Method for producing poly(anthranilamides), poly(anthranilamides) and uses thereof

Abstract

The present invention relates to a process for producing poly(anthranilamide) by polymerization of isatoic anhydride on a starter, preferably in the presence of a solvent, at a reaction temperature in the range of 110°C to 300°C, the starter comprising an aliphatic mono- or diamine containing 5 to 13 carbon atoms, an araliphatic mono- or diamine containing 7 to 15 carbon atoms, an aromatic diamine containing 6 to 13 carbon atoms, a carboxylic acid amide of the formula Ar-(C=O)NHR, where Ar represents an amine NH group or an aromatic group substituted with an NH group, and R represents an aromatic or aliphatic group, or a mixture of the above-mentioned starters, and where a solvent, if used, comprises an organic solvent that is liquid at the reaction temperature, an ionic liquid, or a mixture of these solvents, to obtain poly(anthranilamide) based on the starter. The present invention also relates to the poly(anthranilamide) obtained by the process according to the invention and to its use in the production of fibers or composite materials.

Description

[Technical Field]

[0001] The present invention relates to a process for preparing poly(anthranilamide) by polymerizing isatoic anhydride on a starter, preferably in the presence of a solvent, at a reaction temperature ranging from 110°C to 300°C, wherein the starter comprises an aliphatic mono- or diamine having 5 to 13 carbon atoms, an araliphatic mono- or diamine having 7 to 15 carbon atoms, an aromatic diamine having 6 to 13 carbon atoms, a carboxamide of the formula Ar-(C=O)NHR (where Ar represents an aromatic radical substituted with an aminic NH group or an NH group, and R represents an aromatic or aliphatic radical), or a mixture of the above-mentioned starters, and wherein a solvent, if used, comprises an organic solvent that is liquid at the reaction temperature, an ionic liquid, or a mixture of the above-mentioned solvents, to obtain poly(anthranilamide) based on the starter. The present invention further relates to poly(anthranilamide) obtainable by the process of the present invention and its use in the production of fibers or composite materials. [Background technology]

[0002] Aromatic polyamides (also called aramids), in which amide groups are linked to aromatic groups, are known from the prior art and are sold under trade names such as Kevlar, Twaron (poly(para-phenylene terephthalamide)) or Nomex, Teijinconex (poly(meta-phenylene isophthalamide)). They are used in a variety of fields. A notable example is the production of fibers, especially textile fibers. Fibers produced from aramids are notable for their very high strength, high impact resistance, high elongation at break, and excellent vibration damping. They are also very heat- and fire-resistant. A disadvantage is their high cost compared to many other polymers. Aramids are usually produced by the reaction of aromatic dicarbonyl halides ClCO-Ar 1 -COCl and aromatic diamines H2N-Ar 2-NH2 by polycondensation, and necessarily have a polymer structure with alternating units derived from dicarboxylic acids and diamines (-[-CO-Ar 1 -CO-NH-Ar 2 -NH]-, leading to the AABB polymer structure).

[0003] AF Amin, BP Suthar, and SR Patel, in "Poly(anthranilamide) Synthesis" (in Japanese), describe the preparation of poly(anthranilamide)s having 3 to 10 repeating units. The synthesis is achieved by ring-opening polymerization (hereinafter also referred to as ROP) of isatoic anhydride, and the starters used are HCl (aqueous), anthranilamide (HN-ortho-CH-(C=O)NH), N-methylaniline, and ortho-chloroaniline. Experiments using water, ethanol, ortho-cresol, dilute ammonia, and formamide as starters did not result in the formation of the desired polymer product. Thus, the synthesized polymer can be represented in terms of the following formula: A'-[(O=C)(ortho-C6H4)-NH] n -H A' = Cl, NH-ortho-C6H4-(C=O)NH2, N(CH3)-C6H5 or NH-ortho-C6H4-Cl; n=3~10.

[0004] Considering the relatively small number of repeating units, the products formed should rather be called oligomers. The use of any kind of diamine, aliphatic monoamine, araliphatic monoamine, or N-alkyl or N-aryl carboxamide derived from aromatic carboxylic acid having an amine NH or NH group on the aromatic ring as starter is not described.

[0005] The reaction of isatoic anhydride with various concentrations of ammonia was described as early as 1947 by R.P. Staiger and E.C. Wagner (in "Synthetic Chemistry of Isatoic Anhydride," 1948, Vol. 1, No. 1, pp. 111-114, 1948). At low ammonia concentrations, anthranilamides were obtained by elimination of carbon dioxide. At higher ammonia concentrations, cyclic benzoyl ureas were obtained instead, accompanied by the elimination of water. Furthermore, referring to earlier studies, the formation of "unusual" products from ammonia and isatoic anhydride was also reported, particularly when isatoic anhydride was treated with exactly half an equivalent of ammonia. This resulted in amorphous products described as condensation products. The already cited reference, "Synthetic Chemistry of Isatoic Anhydride," 1948, also refers to earlier studies and refers to these products as "unusual" (unusual in the sense that they are insoluble in ethanol and melt over a wide temperature range). However, according to "Synthetic Chemistry of Isatoic Anhydride," these unusual products have never been systematically characterized, and according to this reference, numerous reports suggest that these "unusual" products are simply mixtures of "normal" products. In Non-Patent Document 3, Robert H. Clark and E. C. Wagner also reported "abnormal" products, which the authors classified as the following types: H2N-ortho-C6H4-(C=O)-[NH-ortho-C6H4-(C=O)] x NHR where x does not exceed a value of 1 or 2. The possibility of forming macromolecular products is only speculative and may also result from association or aggregation.

[0006] US Patent No. 5,999,623 describes polymers having a CC backbone onto which up to 10 anthranilamide units are grafted through divalent bridges. The base polymers forming the CC backbone include, inter alia, differently substituted poly(methacrylates) or polymeric vinyl aromatic hydrocarbons.

[0007] These references do not describe the formation of higher molecular weight poly(anthranilamides), in which high molar mass is achieved through a large number of repeating anthranilamide units (i.e., the formation of "true" anthranilamide polymers, as opposed to oligomers with only a few repeating units or copolymers), rather than through grafting onto another polymer. Conventionally used aramids, with the exception of the poly(para-phenylene terephthalamide) and poly(meta-phenylene isophthalamide) mentioned at the beginning, can be prepared with high molar masses (albeit under very corrosive conditions due to the use of acid chlorides, which are expensive and inconvenient in terms of equipment and process operation) and have very good performance characteristics, but are very costly. Furthermore, the processes commonly used to prepare such aramids are based on polycondensation reactions involving the formation of AABB polymer structures, which require very precise adherence to reaction stoichiometry in order to form polymers with high molar masses.

[0008] Yoshiyuki Sasaki and Pierre H. Dixneuf, "Thermal decarboxylation of isatoic anhydride to form a heat-stable polyamide" (Proc. Appl. Chem. Soc. 1999, 103:111-114, 2001). The reaction occurs upon heating to a temperature still below the melting point. The following structure is suggested for the solid product: ~NH-ortho-C6H4-(C=O)NH-ortho-C6H4-(C=O)~.

[0009] By gel permeation chromatography, the mass-average molar mass M corresponds to approximately five times the mass of isatoic anhydride. w Therefore, the product is an oligomer, which is also consistent with the fact that the observed product is meltable (high molecular weight poly(anthranilamide) is known to be inmeltable without degradation).

[0010] Attempts to catalyze the reaction with dopants were also made. The dopants were used in a ratio of 0.01% of the mass of isatoic anhydride. When doped with anthranilamide, 14% of the theoretically expected amount of CO2 was removed, and when doped with sodium acetate, 81% was removed. This contrasts with the absence of a dopant, which removed only 2% of the theoretically expected amount of CO2. With 1% sodium acetate, a mass-average molar mass of 1280 g / mol was observed, but with high polydispersity. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] U.S. Patent No. 9,683,126 [Non-patent literature]

[0012] [Non-Patent Document 1] J. Macromol. Sci.-Chem. 1982, A17(3), 481-488 [Non-patent document 2] Journal of Organic Chemistry 1948, 13, 347-352 [Non-patent document 3] Journal of Organic Chemistry, 1944, 9, 55-67 [Non-patent document 4] Journal of Organic Chemistry 1987, 52, 315-316 Summary of the Invention [Problem to be solved by the invention]

[0013] Therefore, further improvements in the field of aramid chemistry were needed. [Means for solving the problem]

[0014] Therefore, in view of this need, the present invention provides a process for preparing poly(anthranilamide), comprising: (A) providing isatoic anhydride; (B) polymerizing the isatoic anhydride on a starter, preferably in the presence of a solvent, at a reaction temperature in the range of 110°C to 300°C, particularly in the range of 150°C to 300°C, to obtain a poly(anthranilamide) based on the starter; Including, wherein the starter comprises an aliphatic mono- or diamine having 5 to 13 carbon atoms, an araliphatic mono- or diamine having 7 to 15 carbon atoms, an aromatic diamine having 6 to 13 carbon atoms, a carboxamide of the formula Ar-(C=O)NHR, where Ar represents an aminic NH group or an aromatic radical substituted by an NH group (particularly HN-CH), and R represents an aromatic or aliphatic radical, or a mixture of the above starters; When a solvent is used, the solvent may comprise an organic solvent that is liquid at the reaction temperature, an ionic liquid, or a mixture of the aforementioned solvents. Provide a process.

[0015] The present invention further provides a compound of formula: {H-(HN-(ortho-C6H4)-(C=O) m} x -A-[(O=C)(ortho-C6H4)-NH] n -H (I) (In the formula, m and n represent the number of repeating units, x is 0 (for monofunctional starters) or 1 (for difunctional starters); A is obtained from a starter molecule containing aminic NH or NH groups by removal of hydrogen atoms from all aminic NH and NH groups, wherein the starter molecule is an aliphatic mono- or diamine having 5 to 13 carbon atoms, an araliphatic mono- or diamine having 7 to 15 carbon atoms, an aromatic diamine having 6 to 13 carbon atoms, or a carboxamide of the formula Ar-(C=O)NHR, where Ar represents an aromatic radical (in particular HN-CH) substituted by aminic NH or NH groups, and R represents an aromatic or aliphatic radical, to give a poly(anthranilamide).

[0016] Finally, the present invention provides the use of the poly(anthranilamide) of the present invention in the manufacture of fibers or composite materials from poly(anthranilamide) and (at least) one other material, including a metal, an inorganic substance, or a polymer other than poly(anthranilamide).

[0017] In the terminology of the present invention, the expression amine NH or NH group relates to primary or secondary organic amines (as opposed to other compounds having an NH or NH group, such as in particular amides), i.e. to organic compounds in which the NH or NH group is bound to a carbon atom that does not carry any further heteroatoms.

[0018] Aromatic aliphatic mono- and diamines are understood to mean mono- and diamines having an aromatic group and an aliphatic group, preferably in which all amino groups are bonded to carbon atoms directly adjacent to the aromatic group, as is the case for example in xylylenediamine.

[0019] Organic solvents are understood to mean non-ionic organic solvents, in contrast to ionic liquids (= low-melting point (ie below 100° C.) salts).

[0020] In the context of the present invention, the essential method for determining the number of repeat units m+n is 1H NMR spectroscopy, which provides an average for the number of repeat units from which the number-average molar mass of poly(anthranilamide) can be calculated. Details are provided in the "Analysis" section below.

[0021] A brief summary of various possible embodiments of the present invention follows.

[0022] In a first embodiment of the process of the present invention, which can be combined with all other embodiments, the reaction temperature is in the range of 120°C to 300°C, preferably in the range of 150°C to 300°C, more preferably in the range of 160°C to 280°C, and most preferably in the range of 170°C to 260°C.

[0023] In a second embodiment of the process of the invention, which may be combined with all other embodiments, step (B) is carried out at a pressure ranging from 1.0 bar (absolute) to 5.0 bar (absolute).

[0024] In a third embodiment of the process of the present invention, which may be combined with all other embodiments, the aliphatic primary or secondary mono- or diamine having 5 to 13 carbon atoms comprises neopentylamine, hexamethylenediamine, methylenedicyclohexyldiamine and / or pentamethylenediamine.

[0025] In a fourth embodiment of the process of the present invention, which may be combined with all other embodiments, the araliphatic mono- or diamine having 7 to 15 carbon atoms comprises xylylenediamine.

[0026] In a fifth embodiment of the process of the present invention, which may be combined with all other embodiments, the aromatic diamine having 6 to 13 carbon atoms comprises methylenediphenylenediamine, naphthylenediamine and / or tolylenediamine.

[0027] In a sixth embodiment of the process of the present invention, which may be combined with all other embodiments, the carboxamide of formula Ar—(C═O)NHR comprises N-neopentylanthranilamide (Ar=ortho-C 6 H 4 —NH 2 , R=neopentyl).

[0028] In a seventh embodiment of the process of the invention, which may be combined with all other embodiments except those which envisage the use of a solvent in step (B), the polymerization is carried out in the absence of a solvent, and after step (B), (C)(i) dissolving poly(anthranilamide) in a mineral acid to obtain a solution of poly(anthranilamide) in a mineral acid; (D)(i) isolating the poly(anthranilamide) dissolved in the mineral acid from the mineral acid solution, including precipitating it in water; continues.

[0029] In an eighth embodiment of the process of the invention, which is a specific configuration of the seventh embodiment, the mineral acid comprises sulfuric acid, hydrochloric acid, nitric acid and / or phosphoric acid, in particular sulfuric acid.

[0030] In a ninth embodiment of the process of the invention, which may be combined with all other embodiments except those which exclude the use of a solvent in step (B) or which envisage a pure solvent polymerization for this step, the polymerization is carried out in the presence of a solvent, which comprises an organic solvent which is liquid at the reaction temperature or a mixture of such an organic solvent and an ionic liquid, and in step (B) a poly(anthranilamide) based on the starter is obtained suspended in the solvent, and after step (B) (C)(ii) dissolving the poly(anthranilamides) suspended in the solvent in a mineral acid and separating the poly(anthranilamides) from the solvent to obtain a mineral acid solution of the poly(anthranilamides); (D)(ii) isolating the poly(anthranilamide) dissolved in the mineral acid from the mineral acid solution, including precipitating it in water; continues.

[0031] In a tenth embodiment of the process of the invention, which is a specific configuration of the ninth embodiment, the mineral acid comprises sulfuric acid, hydrochloric acid, nitric acid and / or phosphoric acid, in particular sulfuric acid.

[0032] In an eleventh embodiment of the process of the present invention, which is a specific configuration of the ninth and tenth embodiments, the solvent is removed in step (C)(i) by filtration, centrifugation or phase separation.

[0033] In a twelfth embodiment of the process of the invention, which may be combined with all other embodiments except those which exclude the use of a solvent in step (B) or those in which suspension polymerization is envisaged for this step, the polymerization of isatoic anhydride is carried out in the presence of a solvent, which comprises an ionic liquid or a mixture of an ionic liquid and an organic solvent which is liquid at the reaction temperature, and in step (B) a poly(anthranilic amide) based on the starter is obtained in such a way that it is dissolved in the solvent, and after step (B) (D)(iii) isolating the poly(anthranilamide) dissolved in the solvent from the solution in the solvent, including precipitating it in water; continues.

[0034] In a thirteenth embodiment of the process of the present invention, which is a specific configuration of the ninth to twelfth embodiments, the organic solvent comprises diphenyl ether, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), and / or hexamethylphosphoramide.

[0035] In a fourteenth embodiment of the process of the present invention, which is a specific configuration of the ninth through thirteenth embodiments, the ionic liquid comprises 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium butyrate, 1-butyl-3-methylimidazolium nitrate, 1-butyl-3-methylimidazolium methylsulfonate, and / or dialkylimidazolium phosphate (e.g., butyl-3-methylimidazolium phosphate, dimethylimidazolium diethylphosphate ("MMIM-DEP"), and ethylmethylimidazolium diethylphosphate ("EMIM-DEP"), among others).

[0036] In a fifteenth embodiment of the process of the present invention, which is a specific configuration of the ninth to fourteenth embodiments, precipitation in water is achieved by adding a solution of poly(anthranilamide) to a 5-fold to 20-fold volume excess of water.

[0037] In a sixteenth embodiment of the process of the invention, which may be combined with all other embodiments, the molar ratio of isatoic anhydride to the starter selected in step (B) is in the range from 20 to 2500, preferably in the range from 40 to 2500, more preferably in the range from 50 to 2400, and most preferably in the range from 70 to 2000, in particular to obtain (poly)anthranilamides of formula (I) with values ​​of m+n in the range from 20 to 2500, preferably in the range from 40 to 2500, more preferably in the range from 50 to 2400, and most preferably in the range from 70 to 2000.

[0038] In a seventeenth embodiment of the process of the present invention, which may be combined with all other embodiments, the preparation of isatoic anhydride in step (A) comprises chemical conversion of anthranilic acid.

[0039] In an eighteenth embodiment of the process of the present invention, which is a specific configuration of the seventeenth embodiment, the chemical conversion of anthranilic acid comprises the steps of: carbon monoxide in the presence of a catalyst, especially a Pd or Pt catalyst, or a phosgenation medium selected from phosgene, diphosgene, triphosgene, oxalyl chloride, 1,1-carbonyldiimidazole and / or dimethyl carbonate, It is selected from the reaction with

[0040] In a nineteenth embodiment of the process of the present invention, which is a specific configuration of the seventeenth and eighteenth embodiments, the anthranilic acid is a fermentable carbon-containing compound, preferably a starch hydrolysate, sugarcane juice, sugarbeet juice, a hydrolysate of a lignocellulose-containing raw material, or a mixture thereof; a nitrogen-containing compound, preferably gaseous ammonia, aqueous ammonia, an ammonium salt, urea or a mixture thereof; It is obtained by fermenting raw materials containing

[0041] In a twentieth embodiment of the process of the present invention, which is a specific configuration of the nineteenth embodiment, the fermentable carbon-containing compounds comprise starch hydrolysates, sugarcane juice, sugar beet juice and / or hydrolysates of lignocellulose-containing feedstocks, and the nitrogen-containing compounds comprise gaseous ammonia, aqueous ammonia, ammonium salts and / or urea.

[0042] In a first embodiment of the poly(anthranilamide) of the present invention, which can be combined with all other embodiments, the aliphatic primary or secondary mono- or diamine having 5 to 13 carbon atoms is neopentylamine, hexamethylenediamine, methylenedicyclohexyldiamine, or pentamethylenediamine.

[0043] In a second embodiment of the poly(anthranilamide) of the present invention, which can be combined with all other embodiments, the araliphatic mono- or diamine having 7 to 15 carbon atoms is xylylenediamine.

[0044] In a third embodiment of the poly(anthranilamide) of the present invention, which may be combined with all other embodiments, the aromatic diamine having 6 to 13 carbon atoms is methylenediphenylenediamine, naphthylenediamine, or tolylenediamine.

[0045] In a fourth embodiment of the poly(anthranilamide) of the invention, which may be combined with all other embodiments, the carboxamide of formula Ar—(C═O)NHR is N-neopentylanthranilamide (Ar=ortho-C6H4—NH2, R=neopentyl).

[0046] In a fifth embodiment of the poly(anthranilamide) of the present invention, which can be combined with all other embodiments, m+n is in the range of 20 to 2500, preferably in the range of 40 to 2500, more preferably in the range of 50 to 2400, and most preferably in the range of 70 to 2000.

[0047] In a first embodiment of the use of the invention, the fibers or composite materials are useful for the manufacture of protective equipment (in particular, but not exclusively, clothing articles, such as body armor and bulletproof vests) for protection against fire, shrapnel formation, shrapnel penetration, mechanical impact (including bullets) or cuts.

[0048] In a second embodiment of the use of the invention, which can be combined with all the other embodiments, the fibre or composite material serves for the manufacture of sports equipment.

[0049] The embodiments briefly outlined above and further possible embodiments of the present invention are described in detail below. Unless otherwise stated or clearly evident from the context, all embodiments can be combined with each other as desired. DETAILED DESCRIPTION OF THE INVENTION

[0050] In step (A) of the process of the present invention, isatoic anhydride is prepared for subsequent polymerization. Isatoic anhydride can, in principle, be prepared by any process known in the art for the synthesis of such compounds. Typically, the synthesis proceeds from anthranilic acid (=ortho-aminobenzoic acid) and is achieved, for example, by reaction with phosgene, particularly in a hydrochloric acid medium. Instead of phosgene, it is also possible to use diphosgene, triphosgene, or other phosgenation media known from the prior art, such as oxalyl chloride, 1,1-carbonyldiimidazole, and dimethyl carbonate. Similarly possible is the reaction of anthranilic acid with carbon monoxide in the presence of a catalyst, particularly a Pd or Pt catalyst, to give isatoic anhydride.

[0051] Anthranilic acid can also be prepared by known chemical processes. One example of a suitable chemical method is the reaction of phthalimide with sodium hypochlorite. Phthalimide itself can be obtained from phthalic anhydride and ammonia. The entire process is known. Industrial processes are also described in the patent literature, see, for example, DE 29 02 978 A1 and EP 0 004 635 A1. Furthermore, a fermentative preparation route for anthranilic acid has recently been published, which proceeds from renewable raw materials and is therefore suitable for protecting fossil raw materials and reducing the size of the CO2 footprint. See, for example, WO 2018 / 002088, p. 13, line 26 to p. 22, line 15, and the references cited therein. This fermentation process can also be used in the process of the present invention. Thus, in this embodiment, step (A) of the process of the present invention comprises: a fermentable carbon-containing compound, preferably a starch hydrolysate, sugarcane juice, sugar beet juice, a hydrolysate of a lignocellulose-containing raw material, or a mixture thereof; a nitrogen-containing compound, preferably gaseous ammonia, aqueous ammonia, an ammonium salt, urea or a mixture thereof; It involves fermentation of raw materials containing

[0052] Preferably, the fermentable carbon-containing compounds include starch hydrolysates, sugarcane juice, sugar beet juice and / or hydrolysates of lignocellulose-containing feedstocks, and the nitrogen-containing compounds include gaseous ammonia, aqueous ammonia, ammonium salts and / or urea. Suitable microorganisms for carrying out the fermentation are, in particular, Escherichia coli, Pseudomonas putida, Corynebacterium glutamicum, Ashbya gossypii, Pichia pastoris, Hansenula polymorpha, Yarrowia lipolytica, Zygosaccharomyces bailii or Saccharomyces cerevisiae.

[0053] In step (B) of the process of the present invention, the isatoic anhydride provided in step (A) is polymerized by ring-opening (ROP) and elimination of CO. The starters used according to the present invention include aliphatic mono- or diamines having 5 to 13 carbon atoms, araliphatic mono- or diamines having 7 to 15 carbon atoms, aromatic diamines having 6 to 13 carbon atoms, carboxamides of the formula Ar-(C=O)NHR, where Ar represents an aminic NH group or an aromatic radical (in particular HN-CH) substituted by an NH group, and R represents an aromatic or aliphatic radical, or mixtures of the above-mentioned starters.

[0054] In one embodiment of the present invention, aliphatic primary or secondary mono- or diamines having 5 to 13 carbon atoms are used, particularly preferably neopentylamine, hexamethylenediamine (particularly hexamethylene-1,6-diamine), methylenedicyclohexyldiamine (particularly 2,2'-, 2,4'- and / or 4,4'-methylenedicyclohexyldiamine) and / or pentamethylenediamine (particularly pentamethylene-1,5-diamine).

[0055] In a further embodiment of the present invention, araliphatic mono- or diamines having 7 to 15 carbon atoms are used, particularly preferably xylylenediamines (especially xylylene-1,3-diamine).

[0056] In a further embodiment of the present invention, aromatic diamines having 6 to 13 carbon atoms are used, particularly preferably methylenediphenylenediamines (especially 2,2'-, 2,4'- and / or 4,4'-methylenediphenylenediamine), naphthylenediamines (especially naphthylene-1,5-diamine) and / or tolylenediamines (especially meta- and / or ortho-tolylenediamine).

[0057] In a further embodiment of the invention, carboxamides of formula Ar-(C=O)NHR are used, in particular N-neopentylanthranilamide (Ar=ortho-C6H4-NH2, R=neopentyl).

[0058] The polymerization is carried out at a reaction temperature in the range of 110°C to 300°C, preferably 120°C to 300°C, more preferably 150°C to 300°C, even more preferably 160°C to 280°C, and very particularly preferably 170°C to 260°C. The polymerization can be carried out (i) without a solvent ("neat", "bulk polymerization"), or preferably in the presence of a solvent. In the latter case, suitable solvents are (ii) organic solvents that are liquid at the reaction temperature, (iii) ionic liquids, or (iv) mixtures of the two. Suitable solvents for case (ii) are, in particular, diphenyl ether, N-methyl-2-pyrrolidone (NMP, preferably combined with CaCl2 as a solubilizer), 1,3-dimethyl-2-imidazolidinone (DMI), and / or hexamethylphosphoramide, which are liquid at the appropriate reaction temperature (see above). For case (iii), in principle, the use of ionic liquids known in the art is envisaged, in particular 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium butyrate, 1-butyl-3-methylimidazolium nitrate, 1-butyl-3-methylimidazolium methylsulfonate and / or dialkylimidazolium phosphates (e.g., in particular butyl-3-methylimidazolium phosphate, dimethylimidazolium diethylphosphate ("MMIM-DEP") and ethylmethylimidazolium diethylphosphate ("EMIM-DEP")).

[0059] In the case of solvent-free ROP (i), isatoic anhydride is converted into a molten state, i.e., above a temperature of 230 °C. The above-mentioned upper limit of the reaction temperature is also preferred for solvent-free polymerization. Therefore, the starter should have a sufficiently high boiling point under the selected reaction conditions. In principle, the reaction does not have any specific requirements for the reaction pressure. Therefore, ROP can be carried out at ambient pressure. However, to minimize the loss of starter through evaporation, it is also possible to react the starter with isatoic anhydride at elevated pressure relative to ambient pressure, in particular at pressures in the range of 1.1 bar (absolute) to 5.0 bar (absolute). Similarly, it is also conceivable to start the reaction at ambient or slightly elevated pressure (e.g., 1.1 bar (absolute)) and allow the pressure to increase, particularly preferably up to a defined maximum pressure of 5.0 bar (absolute), for the removal of carbon dioxide. The equipment used for the polymerization is preferably provided with a pressure-maintaining valve that ensures compatibility with the target maximum pressure. The above details regarding pressure may of course also apply to carrying out the reaction in the presence of a solvent.

[0060] In the case of solvent-free runs, the polymerization is initiated in a homogeneous phase (melt). However, as the polymerization proceeds, rapid precipitation of the formed polymer occurs, thus resulting in a suspension of the polymer in the unconverted starter and unconverted monomer. As the polymerization proceeds further, substantial solidification of the entire reaction mixture generally occurs.

[0061] In this case, the post-treatment is preferably as follows: (C)(i) dissolving poly(anthranilamide) in a mineral acid; (D)(i) isolating the poly(anthranilamide) dissolved in the mineral acid from the mineral acid solution, including precipitating it in water; Includes:

[0062] Suitable mineral acids for carrying out step (C)(i) are in particular sulfuric acid, hydrochloric acid, nitric acid and / or phosphoric acid. Sulfuric acid is preferred, in particular sulfuric acid with a mass concentration ranging from 96% to 100%, preferably from 96% to 98%. Dissolution is preferably achieved at a temperature ranging from 20°C to 100°C.

[0063] In step (D)(i) of this embodiment of the process of the present invention, poly(anthranilamide) is isolated from the mineral acid solution obtained in step (C). This is accomplished by precipitation in water. For this purpose, it is preferred to add the mineral acid solution of poly(anthranilamide) to a 5- to 20-fold volume excess of water. The poly(anthranilamide) then precipitates and can be easily removed, for example, by filtration or centrifugation. Further workup steps for purification may follow.

[0064] However, ROP is preferably carried out in the presence of a solvent, whereby, depending on the solvent used, the polymeric product is obtained as a suspension or solution in the selected solvent.

[0065] When organic solvent (ii) is used, a suspension of poly(anthranilamide) is generally obtained in step (B) (suspension polymerization). In this case, the post-treatment of the process product in step (B) is preferably carried out by: (C)(ii) dissolving the poly(anthranilamides) suspended in the solvent in a mineral acid and separating the poly(anthranilamides) from the solvent to obtain a mineral acid solution of the poly(anthranilamides); (D)(ii) isolating the poly(anthranilamide) dissolved in the mineral acid from the mineral acid solution, including precipitating it in water; Includes:

[0066] The preferred conditions described above for case (i) of the dissolution and isolation steps are also applicable to case (ii). Removal of the additionally required organic solvent here is preferably achieved by filtration, centrifugation, or phase separation. Removal can precede dissolution of the poly(anthranilamide) in mineral acid (in which case the solid polyanthranilamide, which generally still contains trapped organic solvent, is filtered off and then dissolved in mineral acid) or can follow it (in which case the organic solvent, which has precipitated or is insoluble in mineral acid, is separated).

[0067] If the solvent used in step (B) is an ionic liquid (iii), this step generally provides a solution of poly(anthranilamide) (solution polymerization). In this case, the dissolution step (step (C) in cases (i) and (ii)) is not necessary, since the polymeric product is already in solution. Therefore, in this case, the post-treatment of the process product in step (B) is preferably (D)(iii) isolating the poly(anthranilamide) dissolved in the solvent from the solution in the solvent, including precipitating it in water; Includes:

[0068] The preferred conditions described above for case (i) for the isolation step are also applicable to case (iii).

[0069] If a mixture of organic solvent and ionic liquid is used in step (B) (iv), the process product is either a solution or a suspension, depending on the mixing ratio. Depending on what is present, further work-up is as described above for case (iii) (solution) or case (ii) (suspension).

[0070] In any case, it is preferable to recycle the recovered solvent. To this end, purification may be necessary, which can be achieved by methods known in the art. Recycling of the ionic solution is particularly important due to its high cost. For this purpose, in step (D)(iii) or step (D)(iv), the ionic solution obtained in the isolation of poly(anthranilamide) is dried at elevated temperature and reduced pressure, in particular at a temperature in the range from 50° C. to 100° C. and a pressure in the range from 1 mbar (absolute) to 100 mbar (absolute).

[0071] When the process product from step (B) is in the form of a solution, it is also envisioned to further process this solution directly to obtain the desired end product, in particular to spin fibers of poly(anthranilamide) directly from the solution.

[0072] The process of the present invention allows for the formation of high molecular weight poly(anthranilamide). Accordingly, the molar ratio of isatoic anhydride to starter can vary widely, particularly in the range of 20 to 2500, preferably 40 to 2500, more preferably 50 to 2400, and most preferably 70 to 2000. The selected molar ratio will, of course, depend on the desired end use of the poly(anthranilamide); therefore, it is also possible to optionally use molar ratios different from those presented above.

[0073] By the process of the present invention, a compound of the formula: {H-[HN-(ortho-C6H4)-(C=O)] m} x -A-[(O=C)(ortho-C6H4)-NH] n -H (I) (In the formula, m and n represent the number of repeating units, x is 0 or 1, A can be obtained from a starter molecule containing aminic NH or NH groups by removing hydrogen atoms from all aminic NH and NH groups, where the starter molecule is an aliphatic mono- or diamine having 5 to 13 carbon atoms, an araliphatic mono- or diamine having 7 to 15 carbon atoms, an aromatic diamine having 6 to 13 carbon atoms, or a poly(anthranilamide) of the formula Ar-(C=O)NHR, where Ar represents an aromatic radical (in particular HN-CH) substituted by aminic NH or NH groups, and R represents an aromatic or aliphatic radical.

[0074] The above-described embodiments of the process of the present invention are also applicable to the poly(anthranilamide) of the present invention, as appropriate. For example, starters used in the preparation of poly(anthranilamide) may include starter molecules such as neopentylamine, hexamethylenediamine (especially hexamethylene-1,6-diamine), methylenedicyclohexyldiamine (especially 2,2'-, 2,4'- and / or 4,4'-methylenedicyclohexyldiamine), pentamethylenediamine (especially pentamethylene-1,5-diamine), xylylenediamine (especially xylylene-1,3-diamine), methylenediphenylenediamine (especially 2,2'-, 2,4'- and / or 4,4'-methylenediphenylenediamine), naphthylenediamine (especially naphthylene-1,5-diamine), tolylenediamine (especially meta- and / or ortho-tolylenediamine) or N-neopentylanthranilamide (Ar=ortho-CH—NH, R=neopentyl), among others. The starter may also comprise two or more different starter molecules.

[0075] In one embodiment, the total number of repeating (O=C)(ortho-CH)-NH- units (i.e., m+n) is between 20 and 2500, preferably between 40 and 2500, more preferably between 50 and 2400, and most preferably between 70 and 2000. In the case of a bifunctional starter molecule, these repeating units are distributed between the two polymer chains being formed. If both amine groups of the starter molecule have the same reactivity (which is the case for a symmetric starter molecule, such as the hexamethylene-1,6-diamine mentioned above), m and n are (at least essentially) equal, i.e., (at least approximately) m=n=(m+n) / 2. If there is a difference in the reactivity of the amine groups, for example, due to steric hindrance or because one amine group is more basic than the other, unequal chain lengths may also be formed.

[0076] The poly(anthranilamide) obtainable according to the present invention is suitable for a variety of applications. Accordingly, the present invention further provides the use of the poly(anthranilamide) of the present invention in the production of fibers or composite materials derived from poly(anthranilamide) and (at least) one other material, including metal, inorganic substances (e.g., concrete), or polymers other than poly(anthranilamide) (e.g., polyurethane). The fibers or composite materials are preferably useful for the production of protective equipment (particularly, but not exclusively, clothing products, such as body armor and bulletproof vests) for protection against fire, shrapnel formation, shrapnel penetration, mechanical impact (including bullets), or cuts. The fibers or composite materials can also be used for the production of sports equipment.

[0077] The invention is explained in more detail below with reference to examples. [Example]

[0078] analysis 1 The number-average molar mass (M) of the resulting poly(anthranilamide) was determined by H NMR spectroscopy (Bruker, AV III HD 600, 600 MHz, pulse sequence zg30, delay time d1: 10 s, 64 scans). n) was determined. Each sample was dissolved in deuterated sulfuric acid. 1 Relevant resonances in the 1 H NMR spectrum are as follows (based on TMS=0 ppm):

[0079] The signals from 8.5 ppm to 7.1 ppm are used for the aromatic protons of the anthranilamide (corresponding to the sum of four protons). The resonances of the protons of the neopentylamine starter have shifts from 3.6 ppm to 3.4 ppm (methylene group, corresponding to the sum of two protons) and from 1.1 ppm to 0.9 ppm (neopentyl group, corresponding to the sum of nine protons).

[0080] The following abbreviations: F(A) = aromatic proton (four protons) resonance area from 8.5 ppm to 7.1 ppm, F(M) = resonance area of ​​the methylene group (two protons) of the starter at 3.6 ppm to 3.4 ppm, F(N) = resonance area of ​​the neopentyl group of the starter (corresponding to the nine protons) from 1.1 ppm to 0.9 ppm; to determine the molar mass M of the polymer according to formula (I) as follows: n Calculate.

[0081] The number of repeat units m+n derived from (O=C)(ortho-C6H4)-NH in the polymer was calculated using the following formula (I) (in the special case, m=0, and therefore m+n=n): n=F(A) / F(M)×9 / 4 (I)

[0082] The molar mass M of the polymer is calculated using the value n according to the following formula (II): n was calculated. M n =86.16g / mol+n×120.14g / mol+1g / mol (II)

[0083] Example 1: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and neopentylamine as a starter in diphenyl ether as a solvent Isatoic anhydride and diphenyl ether were sourced from Sigma-Aldrich, and neopentylamine was sourced from ABCR (Step (A)).

[0084] A 500 mL four-neck flask was equipped with a distillation system, a precision glass stirrer, a temperature probe, a nitrogen supply line, and a gas outlet / gas outlet with a pressure relief valve. Then, 98 g of isatoic anhydride and 171 g of diphenyl ether were weighed in. Nitrogen was introduced at 10 L / h for 20 minutes, during which the mixture was heated to 40°C while stirring at 300 rpm. Then, 0.26 g of neopentylamine was introduced, and the solution was stirred at 180°C for 15 hours (Step (B)). A suspension was obtained.

[0085] During D2SO4, 1 By H NMR, the molar mass M n It was decided that:

[0086] 20 g of the poly(anthranilamide) suspension was dissolved in 20 mL of concentrated sulfuric acid. The precipitated solid (=diphenyl ether solvent) was removed by filtration (step (C)).

[0087] The filtered sulfuric acid solution was added to 300 mL of water (step (D)(ii)). The precipitated solid was isolated by filtration and then dried at 160° C. and 0.05 bar for 24 hours.

[0088] Example 2: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and neopentylamine as a starter in diphenyl ether as a solvent The following differences: 90 g of isatoic anhydride, 130 g of diphenyl ether and 0.80 g of neopentylamine were used. The procedure was as in Example 1, except:

[0089] Example 3: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and neopentylamine as a starter in diphenyl ether as a solvent The following differences: 100 g of isatoic anhydride, 390 g of diphenyl ether and 0.060 g of neopentylamine were used. The procedure was as in Example 1, except:

[0090] The table below compares the results of the analysis.

[0091] [Table 1]

[0092] Example 4: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and hexamethylene-1,6-diamine as a starter in diphenyl ether as a solvent Isatoic anhydride, diphenyl ether and hexamethylene-1,6-diamine were sourced from Sigma-Aldrich (Step (A)).

[0093] A 100 mL four-neck flask was equipped with a distillation system, a precision glass stirrer, a temperature probe, a nitrogen supply line, and a gas outlet / gas outlet with a pressure relief valve. Then, 10 g of isatoic anhydride and 37 g of diphenyl ether were weighed in. Nitrogen was introduced at 10 L / h for 20 minutes, during which the mixture was heated to 40°C while stirring at 300 rpm. Then, 0.050 g of hexamethylene-1,6-diamine was introduced, and the solution was stirred at 180°C for 15 hours (Step (B)). A suspension was obtained.

[0094] During D2SO4, 1 By H NMR, the molar mass M n It was decided that:

[0095] 20 g of the poly(anthranilamide) suspension was dissolved in 20 mL of concentrated sulfuric acid. The precipitated solid (=diphenyl ether solvent) was removed by filtration (step (C)).

[0096] The filtered sulfuric acid solution was added to 300 mL of water (step (D)(ii)). The precipitated solid was isolated by filtration and then dried at 160° C. and 0.05 bar for 24 hours.

[0097] Example 5: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and hexamethylene-1,6-diamine as a starter in diphenyl ether as a solvent The following differences: 10 g of isatoic anhydride, 37 g of diphenyl ether and 0.11 g of hexamethylene-1,6-diamine were used. The procedure was as in Example 4, except:

[0098] Example 6: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and hexamethylene-1,6-diamine as a starter in diphenyl ether as a solvent The following differences: 20 g of isatoic anhydride, 75 g of diphenyl ether and 0.015 g of hexamethylene-1,6-diamine were used. The procedure was as in Example 4, except:

[0099] Example 7: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and hexamethylene-1,6-diamine as a starter in diphenyl ether as a solvent The following differences: 25 g of isatoic anhydride, 140 g of diphenyl ether and 0.005 g of hexamethylene-1,6-diamine were used; The procedure was as in Example 4, except:

[0100] The table below compares the results of the analysis.

[0101] [Table 2]

[0102] Example 8: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as monomer and neopentylamine as starter in ethylmethylimidazolium diethylphosphate (EMIM-DEP) as solvent at 180°C Isatoic anhydride and ethylmethylimidazolium diethylphosphate (EMIM-DEP) were sourced from Sigma-Aldrich, and neopentylamine was sourced from ABCR (Step (A)).

[0103] A 100 mL four-neck flask was equipped with a distillation system, a precision glass stirrer, a temperature probe, a nitrogen supply line, and a gas outlet / gas outlet with a pressure relief valve. Then, 10 g of isatoic anhydride and 28 g of ethylmethylimidazolium diethylphosphate (EMIM-DEP) were weighed in. Nitrogen was introduced at 10 L / h for 20 minutes, during which the mixture was heated to 40 °C while stirring at 300 rpm. Then, 0.010 g of neopentylamine was introduced, and the solution was stirred at 180 °C for 15 hours (Step (B)). A clear solution was obtained.

[0104] The poly(anthranilamide) solution was added to 300 mL of water (step (D)(iii)). The precipitated solid was isolated by filtration and then dried at 160° C. and 0.05 bar for 24 hours.

[0105] Example 9: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and hexamethylene-1,6-diamine as a starter in ethylmethylimidazolium diethylphosphate (EMIM-DEP) as a solvent at 150°C Isatoic anhydride, ethylmethylimidazolium diethylphosphate (EMIM-DEP) and hexamethylene-1,6-diamine were purchased from Sigma-Aldrich (Step (A)).

[0106] A 100 mL four-neck flask was equipped with a distillation system, a precision glass stirrer, a temperature probe, a nitrogen supply line, and a gas outlet / gas outlet with a pressure relief valve. Then, 6 g of isatoic anhydride and 16 g of ethylmethylimidazolium diethylphosphate (EMIM-DEP) were weighed in. Nitrogen was introduced at 10 L / h for 20 minutes, during which time the mixture was heated to 40 °C while stirring at 300 rpm. Then, 0.043 g of hexamethylene-1,6-diamine was introduced, and the solution was stirred at 150 °C for 15 hours (Step (B)). A clear solution was obtained.

[0107] The poly(anthranilamide) solution was added to 300 mL of water (step (D)(iii)). The precipitated solid was isolated by filtration and then dried at 160° C. and 0.05 bar for 24 hours.

[0108] In this experiment, completeness of CO2 removal was checked by weighing the solution before product precipitation. Complete CO2 removal would be expected to yield a solution mass of 4.42 g. A mass of 4.73 g was found, which corresponds to nearly complete CO2 removal, within the accuracy of the measurement.

[0109] Example 10: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and neopentylamine as a starter in N-methyl-2-pyrrolidone (NMP) as a solvent Isatoic anhydride and N-methyl-2-pyrrolidone (NMP) were sourced from Sigma-Aldrich, and neopentylamine was sourced from ABCR (Step (A)).

[0110] A 100 mL four-neck flask was equipped with a distillation system, a precision glass stirrer, a temperature probe, a nitrogen supply line, and a gas outlet / gas outlet with a pressure relief valve. Then, 1 g of isatoic anhydride and 4.5 g of N-methyl-2-pyrrolidone (NMP) were weighed in. Nitrogen was introduced at 10 L / h for 20 minutes, during which the mixture was heated to 40°C while stirring at 300 rpm. Then, 0.001 g of neopentylamine was introduced, and the solution was stirred at 180°C for 15 hours (Step (B)). A suspension was obtained.

[0111] During D2SO4, 1 By H NMR, the molar mass M n It was decided that:

[0112] 1 g of poly(anthranilamide) suspension was dissolved in 1 mL of concentrated sulfuric acid. The precipitated solid (=diphenyl ether solvent) was removed by filtration (step (C)).

[0113] The filtered sulfuric acid solution was added to 15 mL of water (step (D)(ii)). The precipitated solid was isolated by filtration and then dried at 160° C. and 0.05 bar for 24 hours.

[0114] Example 11: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and neopentylamine as a starter in 1,3-dimethyl-2-imidazolidinone (DMI) as a solvent Isatoic anhydride and 1,3-dimethyl-2-imidazolidinone (DMI) were sourced from Sigma-Aldrich, and neopentylamine was sourced from ABCR (Step (A)).

[0115] A 100 mL four-neck flask was equipped with a distillation system, a precision glass stirrer, a temperature probe, a nitrogen supply line, and a gas outlet / gas outlet with a pressure relief valve. Then, 1 g of isatoic anhydride and 4.5 g of 1,3-dimethyl-2-imidazolidinone (DMI) were weighed in. Nitrogen was introduced at 10 L / h for 20 minutes, during which the mixture was heated to 40°C while stirring at 300 rpm. Then, 0.001 g of neopentylamine was introduced, and the solution was stirred at 180°C for 15 hours (Step (B)). A suspension was obtained.

[0116] During D2SO4, 1 By H NMR, the molar mass M n It was decided that:

[0117] 1 g of poly(anthranilamide) suspension was dissolved in 1 mL of concentrated sulfuric acid. The precipitated solid (=diphenyl ether solvent) was removed by filtration (step (C)).

[0118] The filtered sulfuric acid solution was added to 15 mL of water, and the precipitated solid was isolated by filtration and then dried at 160° C. and 0.05 bar for 24 hours (step (D)).

[0119] The table below compares the results of the analysis.

[0120] [Table 3]

[0121] Example 12: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and neopentylamine as a starter in a mixture of N-methyl-2-pyrrolidone (NMP) and ethylmethylimidazolium diethylphosphate (EMIM-DEP) as a solvent Isatoic anhydride, N-methyl-2-pyrrolidone (NMP) and ethylmethylimidazolium diethylphosphate (EMIM-DEP) were sourced from Sigma-Aldrich, and neopentylamine was sourced from ABCR (Step (A)).

[0122] A 100 mL four-neck flask was equipped with a distillation system, a precision glass stirrer, a temperature probe, a nitrogen supply line, and a gas outlet / gas outlet with a pressure relief valve. Then, 1.5 g of isatoic anhydride, 4.5 g of N-methyl-2-pyrrolidone (NMP), and 0.236 g of ethylmethylimidazolium diethylphosphate (EMIM-DEP) were weighed into the flask. Nitrogen was introduced at 10 L / h for 20 minutes, during which the mixture was heated to 40°C while stirring at 300 rpm. Then, 0.001 g of neopentylamine was introduced, and the solution was stirred at 180°C for 15 hours (Step (B)). A suspension was obtained.

[0123] During D2SO4, 1 By H NMR, the molar mass M n It was decided that:

[0124] 1 g of poly(anthranilamide) suspension was dissolved in 1 mL of concentrated sulfuric acid. The precipitated solid (=diphenyl ether solvent) was removed by filtration (step (C)).

[0125] The filtered sulfuric acid solution was added to 15 mL of water (step (D)(ii)). The precipitated solid was isolated by filtration and then dried at 160° C. and 0.05 bar for 24 hours.

[0126] Example 13: Preparation of poly(anthranilamide) by ring-opening polymerization of isatoic anhydride as a monomer and neopentylamine as a starter in a mixture of 1,3-dimethyl-2-imidazolidinone (DMI) and ethylmethylimidazolium diethylphosphate (EMIM-DEP) as a solvent Isatoic anhydride, 1,3-dimethyl-2-imidazolidinone (DMI) and ethylmethylimidazolium diethylphosphate (EMIM-DEP) were obtained from Sigma-Aldrich, and neopentylamine was obtained from ABCR (Step (A)).

[0127] A 100 mL four-neck flask was equipped with a distillation system, a precision glass stirrer, a temperature probe, a nitrogen supply line, and a gas outlet / gas outlet with a pressure relief valve. Then, 1.5 g of isatoic anhydride, 4.5 g of 1,3-dimethyl-2-imidazolidinone (DMI), and 0.236 g of ethylmethylimidazolium diethylphosphate (EMIM-DEP) were weighed into the flask. Nitrogen was introduced at 10 L / h for 20 minutes, during which time the mixture was heated to 40 °C while stirring at 300 rpm. Then, 0.001 g of neopentylamine was introduced, and the solution was stirred at 180 °C for 15 hours (Step (B)). A suspension was obtained.

[0128] During D2SO4, 1 By H NMR, the molar mass M n It was decided that:

[0129] 1 g of poly(anthranilamide) suspension was dissolved in 1 mL of concentrated sulfuric acid. The precipitated solid (=diphenyl ether solvent) was removed by filtration (step (C)).

[0130] The filtered sulfuric acid solution was added to 15 mL of water (step (D)(ii)). The precipitated solid was isolated by filtration and then dried at 160° C. and 0.05 bar for 24 hours.

[0131] The table below compares the results of the analysis.

[0132] [Table 4]

Claims

1. 1. A process for preparing poly(anthranilamide), comprising: (A) providing isatoic anhydride; (B) polymerizing isatoic anhydride on a starter at a reaction temperature in the range of 110° C. to 300° C. so that the molar ratio of isatoic anhydride to starter is in the range of 20 to 2500, or in the range of 40 to 2500, or in the range of 50 to 2400, or in the range of 70 to 2000, to obtain a poly(anthranilamide) based on the starter; Including, wherein the starter is aliphatic mono- or diamines having 5 to 13 carbon atoms; araliphatic mono- or diamines having 7 to 15 carbon atoms, aromatic diamines having 6 to 13 carbon atoms; Formula Ar-(C=O)NHR, where Ar is an amine NH group or NH ２ R represents an aromatic radical or an aliphatic radical, or a mixture of the starters described above, A process comprising: The process is characterized in that the polymerization is carried out in the absence of a solvent, and after step (B): (C)(i) dissolving the poly(anthranilamide) in a mineral acid to obtain a mineral acid solution of the poly(anthranilamide); (D)(i) isolating the poly(anthranilamide) dissolved in the mineral acid from the mineral acid solution, including precipitating it in water; followed by the process is characterized in that the polymerization of the isatoic anhydride is carried out in the presence of a solvent, which comprises an organic solvent that is liquid at the reaction temperature or a mixture of such an organic solvent and an ionic liquid, and in step (B) the poly(anthranilamide) based on the starter is obtained by suspending it in the solvent, and after step (B): (C)(ii) dissolving the poly(anthranilamide) suspended in the solvent in a mineral acid and separating it from the solvent to obtain a mineral acid solution of the poly(anthranilamide); (D)(ii) isolating the poly(anthranilamide) dissolved in the mineral acid from the mineral acid solution, including precipitating it in water; followed by, or the process is characterized in that the polymerization of the isatoic anhydride is carried out in the presence of a solvent, the solvent comprising an ionic liquid or a mixture of an ionic liquid and an organic solvent that is liquid at a reaction temperature, and in step (B), the poly(anthranilamide) based on the starter is obtained by dissolving it in the solvent, and after step (B): (D)(iii) isolating the poly(anthranilamide) dissolved in the solvent from the solution in the solvent, including precipitating it in water. is what follows, a process.

2. aliphatic primary or secondary mono- or diamines having 5 to 13 carbon atoms include neopentylamine, hexamethylenediamine, methylenedicyclohexyldiamine and / or pentamethylenediamine; and / or the araliphatic mono- or diamine having 7 to 15 carbon atoms comprises xylylenediamine; and / or the aromatic diamine having 6 to 13 carbon atoms comprises methylenediphenylenediamine, naphthylenediamine and / or tolylenediamine; and / or The carboxamide of formula Ar—(C═O)NHR comprises N-neopentylanthranilamide; The process of claim 1.

3. formula: {H-(HN-(ortho-C ６ H ４ )-(C=O) ｍ } ｘ -A-[(O═C)(ortho-C ６ H ４ )-NH] ｎ -H (In the formula, m and n represent the number of repeating units; m+n is in the range of 20 to 2500, or 40 to 2500, or 50 to 2400, or 70 to 2000; x is 0 or 1; A is the total of all amine NH groups and NH ２ Removal of a hydrogen atom from the group gives an amine NH group or NH ２ from a starter molecule comprising a group, wherein the starter molecule aliphatic mono- or diamines having 5 to 13 carbon atoms; araliphatic mono- or diamines having 7 to 15 carbon atoms, an aromatic diamine having 6 to 13 carbon atoms, or Formula Ar-(C=O)NHR, where Ar is an amine NH group or NH ２ wherein R represents an aromatic radical or an aliphatic radical.

4. 10. Use of the poly(anthranilamide) of claim 3 in the manufacture of fibers or composite materials from poly(anthranilamide) and another material, including a metal, an inorganic substance, or a polymer other than poly(anthranilamide).

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