• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    The invention relates to a process for the preparation of polyimides by polycondensation of previously prepared stoichiometric salts of polycarboxylic acids or their polyanhydrides and polyamines by heating the salts for dehydration, which is characterized in that a) an aqueous solution of a water-soluble stoichiometric salt of polycarboxylic acid and polyamine is prepared ; b) coating a substrate with the aqueous solution to obtain a coating; and c) the salt contained in the coating is polycondensed by heating.
    公开号:AT519038A1
    申请号:T383/2016
    申请日:2016-08-19
    公开日:2018-03-15
    发明作者:Margarethe Dr Unterlass Miriam；Espana-Orozco Sebastian
    申请人:Univ Wien Tech；
    IPC主号:
    专利说明:

    The present invention relates to a novel production process for polyimides. STATE OF THE ART
    Polyimides are valuable materials for various applications. Their synthesis is usually carried out by polycondensation of diamines with dianhydrides in solution, in the melt or even in a solid state. Surprisingly, it was found several years ago that - despite the elimination of water during the condensation reaction - even water can be used as a solvent for the polyimide synthesis, when so-called "hydrothermal conditions" prevail, to understand a reaction under pressure at temperatures above 100 ° C. (See Hodgkin et al., "Water as a Polymerization Solvent-cyclization of Polyimides: Le Chatelier Confounded", Polym. Prep. (American Chemical Society, Division of Polymer Chemistry) 41, 208 (2000), and WO 99/06470). , When solvents other than water are used, the term "solvothermal conditions" is used at temperatures above their boiling points.
    The mechanism of this condensation reaction proceeds in two stages through the formation of amic acids, which subsequently undergo cyclodehydration to the corresponding imides. Dao et al. In 1999, factors significantly influencing the imidization reaction were investigated (Dao, Hodgkin and Morton, "Important Factors Controlling Synthesis of Imides in Water", High Perform Polym. 11, 205-218 (1999), "Dao 1999") and under Others noted that the higher the temperature of the imidization reaction, the more pure the products.
    The reason why the reaction equilibrium of this dehydration-proceeding cyclization, even in water, as a solvent on the product side, is the changed properties of the solvent under solvothermal conditions. For example, water behaves like a pseudo-organic solvent under these conditions (Hodgkin et al., Supra).
    Furthermore, it is customary to form a stoichiometric salt of diamide and dianhydride before polymerization, which is usually achieved by simply mixing the monomers in
    Water and filtering off the water-insoluble and therefore precipitated salts takes place, as described very recently in WO 2016/032299 A1. The anhydrides undergo hydrolysis to give the free tetracarboxylic acids, of which two carboxyl groups each having one amino group form an ammonium salt (Unterlass et al., "Mechanistic study of hydrothermal synthesis of aromatic polyimides", Polym. Chem. 2011, 2, 1744). In the resulting monomer salts, which are sometimes referred to as "AH salts" (in analogy to polyamide and in particular nylon synthesis), the two monomers are thus present exactly in the molar ratio 1: 1, which is why their subsequent polymerization to very pure polyimides The following is an example of the reaction scheme of two typical aromatic monomers:
    Another modern technology that has been used for several years to synthesize organic compounds and, more recently, polyimides is microwave radiation, which significantly reduces reaction times and increases the selectivity of reactions (Lindstrom et al., "Microwave Assisted Organic Synthesis: a Review ", Tetrahedron 57, 9225-9283 (2001); Perreux et al.," A Tentative Rationalization of Microwave Effects in Organic Synthesis According to the Reaction Medium and Mechanistic Considerations ", Tetrahedron 57, 9199-9223 (2001)). Microwaves have also been used for the synthesis of polyimides (Lewis et al., Accelerated Imidization Reactions using Microwave Radiation, J. Polym., Part A: Polym. Chem. 30, 1647-1653 (1992) and US 5,453. 161).
    A combination of the hydrothermal process described above and heating by means of microwave radiation is also known. On the one hand, Dao et al. (Dao, Groth and Hodgkin, "Microwave-assisted Aqueous Polyimidization Using High-throughput Techniques", Macromol., Rapid Commun., 28, 604-607 (2007); "Dao, 2007") using a ternary monomer mixture of a diamine (4 , 4'-oxydi-aniline, ODA) and two dianhydrides (4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, 6-FDA, pyromellitic dianhydride, PMDA) at temperatures between 120 ° C and 200 ° C found that the best results be achieved at 180-200 ° C, if the goal is the highest possible molecular weight of the thereby obtained random (block) copolymers of the following formula:
    And on the other hand, only a few years ago Brunei et al. (Brunei, Marestin, Martin and Mercier, "Water-Bome Polyimides via Microwave Assisted Polymerization", High Perform, Polym. 22, 82-94 (2010)) using a binary polyimide of ODA and 4,4 '- (4, 4'-isopropylidenediphenoxy) bis (phthalic anhydride) (bisphenol A dianhydride, BPADA)
    once again confirms that microwave use significantly reduces the reaction times, i. can be shortened from 4 to 12 h to only 5 to 10 min. The sales generated in this short time, however, are extremely low at only about 20%. In both cases, however, no crystalline products could be developed.
    US 2008/300360 A1 discloses an alternative process using water as a solvent to prepare waterborne coating solutions.
    However, it is not assumed that AH salts, but it is first from previously dehydrated polyamines and polyanhydrides in the presence of a defined proportion of e.g. From 5 to 60 mole percent of monoanhydrides as terminators prepolymers, i. low molecular weight oligomers prepared from which, as a result, suspensions or, after grinding them to obtain smaller particle sizes, colloidal solutions are formed in water which can be used to coat surfaces. In order to prepare stable suspensions and colloidal solutions, it is also preferable to add suspension stabilizers to the prepolymers obtained, which are characterized as being insoluble in water. These aqueous systems are made into coatings, particularly laminates, by application to a surface, evaporation of the water, and heating to initiate polycondensation of the prepolymers into molecular weight molecular weight of at least 10,000.
    With respect to solvothermal synthesis of polyimides, the present inventors have recently found that under hydrothermal conditions, crystalline polyimides may well be obtained when either the solvent is heated to solvothermal conditions and only then the monomers are added to initiate the reaction or the monomers are mixed with the solvent and the mixture is heated to solvothermal conditions within 5 minutes, during which the reaction temperature is kept solid under the polymerization temperature of the monomers (B. Baumgartner, MJ Bojdys, P. Skrinjar and MM Unterlass, "Design Strategies in Hydrothermal Polymerization of Polyimides", Macromol Chem. Phys., 217, 485-500 (2016)].
    Despite these advantageous recent developments, the high expenditure on apparatus and energy for producing hydrothermal conditions in order to be able to use water as solvent for the polycondensation reaction continues to represent a considerable disadvantage. Against this background, the object of the present invention was to provide a process that this disadvantage can be overcome.
    DISCLOSURE OF THE INVENTION
    The present invention solves this problem by providing a process for the preparation of polyimides by polycondensation of previously prepared stoichiometric salts of polycarboxylic acids or their polyanhydrides and polyamines by heating the salts for dehydration, which is characterized in that a) an aqueous solution of a water-soluble stoichiometric salt made of polycarboxylic acid and polyamine; b) coating a substrate with the aqueous solution to obtain a coating; and c) the salt contained in the coating is polycondensed by heating.
    This invention is based on the inventors' most surprising discovery that some polycarboxylic acid-polyamide monomer salts-in contrast to all other known such salts-are water soluble and therefore do not precipitate upon mixing of the monomers from an aqueous solution. Because of this unique property, it is possible to apply such an aqueous solution of the monomer salts to a support or a substrate, and subject the resulting film to polycondensation by heating.
    In preferred embodiments of the invention, the coating obtained in step b) is dried prior to the polycondensation in step c), whereby a film or a solid film formed on the substrate, which is easier to handle than the wet coating.
    The water-soluble stoichiometric salt is preferably prepared in step a) by mixing stoichiometric amounts of polycarboxylic acid or its polyanhydride and polyamine in water or in an aqueous solvent mixture.
    Furthermore, the water-soluble stoichiometric salt is preferably precipitated by the addition of at least one organic solvent for intermediate storage before the polycondensation. The organic solvent used therefor is not particularly limited so long as it sufficiently lowers the solubility of the stoichiometric salt in the formed aqueous solvent mixture to cause precipitation thereof, provided that it is itself a nonsolvent for the stoichiometric salt. Both water-miscible and water-immiscible solvents can be used for this purpose, for example alcohols, e.g. such as methanol or other lower alcohols, ethers, e.g. THF, acetone, etc.
    In preferred embodiments of the present invention, in step b), a film is drawn from the aqueous solution of the water-soluble stoichiometric salt on a substrate so as to optionally form a composite material after subsequent polycondensation of the salt to the corresponding polyimide or, after stripping the cured polyimide film from the substrate. to obtain a polyimide film.
    Preferably, according to the present invention, a water-soluble stoichiometric salt is made from a tetracarboxylic acid and a diamine and polycondensed since these are the most common starting materials in polyimide production. However, of course, combinations of other polyhydric amines and / or polycarboxylic acids or their anhydrides are also possible, e.g. the preparation of stoichiometric salts of triamine and dianhydride, diamine and trianhydride, triamine and trianhydride, etc. as long as these monomers form water-soluble salts in the corresponding stoichiometric composition.
    The tetracarboxylic acid is particularly preferably selected from benzophenone tetracarboxylic acid, tetrahydrofurantetracarboxylic acid, butane tetracarboxylic acid and their dianhydrides, since the inventors have already found water-soluble stoichiometric salts of these polycarboxylic acids. For the same reason, the diamine is preferably selected from benzenedimethanamine and ethylenediamine. In particular, the stoichiometric salts are selected from 1 .S-benzene dimethanolammonium dihydrogen S.SAA benzophenone tetracarboxylate (1), 1,3-benzene dimethy ammonium dihydrogen 1,2,3,4-butanetetracarboxylate (2), 1,3-benzene dimethy ammonium dihydrogen tetrahydrofuran · 2,3,4,5-tetracarboxylate (3), ethane-1,2-diammonium dihydrogen-3,3,4,4-benzophenone tetracarboxylate (4), Ethane-1,2-diammonium dihydrogen-tetrahydrofuran-2,3,4,5-tetra-carboxylate (5) and their hydrates selected, with which excellent results have already been achieved in the inventive method, the hydrates easier to produce in crystalline form are as the anhydrous ammonium salts.
    Since these salts are all new, i. have been synthesized and characterized for the first time by the inventors, which at the same time is the reason why their solubility in water has not yet been discovered, the present invention also provides, in a second aspect, these specific compounds, namely: 1,3-benzenedimethanammonium dihydrogen-3 , 3 ', 4,4'-benzophenone tetracarboxylate (1):
    (1) 1,3-benzenedimethanammonium dihydrogen-1,2,3,4-butanetetracarboxylate (2):
    (2) 1,3-benzenedimethanammonium dihydrogen tetrahydrofuran-2,3,4,5-tetracarboxylate (3):
    (3)
    Ethane-1-diammonium dihydrogen S.S'A.sup.-benzophenone tetracarboxylate (4):
    (4)
    Ethane-1,2-diammonium dihydrogen tetrahydrofuran-2,3,4,5-tetracarboxylate (5):
    (5)
    Furthermore, the present invention also provides two novel polyimides synthesized and characterized for the first time by the inventors - from the corresponding water-soluble stoichiometric salts (3) and (5), namely: poly (N, N'-benzene-IS dimethylene, tetrahydrofuran). tetracarboxylic diimide) (6):
    (6) and
    Poly (N, N '- (1,2-ethylene) tetrahydrofuran-2,3,4,5-tetracarboxylic acid diimide) (7):
    (7)
    BRIEF DESCRIPTION OF THE DRAWINGS
    The present invention will now be further described, by way of non-limitative example, with reference to the accompanying drawings, in which:
    Figs. 1 to 5 show IR spectra of the water-soluble stoichiometric monomer salts obtained in Examples 1, 4, 6, 7 and 8.
    Figs. 6 and 7 show IR spectra of the polyimides obtained in Examples 12 and 13.
    EXAMPLES
    All reagents used in the experiments below are commercially available and used without further purification. The IR spectra shown in the accompanying drawings were recorded by FT-IR ATR spectroscopy on a Bruker Tensor 27 and 1 H NMR spectra on an Avance 250, also Bruker, at 250 MHz. By "Tp" below is meant the solid state polymerization temperature of the obtained stoichiometric salts.
    example 1
    Preparation of 1-S-benzenedimethyne-ammonium-dihydrogen-S. SAA-benzophenone-tetracarboxylate (1)
    (1) 150 mg (0.47 mmol) of S.SAA benzophenone tetracarboxylic dianhydride were dissolved in 10 ml of dist. Water, and 61.4 μl (0.47 mmol) of 1,3-benzenedimethanamine was added to form a clear, yellowish solution. After stirring for 30 minutes, the water was removed on a rotary evaporator in a water bath (50 ° C) in a vacuum of about 60 mbar and the residue dried under high vacuum. The title compound was quantitatively obtained as a colorless amorphous solid whose IR spectrum is shown in FIG. The solid is highly hygroscopic and gradually deliquesces in the air to a yellow liquid phase of the tetrahydrate.
    Tp .: 151 ° C (DSC) and 161 ° C (T6A) (heating rate: 10 K / min) 1 H-NMR (250 MHz, DMSO-de) δ: 8.51 (d, 2H, ar), 8 , 32 (d, 2H, ar), 7.85 (q, 2H, ar), 7.45 (m, 4H, ar), 4.01 (s, 4H, aliph). IR (cm-1): 2882, 2619, 1694, 1601, 1540, 1359.
    Example 2
    Precipitation of the tetrahydrate of (1) by addition of solvent
    The batch of Example 1 was repeated, to which 30 ml of THF were added to the resulting aqueous solution of (1) (here: in 5 ml of distilled water), a precipitate forming in the form of a white turbidity. The mixture was allowed to stand overnight, with the initial precipitate forming a yellow colored second liquid phase, which crystallized after a further 24 hours of rest to colorless crystals.
    The data correlated with those of Example 1, except for the presence of water.
    Example 3
    Preparation of (1) as an aqueous solution and coating of a surface
    Example 1 was repeated, using instead of the isolation of the stoichiometric salt (1) by evaporation of the water, the aqueous solution for coating a glass plate. For this purpose, a few drops of the solution were dropped on a glass plate and allowed to air dry. Subsequently, the polycondensation to poly (N, N '- (benzene-1,3-dimethylene) benzophenone-3,3', 4,4'-tetra-carbodiimide) was carried out in a vacuum oven maintained at 200 ° C overnight. The IR spectrum of the polyimide thus obtained corresponded to that of the product known from the literature.
    Example 4
    Preparation of 1,3-benzenedimethanammonium dihydrogen-1,2,3,4-butanetetra-carboxylate (2):
    (2) 150 mg (0.64 mmol) of 1,2,3,4-butanetetracarboxylic acid were dissolved in 10 ml of dist. Water was dissolved, and 84.5 μΙ (0.64 mmol) of 1,3-benzenedimethanamine were added all at once, after which the reaction mixture was shaken until a clear solution had formed. Work-up and drying were carried out analogously to Example 1, the title compound being obtained in quantitative yield as a hydroscopic, colorless, amorphous solid whose IR spectrum is shown in FIG.
    Tp .: 151 ° C (TGA) 1 H NMR (250 MHz, D 2 O): 7.5 (m, 4H, ar), 4.2 (s, 4H, aliph), 2.9 (m, 2H, aliph), 2,6 (m, 2H, aliph), 2,4 (m, 2H, aliph). IR (cnr1): 3386, 2918, 2626, 1701, 1620, 1542.
    Example 5
    Precipitation of the tetrahydrate of (2) by solvent addition
    The batch of Example 4 was repeated, to which 30 ml of THF were added to the resulting aqueous solution of (2) (here: in 5 ml of distilled water), a precipitate forming in the form of a white turbidity. The mixture was allowed to stand overnight, with the initial precipitate forming a yellow colored second liquid phase, which crystallized after a further 24 hours of rest to colorless crystals.
    • WWW
    The data correlated with those of Example 4, except for the presence of water.
    Example 6
    Preparation of 1,3-benzenedimethanammonium dihydrogen tetrahydrofuran-2,3,4,5-tetracarboxylate (3):
    (3) 150 mg (0.60 mmol) of tetrahydrofuran-2,3,4,5-tetracarboxylic acid were dissolved in 10 ml of dist. Water was dissolved and 79.8 pl (0.60 mmol) of 1,3-benzenedimethanamine was added in one portion, after which the reaction mixture was shaken until a clear solution had formed. Work-up and drying were carried out analogously to Example 1, giving a hydroscopic, colorless, amorphous solid in quantitative yield, the IR spectrum of which is shown in FIG.
    Mp .: 62 ° C (DSC)
    Tp .: 144 ° C (DSC) and 151 ° C (TGA) (heating rate: 10 K / min) 1H-NMR (250 MHz, DMSO-de) δ: 7.5 (s, 1H, ar), 7 , 4 (m, 3H, ar), 4.4 (m, 2H, aliph), 4.0 (s, 4H, aliph), 3.0 (m, 2H, aliph). IR (cm1): 3393, 3052, 2929, 1714, 1600, 1568. ········· · · · ·
    Example 7
    Preparation of ethane-1,2-diammonium dihydrogen-3,3,4,4,4-benzophenone tetracarboxylate (4):
    (4) 150 mg (0.47 mmol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride were dissolved in 10 ml of dist. Dissolved water and 31.1 pl (0.47 mmol) of 1,2-ethylenediamine were added all at once, after which the reaction mixture was shaken until a clear solution had formed. Work-up and drying were carried out analogously to Example 1, giving a hydroscopic, colorless, amorphous solid in quantitative yield, the IR spectrum of which is shown in FIG. 4.
    Tp .: 128 ° C (DSC) and 149 ° C (TGA) (heating rate: 10 K / min) 1 H-NMR (250 MHz, D 2 O) δ: 8.1 (d, 2H, ar), 7.9 (q, 2H, ar), 7.7 (d, 2H, ar), 3.4 (s, 4H, aliph). IR (cm x 1): 3386, 3030, 2929, 1699, 1602, 1541.
    Example 8
    Preparation of ethane-1,2-diammonium dihydrogen tetrahydrofuran-2,3,4,5-tetra-carboxylate (5):
    (5) ············· · 150 mg (0.60 mmol) of tetrahydrofuran-2,3,4,5-tetracarboxylic acid were dissolved in 10 ml of dist. Water was dissolved and 40.4 μΙ (0.60 mmol) of 1,2-ethylenediamine were added in one portion, after which the reaction mixture was shaken until a clear solution had formed. Work-up and drying were carried out analogously to Example 1, giving a hydroscopic, colorless, amorphous solid whose IR spectrum is shown in FIG. 5.
    Tp .: 128 ° C (DSC) and 149 ° C (TGA) (heating rate: 10 K / min) 1 H-NMR (250 MHz, D 2 O) δ: 4.8 (m, 2H, aliph), 3.5 (m, 2H, aliph), 3,4 (s, 4H, aliph). IR (cnr1): 3400, 3031, 2926, 1713, 1600, 1561.
    Examples 9 to 13
    Coating and polycondensation
    The batches of Examples 1, 4, 6, 7 and 8 were repeated, using the aqueous solutions for coating glass plates, similar to Example 3, instead of isolating the stoichiometric salts. For this purpose, 5 to 10 ml of the respective aqueous solution were applied to a glass plate, which was then heated in an oven at a heating rate of 5 K / min to 250 ° C and then maintained at this temperature for 30 min.
    The polyimides thus obtained were three products known from the literature, namely in Example 9 (with the stoichiometric salt obtained analogously to Example 1): poly (N, N '- (benzene-1,3-dimethylene) benzophenone-3,3', 4, 4'-tetracarboxylic diimide); in Example 10 (with the stoichiometric salt obtained analogously to Example 4): poly (N, N '- (benzene-1,3-dimethylene) butane-1,2,3,4-tetracarboxylic diimide); and in Example 11 (with the stoichiometric salt obtained analogously to Example 7): PolyiN.N'-il.Z-ethylene-benzophenone-S.S '^^' - tetracarboxylic diimide); and two previously unknown polyimides, namely: in Example 12 (with the stoichiometric salt obtained analogously to Example 6): poly (N, N '- (benzene-1,3-dimethylene) tetrahydrofuran-2,3,4,5-tetracarboxylic diimide ) (6); and in Example 13 (with the stoichiometric salt obtained analogously to Example 8): poly (N, N '- (1,2-ethylene) tetrahydrofuran-2,3,4,5-tetracarboxylic acid diimide) (7): ···· ··· ··· ···
    These polyimides were analyzed inter alia by means of IR spectroscopy. The IR spectra of the products of Examples 9 to 11 corresponded to those of the polyimides known from the literature.
    Of the novel polyimides (6) and (7), in addition to the IR spectra shown in Figs. 6 and 7, the decomposition points were determined, and polyimide (6) was further subjected to a 1H-NMR spectrum (for polyimide (7 impossible because it was insoluble in the solvents tested), giving the data overleaf.
    Poly (N, N '- (benzene-1,3-dimethylene) tetrahydrofuran-2,3,4,5-tetracarboxylic acid diimide) (6):
    (6)
    Mp .: 456 ° C (dec.) (TGA, heating rate: 10 K / min) 1 H-NMR (250 MHz, DMSO-de) δ: 7.3 (s, 1H, ar), 7.1 (d, 3H, ar), 5.2 (t, 1H, aliph), 4.7 (s, 1H, aliph), 4.6 (s, 2H, aliph), 4.5 (s, 2H, aliph), 3 , 9 (s, 2H, aliph). IR (cm-1): 1784, 1695, 1333. • ·············
    Poly (N, N '- (1,2-ethylene) tetrahydrofuran-2,3,4,5-tetracarboxylic acid diimide) (7):
    (7)
    Mp: 438 ° C (dec.) (TGA, heating rate: 10 K / min) IR (cm -1): 1785, 1690, 1339.
    The present invention thus provides a method by which polyimide coatings can be prepared from aqueous solutions of stoichiometric monomer salts, which is a significant advantage over the prior art, as the use of expensive and only with enormous energy expenditure to be removed solvent limited or even can be completely avoided.
    Moreover, the invention should not be limited to the five monomer combinations disclosed herein, especially since the person skilled in the art - who now has the knowledge that such water-soluble monomer salts actually exist - is easily able to do so by simple routine experiments, including other combinations of polycarboxylic acid or Polyanhydride and polyamines, which give a water-soluble stoichiometric salt.
    权利要求:
    Claims (7)
    [1]
    (1) 13. 1,3-Benzoldimethanammonium dihydrogen-1,2,3,4-butanetetracarboxylate (2):

    1. A process for the preparation of polyimides by polycondensation of previously prepared stoichiometric salts of polycarboxylic acids or their polyanhydrides and polyamines by heating the salts for dehydration, characterized in that a) an aqueous solution of a water-soluble stoichiometric salt of polycarboxylic acid and polyamine is prepared; b) coating a substrate with the aqueous solution to obtain a coating; and c) the salt contained in the coating is polycondensed by heating.
    [2]
    (2) 14. 1,3-Benzenedimethanammonium dihydrogen tetrahydrofuran-2,3,4,5-tetracarboxylate (3):

    2. The method according to claim 1, characterized in that the coating obtained in step b) is dried before the polycondensation in step c).
    [3]
    (3) ·· Μ ··· · «· · · ·
    15. Ethane-1,2-diammonium dihydrogen-3,3 ', 4,4'-benzophenone tetracarboxylate (4):

    3. The method according to claim 1 or 2, characterized in that the water-soluble stoichiometric salt is prepared in step a) by mixing stoichiometric amounts of polycarboxylic acid or its polyanhydride and polyamine in water or in an aqueous solvent mixture.
    [4]
    (4)
    16. Ethane-1,2-diammonium dihydrogen tetrahydrofuran-2,3,4,5-tetracarboxylate (5):

    4. The method according to claim 3, characterized in that the water-soluble stoichiometric salt is precipitated by the addition of an organic solvent for intermediate storage before the polycondensation.
    [5]
    (5)
    17. Poly (N, N '- (benzene-1,3-dimethylene) tetrahydrofuran-2,3,4,5-tetracarboxylic acid diimide) (6):

    5. The method according to any one of the preceding claims, characterized in that in step b) a film is drawn from the aqueous solution of the water-soluble stoichiometric salt on a substrate.
    [6]
    (6) ·· ·· ·· ♦ · ♦ · ···
    18. Poly (N, N '- (1,2-ethylene) tetrahydrofuran-2,3,4,5-tetracarboxylic acid diimide) (7):

    6. The method according to any one of the preceding claims, characterized in that a water-soluble stoichiometric salt of a tetracarboxylic acid and a diamine is made and polycondensed.
    7. The method according to claim 6, characterized in that the tetracarboxylic acid from Benzophenontetracarbonsäure, Tetrahydrofurantetracarbonsäure, Butantetracarbonsäure and their dianhydrides is selected.
    8. The method according to claim 6 or 7, characterized in that the diamine is selected from benzenedimethanamine and ethylenediamine.
    9. The method according to claim 8, characterized in that the stoichiometric salt of 1,3-benzenedimethanammonium dihydrogen-3,3 ', 4,4'-benzophenonetetracarboxylate (1), 1,3-benzenedimethanammonium dihydrogen-1, 2,3,4-butanetetracarboxy-lat (2), 1,3-benzenedimethanammonium dihydrogen tetrahydrofuran-2,3,4,5-tetracarboxylate (3), ethane-1-diammonium dihydrogen S.S. '^^' - Benzophenontetracarboxylat (4) and ethane-1,2-diammonium dihydrogen tetrahydrofuran-2,3,4,5-tetracarboxylate (5) is selected.
    10. The method according to claim 9, characterized in that is used as the stoichiometric salt of 1,3-benzenedimethanammonium dihydrogen-tetrahydrofuran-2,3,4,5-tetra-carboxylate (3) and in the polycondensation of the polyimide poly (N, N '- (benzene-1,3-dimethylene) tetrahydrofuran-2,3,4,5-tetracarboxylic diimide) (6).
    11. The method according to claim 9, characterized in that as a stoichiometric salt ethane-1,2-diammonium dihydrogen-tetrahydrofuran-2,3,4,5-tetracarboxy-lat (5) is used and in the polycondensation of the polyimide poly ( N, N '- (1,2-ethylene) tetrahydrofuran-2,3,4,5-tetracarboxylic acid diimide) (7). 12. 1,3-Benzenedimethanammonium dihydrogen-3,3 '(4,4'-benzophenonetetracarboxylate (1):

    [7]
    (7)
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    同族专利:
    公开号 | 公开日
    AT519038B1|2018-11-15|
    EP3500617A1|2019-06-26|
    US20190177483A1|2019-06-13|
    WO2018032023A1|2018-02-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE1904396A1|1969-01-30|1970-07-16|Veba Chemie Nor Gmbh|Process for the production of polyimides via polyamido acids|
    EP1029884A1|1999-02-15|2000-08-23|Sumitomo Bakelite Company Limited|Method for producing polyimide resin|
    WO2016032299A1|2014-08-29|2016-03-03|연세대학교 원주산학협력단|Polyimide preparation method using monomer salt|WO2021258120A2|2020-06-23|2021-12-30|Technische Universität Wien|Process for preparing polyimides|DE1917274C3|1969-04-03|1981-04-30|Chemische Werke Hüls AG, 4370 Marl|Process for the preparation of polymers containing imide groups|
    JP2000319389A|1999-05-07|2000-11-21|Unitika Ltd|Polyimide precursor aqueous solution and its production, polyimide coating film obtained therefrom and its production|
    JP4484349B2|2000-10-18|2010-06-16|ユニチカ株式会社|Fluororesin aqueous dispersion, coating film obtained therefrom and method for producing the same|
    JP5982320B2|2012-05-17|2016-08-31|Ｊｆｅケミカル株式会社|Coating agent composition and coating film forming method|AT517146A2|2015-05-13|2016-11-15|Technische Universität Wien|Process for the preparation of crystalline polyimides|
    AT522304A2|2019-03-15|2020-10-15|Univ Wien Tech|Process for the production of polyimides|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA383/2016A|AT519038B1|2016-08-19|2016-08-19|Production process for polyimides|ATA383/2016A| AT519038B1|2016-08-19|2016-08-19|Production process for polyimides|
    US16/325,759| US20190177483A1|2016-08-19|2017-08-21|Method for producing polyimides|
    PCT/AT2017/000058| WO2018032023A1|2016-08-19|2017-08-21|Method for producing polyimides|
    EP17777150.8A| EP3500617A1|2016-08-19|2017-08-21|Method for producing polyimides|
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