclo-hexane carboxylic Diane hydride 2.242g (0.01mol) and 4,4'-methylenebis (cyclo-hexyl after loading on the amine) 2.104g (0.01mol), each followed by dispersion by the addition of 10mL of water to each flask. Each mixture thus obtained, at 30 ℃ and then was placed in a 100-mL 1-neck round bottom flask was replaced with nitrogen gas was added to 20mL of water was stirred for 18 hours. Then the monomer salt was vacuum dried for one day and then the mixture was gravity filtered, the obtained solid was prepared in the.

Then the entire aliphatic polyimide was prepared by heating at 300 ℃ for 8 hours using an electric furnace, the monomer salt. 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: I preparing an aliphatic polyimide

Into 40mL of water in a 100-mL 1-neck round bottom flask was replaced with nitrogen gas 1,2,4,5-tetramethyl cyclo-hexane carboxylic Diane hydride 2.242g (0.01mol) and 4,4'-methylene-bis ( cyclo hexylamine) after the 2.104g (0.01mol) loaded at a time and stirred for 12 hours at 25 ℃. Then the monomer salt was vacuum dried for one day and then the mixture was gravity filtered, the obtained solid was prepared in the.

But then heated to 24 hours at 80 ℃ using an electric furnace, the monomer salt was possible to synthesize the entire aliphatic polyimide. In the infrared absorption spectrum of the synthesized polymer were already C = O absorption band of deugi observed at 1785cm -1 can be found in a typical polyimide (FIG. 5).

Comparative Example 1-2: I preparing an aliphatic polyimide

Into 40mL of water in a 100-mL 1-neck round bottom flask was replaced with nitrogen gas 1,2,4,5-tetramethyl cyclo-hexane carboxylic Diane hydride 2.242g (0.01mol) and 4,4'-methylene-bis ( cyclo hexylamine) after the 2.104g (0.01mol) loaded at a time and stirred for 12 hours at 25 ℃. Then the monomer salt was vacuum dried for one day and then the mixture was gravity filtered, the obtained solid was prepared in the.

But then with heating for one minute at 180 ℃ using an electric furnace, the monomer salt was possible to synthesize the entire aliphatic polyimide. In the infrared absorption spectrum of the synthesized polymer were already C = O absorption band of deugi observed at 1785cm -1 can be found in a typical polyimide (Fig. 6).

Comparative Example 1-3: before the production of an aromatic polyimide

A 100-mL two-necked replaced with nitrogen gas into the pyrrolidone 45 mL N- methyl-2 in a round bottom flask 4,4 oxidase should pipe Talic hydride 3.102g (0.01mol) and 4,4 ' oxy dimethyl aniline, insert the 2.002g (0.01mol) was 18 hours at 25 ℃ was synthesized monomer salt. Then it was re-precipitated by the mixture using water as. Gravity filtered and water 100mL and obtain a polyamic acid is dried by vacuum drying after washing with 100mL of methanol.

After the chemical has already put a 5mL of pyridine in acetic anhydride tikan 3mL and to the solution to lower the temperature in the encoding method 170 ℃ to room temperature and then refluxed for 5 hours to a reprecipitation using a large excess of ice water. And then washed with water 100mL and methyl alcohol 100mL was synthesized wholly aromatic polyimides, and vacuum drying (thermal imidization method in 12 hours heating. The temperature was raised step by step in an oven or hot plate for the synthesis of polyamic acid solution to 250 ~ 300 ℃ method can be obtained a polyimide) using that. 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: I preparing an aliphatic polyimide

In a 100-mL 2 neck round bottom flask was replaced with nitrogen gas into the N- methyl-pyrrolidone 40 mL 1,2,4,5- tetra-cyclo-hexane carboxylic Diane hydride 2.242g (0.01mol) and 4,4'-methylenebis (cyclo-hexyl amine), insert a 2.002g (0.01mol) was 18 hours at 25 ℃ to synthesize the polyamic acid solution. Then it was re-precipitated by the mixture using water as. Gravity filtered and water 100mL and obtain a polyamic acid is dried by vacuum drying after washing with 100mL of methanol.

After the chemical has already put a 5mL of pyridine in acetic anhydride tikan 3mL and to the solution to lower the temperature in the encoding method 170 ℃ to room temperature and then refluxed for 5 hours to a reprecipitation using a large excess of ice water. And then washed with water 100mL and methyl alcohol 100mL were synthesized before aliphatic polyimides, and vacuum drying (thermal imidization method in 12 hours heating. The temperature was raised step by step in an oven or hot plate for the synthesis of polyamic acid solution to 250 ~ 300 ℃ method can be obtained a polyimide) using that. 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).

Examples 2-1: before the production of an aromatic polyimide composite film

Pyromellitic Diane hydride (10.906g) and 4,4'-oxy-dimethyl aniline (10.012g) was added to a water and yes the pin-oxide (5.00g) in the overall composition compared to 5wt% by weight for 24 hours at 25 ℃ It was dispersed with an agitator to prepare a monomer salt composition.

Next it was applied to rotate the above composition on a glass plate to prepare a polyimide composite film was raised slowly temperature at atmospheric pressure using a heating until the final temperature reached 250 ℃ for 7 hours and held there for one hour (Fig. 9 and Fig. 10).

Example 2-2: Preparation of a portion aliphatic polyimide composite film

Dispersed in fatigue mellitic tick Diane hydride (10.906g) and hexamethylene diamine (5.810g) and mica (mica) equipped with a stirrer for 24 hours at 25 ℃ and then the mixture (5.00g) was prepared in a monomeric salt composition.

The following were prepared in a polyimide composite film was spin-coated, and maintained for up to temperature slowly at atmospheric pressure using a heating until the final temperature reached 250 ℃ for 7 hours 1 hour the composition on a glass plate.

Example 2-3: Preparation of a portion aliphatic polyimide composite film

4,4 oxidase pipe Talic Diane hydride (15.510g) and hexamethylene diamine (5.810g) and yes and dispersed followed by the addition of a pin-oxide (5.00g) at 25 ℃ with a stirrer for 24 hours, the monomer salt composition It was prepared.

Next it was applied to rotate the above composition on a glass plate to prepare a polyimide composite film was raised slowly temperature at atmospheric pressure using a heating until the final temperature for 7 hours to reach 250 ℃ held for one hour (Fig. 15).

Example 2-4: Preparation of an aliphatic polyimide composite film former

1,2,4,5-tetrahydro that cyclo-hexane carboxylic Diane hydride (11.208g) and hexamethylene diamine (5.810g) and pre-dispersed in water with 1wt% yes followed by the addition of pins oxide mixture (5.00g) It was dispersed by a stirrer for 24 hours at 25 ℃ to prepare a monomer salt composition.

The following were prepared in a polyimide composite film was spin-coated, and maintained for up to gradually temperature at atmospheric pressure using a heating until the final temperature reached 250 ℃ for 7 hours 1 hour the composition on a glass plate (11, Figures 12 and 16)

Example 2-5: Preparation of an aliphatic polyimide composite film former

1,2,3,4-tetramethyl cyclo butane carboxylic Diane hydride (9.805g) and 4,4'-methylene bis (2-methyl cyclo hexyl amine) (11.920g) and the mica (mica) (5.00g) It was added and dispersed with a stirrer for 24 hours at 25 ℃ to prepare a monomer salt composition.

The following were prepared in a polyimide composite film was spin-coated, and maintained for up to temperature slowly at atmospheric pressure using a heating until the final temperature reached 250 ℃ for 7 hours 1 hour the composition on a glass plate.

Example 2-6: Preparation of an aliphatic polyimide composite film former

1,2,3,4-tetramethyl cyclo-pentane carboxylic Diane hydride (10.507g) and 4,4'-methylenebis (cyclo-hexyl amine) (10.518g), and carbon nanotubes was added to (5.00g) 25 It was dispersed by a stirrer for 24 hours to prepare a monomer ℃ salt composition.

The following were prepared in a polyimide composite film was spin-coated, and maintained for up to temperature slowly at atmospheric pressure using a heating until the final temperature reached 250 ℃ for 7 hours 1 hour the composition on a glass plate.

Comparative Example 2-1: before the production of an aromatic polyimide composite film

Into the N- methyl-2-pyrrolidone in a 100-mL 2 neck round bottom flask was replaced with nitrogen gas pyromellitic Diane hydride (6.543g) and 4,4'-oxy-insert the die aniline (6.072g) to 18 hours at 25 ℃ then it was synthesized polyamic acid solution 10wt%.

It was added and then the graphene oxide (5.00g) to the solution and dispersed by a stirrer for 18 hours at 25 ℃ to prepare a composition.

The following were prepared in a polyimide composite film was spin-coated, and maintained for up to temperature slowly at atmospheric pressure using a heating until reaching the final temperature for 11 to 300 ℃ 1 hour the composition on a glass plate.

Comparative Example 2-2: Preparation of partial aliphatic polyimide composite film

Into the N- methyl-2-pyrrolidone in a 100-mL 2 neck round bottom flask was replaced with nitrogen gas pyromellitic Diane hydride (7.634g) in 25 ℃ after inserting the hexamethylene diamine (4.067g) by reacting 18 hours, to synthesize a polyamic acid solution of 10wt%.

It was added and then the graphene oxide (5.00g) to the solution and dispersed by a stirrer for 18 hours at 25 ℃ to prepare a composition.

The following were prepared in a polyimide composite film was spin-coated, and maintained for up to temperature slowly at atmospheric pressure using a heating until reaching the final temperature for 11 to 300 ℃ 1 hour the composition on a glass plate.

Comparative Example 2-3: Preparation of partial aliphatic polyimide composite film

Into the N- methyl-2-pyrrolidone in a 100-mL 2 neck round bottom flask was replaced with nitrogen gas is 4,4'-oxy pipe Talic Diane hydride (9.306g) and hexamethylene diamine (3.486g) to the 18 hours at 25 ℃ it was synthesized 10wt% polyamic acid solution was placed.

It was added and then the graphene oxide (5.00g) to the solution and dispersed by a stirrer for 18 hours at 25 ℃ to prepare a composition.

The following were prepared in a polyimide composite film was spin-coated, and maintained for up to gradually temperature at atmospheric pressure using a heating until reaching the final temperature to 300 ℃ for 11 hours 1 hour the composition on a glass plate (Fig. 13)

Comparative Example 2-4: Preparation of an aliphatic polyimide composite film former

Nitrogen gas into the 100-mL 2 gu N, N- dimethyl-acetamide To a round bottom flask was added 1,2,4,5-tetramethyl cyclo-hexane carboxylic Diane hydride (7.845g) and hexamethylene diamine substituted with ( 4.067g) by the 18-hour reaction at 25 ℃ after loading was synthesized from 10wt% solution of polyamic acid.

It was added and then the graphene oxide (5.00g) to the solution and dispersed by a stirrer for 18 hours at 25 ℃ to prepare a composition.

Next was applied to rotate the above composition on a glass plate and kept up slowly temperature until use a heater to a final temperature at atmospheric pressure for 11 hours reached 300 ℃ for 1 hour to prepare a polyimide composite film (14).

Figure PCTKR2015009102-appb-T000001

Performed As can be seen in Table 1, Examples 1-1 to 1-4 in the monomer salt was prepared using the process is carried out in the water at a temperature ranging from 20 to 30 ℃ 12 to 24 hours range, the monomer salt to 180 to 350 ℃ was confirmed that the thus obtained polyester having a high molecular weight polyimide to 6 to 24 hours at a temperature range of heat treatment.

On the other hand, Comparative Example 1-1 and Comparative Example 1-2 were carried out the heat treatment of the monomer salts prepared at temperatures below 160 ℃, or time of less than 5 minutes, it was confirmed that the polyimide can not be obtained by the method . In addition, Comparative Example 1-3 and Comparative Example 1-4, but by performing a conventional method for manufacturing a polyimide precursor by combining a polyamic acid obtained by using an organic solvent a polyimide, carried the obtained polyimide Example 1 1 to prepare a polyimide obtained in 1-4 was confirmed that with a low level of molecular weights.

Figure PCTKR2015009102-appb-T000002

On the other hand, according to the method of Table 2 can be found in Examples 2-1 to 2-6 as shown, manufactured with the monomer composition and then the salt was applied to a glass plate and slowly rotating the solution temperature was raised to 250 ℃ from room temperature for 8 hours the heat treatment could be obtained as a polyimide composite film. The polyimide film composite was confirmed that having a more improved mechanical properties and thermal properties as compared with a polyimide composite film manufactured by the process common polyimide film.

In particular, in Figure 15, and when 16, the monomer salt synthesis and at the same time one prepared by dispersing the dispersion material polyimide film composite was confirmed that the dispersion material evenly distributed.

On the other hand, in Comparative Example 2-1 it confirmed that the polyimide composite film manufactured by a mungchyeojyeo to 2-3 is not a conventional polyimide composite film made during the dispersion material is not uniformly dispersed in the organic solvent, which found in Figures 13 and 14 could. In particular, Comparative example 2-4 was due to a crack caused on the film to determine the mechanical properties. Preparative a polyimide composite film was found not to be well-dispersed material is dispersed to lower the mechanical properties and thermal properties.

Example 3-1: Production of wholly aromatic polyimide composite

2.18g pyromellitic Diane hydride, into an oxy-4,4'-dimethyl aniline, and 2.00g of distilled water, 100ml round bottom flask was prepared a monomer salt at room temperature.

Next in a ball mill followed by the addition of 0.01g of the montmorillonite in the monomer salt of the thus obtained 0.10g milled for one hour to prepare a powder composition.

And then heated for 6 hours at 200 ℃ at atmospheric pressure using a heating said powder composition to prepare a wholly aromatic polyimide composite.

Example 3-2: Production of wholly aromatic polyimide composite

3.10g of 4,4'-oxidase into the pipe Talic anhydride, 4,4'-oxy-dimethyl aniline and 2.00g of distilled water, 100ml round bottom flask was prepared a monomer salt at room temperature.

After then adding 0.01g of graphene oxide of the monomer salt of the thus obtained 0.10g as using a ball mill and milled for one hour to prepare a powder composition.

And then heated for 6 hours at 200 ℃ at atmospheric pressure using a heating said powder composition to prepare a wholly aromatic polyimide composite.

Example 3-3: Preparation of a portion aliphatic polyimide composite

Fatigue 2.18g mellitic tick Diane hydride, into the 4,4'-methylenebis (cyclo-hexyl amine) and distilled 100ml of 2.10g in the round bottom flask to prepare a monomer salt at room temperature.

Next in a ball mill followed by the addition of the bentonite 0.01g of the monomer salt of the thus obtained 0.10g milled for one hour to prepare a powder composition.

Next, the powder composition was prepared by using a heater for heating at 200 ℃ at atmospheric pressure for 6 hours parts aliphatic polyimide composite.

Example 3-4: Preparation of a portion aliphatic polyimide composite

3.10g of 4,4'- oxidase into the hexamethylene diamine and distilled water, 100ml of the inner pipe Talic hydride, 1.16g in round bottom flask to prepare a monomer salt at room temperature.

After then adding 0.01g of graphene oxide of the monomer salt of the thus obtained 0.10g as using a ball mill and milled for one hour to prepare a powder composition.

Next, the powder composition was prepared by using a heater for heating at 200 ℃ at atmospheric pressure for 6 hours parts aliphatic polyimide composite.

Example 3-5: Production of former aliphatic polyimide composite

2.24g 1,2,4,5- tetra-cyclo-hexane-carboxylic Diane hydride, into the 4,4'-methylenebis (cyclo-hexyl amine) and distilled 100ml of 2.10g in the round bottom flask at room temperature to prepare a monomer salt It was.

Next in a ball mill followed by the addition of 0.01g of the montmorillonite in the monomer salt of the thus obtained 0.10g milled for one hour to prepare a powder composition.

And then heated for 6 hours at 200 ℃ at atmospheric pressure using a heating said powder composition to prepare a pre aliphatic polyimide composite.

Example 3-6: Production of former aliphatic polyimide composite

Insert the 2.24g of 1,2,4,5-tetramethyl cyclo-hexane carboxylic Diane hydride, 1.16g of hexamethylene diamine and 100ml of distilled water in a round-bottom flask was prepared a monomer salt at room temperature.

Next in a ball mill followed by the addition of the bentonite 0.01g of the monomer salt of the thus obtained 0.10g milled for one hour to prepare a powder composition.

And then heated for 6 hours at 200 ℃ at atmospheric pressure using a heating said powder composition to prepare a pre aliphatic polyimide composite.

Comparative Example 3-1: Production of wholly aromatic polyimide composite

2.18g pyromellitic Diane hydride, into an oxy-4,4'-dimethyl aniline, and 2.00g of distilled water, 100ml round bottom flask was prepared a monomer salt at room temperature.

Next, using a ball mill was added to 9.90g of montmorillonite to 99wt% as compared to the total weight of the monomer composition of the obtained salt 0.10g milled for one hour to prepare a powder composition.

And then heated for 6 hours at 200 ℃ at atmospheric pressure using a heating said powder composition to prepare a wholly aromatic polyimide composite.

Comparative Example 3-2: Production of former aliphatic polyimide composite

Insert the 2.24g of 1,2,4,5-tetramethyl cyclo-hexane carboxylic Diane hydride, 1.16g of hexamethylene diamine and 100ml of distilled water in a round-bottom flask was prepared a monomer salt at room temperature.

After then adding the bentonite 0.01g of the monomer salt of the thus obtained 0.10g to prepare a pre aliphatic polyimide composite by heating at 200 ℃ at atmospheric pressure using a heater without a separate milling process for 6 hours.

Comparative Example 3-3: Production of wholly aromatic polyimide composite

In a 100-mL 2 neck round bottom flask was replaced with nitrogen gas N- methyl-2-pyrrolidone into the money of 3.10g 4,4 oxidase pipe Talic anhydride and 2.00g of 4,4'-oxy after loading the die aniline was 24 hours at 25 ℃ was synthesized from 10wt% solution of polyamic acid.

Next it was added a 0.51g of graphene oxide to the solution and dispersed by a stirrer for 18 hours at 25 ℃ to prepare a composition.

The following were prepared in a polyimide composite film was spin-coated, and maintained for up to temperature slowly at atmospheric pressure using a heating until reaching the final temperature for 11 to 300 ℃ 1 hour the composition on a glass plate.

Comparative Example 3-4: Production of wholly aromatic polyimide composite

Nitrogen gas having 100-mL round bottom flask was placed 2 configured on the N- methyl-2-pyrrolidone was placed a pyromellitic Diane hydride and 2.00g of 4,4'-oxy-dimethyl aniline in 25 2.18g substituted with to 24 hours at ℃ to synthesize the polyamic acid solution of 10wt%.

It was then added to the montmorillonite of 0.42g to this solution and dispersed with a stirrer for 18 hours at 25 ℃ to prepare a composition.

The following were prepared in a polyimide composite film was spin-coated, and maintained for up to temperature slowly at atmospheric pressure using a heating until reaching the final temperature for 11 to 300 ℃ 1 hour the composition on a glass plate.

Comparative Example 3-5: Production of former aliphatic polyimide composite

Nitrogen gas having 100-mL round bottom flask was placed 2 configured on the N- methyl-2-pyrrolidone of 1,2,4,5-tetramethyl cyclo-hexane carboxylic Diane hydride 2.10g and 2.24g of 4 substituted with, 4,4'-methylenebis (cyclo-hexyl amine) was 24 hours at 25 ℃, insert the synthesized a 10wt% solution of polyamic acid.

It was then added to the montmorillonite of 0.43g to this solution and dispersed with a stirrer for 18 hours at 25 ℃ to prepare a composition.

The following were prepared in a polyimide composite film was spin-coated, and maintained for up to temperature slowly at atmospheric pressure using a heating until reaching the final temperature for 11 to 300 ℃ 1 hour the composition on a glass plate.

Comparative Example 3-6: Production of former aliphatic polyimide composite

N- methyl in a 100-mL 2 neck round bottom flask was replaced with nitrogen gas into the blood-2-pyrrolidone 2.24g of 1,2,4,5- tetra-cyclo-hexane-carboxylic Diane hydride and 1.16g of hexamethylene after loading the diamine to 24 hours at 25 ℃ was synthesized from 10wt% solution of polyamic acid.

Next it was added a 0.34g of bentonite to the solution and dispersed by a stirrer for 18 hours at 25 ℃ to prepare a composition.

The following were prepared in a polyimide composite film was spin-coated, and maintained for up to temperature slowly at atmospheric pressure using a heating until reaching the final temperature for 11 to 300 ℃ 1 hour the composition on a glass plate.

Comparative Example 3-7: Production of wholly aromatic polyimide composite

Polyamic to a polyamic acid synthesized in Comparative Example 3, the dry solid obtained re-precipitation handed down to clean distilled water to prepare a solid acid.

Next, 0.01g of the polyamic acid of the 0.10g yes using a ball mill followed by the addition of the oxide to the pin mill for one hour to prepare a powder composition.

And then heated for 6 hours at 200 ℃ at atmospheric pressure using a heating said powder composition to prepare a wholly aromatic polyimide composite.

Comparative Example 3-8: Production of wholly aromatic polyimide composite

Polyamic to a polyamic acid synthesized in Comparative Example 4, drying the solid obtained re-precipitation handed down to clean distilled water to prepare a solid acid.

Next to the mill followed by the addition of 0.01g of the montmorillonite in the polyamic acid of 0.10g using a ball mill for one hour to prepare a powder composition.

And then heated for 6 hours at 200 ℃ at atmospheric pressure using a heating said powder composition to prepare a wholly aromatic polyimide composite.

Comparative Example 3-9: Production of former aliphatic polyimide composite

Polyamic to a polyamic acid synthesized in Comparative Example 5, the dried solid obtained re-precipitation handed down to clean distilled water to prepare a solid acid.

Next to the mill followed by the addition of 0.01g of the montmorillonite in the polyamic acid of 0.10g using a ball mill for one hour to prepare a powder composition.

And then heated for 6 hours at 200 ℃ at atmospheric pressure using a heating said powder composition to prepare a pre aliphatic polyimide composite.

Comparative Examples 3-10: All of preparing an aliphatic polyimide composite

Polyamic to a polyamic acid prepared in Comparative Example 6, drying the solid obtained re-precipitation handed down to clean distilled water to prepare a solid acid.

Next, using a bentonite in a ball mill to 0.01g 0.10g of the polyamic acid is milled for one hour to prepare a powder composition.

And then heated for 6 hours at 200 ℃ at atmospheric pressure using a heating said powder composition to prepare a pre aliphatic polyimide composite.

Figure PCTKR2015009102-appb-T000003

Figure PCTKR2015009102-appb-T000004

If the embodiment, as shown in Table 3 according to Examples 3-1 to 3-6, mixing a dispersing material and a monomer salt milling and heating can be obtained a polyimide composite material. The polyimide composite material was confirmed, that having enhanced mechanical properties and thermal properties compared to a polyimide composite material made of a general polyimide composite production method.

On the other hand, as shown in Table 4 were mixed with 99wt% compared to the polyimide composites of the total composition, the dispersed material in the monomer salt synthesized in Example 3-1 was reduced significantly the mechanical properties and thermal properties compared to Example 3-2 put the dispersion material in the monomer salt synthesized in the polyimide composite manufacture without any milling process was reduced significantly the mechanical properties and thermal properties. Comparative Example 3-3 polyimide composite the polyamic acid synthesized in to 3-6 prepared by adding dispersion materials and solvent but can determine improved results as compared with the mechanical properties and thermal properties of a typical polyimide Example 3 1 to showed a lower result than the polyimide composite prepared in Comparative examples 3-6 to 3-7 a polyimide composite material prepared by adding a dispersion of the solid material in the polyamic acid synthesized in 3-9 is not dispersed well dispersed substance this was not isolated from one another and dispersed polyimide material was confirmed to decrease significantly the mechanical properties and thermal properties.

Example 4-1: Production of wholly aromatic and aliphatic part polyimide copolymer

Pyromellitic Diane hydride (2.18g) in 2.18g, into the oxy-4,4 dimethyl aniline and 2.00g of distilled water to 100ml round-bottom flask was prepared a monomer salt A at room temperature. In addition, the oxy-4,4 of 3.10g into a pipe Talic anhydride, hexamethylene diamine and distilled water in a 100ml round bottom flask was added 1.16g of the monomer salt was prepared in B at room temperature.

Next, to prepare a fine powder by milling for the monomer and the salt A were mixed by using a ball mill 1.00g each B 1 hours.

The following were prepared wholly aromatic and aliphatic part polyimide copolymer by heating at 200 ℃ at atmospheric pressure for 6 hours by using a fine powder by heating the.

Example 4-2: Production of wholly aromatic and aliphatic polyimide copolymer I

2.18g pyromellitic Diane hydride, into an oxy-4,4'-dimethyl aniline, and 2.00g of distilled water to 100ml round-bottom flask was prepared a monomer salt A at room temperature. Also put 2.24g 1,2,4,5- tetra-cyclo-hexane-carboxylic Diane hydride, 4,4'-methylenebis (cyclo-hexyl amine) and 2.10g of distilled water in a 100ml round bottom flask at room temperature, the monomer salt B It was prepared.

Next, to prepare a fine powder by milling for the monomer and the salt A were mixed by using a ball mill 1.00g each B 1 hours.

The following were prepared wholly aromatic and aliphatic polyimide copolymer before and heated at 200 ℃ at atmospheric pressure for 6 hours by using a fine powder by heating the.

Example 4-3: Production of wholly aromatic and aliphatic polyimide copolymer I

2.18g pyromellitic Diane hydride, into an oxy-4,4'-dimethyl aniline, and 2.00g of distilled water to 100ml round-bottom flask was prepared a monomer salt A at room temperature. In addition, insert the 1,2,4,5-tetramethyl cyclo-hexane carboxylic Diane hydride, hexamethylene diamine and distilled water, 1.16g of 2.24g in 100ml round bottom flask was prepared a monomer salt B at room temperature.

Next, to prepare a fine powder by milling for the monomer and the salt A were mixed by using a ball mill 1.00g each B 1 hours.

The following were prepared wholly aromatic and aliphatic polyimide copolymer before and heated at 200 ℃ at atmospheric pressure for 6 hours by using a fine powder by heating the.

Example 4-4: Production of wholly aromatic and aliphatic part polyimide copolymer

The 4,4'-oxy of 3.10g into a 4,4'-oxy-dimethyl aniline, and distilled water of not tape Talic hydride, 2.00g in 100ml round bottom flask was prepared a monomer salt A at room temperature. In addition, insert the Diane pyromellitic anhydride, 4,4'-methylenebis (cyclo-hexyl amine) and 2.10g of distilled water, 2.18g of a 100ml round-bottom flask was prepared a monomer salt B at room temperature.

Next, to prepare a fine powder by milling for the monomer and the salt A were mixed by using a ball mill 1.00g each B 1 hours.

The following were prepared wholly aromatic and aliphatic part polyimide copolymer by heating at 200 ℃ at atmospheric pressure for 6 hours by using a fine powder by heating the.

Example 4-5: Production of wholly aromatic and aliphatic polyimide copolymer I

The 4,4'-oxy of 3.10g into a 4,4'-oxy-dimethyl aniline, and distilled water of not tape Talic hydride, 2.00g in 100ml round bottom flask was prepared a monomer salt A at room temperature. Also put 2.24g 1,2,4,5- tetra-cyclo-hexane-carboxylic Diane hydride, 4,4'-methylenebis (cyclo-hexyl amine) and 2.10g of distilled water in a 100ml round bottom flask at room temperature, the monomer salt B It was prepared.

Next, to prepare a fine powder by milling for the monomer and the salt A were mixed by using a ball mill 1.00g each B 1 hours.

The following were prepared wholly aromatic and aliphatic polyimide copolymer before and heated at 200 ℃ at atmospheric pressure for 6 hours by using a fine powder by heating the.

Example 4-6: Production of wholly aromatic and aliphatic polyimide copolymer I

The 4,4'-oxy of 3.10g into a 4,4'-oxy-dimethyl aniline, and distilled water of not tape Talic hydride, 2.00g in 100ml round bottom flask was prepared a monomer salt A at room temperature. In addition, insert the 1,2,4,5-tetramethyl cyclo-hexane carboxylic Diane hydride, hexamethylene diamine and distilled water, 1.16g of 2.24g in 100ml round bottom flask was prepared a monomer salt B at room temperature.

Next, to prepare a fine powder by milling for the monomer and the salt A were mixed by using a ball mill 1.00g each B 1 hours.

The following were prepared wholly aromatic and aliphatic polyimide copolymer before and heated at 200 ℃ at atmospheric pressure for 6 hours by using a fine powder by heating the.

Comparative Example 4-1: Production of wholly aromatic and aliphatic polyimide copolymer I

2.18g pyromellitic Diane hydride, into an oxy-4,4'-dimethyl aniline, and 2.00g of distilled water to 100ml round-bottom flask was prepared a monomer salt A at room temperature. Also put 2.24g 1,2,4,5- tetra-cyclo-hexane-carboxylic Diane hydride, 4,4'-methylenebis (cyclo-hexyl amine) and 2.10g of distilled water in a 100ml round bottom flask at room temperature, the monomer salt B It was prepared.

After then the mixture by each 1.00g of the salt monomers A and B was heated at 200 ℃ at atmospheric pressure for 6 hours by using a heating the mixture to prepare a wholly aromatic and aliphatic former polyimide copolymer.

Comparative Example 4-2: Production of wholly aromatic and aliphatic polyimide copolymer I

The 4,4'-oxy of 3.10g into a 4,4'-oxy-dimethyl aniline, and distilled water of not tape Talic hydride, 2.00g in 100ml round bottom flask was prepared a monomer salt A at room temperature. In addition, insert the 1,2,4,5-tetramethyl cyclo-hexane carboxylic Diane hydride, hexamethylene diamine and distilled water, 1.16g of 2.24g in 100ml round bottom flask was prepared a monomer salt B at room temperature.

After then the mixture by each 1.00g of the salt monomers A and B was heated at 200 ℃ at atmospheric pressure for 6 hours by using a heating the mixture to prepare a wholly aromatic and aliphatic former polyimide copolymer.

Comparative Example 4-3: Production of wholly aromatic and aliphatic polyimide copolymer I

Nitrogen gas having 100-mL round bottom flask was placed 2 configured on the N- methyl-2-pyrrolidone was placed a pyromellitic Diane hydride and 2.00g of 4,4'-oxy-dimethyl aniline in 25 2.18g substituted with to 24 hours at ℃ ethylamine a 10wt% solution of polyamic acid. In addition, a 100-mL substituted with nitrogen gas, 2-methyl-N- To a round bottom flask was added 2-pyrrolidone into the money 2.24g of 1,2,4,5- tetra-cyclo-hexane-carboxylic Diane hydride and 1.16g of hexamethylene to 24 hours at 25 ℃ after inserting a methylene-diamine was prepared using 10wt% solution of polyamic acid B.

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

The following final temperature for 11 hours under atmospheric pressure by using a rotary coating, and heating the polyamic acid solution on a glass plate to place the slow temperature until it reaches 300 ℃ held for one hour to a wholly aromatic and around the aliphatic polyimide copolymer It was prepared.

Comparative Example 4-4: Production of wholly aromatic and aliphatic polyimide copolymer I

In a 100-mL 2 neck round bottom flask was replaced with nitrogen gas N- methyl-2-pyrrolidone into the money of 3.10g 4,4 oxidase pipe Talic anhydride and 2.00g of 4,4'-oxy after loading the die aniline was 24 hours at 25 ℃ ethylamine a 10wt% solution of polyamic acid. In addition, nitrogen gas 100-mL round bottom flask was placed 2 configured on the N- methyl-2-pyrrolidone of 1,2,4,5-tetramethyl cyclo-hexane carboxylic Diane hydride 2.10g and 2.24g of 4 substituted with 4,4'-methylenebis to 24 hours at 25 ℃, insert the (cyclo hexylamine) it was synthesized in a 10wt% solution of polyamic acid B.

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

The following final temperature for 11 hours under atmospheric pressure by using a rotary coating, and heating the polyamic acid solution on a glass plate to place the slow temperature until it reaches 300 ℃ held for one hour to a wholly aromatic and around the aliphatic polyimide copolymer It was prepared.

Comparative Example 4-5: Production of wholly aromatic and aliphatic polyimide copolymer I

Nitrogen gas having 100-mL round bottom flask was placed 2 configured on the N- methyl-2-pyrrolidone was placed a pyromellitic Diane hydride and 2.00g of 4,4'-oxy-dimethyl aniline in 25 2.18g substituted with to 24 hours at ℃ to synthesize the polyamic acid solution of 10wt%. After re-precipitating the polyamic acid solution into a clean distilled water to prepare a polyamic acid A and dried.

Next, into the N- methyl-2-pyrrolidone in a 100-mL 2 neck round bottom flask was replaced with nitrogen gas 2.24g of 1,2,4,5-cyclo-hexane solution of carboxylic Diane hydride and 2.10g 4,4'-methylenebis (cyclo-hexyl amine) was 24 hours at 25 ℃, insert the synthesized a 10wt% solution of polyamic acid. After the polyamic acid solution was re-precipitated in pure distilled water to prepare a polyamic acid is dried to B.

And then using the polyamic acid A and B were mixed by a ball mill to prepare a fine powder 1.00g each milled for 1 hour.

The following were prepared wholly aromatic and aliphatic polyimide copolymer before and heated at 200 ℃ at atmospheric pressure for 6 hours by using a fine powder by heating the.

Comparative Example 4-6: The wholly aromatic and aliphatic before the air producing a polyimide polymer

In a 100-mL 2 neck round bottom flask was replaced with nitrogen gas N- methyl-2-pyrrolidone into the money of 3.10g 4,4 oxidase pipe Talic anhydride and 2.00g of 4,4'-oxy after loading the die aniline was 24 hours at 25 ℃ was synthesized from 10wt% solution of polyamic acid. After re-precipitating the polyamic acid solution into a clean distilled water to prepare a polyamic acid A and dried.

Next, into the N- methyl-2-pyrrolidone in a 100-mL 2 neck round bottom flask was replaced with nitrogen gas 2.24g of 1,2,4,5-cyclo-hexane solution of carboxylic Diane hydride and 2.10g 4,4'-methylenebis (cyclo-hexyl amine) was 24 hours at 25 ℃, insert the synthesized a 10wt% solution of polyamic acid. After the polyamic acid solution was re-precipitated in pure distilled water to prepare a polyamic acid is dried to B.

And then using the polyamic acid A and B were mixed by a ball mill to prepare a fine powder 1.00g each milled for 1 hour.

The following were prepared wholly aromatic and aliphatic polyimide copolymer before and heated at 200 ℃ at atmospheric pressure for 6 hours by using a fine powder by heating the.

Figure PCTKR2015009102-appb-T000005

Figure PCTKR2015009102-appb-T000006

If the embodiment according to the Table As can be seen from Example 5 4-1 to 4-6, mixing the prepared salt monomer 2 species and crushing and heating were obtained polyimide copolymer. The polyimide copolymer was confirmed that having improved thermal properties and molecular weight as opposed to a polyimide copolymer produced in the usual polyimide copolymer production method.

On the other hand, as shown in Table 6. Comparative Examples 4-1 to 4-2, according to a mixed to prepare a monomer salt prepared two kinds of polyimide composition was confirmed that does not go through the pulverization process to form the polyimide copolymer, It was confirmed from the molecular weight and thermal properties. Comparative Example 4-3 A polyimide copolymer mixture of the synthesized polyamic acid solution prepared according to the 4-4 polyimide copolymer in a well, but the embodiment is a low molecular weight compared to polyimide copolymers prepared according to the present invention form It was confirmed. In addition, Comparative Example 4-5 polyimide composition was mixed with the synthesized polyamic acid produced according to to 4-6 was confirmed that it is not formed in the polyimide copolymer.

The invention of synthetic steps are greatly reduced, and the reaction proceeds under mild conditions when manufacturing the monomer salt, the method for producing a polyimide, a polyimide copolymer or a polyimide composite material using the above prepared monomer salt and prepared by this It provides a polyimide, a polyimide or a polyimide copolymer complex.

Claims (20)

  1. a) preparing a monomer mixture into a salt Diane hydride (dianhydride) and a diamine monomer (diamine) monomer in water;
    b) step of the monomer salt mixture recovered monomer salts Evaporation of the filtration and drying, or water; And
    Polyimide manufacturing method including a; c) preparing a polyimide by heating the monomer salt.
  2. According to claim 1,
    The Diane hydride is 1 or more kinds of Diane hydride, the diamine is at least one method of producing a polyimide diamond minin.
  3. According to claim 1,
    Polyimide manufacturing method comprising the steps for loading the further step a) of the monomer salt mixture produced during the dispersion material.
  4. According to claim 1,
    Diane the hydride method for producing an aromatic or aliphatic Diane hydride polyimide.
  5. According to claim 1,
    The Diane hydride Diane hydride polyimide production method of the formula 1 below.
    Figure PCTKR2015009102-appb-I000016
    <Formula 1>
    (R 1 in the formula 1 is the chemical structure:
    Figure PCTKR2015009102-appb-I000017
    Figure PCTKR2015009102-appb-I000018
    Figure PCTKR2015009102-appb-I000019
    Figure PCTKR2015009102-appb-I000020
    It is selected from the group consisting of a.)
  6. According to claim 1,
    The diamine A method of manufacturing an aromatic or aliphatic diamine minin polyimide.
  7. According to claim 1,
    The diamines are diamine minin polyimide production method of the formula (2) below.
    Figure PCTKR2015009102-appb-I000021
    <Formula 2>
    (R 2 is the chemical structure of the following in formula (2)
    Figure PCTKR2015009102-appb-I000022
    Figure PCTKR2015009102-appb-I000023
    Figure PCTKR2015009102-appb-I000024
    Figure PCTKR2015009102-appb-I000025
    Figure PCTKR2015009102-appb-I000026
    Figure PCTKR2015009102-appb-I000027
    Figure PCTKR2015009102-appb-I000028
    Figure PCTKR2015009102-appb-I000029
    Figure PCTKR2015009102-appb-I000030
    It is selected from the group consisting of. On the other hand, the x is an integer satisfying the 1≤x≤50, wherein n is a natural number ranging from 1 to 20, W, an alkyl group or an aryl group between the X, Y are each a carbon number of 1 to 30, Z is an ester group , an amide group, is already selected from the group consisting of an deugi and ether.)
  8. 4. The method of claim 3,
    The dispersion material is a method for producing a polyimide of one or more materials selected from the group consisting of organic materials and inorganic materials.
  9. The method of claim 8,
    The organic material is a polyether ether is at least one method of producing the polyimide is selected from the group consisting of ketones and polypropylene sulfide.
  10. The method of claim 8,
    The inorganic material is one or more polyimide method is selected from the group consisting of graphite, zinc oxide, silicates, kaolinite, smectite, graphene oxide, zirconium dioxide, and carbon nanotubes.
  11. According to claim 1,
    It said step a) process for producing the polyimide to be carried out in the range of 5 to 55 ℃ temperature.
  12. According to claim 1,
    It said step a) process for producing the polyimide to be carried out for a day to 5 hours.
  13. According to claim 1,
    Polyimides method further comprising the step of obtaining the water from the filtrate obtained by the filtration in step b) by adding the salt and evaporated.
  14. According to claim 1,
    Polyimides method further comprising recovering the solvent by cooling and condensing the water vapor produced by the evaporation in step b).
  15. According to claim 1,
    Step c) The method for producing the polyimide to be carried out in a temperature range from 150 to 450 ℃.
  16. According to claim 1,
    Step c) The method of manufacturing the polyimide is carried out for 10 minutes to 3 days.
  17. The polyimide can be poly imide prepared according to 1, wherein the average molecular weight of 5,000 to 1,000,000.
  18. Claim 3 wherein the complex form of the poly-imide number average molecular weight of 50,000 to 2,000,000 of the polyimide prepared according to the.
  19. According to claim 1,
    Wherein c) at the same time as the imidization step, film processing, including melt processing, the hollow processing, calendar processing, and sintering; Casting, lamination, compression molding, injection molding, blow molding, rotational molding, the molded product processing, including thermoforming and slush molding; And wet spinning, dry spinning and melt spinning the fiber modification comprising; method of producing a polyimide shaped article further comprising the step of processing the at least one processing method selected from the group consisting of.
  20. Polyimide shaped article produced according to claim 19, wherein the at least one selected from a polyimide film, a highly heat-resistant engineering plastics, adhesives, tapes, fibers, liquid crystal orientation film, an interlayer insulator, coating resin, the group consisting of a printed circuit board and the flexible display substrate polyimide molded product is used for the purpose.
PCT/KR2015/009102 2014-08-29 2015-08-29 Polyimide preparation method using monomer salt WO2016032299A1 (en)

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KR20140123904A KR20160033009A (en) 2014-09-17 2014-09-17 Preparation method for polyimide product and the polyimide product thereby
KR10-2015-0050470 2015-04-09
KR20150050470A KR101728830B1 (en) 2015-04-09 2015-04-09 Preparation method for polyimide composites from monomer
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07145321A (en) * 1993-11-22 1995-06-06 Mitsui Toatsu Chem Inc Extruded polyimide molding with slip property
JP2000302897A (en) * 1999-04-22 2000-10-31 Kanegafuchi Chem Ind Co Ltd Preparation of polyimide-based film
US6790930B1 (en) * 1999-10-06 2004-09-14 Kaneka Corporation Process for producing polyimide resin
US20080300360A1 (en) * 2007-05-31 2008-12-04 The Boeing Company Water-entrained-polyimide chemical compositions for use in high-performance composite fabrication
KR20110110955A (en) * 2010-04-02 2011-10-10 부산대학교 산학협력단 Polyimide nanocomposites and method for making the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07145321A (en) * 1993-11-22 1995-06-06 Mitsui Toatsu Chem Inc Extruded polyimide molding with slip property
JP2000302897A (en) * 1999-04-22 2000-10-31 Kanegafuchi Chem Ind Co Ltd Preparation of polyimide-based film
US6790930B1 (en) * 1999-10-06 2004-09-14 Kaneka Corporation Process for producing polyimide resin
US20080300360A1 (en) * 2007-05-31 2008-12-04 The Boeing Company Water-entrained-polyimide chemical compositions for use in high-performance composite fabrication
KR20110110955A (en) * 2010-04-02 2011-10-10 부산대학교 산학협력단 Polyimide nanocomposites and method for making the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ITOY A. K. ET AL.: "High-Pressure Synthesis of Aliphatic Polyimides via Salt Monomers Composed of Aliphatic Diamines and Oxydiphthalic Acid", MACROMOLECULES, vol. 27, 1994, pages 4101 - 4105, XP000456651, DOI: doi:10.1021/ma00093a011 *

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