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WO2016032299A1 - Procédé de préparation de polyimide au moyen d'un sel monomère - Google Patents

Procédé de préparation de polyimide au moyen d'un sel monomère Download PDF

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Publication number
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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Prior art keywords
polyimide
monomer
prepare
group
dianhydride
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PCT/KR2015/009102
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English (en)
Korean (ko)
Inventor
정찬문
유환철
이재희
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Industry Academic Cooperation Foundation of Yonsei University
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Industry Academic Cooperation Foundation of Yonsei University
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Priority claimed from KR1020140114159A external-priority patent/KR101548877B1/ko
Priority claimed from KR1020140123904A external-priority patent/KR20160033009A/ko
Priority claimed from KR1020150050470A external-priority patent/KR101728830B1/ko
Priority claimed from KR1020150114105A external-priority patent/KR101755245B1/ko
Application filed by Industry Academic Cooperation Foundation of Yonsei University filed Critical Industry Academic Cooperation Foundation of Yonsei University
Publication of WO2016032299A1 publication Critical patent/WO2016032299A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular 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
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • 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.
  • 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.
  • PI polyimide
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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
  • a polyimide molded article for use in one or more applications selected from the group consisting of substrates.
  • 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.
  • Figure 9 shows the FT-IR spectrum of the monomer salt according to Example 2-1 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.
  • Figure 21 shows the FT-IR spectrum of the polyimide composite according to Examples 3-6 of the present invention.
  • Example 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.
  • 26 shows the FT-IR spectrum of the polyimide copolymer according to Example 4-5 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.
  • 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, excellent mechanical properties and higher thermal properties than the polyimide prepared according to the conventional method.
  • Polyimide manufacturing method 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.
  • a dianhydride monomer and a diamine monomer are added to water to prepare a monomer salt mixture (step a).
  • the dianhydride may be one or more dianhydrides, the dianhydride may be aromatic or aliphatic.
  • the dianhydride when used in two or more types, a polyimide in the form of a copolymer may be prepared.
  • the dianhydride may include a compound of Formula 1 below.
  • R 1 is the chemical structure of
  • the diamine may be one or more diamines, the diamine may be aromatic or aliphatic.
  • the diamine when used in two or more types, a polyimide in the form of a copolymer may be prepared.
  • the diamine may include a compound of Formula 2 below.
  • 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 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.
  • 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.
  • 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.
  • the monomer salt mixture of step a) 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.
  • 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.
  • the organic material may be at least one material selected from the group consisting of polyether ether ketone and polypropylene sulfide.
  • 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.
  • 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.
  • the dispersion material 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%.
  • 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.
  • the monomer salt mixture when preparing the monomer salt mixture, it may further include one or more additives selected from the group consisting of dispersants and thickeners.
  • the dispersant may be one or more dispersants selected from the group consisting of surfactants of cations, anions and nonions.
  • 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.
  • 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.
  • step a) may be carried out in the temperature range of 5 to 55 °C °C, in detail may be carried out in the temperature range of 10 to 35 °C. 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.
  • 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.
  • the monomer salt mixture is filtered and dried, or water is evaporated to recover the monomer salts of dianhydride and diamine (step b).
  • 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.
  • filtering the mixture may yield a solid, and the obtained solid may be dried to prepare a salt.
  • a salt may be further obtained by evaporating the filtrate obtained in the said filtration process.
  • salts may be prepared by evaporating the water in the mixture.
  • the water vapor generated by the evaporation may be cooled and condensed to recover the water and reuse.
  • 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.
  • 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.
  • 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.
  • natural evaporation membrane evaporation
  • thermal evaporation pervaporation
  • vacuum evaporation vacuum evaporation
  • co-vacuum evaporation co-vacuum evaporation
  • rotary concentrated evaporation method can be.
  • the drying or evaporation may be performed under conditions of 1 atm or less.
  • the drying or evaporation may be carried out in a temperature range of -60 to 200 °C.
  • the drying or evaporation is carried out at a temperature of less than -60 °C 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 °C.
  • step c when the monomer salt obtained through the above process is heated, imidization proceeds to prepare a polyimide (step c).
  • step c) may be carried out in a temperature range of 150 to 450 °C. 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 °C imidization may not proceed, when carried out at a temperature of more than 450 °C may cause thermal decomposition of the monomer or polymer itself.
  • 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.
  • 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.
  • 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.
  • the reaction pressure is more than 1000 bar, damage to the reaction vessel may be caused.
  • step c) may be performed in an atmosphere or inert gas atmosphere.
  • 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.
  • step c) 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m
  • 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 ⁇ m
  • Roll crushers, edge runners, hammer crushers and disc crushers can be used as heavy mills
  • ball mills, jet mills, port mills, turbo mills, supermicron mills, roller mills, raymond mills and tube mills can be used as grinding mills.
  • the grinding process may be performed by a grinder.
  • the powder particle size included in the composition through the grinding process may have a range of 100nm to 10mm.
  • 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 ⁇ m.
  • 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.
  • the grinding process is also the same as described above.
  • the molding proceeds simultaneously with the imidization, thereby producing a polyimide molded article.
  • 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.
  • 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.
  • 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.
  • the monomer salt was heated at 350 ° C. for 6 hours using an electric furnace to synthesize a wholly aromatic polyimide.
  • 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).
  • the monomer salt was heated at 350 ° C. for 6 hours using an electric furnace to synthesize a partial aliphatic polyimide.
  • the monomer salt was heated at 300 ° C. for 8 hours using an electric furnace to synthesize a partial aliphatic polyimide.
  • 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).
  • the monomer salt was heated at 300 ° C. for 8 hours using an electric furnace to synthesize all aliphatic polyimide.
  • the C O absorption band, already CN absorption band at 1374cm -1 for deugi observed at 1 and 1714cm -1 (Fig. 4).
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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.
  • 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).
  • 1,2,4,5-cyclohexanetetracarboxylic dianhydride 11.208g
  • hexamethylene diamine 5.810g
  • graphene oxide mixture 5.00g
  • the monomer salt composition was prepared by dispersing at 25 ° C. for 24 hours with a stirrer.
  • 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)
  • 1,2,3,4-cyclobutanetetracarboxylic dianhydride 9.805g
  • 4,4'-methylenebis (2-methylcyclohexylamine) 11.920g
  • mica mica
  • the monomer salt composition was prepared by dispersing with a stirrer at 25 ° C. for 24 hours.
  • 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.
  • 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 ⁇ ⁇ for 24 hours.
  • 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.
  • 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 °C for 18 hours to synthesize a 10wt% polyamic acid solution.
  • 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.
  • 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.
  • 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.
  • 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 °C 18 hours to synthesize a 10wt% polyamic acid solution.
  • 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).
  • 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.
  • 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).
  • 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 °C having a high molecular weight.
  • Comparative Example 1-1 and Comparative Example 1-2 the prepared monomer salt was heat-treated at a temperature of less than 160 °C, or less than 5 minutes, it was confirmed that the polyimide can not be obtained by the above method. .
  • 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.
  • 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.
  • 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.
  • 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.
  • the fine powder composition was heated at 200 ° C. for 6 hours using a heater to prepare a wholly aromatic polyimide composite.
  • the fine powder composition was heated at 200 ° C. for 6 hours using a heater to prepare a wholly aromatic polyimide composite.
  • the fine powder composition was heated at 200 ° C. for 6 hours using a heater to prepare a aliphatic polyimide composite.
  • the fine powder composition was heated at 200 ° C. for 6 hours using a heater to prepare a aliphatic polyimide composite.
  • the fine powder composition was heated at 200 ° C. for 6 hours at atmospheric pressure using a heater to prepare an aliphatic polyimide composite.
  • the fine powder composition was heated at 200 ° C. for 6 hours at atmospheric pressure using a heater to prepare an aliphatic polyimide composite.
  • the fine powder composition was heated at 200 ° C. for 6 hours using a heater to prepare a wholly 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the fine powder composition was heated at 200 ° C. for 6 hours using a heater to prepare a wholly 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.
  • the fine powder composition was heated at 200 ° C. for 6 hours using a heater to prepare a wholly aromatic 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.
  • the fine powder composition was heated at 200 ° C. for 6 hours at atmospheric pressure using a heater to prepare an 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.
  • the fine powder composition was heated at 200 ° C. for 6 hours at atmospheric pressure using a heater to prepare an aliphatic polyimide composite.
  • 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.
  • 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.
  • the polyimide and the dispersion were separated from each other, and the mechanical and thermal properties were greatly reduced.
  • the fine powder was heated at 200 ° C. for 6 hours using a heater to prepare a wholly aromatic and partially aliphatic polyimide copolymer.
  • the fine powder was heated at 200 ° C. for 6 hours using a heater to prepare the wholly aromatic and all-aliphatic polyimide copolymer.
  • monomer salt A 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.
  • the fine powder was heated at 200 ° C. for 6 hours using a heater to prepare the wholly aromatic and all-aliphatic polyimide copolymer.
  • the fine powder was heated at 200 ° C. for 6 hours using a heater to prepare a wholly aromatic and partially aliphatic polyimide copolymer.
  • the fine powder was heated at 200 ° C. for 6 hours using a heater to prepare the wholly aromatic and all-aliphatic polyimide copolymer.
  • monomer salt A 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.
  • the fine powder was heated at 200 ° C. for 6 hours using a heater to prepare the wholly aromatic and all-aliphatic polyimide copolymer.
  • monomer salt A 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the fine powder was heated at 200 ° C. for 6 hours using a heater to prepare the wholly aromatic and all-aliphatic 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, 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.
  • 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.
  • the fine powder was heated at 200 ° C. for 6 hours using a heater to prepare the wholly aromatic and all-aliphatic polyimide copolymer.
  • 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.
  • 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.

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Abstract

L'invention concerne un procédé de préparation de polyimide, ainsi qu'un polyimide ainsi obtenu, le procédé consistant : a) à préparer un mélange de sels monomères par le placement dans de l'eau d'un monomère dianhydride et d'un monomère diamine ; b) à récupérer un sel monomère par filtration et séchage du mélange de sels monomères ou par évaporation de l'eau ; et c) à préparer un polyimide par chauffage du sel monomère. Selon l'invention, la préparation d'un polyimide, d'un copolymère de polyimide ou d'un composite de polyimide est réalisée dans des conditions modérées, le procédé de préparation est simple et économique et il est respectueux de l'environnement car il n'utilise pas de solvants organiques, et le polyimide présente un poids moléculaire élevé, d'excellentes propriétés mécaniques et des caractéristiques thermiques élevées par rapport à un polyimide obtenu par la mise en oeuvre d'un procédé classique.
PCT/KR2015/009102 2014-08-29 2015-08-29 Procédé de préparation de polyimide au moyen d'un sel monomère Ceased WO2016032299A1 (fr)

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KR1020140114159A KR101548877B1 (ko) 2014-08-29 2014-08-29 단량체의 염을 거쳐 제조되는 폴리이미드 및 그 제조방법
KR10-2014-0123904 2014-09-17
KR1020140123904A KR20160033009A (ko) 2014-09-17 2014-09-17 단량체의 염을 사용한 폴리이미드 성형품 제조방법
KR1020150050470A KR101728830B1 (ko) 2015-04-09 2015-04-09 단량체를 이용한 폴리이미드 복합체 제조방법
KR10-2015-0050470 2015-04-09
KR10-2015-0114105 2015-08-12
KR1020150114105A KR101755245B1 (ko) 2015-08-12 2015-08-12 단량체 염을 이용한 폴리이미드 복합체 제조방법

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AT519038A1 (de) * 2016-08-19 2018-03-15 Univ Wien Tech Herstellungsverfahren für Polyimide
CN109912618A (zh) * 2019-03-20 2019-06-21 浙江福斯特新材料研究院有限公司 一种多官能度有机酸酐及低介电常数超支化聚酰亚胺薄膜
WO2019156717A3 (fr) * 2017-10-05 2019-10-24 Zymergen Inc. Polyimides optiquement transparents
DE102020104587A1 (de) * 2019-02-22 2020-08-27 Dupont Electronics, Inc. Polyimidfilme und elektronische vorrichtungen
CN112090169A (zh) * 2020-08-12 2020-12-18 柳州紫荆技术转移中心有限公司 一种用于污水处理的高效集成净水设备石墨烯复合过滤材料制备方法
CN112194792A (zh) * 2020-06-16 2021-01-08 中国科学院长春应用化学研究所 一种高强度低热膨胀透明聚酰亚胺及其制备方法
CN112759763A (zh) * 2021-01-20 2021-05-07 株洲时代新材料科技股份有限公司 聚酰亚胺复合胶液、黑色哑光聚酰亚胺材料及制备和应用
WO2021258120A2 (fr) 2020-06-23 2021-12-30 Technische Universität Wien Procédé de production de polyimides
US11294281B2 (en) 2019-06-28 2022-04-05 Hutchinson Technology Incorporated Chain extenders and formulations thereof for improving elongation in photosensitive polyimide
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AT519038A1 (de) * 2016-08-19 2018-03-15 Univ Wien Tech Herstellungsverfahren für Polyimide
AT519038B1 (de) * 2016-08-19 2018-11-15 Univ Wien Tech Herstellungsverfahren für Polyimide
US12441841B2 (en) 2017-10-05 2025-10-14 Akron Polymer Systems, Inc. Optically transparent polyimides
WO2019156717A3 (fr) * 2017-10-05 2019-10-24 Zymergen Inc. Polyimides optiquement transparents
US11359061B2 (en) 2019-02-22 2022-06-14 Dupont Electronics, Inc. Polyimide films and electronic devices
US11643515B2 (en) 2019-02-22 2023-05-09 Dupont Electronics, Inc. Polyimide compositions and polyimide solutions
DE102020104587B4 (de) 2019-02-22 2024-10-31 Dupont Electronics, Inc. Polyimidfilme und elektronische vorrichtungen
DE102020104587A1 (de) * 2019-02-22 2020-08-27 Dupont Electronics, Inc. Polyimidfilme und elektronische vorrichtungen
CN109912618A (zh) * 2019-03-20 2019-06-21 浙江福斯特新材料研究院有限公司 一种多官能度有机酸酐及低介电常数超支化聚酰亚胺薄膜
US12386258B2 (en) 2019-06-28 2025-08-12 Hutchinson Technology Incorporated Chain extenders and formulations thereof for improving elongation in photosensitive polyimide
US11294281B2 (en) 2019-06-28 2022-04-05 Hutchinson Technology Incorporated Chain extenders and formulations thereof for improving elongation in photosensitive polyimide
CN112194792A (zh) * 2020-06-16 2021-01-08 中国科学院长春应用化学研究所 一种高强度低热膨胀透明聚酰亚胺及其制备方法
CN112194792B (zh) * 2020-06-16 2022-03-29 中国科学院长春应用化学研究所 一种高强度低热膨胀透明聚酰亚胺及其制备方法
WO2021258120A2 (fr) 2020-06-23 2021-12-30 Technische Universität Wien Procédé de production de polyimides
CN112090169A (zh) * 2020-08-12 2020-12-18 柳州紫荆技术转移中心有限公司 一种用于污水处理的高效集成净水设备石墨烯复合过滤材料制备方法
CN112759763B (zh) * 2021-01-20 2022-05-17 株洲时代新材料科技股份有限公司 聚酰亚胺复合胶液、黑色哑光聚酰亚胺材料及制备和应用
CN112759763A (zh) * 2021-01-20 2021-05-07 株洲时代新材料科技股份有限公司 聚酰亚胺复合胶液、黑色哑光聚酰亚胺材料及制备和应用
WO2023056263A1 (fr) * 2021-10-01 2023-04-06 Zymergen Inc. Polyimides à base de cadavérine

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