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WO2015190645A1 - Procédé de préparation de polyimide à l'aide d'eau comme milieu de dispersion et procédé pour récupérer l'eau - Google Patents

Procédé de préparation de polyimide à l'aide d'eau comme milieu de dispersion et procédé pour récupérer l'eau Download PDF

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Publication number
WO2015190645A1
WO2015190645A1 PCT/KR2014/007426 KR2014007426W WO2015190645A1 WO 2015190645 A1 WO2015190645 A1 WO 2015190645A1 KR 2014007426 W KR2014007426 W KR 2014007426W WO 2015190645 A1 WO2015190645 A1 WO 2015190645A1
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polyimide
water
reaction
producing
group
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Korean (ko)
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정찬문
유환철
이웅희
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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 KR1020140070392A external-priority patent/KR20150141839A/ko
Priority claimed from KR1020140101005A external-priority patent/KR20160017460A/ko
Application filed by Industry Academic Cooperation Foundation of Yonsei University filed Critical Industry Academic Cooperation Foundation of Yonsei University
Priority to CN201480079787.3A priority Critical patent/CN106459411B/zh
Publication of WO2015190645A1 publication Critical patent/WO2015190645A1/fr
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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
    • 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
    • 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
    • C08J5/18—Manufacture of films or sheets
    • 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, and more particularly, by using water as a dispersion medium, organic waste liquid does not occur, which is environmentally friendly, low in manufacturing cost, and minimizes residual solvent after drying. It relates to a method for producing polyamide used as a method and to recover water used as a dispersion medium.
  • High heat-resistant polymer materials are essential materials for miniaturization, high performance, and high reliability of products according to the development of advanced technology.
  • films In the form of film, molded products, textiles, paints, adhesives, and composites, aerospace, aviation, electricity / electronics, automobiles And a wide range of industrial fields such as precision instruments.
  • films have been mainly developed as electronic materials and packaging materials, and they are classified into general purpose engineering plastic films centered on polyester films, and are used as flexible circuit boards because of their high heat resistance, chemical resistance and electrical properties.
  • the polyimide in the material has excellent mechanical strength, chemical resistance, weather resistance and heat resistance based on the chemical stability of the imide ring. In addition, it is easy to synthesize, can make a thin film, and has the advantage that no crosslinking group for curing. In addition, due to its excellent electrical properties, it has been spotlighted as a high functional polymer material in the field of microelectronics and optics.
  • the use of the polyimide is used as a surface protection material such as a flexible circuit board or an integrated circuit, or as a base resin, to form an interlayer insulating film or a protective film of a semiconductor ultrafine circuit.
  • a surface protection material such as a flexible circuit board or an integrated circuit, or as a base resin
  • an interlayer insulating film or a protective film of a semiconductor ultrafine circuit In recent years, weight reduction and miniaturization of products have been important in the display field.
  • glass substrates that are currently used have a disadvantage of being heavy, broken and difficult to process continuously. For this reason, research is being conducted to utilize a polyimide substrate having a merit of being lightweight, flexible, and continuous process in place of a glass substrate for flexible display fabrication.
  • a polyamic acid precursor is first synthesized by the reaction of dianhydride and diamine, and the second step is to prepare a polyimide by imidizing the polyamic acid in the next step.
  • the first step is a step of preparing a polyamic acid.
  • Diane hydride is added to a reaction solution in which diamine is dissolved to form a polyamic acid by ring opening and polyaddition reaction.
  • the reaction solvent to be used is N, N - dimethylacetamide, N, N - a polar organic solvent such as dimethylformamide, N- methyl-2-pyrrolidone are mainly used.
  • the polyamic acid prepared in step 1 is imidized by dehydration and ring-closure reaction by chemical or thermal method to synthesize polyimide.
  • the chemical imidization method is a method in which a chemical dehydrating agent represented by acid anhydrides such as acetic anhydride and tertiary amines such as pyridine are added to a solution of polyamic acid as a precursor and heated at 160 ° C or higher.
  • the thermal imidization method is a method of thermally imidating by applying a solution of polyamic acid as a precursor to a substrate, evaporating the solvent and heating to 250 ⁇ 350 °C without chemical dehydrating agent and catalyst.
  • the second method uses a N-silylation reaction to increase the molecular weight of the polyimide by preventing the formation of amic acid and diamine salts, which is a disadvantage of the first method.
  • Diamine and chlorotrimethylsilane are reacted to synthesize diamine protected with N-trimethylsilyl group, and then polyimide is synthesized using the protected diamine via polyamic acid protected with N-trimethylsilyl group.
  • organic solvents are used for the synthesis of diamines protected with N-trimethylsilyl groups and for the synthesis of polyimides.
  • the disadvantage of the N-silylation method is that the chlorotrimethylsilane reagent for synthesizing N-trimethylsilyl group-protected aliphatic diamine is expensive and very sensitive to moisture, which makes it difficult to handle.
  • the disadvantage is that it becomes more complex than the first synthesis method.
  • the third method is to use meta-cresol as a solvent, add meta-cresol as a solvent, add dianhydride and diamine, and send the reaction for a long time by raising the temperature step by step.
  • the method using the meta-cresol has the disadvantage that the reaction time is longer than 64 hours and the reaction time is long and still has an unsatisfactory molecular weight and the drying time is long and the irritating smell is severe because of the use of the meta-cresol solvent.
  • the fourth method is an in-situ silylation method, and the second method, N-silylation method, is intended to solve the disadvantages sensitive to moisture.
  • Diamine was added to the reactor containing the organic solvent, followed by chlorotrimethylsilane at low temperature, followed by dianhydride to synthesize polyamic acid protected with N-trimethylsilyl group, followed by chemical imidization or thermal imidization reaction. Synthesize polyimide.
  • Disadvantages of the in-situ silylation synthesis method are long reaction times, improved molecular weight but high chlorotrimethylsilane reagents, high imidization catalysts, long drying times and protecting groups in polyamic acids protected with N-trimethylsilyl groups.
  • a reprecipitation process may be required, and even in the case of an all-aliphatic polyimide, sufficient transparency cannot be obtained.
  • a full aromatic polyimide synthesis method is disclosed in High Performance Polymers, 15: 269-279, 2003 and High Performance Polymers, 18: 31-44, 2006.
  • dianhydride is first added to water and heated at reflux to hydrolyze to synthesize tetracarboxylic acid.
  • Diamine is added to this solution to form a salt precipitate of tetracarboxylic acid and diamine.
  • the mixture of sediment and water is then transferred to the glassliner of the pressure device, followed by the operation of bleeding air and filling with nitrogen several times to make a nitrogen atmosphere. Nitrogen was added to the mixture to raise the pressure to 20 psi and then heated at 135 ° C.
  • the solvent used in the normal polyimide manufacturing process is often difficult to recycle because it is mixed with impurities even if it must be removed or recovered.
  • a patent related to a system for circulating distilled water but in this case, a filter part for filtering raw water, a filter part for adsorption filtration of filtered water, a sewage bucket for recovering sewage generated after the reaction, and a filter part for filtering the same.
  • a filter part for filtering raw water a filter part for adsorption filtration of filtered water
  • a sewage bucket for recovering sewage generated after the reaction
  • a filter part for filtering the same since it consists of a device of a very complicated structure such as a sterilizer to sterilize it, there is a disadvantage that is not economical in terms of cost.
  • Patent Documents Korean Patent 1,004,096, Korean Patent 449,798, Korean Patent 0717377, US Patent 7,053,168, International Patent Application 2012-091231 (WO2012 / 91231), International Patent Application PCT / JP2011 / 066144 ( WO 2012/008543), Korean Patent No. 826,294
  • Non-Patent Document Polymer Science and Technology Vol. 24, No. 1, pp. 3-9, Jin Young Park et al., Preparation and application of polyimide based particles; Macromolecules 2002, 35, 2277-2281 Yasufumi Watanabe, Yoshimasa Sakai, Yuji Shibasaki, Shinji Ando, and Mitsuru Ueda Synthesis of Wholly Alicyclic Polyimides from N-Silylated Alicyclic Diamines and Alicyclic Dianhydrides; Journal of photopolymer Science and Technology Volume 16, Number 2 (2003) Youshiyuki Oishi, Shu Ondera, Jan Oravec, Kunio Mori, Shinji Ando, Yoshiharu Terui, and kazuhiko Maeda Synthesis of Fluorine-Containing wholly Alicyclic Polyimide by In Situ Silylation Method; Macromolecules 2009, 42, 5892-5894 Dulce M.
  • Hodgkin Water as Solvent in Polyimide Synthesis Thermoset and Thermoplastic Examlpes; High Performance Polymers, 18: 31-44, 2006 John Chiefari, Buu Dao, Andrew M. Groth and Jonathan H. Hodgkin Water as Solvent in Polyimides Synthesis II: Processable Aromatic Polyimide
  • the present invention proposes a new production method using water as a dispersion medium in order to solve problems such as environmental pollution, an increase in manufacturing cost, residual solvent, and the like caused by using an organic solvent in a conventional method for producing polyimide.
  • the reaction temperature and time, the reaction reagents the synthesis step is reduced to propose a new manufacturing method which is very simple and reduced manufacturing costs.
  • the present invention is to provide a polyimide having a very high molecular weight and excellent mechanical properties compared to the polymer prepared by the conventional synthesis method having a high thermal properties.
  • the present invention is to provide a method for recovering the water used as a dispersion medium.
  • the present invention provides a method for preparing a polyimide by dispersing a dianhydride compound and a diamine compound in water and then reacting in a sealed pressure vessel under a temperature condition of 5 ° C. or higher and producing a polyimide.
  • a polyimide produced by the conventional synthesis method there is no problem of residual solvent and very high molecular weight. can do.
  • by easily recovering and recycling the water used in the reaction more economical manufacturing is possible and resources can be saved to reduce environmental pollution.
  • the present invention by using water as the reaction dispersion medium in the production of polyimide, there is an advantage that the organic waste solution does not occur, which is environmentally friendly, inexpensive to manufacture, and the residual solvent is minimized after drying so that there is no problem such as deterioration of physical properties due to the residual solvent.
  • the purchase cost of the water is reduced to reduce the polyimide manufacturing cost, thereby making it more economical and saving resources to reduce environmental pollution.
  • the present invention has the advantage that the reaction temperature is low, the reaction step is short and the reaction time is short compared to the conventional manufacturing method by applying a pressure in the production of polyimide, the prepared polyimide is a polyimide prepared by the conventional method Compared with the thermal stability, the molecular weight is large.
  • 1 is an FT-IR spectrum of a pyromellitic dianhydride and a 4,4'-oxydianiline polyimide according to Example 1;
  • 2 is an FT-IR spectrum of 1,2,4,5-cyclocyclotetracarboxylic dianhydride and 4,4′-oxydianiline polyimide according to Example 2;
  • 3 is an FT-IR spectrum of 1,2,4,5-cyclocyclotetracarboxylic dianhydride and 4,4-methylenebis (2-methylcyclohexylamine) polyimide according to Example 3;
  • 4 is an FT-IR spectrum of 5.9605 g of 1,2,4,5-cyclocyclotetracarboxylic dianhydride and 4,4-methylenebis (2-methylcyclohexylamine) polyimide according to Example 5;
  • 5 is an FT-IR spectrum of 1,2,3,4-cyclopentane-tetracarboxylic dianhydride and 3- (aminomethyl) -3,5,5-trimethyl
  • FIG. ; 6 is an FT-IR spectrum of 3- (aminomethyl) -3,5,5-trimethylcyclohexanamine and 3- (aminomethyl) -3,5,5-trimethylcyclohexaneamine polyimide according to Comparative Example 2.
  • FIG. ; 7 is an FT-IR spectrum of 3- (aminomethyl) -3,5,5-trimethylcyclohexanamine and 3- (aminomethyl) -3,5,5-trimethylcyclohexanamine polyimide according to Comparative Example 3.
  • the present invention is to prepare a polyimide by dispersing the dianhydride compound and the diamine compound in water and then placing the mixture in a pressure vessel and sealing the reaction under a pressure applied in the reaction temperature range of 5 °C to 400 °C It is a manufacturing method of a polyimide.
  • the present invention comprises the steps of: a) dispersing the dianhydride compound and the diamine compound in water; And b) sealing the dispersion in a pressure vessel, and reacting the dianhydride compound with the diamine compound at a temperature of 5 ° C. to 400 ° C. and pressurization conditions.
  • the present invention also provides a method for preparing a hydride compound comprising: a) dispersing a dianhydride compound and a diamine compound in water; b) after the dispersion is put in a pressure vessel and sealed, reacting the dianhydride compound and the diamine compound at a temperature of 5 °C to 400 °C and pressurized conditions; And (c) recovering water by cooling and condensing water vapor generated in step (b) from the pressure vessel after the completion of step (b).
  • steam may occur during step (b), and water may be recovered by cooling and condensing the steam, wherein the water may be distilled water.
  • the polyimide prepared according to the method may be a fully aromatic polyimide, a partially aliphatic polyimide or a fully aliphatic polyimide.
  • Dianehydride compounds that can be used in the present invention are substituted or unsubstituted aromatic or aliphatic dianhydride compounds.
  • a substituted or unsubstituted aromatic or aliphatic dianhydride represented by the following formula (1) may be used as the dianhydride.
  • the dianhydride compound may use one or two or more dianhydrides.
  • the diamine may be substituted or unsubstituted aromatic or aliphatic diamine.
  • the diamine may be a substituted or unsubstituted aromatic or aliphatic diamine represented by the following formula (2).
  • x may be an integer satisfying 1 ⁇ x ⁇ 50, preferably an integer satisfying 3 ⁇ x ⁇ 20.
  • 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 selected from an ester group, an amide group, an imide group, and an ether group.
  • the diamine compound may use one kind or two or more kinds of diamines.
  • water may be water in any state, such as distilled water, deionized water, tap water.
  • the reaction temperature preferably has a range of 5 °C to 400 °C. More specifically, it is 20 degreeC-250 degreeC. If the reaction temperature is less than 5 °C the reaction rate is too slow to make polyimide practically difficult, if the temperature exceeds 400 °C may cause thermal decomposition of the monomer or polymer.
  • the reaction time of step b) is preferably in the range of 5 minutes to 5 days. More specifically, the reaction may be performed for 10 minutes to 10 hours, even more specifically for 10 minutes to 5 hours. If the reaction time is less than 5 minutes, the reaction does not proceed well, if more than 5 days may cause hydrolysis of the polymer.
  • the pressing conditions of step b) is preferably in the range of 1 bar to 1000 bar. More specifically, it is 1 bar to 500 bar. If the reaction pressure is less than 1 bar, the reaction does not proceed well, and if it is more than 1000 bar may cause damage to the reaction vessel.
  • the method of pressurizing is composed of one or two or more methods selected from the method of forming water vapor pressure in the pressure vessel, injecting an inert gas into the pressure vessel, or compressing the pressure vessel. do.
  • the inert gas is at least one gas selected from the group consisting of nitrogen, argon, helium, neon, krypton and xenon.
  • the reaction product of step b) may further comprise the step of filtration and drying to obtain a polyimide.
  • a polyimide film prepared by dissolving a polyimide prepared according to the above method in an organic solvent and applying the solution to a substrate.
  • organic solvent N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide Seed, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, meta-cresol, gamma-butyrolactone, ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, butyl
  • solvents selected from the group consisting of carbitol acetate, ethylene glycol, ethyl lactate, butyl lactate, cyclohe
  • the concentration of polyimide in the solution may be from 1 to 90 wt%. If the solubility of the polyimide is low and it is difficult to prepare a polyimide solution, the polyamic acid is dissolved in an organic solvent and applied to a substrate, thereby producing a polyimide film by thermal imidization.
  • a small amount of an additive such as a wetting enhancer may be added if necessary for the polyimide or polyamic acid solution.
  • the additive is preferably added 0.001 to 5% by weight based on the polyimide or polyamic acid. More specifically, 0.01 to 2% by weight can be added.
  • a coating method of a polyimide or polyamic acid composition for forming a polyimide film spin coating method, dipping method, flexo printing method, inkjet printing method, spraying method, potting method, screen A printing method or the like can be used.
  • spin coating method as a method for obtaining a thick film of 10 ⁇ m or more, the bar coat coating method, the slit coating coating method, the screen printing method, the spin coating method and the like are preferable.
  • a molded article formed by compression molding, injection molding, slush molding, blow molding, extrusion molding or spinning method of the polyimide prepared according to the above method.
  • Polyimide synthesized by the manufacturing method of the present invention is a wide range of industries such as space, aviation, electrical / electronics, semiconductors, transparent / flexible displays, liquid crystal alignment film, automotive, precision equipment, packaging, medical materials, separators, fuel cells, secondary batteries It can be used in the field.
  • the water vapor was discharged from the pressure vessel and passed through the transfer tube and the cooler sequentially to cool and condense the steam to recover about 180 mL of distilled water.
  • Nuclear magnetic resonance analysis (NMR) of the recovered distilled water confirmed that no impurities were present.
  • the CN absorption band of the imide group was observed at 1369 cm ⁇ 1 .
  • Nuclear magnetic resonance analysis (NMR) of the recovered distilled water confirmed that no impurities were present.
  • the CN absorption band of the imide group was observed at 1365 cm ⁇ 1 .
  • Nuclear magnetic resonance analysis (NMR) of the recovered distilled water confirmed that no impurities were present.
  • the CN absorption band of the imide group was observed at 1364 cm ⁇ 1 .
  • Nuclear magnetic resonance analysis (NMR) of the recovered distilled water confirmed that no impurities were present.
  • the CN absorption band of the imide group was observed at 1364 cm -1 .
  • a cleaning process of a silicon wafer to be used as a substrate Prior to thin film fabrication, a cleaning process of a silicon wafer to be used as a substrate was performed. This process removes various contaminants such as particles, organic contaminants, metal contaminants and natural oxide films. Contaminants were removed by heating at 120 ° C. for 3 hours using a Piranha solution in which sulfuric acid and hydrogen peroxide were mixed at a ratio of 7: 3. Thereafter, 0.20 g of the synthesized polyimide was dissolved in 2.0 mL of N, N-dimethylacetamide or N, N-dimethylformamide, filtered through a microfilter having a pore size of 0.2 ⁇ m, and then washed at 500 rpm.
  • a polyimide thin film was prepared by annealing after removing the solvent after performing a two-stage spin coating of 10 seconds and 1500 rpm for 50 seconds.
  • a polyimide thin film was prepared by casting a polyimide solution on a substrate and removing the solvent and annealing.
  • a polyimide was obtained by heating the synthesized polyamic acid solution step by step in an oven or a hot plate at 250 to 300 ° C. and heating it for 12 hours.
  • the C O absorption band of the imide group at 1774 cm ⁇ 1 and 1713 cm ⁇ 1
  • the CN absorption band of the imide group at 1368 cm ⁇ 1 .
  • a polyimide was obtained by heating the synthesized polyamic acid solution step by step in an oven or a hot plate at 250 to 300 ° C. and heating it for 12 hours.
  • the CN absorption band of the imide group was observed at 1368 cm ⁇ 1 .
  • NMP N-methyl-2-pyrrolidone
  • a polyimide was obtained by heating the synthesized polyamic acid solution step by step in an oven or a hot plate at 250 to 300 ° C. and heating it for 12 hours.
  • the CN absorption band of the imide group was observed at 1367 cm ⁇ 1 .
  • the C O absorption band of the imide group was observed at 1773 cm -1 and 1712 cm -1 , and the CN absorption band of the imide group was observed at 1367 cm -1 .
  • Examples 1 to 3 of the present invention the maximum imidization temperature is lower, the reaction time is shorter, and the reaction step is less than that of Comparative Examples 1 to 4, which is a conventional method.
  • the reaction proceeds in water without using a catalyst and an organic solvent. It was confirmed that the polyimide synthesized in Examples 1 to 3 had a higher pyrolysis temperature and a very high molecular weight than the polyimide synthesized in Comparative Examples 1 to 4. In addition, as illustrated in Example 5, it was possible to recover and recycle the water used to prepare the polyimide.
  • the polyimide synthesis method of the present invention is simpler, less expensive to manufacture and environmentally friendly than the conventional method, and the polyimide synthesized by the method of the present invention has a very high molecular weight compared to the polyimide prepared by the conventional synthesis method. It can be seen that it has mechanical properties and high thermal properties.
  • Polyimide synthesized by the manufacturing method of the present invention is a wide range of industries such as space, aviation, electrical / electronics, semiconductors, transparent / flexible displays, liquid crystal alignment film, automotive, precision equipment, packaging, medical materials, separators, fuel cells, secondary batteries It can be used in the field.

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Abstract

La présente invention concerne un procédé de préparation d'un polyimide à l'aide d'eau en tant que milieu de dispersion pour la réaction, et plus particulièrement, un procédé consistant à préparer un polyimide par dispersion d'un composé dianhydride et d'un composé diamine dans de l'eau et à faire réagir les composés dans un état sous pression à l'intérieur d'un récipient sous pression fermé hermétiquement dans des conditions de température de 5°C ou plus. La présente invention concerne également un procédé pour récupérer l'eau, consistant à évacuer la vapeur générée pendant la préparation du polyamide et à refroidir et à condenser la vapeur. Grâce à l'utilisation d'eau comme milieu de dispersion, le procédé selon la présente invention ne génère pas de déchets fluides à base organique et est ainsi respectueux de l'environnement, réduit les coûts de production, réduit au minimum les solvants résiduels après séchage et, de ce fait, ne présente pas le problème de dégradation des propriétés physiques en raison des solvants résiduels, et est avantageux en ce que la température de réaction est inférieure, les étapes de réaction sont réduites et le temps de réaction est raccourci par rapport aux procédés classiques. Étant donné que l'eau peut être récupérée après la réaction, le procédé permet également de recycler l'eau et est par conséquent économique et très respectueux de l'environnement. En outre, le polyimide préparé par le procédé selon la présente invention présente l'avantage d'augmenter la stabilité thermique et le poids moléculaire par rapport à des polyimides préparés par des procédés de synthèse classiques.
PCT/KR2014/007426 2014-06-10 2014-08-11 Procédé de préparation de polyimide à l'aide d'eau comme milieu de dispersion et procédé pour récupérer l'eau Ceased WO2015190645A1 (fr)

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CN201480079787.3A CN106459411B (zh) 2014-06-10 2014-08-11 将水用作分散介质的聚酰亚胺的制备方法及水的回收方法

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KR1020140070392A KR20150141839A (ko) 2014-06-10 2014-06-10 물을 분산매로 사용한 폴리이미드의 제조방법
KR10-2014-0070392 2014-06-10
KR10-2014-0101005 2014-08-06
KR1020140101005A KR20160017460A (ko) 2014-08-06 2014-08-06 물을 분산매로 사용한 폴리이미드의 제조에 있어서, 물을 회수하는 방법

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2018080870A1 (fr) * 2016-10-25 2018-05-03 Fujifilm Electronic Materials U.S.A., Inc. Polyimides
WO2018085087A1 (fr) * 2016-11-01 2018-05-11 Fujifilm Electronic Materials U.S.A., Inc. Polyimides
CN112694614A (zh) * 2020-12-29 2021-04-23 浙江清和新材料科技有限公司 一种水相合成聚酰亚胺的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN111925524B (zh) * 2020-08-20 2021-05-28 吉林大学 一种柔性耐高温的聚酰亚胺前驱体凝胶及其制备方法和应用、一种聚酰亚胺柔性蜂窝结构
CN112625017B (zh) * 2020-12-01 2023-12-19 中国科学院长春应用化学研究所 一种酰胺二酐、其制备方法及应用
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
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