Method for producing poly(o-aminobenzamide), poly(o-aminobenzamide) and use thereof

Abstract

The present invention relates to a process for preparing poly(o-aminobenzamide) by polymerizing isatoic anhydride onto an initiator at a reaction temperature of 110° C. to 300° C., preferably in the presence of a solvent, wherein the initiator comprises an aliphatic monoamine or diamine having 5 to 13 carbon atoms, an aromatic aliphatic monoamine 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, wherein Ar refers to an aromatic group substituted by an amine NH or NH2 group and R represents an aromatic or aliphatic group, or a mixture of the above initiators, and wherein if a solvent is used, it comprises an organic solvent, an ionic liquid or a mixture of these solvents in liquid form at the reaction temperature, to obtain a poly(o-aminobenzamide) based on the initiator. The present invention also relates to the poly(o-aminobenzamide) obtainable with the process of the invention and their use in the production of fibers or composite materials.

Description

[0001] The present invention relates to a process for preparing poly(o-aminobenzamide) by polymerizing isatoic anhydride onto a starter at a reaction temperature of 110° C. to 300° C., preferably in the presence of a solvent, wherein the starter comprises an aliphatic monoamine or diamine having 5 to 13 carbon atoms, an aromatic aliphatic monoamine 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, wherein Ar is an aromatic group substituted by an amine NH or NH2 group and R is an aromatic or aliphatic group, or a mixture of the above starters, and wherein if a solvent is used, it comprises an organic solvent, an ionic liquid or a mixture of the above solvents in liquid form at the reaction temperature, to obtain a poly(o-aminobenzamide) based on the starter. The present invention further relates to the poly(o-aminobenzamide) obtainable by the process of the invention and their use in the production of fibers or composite materials.

[0002] Aromatic polyamides (also called aramids) in which amide groups are bonded to aromatic groups are known in the prior art and are distributed under trade names such as Kevlar, Twaron (poly(p-phenylene terephthalamide)) or Nomex, Teijinconex (poly(m-phenylene isophthalamide)). They can be used in a variety of fields. A prominent example is the production of fibers, especially textile fibers. Fibers made of aramid are known for their extremely high strength, high impact resistance, high elongation at break and good vibration damping. They are also very heat-resistant and fire-resistant. One disadvantage is the high cost compared to many other polymers. Aramids are usually made from aromatic dicarbonyl halides ClCO-Ar 1 -COCl and aromatic diamine H2N-Ar 2 -NH2 is prepared by polycondensation, which necessarily results in a polymer structure with alternating units derived from dicarboxylic acids and diamines (-[-CO-Ar 1 -CO-NH-Ar 2 -NH]-; AABB polymer structure).

[0003] AFAmin, BP Suthar and SR Patel describe the preparation of poly(o-aminobenzamide)s having 3 to 10 repeating units in J. Macromol. Sci.-Chem. 1982, A17(3), 481-488. The synthesis is achieved by ring-opening polymerization (hereinafter also referred to as ROP) of isatoic anhydride, the initiator being HCl. (aq) , o-aminobenzamide (H2N-ortho-C6H4-(C=O)NH2), N-methylaniline and o-chloroaniline. Experiments using water, ethanol, o-cresol, dilute ammonia and formamide as initiators did not result in the formation of the desired polymer product. Therefore, the synthesized polymer can be represented by the chemical formula as follows:

[0004] ·A′-[(O=C)(ortho-C6H4)-NH] n -H

[0005] A′=Cl, NH-ortho-C6H4-(C=O)NH2, N(CH3)-C6H5 or NH-ortho-C6H4-Cl;

[0006] n = 3 to 10.

[0007] In view of the relatively low number of repeating units, the products formed should rather be called oligomers. The use of various kinds of diamines, aliphatic monoamines, araliphatic monoamines or N-alkyl- or N-arylcarboxamides derived from aromatic carboxylic acids having amine NH or NH2 groups on the aromatic ring as starters is not described.

[0008] As early as 1947, RP Staiger and EC Wagner described the reaction of isatoic anhydride with various concentrations of ammonia (published in Journal of Organic Chemistry 1948, 13, 347-352 in 1948). At low ammonia concentrations, o-aminobenzamide is obtained with elimination of carbon dioxide. At higher ammonia concentrations, cyclic benzoyl urea is obtained instead, with elimination of water. With reference to earlier studies, the formation of so-called "abnormal" products from ammonia and isatoic anhydride is also reported, in particular when isatoic anhydride is treated with only half an equivalent of ammonia. This provides an amorphous product, which is described as a condensation product. The already cited reference J. Macromol. Sci.-Chem. 1982, A17 (3), 481-488 also refers to so-called "abnormal products" with reference to earlier studies (abnormal means that these products are insoluble in ethanol and melt in a wide temperature range). However, according to J. Macromol. Sci.-Chem. 1982, A17 (3), 481-488, these abnormal products have never been systematically characterized, and according to this reference, a large number of reports indicate that such "abnormal" products are just mixtures of "normal" products. Robert H. Clark and EC Wagner also reported so-called "abnormal" products in Journal of Organic Chemistry, 1944, 9, 55-67, where the authors estimated that they were oligoamides of the following type:

[0009] H2N-ortho-C6H4-(C=O)-[NH-ortho-C6H4-(C=O)] x NHR

[0010] wherein x does not exceed a value of 1 or 2. The formation of macromolecular products is only suspected and is also due to possible association or aggregation.

[0011] US Pat. No. 9,683,126 B2 describes polymers having a CC backbone onto which up to 10 anthranilamide units are grafted via divalent bridges. The base polymers forming the CC backbone are, in particular, differently substituted poly(methacrylates) or polymeric vinylaromatics.

[0012] The formation of relatively high molecular weight poly(anthranilide)s in which the high molar mass is achieved by a large number of anthranilamide repeating units and not by grafting onto another polymer (i.e. the formation of "true" anthranilamide polymers and not of oligomers or copolymers of only a few repeating units) is not described in these references. Other more commonly used aramids, such as the poly(p-phenylene terephthalamide) or poly(m-phenylene isophthalamide) mentioned at the outset, although they can be prepared in high molar masses (even though this is expensive in terms of apparatus and process technology due to the use of acid chlorides under extremely corrosive conditions) and also have very good application properties, are very expensive. Furthermore, the common process for preparing these aramids is based on polycondensation reactions to form AABB polymer structures, which requires very precise adherence to the reaction stoichiometry in order to form polymers with high molar masses.

[0013] Yoshiyuki Sasaki and Pierre H. Dixneuf describe the thermal decarboxylation of isatoic anhydride to form heat-stable polyamides in Journal of Organic Chemistry 1987, 52, 315-316. The reaction occurs when heated to a temperature still below the melting point. The following structure is proposed for the solid product:

[0014] ~NH-ortho-C6H4-(C=O)NH-ortho-C6H4-(C=O)~.

[0015] The mass average molar mass M was determined by gel permeation chromatography. w , which corresponds to about 5 times the mass of isatoic anhydride. It is therefore an oligomer, which is also consistent with the fact that the product is found to be fusible. (It is known that high molecular weight poly(o-aminobenzamide) cannot be melted without decomposition).

[0016] It was also attempted to catalyze the reaction with the aid of a doping agent. The doping agent was used in a proportion of 0.01% of the mass of isatoic anhydride. In the case of doping with o-aminobenzamide, 14% of the theoretically expected amount of CO2 was eliminated, and in the case of doping with sodium acetate, 81% was eliminated. In contrast, in the absence of a doping agent, only 2% of the theoretically expected amount of CO2 was eliminated. When 1% sodium acetate was used, a mass-average molar mass of 1280 g / mol was found, but with a high polydispersity.

[0017] Therefore, further improvements are needed in the field of aramid chemistry.

[0018] Taking this need into account, the subject of the present invention is therefore a process for preparing poly(o-aminobenzamide) comprising the steps of:

[0019] (A) providing isatoic anhydride;

[0020] (B) polymerizing isatoic anhydride onto an initiator at a reaction temperature of 110° C. to 300° C., especially 150° C. to 300° C., preferably in the presence of a solvent,

[0021] wherein the initiator comprises an aliphatic monoamine or diamine having 5 to 13 carbon atoms, an aromatic aliphatic monoamine 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, wherein Ar is an aromatic group substituted by an amine NH or NH2 group (especially H2N-C6H4) and R is an aromatic or aliphatic group, or a mixture of the above initiators,

[0022] Wherein, if a solvent is used, it comprises an organic solvent, an ionic liquid or a mixture of the above solvents which is in liquid form at the reaction temperature,

[0023] To obtain the initiator-based poly(o-aminobenzamide).

[0024] Another subject of the invention is a poly(o-aminobenzamide) of the formula

[0025] {H-[HN-(ortho-C6H4)-(C=O)] m} x -A-[(O=C)(ortho-C6H4)-NH] n -H (I)

[0026] in

[0027] m and n refer to the number of repeating units,

[0028] x is 0 (in the case of a monofunctional initiator) or 1 (in the case of a difunctional initiator), A is formed by a starter molecule comprising an aminic NH or NH2 group by removing hydrogen atoms from all aminic NH or NH2 groups, wherein the starter molecule is an aliphatic monoamine or diamine having 5 to 13 carbon atoms, an aromatic aliphatic monoamine 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, wherein Ar is an aromatic group substituted by an aminic NH or NH2 group (especially H2N-C6H4) and R is an aromatic or aliphatic group.

[0029] Finally, the present invention relates to the use of the poly(anthranilide) according to the invention for producing fibers or composite materials from poly(anthranilide) and (at least) one further material comprising a metal, a mineral material or a polymer different from poly(anthranilide).

[0030] In the terminology of the present invention, the term amine NH or NH2 group refers to a primary or secondary organic amine (rather than other compounds having NH or NH2 groups, such as in particular amides), i.e. to an organic compound in which the NH or NH2 group is bonded to a carbon atom without an additional heteroatom.

[0031] Araliphatic monoamines and diamines are understood to mean those monoamines and diamines which have aromatic and aliphatic groups. All amino groups in such monoamines or diamines are preferably bonded to those carbon atoms which are directly adjacent to the aromatic group, for example in the case of xylylenediamine.

[0032] Organic solvents are understood to mean non-ionic organic solvents, rather than ionic liquids (=salts with a low (ie below 100° C.) melting point).

[0033] The method that is crucial for determining the number of repeating units m+n in the present invention is 1 H NMR spectroscopy. This gives an average value for the number of repeating units, from which the number-average molar mass of the poly(o-aminobenzamide) can be calculated. The details are described in the "Analysis" section below.

[0034] Below first Overview Various possible embodiments of the invention.

[0035] 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, most preferably in the range of 170°C to 260°C.

[0036] In a second embodiment of the process according to the invention, which can be combined with all other embodiments, step (B) is carried out at 1.0 bar. (abs.) Up to 5.0 bar (abs.) under pressure.

[0037] In a third embodiment of the process according to the invention, which can 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.

[0038] In a fourth embodiment of the process according to the invention, which can be combined with all the other embodiments, the aromatic aliphatic mono- or diamine having 7 to 15 carbon atoms comprises xylylenediamine.

[0039] In a fifth embodiment of the process according to the invention, which can be combined with all the other embodiments, the aromatic diamine having 6 to 13 carbon atoms comprises methylenediphenylenediamine, naphthalenediamine and / or toluenediamine.

[0040] In a sixth embodiment of the process according to the invention, which can be combined with all other embodiments, the carboxamide of the formula Ar-(C=O)NHR comprises N-neopentylanthranilic acid amide (Ar=ortho-C6H4-NH2; R=neopentyl).

[0041] In a seventh embodiment of the process of the invention, which can be combined with all other embodiments except those envisaging the use of a solvent in step (B), the polymerization is carried out in the absence of a solvent, wherein after step (B):

[0042] (C) (i) dissolving poly(o-aminobenzamide) in an inorganic acid to obtain an inorganic acid solution of poly(o-aminobenzamide);

[0043] (D) (i) isolating the poly(o-aminobenzamide) dissolved in the mineral acid from the mineral acid solution, which comprises the step of precipitation in water.

[0044] In an eighth embodiment of the process according to the invention, which is a special configuration of the seventh embodiment, the inorganic acid comprises sulfuric acid, hydrochloric acid, nitric acid and / or phosphoric acid, in particular sulfuric acid.

[0045] In a ninth embodiment of the process of the invention, combinable with all other embodiments except those which exclude the use of a solvent in step (B) or envisage the use of pure solvent polymerization for this step, the polymerization is carried out in the presence of a solvent, wherein the solvent comprises an organic solvent which is in liquid form at the reaction temperature, or comprises a mixture of such an organic solvent and an ionic liquid, and in step (B) the poly(o-aminobenzamide) based on the initiator is obtained in suspension in the solvent, wherein after step (B):

[0046] (C)(ii) dissolving the poly(othaminobenzamide) suspended in the solvent in an inorganic acid and separating the solvent to obtain an inorganic acid solution of the poly(othaminobenzamide);

[0047] (D)(ii) isolating the poly(o-aminobenzamide) dissolved in the inorganic acid from the inorganic acid solution, which comprises the step of precipitation in water.

[0048] In a tenth embodiment of the process according to the invention, which is a special configuration of the ninth embodiment, the inorganic acid comprises sulfuric acid, hydrochloric acid, nitric acid and / or phosphoric acid, in particular sulfuric acid.

[0049] In an eleventh embodiment of the process according to the invention which is a special configuration of the ninth and tenth embodiments, the solvent is removed in step (C)(i) by filtration, centrifugation or phase separation.

[0050] In a twelfth embodiment of the process of the invention, combinable with all other embodiments except those which exclude the use of a solvent in step (B) or envisage the use of suspension polymerization for this step, the polymerization of isatoic anhydride is carried out in the presence of a solvent, wherein the solvent comprises an ionic liquid or a mixture of an ionic liquid and an organic solvent which is in liquid form at the reaction temperature, and in step (B) the poly(o-aminobenzamide) based on the initiator is obtained dissolved in the solvent, wherein after step (B):

[0051] (D)(iii) isolating the poly(o-aminobenzamide) dissolved in the solvent from the solution in the solvent, which comprises the step of precipitation in water.

[0052] In a thirteenth embodiment of the method 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 hexamethylphosphoric triamide.

[0053] In a fourteenth embodiment of the method of the present invention, which is a specific configuration of the ninth to 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 methanesulfonate and / or dialkylimidazolium phosphate (such as, in particular, butyl-3-methylimidazolium phosphate, diethyldimethylimidazolium phosphate ("MMIM-DEP") and diethylethylmethylimidazolium phosphate ("EMIM-DEP")).

[0054] In a fifteenth embodiment of the method of the invention, which is a special configuration of the seventh to fourteenth embodiments, precipitation in water is achieved by adding a solution of poly(o-aminobenzamide) to a 5-fold to 20-fold volume excess of water.

[0055] In a sixteenth embodiment of the process according to the invention, which can be combined with all other embodiments, the molar ratio of isatoic anhydride to the starter selected in step (B) 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, most preferably in the range of 70 to 2000, in order in particular to obtain (poly)o-aminobenzamide of formula (I) having a value of m+n in the range of 20 to 2500, preferably in the range of 40 to 2500, more preferably in the range of 50 to 2400, most preferably in the range of 70 to 2000.

[0056] In a seventeenth embodiment of the process of the invention, which can be combined with all other embodiments, the provision of isatoic anhydride in step (A) comprises chemical conversion of anthranilic acid.

[0057] In an eighteenth embodiment of the method of the present invention as a special configuration of the seventeenth embodiment, the chemical conversion of anthranilic acid is selected from anthranilic acid

[0058] with carbon monoxide in the presence of a catalyst, in particular in the presence of a Pd or Pt catalyst, or

[0059] Reaction with a phosgenation medium selected from phosgene, diphosgene, triphosgene, oxalyl chloride, 1,1-carbonyldiimidazole and / or dimethyl carbonate.

[0060] In a nineteenth embodiment of the method of the present invention as a special configuration of the seventeenth and eighteenth embodiments, anthranilic acid is obtained by fermenting a raw material comprising

[0061] fermentable carbon-containing compounds, preferably starch hydrolysates, sugar cane juice, beet juice, hydrolysates of lignocellulose-containing raw materials or mixtures thereof,

[0062] and

[0063] A nitrogen-containing compound, preferably ammonia gas, ammonia water, an ammonium salt, urea or a mixture thereof.

[0064] In the twentieth embodiment of the method of the present invention, which is a specific configuration of the nineteenth embodiment, the fermentable carbon-containing compounds comprise starch hydrolysates, sugar cane juice, beet juice and / or hydrolysates of lignocellulose-containing raw materials, and wherein the nitrogen-containing compounds comprise ammonia gas, ammonia water, ammonium salts and / or urea.

[0065] In the present invention which can be combined with all other embodiments Poly(o-aminobenzamide) In a first embodiment of the invention, the aliphatic primary or secondary monoamine or diamine having 5 to 13 carbon atoms is neopentylamine, hexamethylenediamine, methylenedicyclohexyldiamine or pentamethylenediamine.

[0066] In a second embodiment of the poly(o-aminobenzamide) of the invention, which is combinable with all other embodiments, the aromatic aliphatic mono- or diamine having 7 to 15 carbon atoms is xylylenediamine.

[0067] In a third embodiment of the poly(o-aminobenzamide) of the invention, which can be combined with all the other embodiments, the aromatic diamine having 6 to 13 carbon atoms is methylenediphenylenediamine, naphthalenediamine or toluenediamine.

[0068] In a fourth embodiment of the poly(anthranilide) of the invention, which can be combined with all other embodiments, the carboxamide of formula Ar-(C=O)NHR is N-neopentylanthranilide (Ar=ortho-C6H4-NH2; R=neopentyl).

[0069] In a fifth embodiment of the poly(o-aminobenzamide) of the present invention, which may 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, most preferably in the range of 70 to 2000.

[0070] In a first embodiment of the use of the invention, the fibers or composite materials are used to produce protective equipment (especially, but not limited to, clothing articles such as protective suits and protective vests) to protect against fire, fragmentation, fragment penetration, mechanical impact (including shooting) or cuts.

[0071] In a second embodiment of the use according to the invention, which can be combined with all other embodiments, the fibers or composite materials are used for producing sports equipment.

[0072] The above-summarized embodiments of the invention and further possible embodiments are explained in more detail below.Herein, all embodiments can be combined with one another as desired, unless otherwise stated or clearly evident from the context.

[0073] In step (A) of the process of the invention, isatoic anhydride is provided for subsequent polymerization. Here, isatoic anhydride can in principle be prepared by all methods known in the professional field for the synthesis of this compound. Usually, the synthesis starts with anthranilic acid (= anthranilic acid) and is achieved, for example, by its reaction with phosgene, especially in a hydrochloric acid medium. Instead of phosgene, diphosgene, triphosgene or other phosgenation media known in the prior art, such as oxalyl chloride, 1,1-carbonyldiimidazole and dimethyl carbonate, can also be used. It is also possible that anthranilic acid reacts with carbon monoxide in the presence of a catalyst, especially in the presence of a Pd or Pt catalyst, to obtain isatoic anhydride.

[0074] Anthranilic acid can in turn be prepared by known chemical methods. An 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 well known. Industrial processes are also described in the patent literature; see, for example, DE 29 02 978 A1 and EP 0 004635 A2. In addition, a fermentative preparation route for anthranilic acid has recently been disclosed, which starts from renewable raw materials and is therefore suitable for protecting fossil raw materials and reducing the so-called CO2 footprint; see, for example, WO 2018 / 002088 A1, page 13, line 26 to page 22, line 15, and the literature cited therein. This fermentation method can also be used for the method according to the invention. In this embodiment, step (A) of the method according to the invention therefore comprises fermentation of a raw material, which comprises

[0075] fermentable carbon-containing compounds, preferably starch hydrolysates, sugar cane juice, beet juice, hydrolysates of lignocellulose-containing raw materials or mixtures thereof,

[0076] and

[0077] A nitrogen-containing compound, preferably ammonia gas, ammonia water, an ammonium salt, urea or a mixture thereof.

[0078] Preferably, the fermentable carbon-containing compound comprises a hydrolysate of starch, sugar cane juice, beet juice and / or a hydrolysate of a lignocellulose-containing raw material, and wherein the nitrogen-containing compound comprises ammonia, ammonia water, an ammonium salt and / or urea. Suitable microorganisms for fermentation are in particular Escherichia coli, Pseudomonas putida, Corynebacterium glutamicum, Ashbya gossypii, Pichia pastoris, Hansenula polymorpha, Yarrowia lipolytica, Zygosaccharomyces bailii or Saccharomyces cerevisiae.

[0079] In step (B) of the process according to the invention, the isatoic anhydride provided in step (A) is subjected to a ring-opening polymerization (ROP) with elimination of CO2. The initiators used according to the invention comprise aliphatic monoamines or diamines having 5 to 13 carbon atoms, aromatic aliphatic monoamines or diamines having 7 to 15 carbon atoms, aromatic diamines having 6 to 13 carbon atoms, carboxamides of the formula Ar-(C=O)NHR, wherein Ar is an aromatic group substituted by an amine NH or NH2 group (especially H2N-C6H4) and R is an aromatic or aliphatic group, or a mixture of the above-mentioned initiators.

[0080] 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 (especially hexamethylene-1,6-diamine), methylenedicyclohexyldiamine (especially 2,2′-, 2,4′- and / or 4,4′-methylenedicyclohexyldiamine) and / or pentamethylenediamine (especially pentamethylene-1,5-diamine).

[0081] In a further embodiment of the invention, aromatic aliphatic mono- or diamines having 7 to 15 carbon atoms are used, particularly preferably xylylenediamine (especially xylene-1,3-diamine).

[0082] In a further embodiment of the invention, use is made of aromatic diamines having 6 to 13 carbon atoms, particularly preferably methylenediphenylenediamine (especially 2,2′-, 2,4′- and / or 4,4′-methylenediphenylenediamine), naphthalenediamine (especially naphthalene-1,5-diamine) and / or toluenediamine (especially m- and / or o-toluenediamine).

[0083] In another embodiment of the invention, use is made of a carboxamide of the formula Ar-(C=O)NHR, in particular N-neopentylanthranilic acid amide (Ar=ortho-C6H4-NH2; R=neopentyl).

[0084] The polymerization is carried out at a reaction temperature 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., very particularly preferably 170° C. to 260° C. The polymerization can be carried out (i) without solvent (“neat”, “bulk polymerization”) or preferably in the presence of a solvent. In the latter case, suitable solvents are (ii) organic solvents which are liquid at the reaction temperature, (iii) ionic liquids or (iv) mixtures of the two. Suitable solvents for case (ii) are especially diphenyl ether, N-methyl-2-pyrrolidone (NMP; preferably in combination with CaCl2 as solubilizer), 1,3-dimethyl-2-imidazolidinone (DMI) and / or hexamethylphosphoric triamide. These are in liquid form at suitable reaction temperatures (see above). For case (iii), it is conceivable in principle to use the ionic liquids known in the art, 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 methanesulfonate and / or dialkylimidazolium phosphates, such as in particular butyl-3-methylimidazolium phosphate, diethyldimethylimidazolium phosphate ("MMIM-DEP") and diethylethylmethylimidazolium phosphate ("EMIM-DEP")).

[0085] In the case of ROP without solvent (i), isatoic anhydride is converted in the molten state, i.e. at temperatures above 230° C. The upper limit of the reaction temperature mentioned above also preferably applies to solvent-free polymerization. The initiator should therefore have a sufficiently high boiling point under the selected reaction conditions. In principle, the reaction has no particular requirements on the reaction pressure. ROP can therefore be carried out at ambient pressure. However, it is also possible to carry out the reaction at elevated pressure relative to ambient pressure, in particular at 1.1 bar. (abs.) Up to 5.0 bar (abs.) The starter is reacted with isatoic anhydride under a pressure of 1.5 bar to avoid as much as possible the loss of starter by evaporation. It is also conceivable to react the starter with isatoic anhydride under ambient pressure or slightly elevated pressure (e.g. 1.1 bar). (abs.) ) and the pressure is allowed to increase due to elimination of carbon dioxide, in particular up to preferably 5.0 bar (abs.) The apparatus for the polymerization is preferably equipped with a pressure-maintaining valve to ensure compliance with the target maximum pressure. The above details about the pressure also apply, of course, to the reaction in the presence of a solvent.

[0086] In the case of being carried out without a solvent, the polymerization starts in a homogeneous phase (in the melt). However, as the polymerization proceeds, the polymer formed precipitates rapidly, so that a suspension of the polymer in the unconverted initiator and the unconverted monomer is obtained. As the polymerization proceeds further, the entire reaction mixture generally solidifies substantially.

[0087] Post-processing in this case preferably comprises the following steps:

[0088] (C)(i) dissolving poly(o-aminobenzamide) in a mineral acid;

[0089] (D) (i) isolating the poly(o-aminobenzamide) dissolved in the mineral acid from the mineral acid solution, which comprises the step of precipitation in water.

[0090] Suitable inorganic 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 in a mass concentration of 96% to 100%, preferably 96% to 98%. The dissolution is preferably carried out at a temperature of 20° C. to 100° C.

[0091] In step (D)(i) of this embodiment of the process according to the invention, the poly(o-aminobenzamide) is separated from the mineral acid solution obtained in step (C). This is achieved by precipitation with water. For this purpose, the mineral acid solution of the poly(o-aminobenzamide) is preferably added to a 5-fold to 20-fold volume excess of water. The poly(o-aminobenzamide) precipitates out here and can be easily removed, for example by filtration or centrifugation. Further post-treatment steps for purification can then be carried out.

[0092] However, ROP prefers In the presence of solvent Depending on the solvent used, the polymer product is obtained here as a suspension or solution in the chosen solvent.

[0093] If you use Organic solvents (ii), then in step (B) a suspension of poly(o-aminobenzamide) is generally obtained (suspension polymerization). In this case, the post-treatment of the process product in step (B) preferably comprises the steps of:

[0094] (C)(ii) dissolving the poly(othaminobenzamide) suspended in the solvent in an inorganic acid and separating the solvent to obtain an inorganic acid solution of the poly(othaminobenzamide);

[0095] (D)(ii) isolating the poly(o-aminobenzamide) dissolved in the inorganic acid from the inorganic acid solution, which comprises the step of precipitation in water.

[0096] The preferred conditions for the dissolution and separation steps mentioned above for case (i) also apply to case (ii). The removal of the organic solvent, which is additionally required here, is preferably carried out by filtration, centrifugation or phase separation. This removal can be carried out both before the poly(o-aminobenzamide) is dissolved in the mineral acid (in which case the solid poly(o-aminobenzamide) which usually still contains entrained organic solvent is filtered off and then dissolved in the mineral acid) and after it (in which case the organic solvent which has precipitated in the mineral acid or is insoluble is separated off).

[0097] If the solvent used in step B is an ionic liquid (iii), this step generally results in a solution of poly(o-aminobenzamide) (solution polymerization). Since the polymer product is already in solution in this case, no dissolution step (step (C) in cases (i) and (ii)) is required. In this case, the workup of the process product in step (B) therefore preferably comprises the steps:

[0098] (D)(iii) isolating the poly(o-aminobenzamide) dissolved in the solvent from the solution in the solvent, which comprises the step of precipitation in water.

[0099] The preferred conditions for the separation step mentioned above for case (i) also apply to case (iii).

[0100] If a mixture (iv) of an organic solvent and an ionic liquid is used in step (B), the process product is a solution or a suspension depending on the mixing ratio. Depending on the presence, further workup is as described above for case (iii) (solution) or for case (ii) (suspension).

[0101] The recovered solvent is preferably recycled in each case. For this purpose, purification may be necessary, which can be achieved by methods known in the art. Due to their high price, the recycling of ionic liquids is particularly important. For this purpose, the ionic liquid obtained in the separation of the poly(o-aminobenzamide) in step (D)(iii) or step (D)(iv) is dried at elevated temperature and reduced pressure, in particular at a temperature of 50° C. to 100° C. and 1 mbar. (abs.) Up to 100 mbar (abs.) Dry under pressure.

[0102] When the process product from step (B) is in the form of a solution, it is also conceivable to further process this solution directly to give the desired end product, in particular to spin fibers of poly(o-aminobenzamide) directly from the solution.

[0103] The process of the invention enables the formation of high molecular weight poly(o-aminobenzamide). The molar ratio of isatoic anhydride to initiator can therefore vary within wide ranges and can in particular be in the range of 20 to 2500, preferably 40 to 2500, more preferably 50 to 2400, most preferably in the range of 70 to 2000. The molar ratio chosen will of course depend on the desired field of application of the poly(o-aminobenzamide); therefore, molar ratios different from the figures given above can also be used as desired.

[0104] By the method of the present invention, a poly(o-aminobenzamide) of the formula

[0105] {H-[HN-(ortho-C6H4)-(C=O)] m} x -A-[(O=C)(ortho-C6H4)-NH] n -H (I)

[0106] in

[0107] m and n refer to the number of repeating units,

[0108] x is 0 or 1,

[0109] A is generated from a starter molecule containing amine NH or NH2 groups by removing hydrogen atoms from all amine NH or NH2 groups, wherein the starter molecule is an aliphatic monoamine or diamine having 5 to 13 carbon atoms, an aromatic aliphatic monoamine 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, wherein Ar refers to an aromatic group substituted by an amine NH or NH2 group (especially H2N-C6H4) and R refers to an aromatic or aliphatic group.

[0110] The embodiments mentioned above for the process of the invention also apply correspondingly to the poly(o-aminobenzamide) of the invention. For example, the starter used for the preparation of the poly(o-aminobenzamide) may comprise 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), benzylenediamine (especially benzene-1,3-dimethylamine), methylenediphenylenediamine (especially 2,2′-, 2,4′- and / or 4,4′-methylenediphenylenediamine), naphthalenediamine (especially naphthalene-1,5-diamine), toluenediamine (especially m- and / or o-toluenediamine) or N-neopentylanthranilide (Ar=ortho-C6H4-NH2; R=neopentyl). The initiator may also comprise a plurality of different initiator molecules.

[0111] In one embodiment, the total number of (O=C)(ortho-C6H4)-NH-repeat units (i.e. m+n) is from 20 to 2500, preferably from 40 to 2500, more preferably from 50 to 2400 and most preferably from 70 to 2000. In the case of bifunctional starter molecules, these repeat units are distributed between the two polymer chains formed. When the two amine groups of the starter molecule have the same reactivity (which is the case for symmetrical starter molecules, for example in the above-mentioned hexamethylene-1,6-diamine), then m and n are (at least substantially) equal, which means (at least approximately): m=n=(m+n) / 2. Unequal chain lengths may also form if there are differences in the reactivity of the amine groups, for example due to steric hindrance or due to the higher basicity of one amine group than the other.

[0112] The poly(o-aminobenzamide) obtainable according to the invention is suitable for various applications. Therefore, another subject of the present invention is the use of the poly(o-aminobenzamide) according to the invention in the production of fibers or composite materials from poly(o-aminobenzamide) and (at least) one other material, which comprises a metal, a mineral material (e.g. concrete) or a polymer different from poly(o-aminobenzamide) (e.g. polyurethane). The fibers or composite materials are preferably used for the production of protective equipment (in particular, but not limited to, clothing items, such as protective clothing and protective vests) for protection against fire, debris formation, debris penetration, mechanical impact (including shooting) or cuts. The fibers or composite materials can also be used to produce sports equipment.

[0113] The present invention is explained in more detail below with reference to examples. Example:

[0114] analyze

[0115] The number average molar mass (M n ) 1 H NMR spectroscopy (Bruker, AV III HD 600, 600 MHz; pulse sequence zg30, delay time d1: 10 s, 64 scans) The samples were each dissolved in deuterated sulfuric acid. 1 The relevant resonances in the H NMR spectrum (based on TMS = 0 ppm) are as follows:

[0116] The signals at 8.5-7.1 ppm are for the aromatic protons of anthranilamide (corresponding to the integration of 4 protons). The resonances of the protons of the neopentylamine initiator have a shift of 3.6-3.4 ppm (methylene, corresponding to the integration of 2 protons) and 1.1-0.9 ppm (neopentyl, corresponding to the integration of 9 protons).

[0117] The molar mass M of the polymer is calculated according to formula (I) as follows: n , where the following abbreviations are used:

[0118] F(A) = resonance area of ​​aromatic protons (4 protons) at 8.5-7.1 ppm;

[0119] F(M) = resonance area of ​​the methylene group (2 protons) of the initiator at 3.6-3.4 ppm;

[0120] F(N) = the resonance area of ​​the neopentyl group of the initiator (corresponding to 9 protons) at 1.1-0.9 ppm

[0121] The following formula (I) is used to calculate the number of repeating units m+n (in the specific case, m=0, so m+n=n) from (O=C)(ortho-C6H4)-NH in the polymer:

[0122]

[0123] The molar mass M of the polymer is calculated from the value n by the following formula (II): n :

[0124] M n =86.16g / mol+n·120.14g / mol+1g / mol (II)

[0125] Example 1: Preparation of a catalytic reaction using isatoic anhydride as a monomer and neopentylamine as an initiator in diphenyl ether as a solvent Preparation of poly(o-aminobenzamide) by cyclopolymerization

[0126] Isatoic anhydride and diphenyl ether were from Sigma-Aldrich, and neopentylamine was from ABCR (step (A)).

[0127] A 500 ml four-necked flask was equipped with a distillation bridge, a precision glass (KPG) stirrer, a temperature probe, a nitrogen feed and a gas outlet / gas outlet with a pressure relief valve. Subsequently, 98 g of isatoic anhydride and 171 g of diphenyl ether were weighed in. Nitrogen was introduced at 10 L / h for 20 minutes, wherein the mixture was heated to 40° C. while stirring at 300 rpm. Subsequently, 0.26 g of neopentylamine was introduced and the solution was stirred at 180° C. for 15 hours (step (B)). A suspension was obtained.

[0128] With the help of D2SO4 1 H NMR determination of the molar mass M according to formula (II) n .

[0129] 20 g of the poly(o-aminobenzamide) suspension was dissolved in 20 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 300 ml of water (step (D)(ii)). The precipitated solid was isolated by filtration and then dried at 160° C. at 0.05 bar for 24 hours.

[0131] Example 2: Preparation of a catalytic reaction using isatoic anhydride as a monomer and neopentylamine as an initiator in diphenyl ether as a solvent Preparation of poly(o-aminobenzamide) by cyclopolymerization

[0132] The procedure was as in Example 1, except for the following differences:

[0133] 90 g of isatoic anhydride, 130 g of diphenyl ether and 0.80 g of neopentylamine were used.

[0134] Example 3: Preparation of a catalytic reaction using isatoic anhydride as a monomer and neopentylamine as an initiator in diphenyl ether as a solvent Preparation of poly(o-aminobenzamide) by cyclopolymerization

[0135] The procedure was as in Example 1, except for the following differences:

[0136] 100 g of isatoic anhydride, 390 g of diphenyl ether and 0.060 g of neopentylamine were used.

[0137] The table below compares the analysis results.

[0138] Table 1: Properties of poly(o-aminobenzamide) prepared in Examples 1, 2 and 3

[0139]

[0140] Example 4: Using isatoic anhydride as a monomer and hexamethylene-1,6-diamine as an initiator in diphenyl ether as Preparation of Poly(o-aminobenzamide) by Ring-Opening Polymerization in Solvent

[0141] Isatoic anhydride, diphenyl ether and hexamethylene-1,6-diamine were from Sigma-Aldrich (step (A)).

[0142] A 100 ml four-necked flask was equipped with a distillation bridge, a precision glass stirrer, a temperature probe, a nitrogen feed and a gas outlet / gas outlet with a pressure relief valve. Subsequently, 10 g of isatoic anhydride and 37 g of diphenyl ether were weighed in. Nitrogen was introduced at 10 L / h for 20 minutes, wherein the mixture was heated to 40° C. while stirring at 300 rpm. Subsequently, 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.

[0143] With the help of D2SO4 1 H NMR determination of the molar mass M according to formula (II) n .

[0144] 20 g of the poly(o-aminobenzamide) suspension was dissolved in 20 ml of concentrated sulfuric acid. The precipitated solid (= diphenyl ether solvent) was removed by filtration (step (C)).

[0145] 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. at 0.05 bar for 24 hours.

[0146] Example 5: Using isatoic anhydride as a monomer and hexamethylene-1,6-diamine as an initiator in diphenyl ether as Preparation of Poly(o-aminobenzamide) by Ring-Opening Polymerization in Solvent

[0147] Proceed as in Example 4, except for the following differences:

[0148] 10 g of isatoic anhydride, 37 g of diphenyl ether and 0.11 g of hexamethylene-1,6-diamine were used.

[0149] Example 6: Using isatoic anhydride as a monomer and hexamethylene-1,6-diamine as an initiator in diphenyl ether as Preparation of Poly(o-aminobenzamide) by Ring-Opening Polymerization in Solvent

[0150] Proceed as in Example 4, except for the following differences:

[0151] 20 g of isatoic anhydride, 75 g of diphenyl ether and 0.015 g of hexamethylene-1,6-diamine were used.

[0152] Example 7: Using isatoic anhydride as a monomer and hexamethylene-1,6-diamine as an initiator in diphenyl ether as Preparation of Poly(o-aminobenzamide) by Ring-Opening Polymerization in Solvent

[0153] Proceed as in Example 4, except for the following differences:

[0154] 25 g of isatoic anhydride, 140 g of diphenyl ether and 0.005 g of hexamethylene-1,6-diamine were used.

[0155] The table below compares the analysis results.

[0156] Table 2: Properties of poly(o-aminobenzamide) prepared in Examples 4 to 7

[0157]

[0158]

[0159] Example 8: Using isatoic anhydride as a monomer and neopentylamine as an initiator in diethylphosphoethylmethylimidazole Preparation of poly(o-aminobenzamide) by ring-opening polymerization at 180°C in EMIM-DEP solvent

[0160] Isatoic anhydride and ethylmethylimidazolium diethylphosphate (EMIM-DEP) were from Sigma-Aldrich, and neopentylamine was from ABCR (step (A)).

[0161] A 100 ml four-necked flask was equipped with a distillation bridge, a precision glass stirrer, a temperature probe, a nitrogen feed and a gas outlet / gas outlet with a pressure relief valve. Subsequently, 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, wherein the mixture was heated to 40° C. while stirring at 300 rpm. Subsequently, 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.

[0162] The poly(o-aminobenzamide) solution was added to 300 ml of water (step (D)(iii)). The precipitated solid was isolated by filtration and then dried at 160° C. at 0.05 bar for 24 hours.

[0163] Example 9: Using isatoic anhydride as a monomer and hexamethylene-1,6-diamine as an initiator in diethylphosphonic acid Preparation of poly(o-aminobenzamide) by ring-opening polymerization at 150°C in ethylmethylimidazolium (EMIM-DEP) as solvent

[0164] Isatoic anhydride, ethylmethylimidazolium diethylphosphate (EMIM-DEP) and hexamethylene-1,6-diamine were from Sigma-Aldrich (step (A)).

[0165] A 100 ml four-necked flask was equipped with a distillation bridge, a precision glass stirrer, a temperature probe, a nitrogen feed and a gas outlet / gas outlet with a pressure relief valve. Subsequently, 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, wherein the mixture was heated to 40° C. while stirring at 300 rpm. Subsequently, 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.

[0166] The poly(o-aminobenzamide) solution was added to 300 ml of water (step (D)(iii)). The precipitated solid was isolated by filtration and then dried at 160° C. at 0.05 bar for 24 hours.

[0167] In this experiment, the completeness of the CO2 elimination was checked by weighing the solution before the product precipitated. In the case of complete elimination of CO2, the mass of the resulting solution would be expected to be 4.42 g. A mass of 4.73 g was measured, which corresponds to a substantially complete elimination of CO2 within the accuracy of the measurement.

[0168] Example 10: Using isatoic anhydride as a monomer and neopentylamine as an initiator in N-methyl-2-pyrrolidone Preparation of poly(o-aminobenzamide) by ring-opening polymerization in NMP as solvent

[0169] Isatoic anhydride and N-methyl-2-pyrrolidone (NMP) were from Sigma-Aldrich, and neopentylamine was from ABCR (step (A)).

[0170] A 100 ml four-necked flask was equipped with a distillation bridge, a precision glass stirrer, a temperature probe, a nitrogen feed and a gas outlet / gas outlet with a pressure relief valve. Subsequently, 1 gram 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, wherein the mixture was heated to 40° C. while stirring at 300 rpm. Subsequently, 0.001 g of neopentylamine was introduced and the solution was stirred at 180° C. for 15 hours (step (B)). A suspension was obtained.

[0171] With the help of D2SO4 1 H NMR determination of the molar mass M according to formula (II) n .

[0172] 1 g of the poly(o-aminobenzamide) suspension was dissolved in 1 ml of concentrated sulfuric acid. The precipitated solid (= diphenyl ether solvent) was removed by filtration (step (C)).

[0173] 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. at 0.05 bar for 24 hours.

[0174] Example 11: Using isatoic anhydride as a monomer and neopentylamine as an initiator in 1,3-dimethyl-2-imidazolidine Preparation of poly(o-aminobenzamide) by ring-opening polymerization in ketone (DMI) as solvent

[0175] Isatoic anhydride and 1,3-dimethyl-2-imidazolidinone (DMI) were from Sigma-Aldrich, and neopentylamine was from ABCR (step (A)).

[0176] A 100 ml four-necked flask was equipped with a distillation bridge, a precision glass stirrer, a temperature probe, a nitrogen feed and a gas outlet / gas outlet with a pressure relief valve. Subsequently, 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, wherein the mixture was heated to 40° C. while stirring at 300 rpm. Subsequently, 0.001 g of neopentylamine was introduced and the solution was stirred at 180° C. for 15 hours (step (B)). A suspension was obtained.

[0177] With the help of D2SO4 1 H NMR determination of the molar mass M according to formula (II) n .

[0178] 1 g of the poly(o-aminobenzamide) suspension was dissolved in 1 ml of concentrated sulfuric acid. The precipitated solid (= diphenyl ether solvent) was removed by filtration (step (C)).

[0179] The filtered sulfuric acid solution was added to 15 ml of water. The precipitated solid was separated by filtration and then dried at 160° C. at 0.05 bar for 24 hours (step (D)).

[0180] The table below compares the analysis results.

[0181] Table 3: Properties of poly(o-aminobenzamide) prepared in Examples 10 and 11

[0182]

[0183] Example 12: Using isatoic anhydride as a monomer and neopentylamine as an initiator in N-methyl-2-pyrrolidone The mixture of NMP and ethylmethylimidazolium diethylphosphate (EMIM-DEP) was used as the solvent for the ring-opening polymerization of the polymer. (o-aminobenzamide)

[0184] Isatoic anhydride, N-methyl-2-pyrrolidone (NMP) and ethylmethylimidazolium diethylphosphate (EMIM-DEP) were from Sigma-Aldrich, and neopentylamine was from ABCR (step (A)).

[0185] A 100 ml four-necked flask was equipped with a distillation bridge, a precision glass stirrer, a temperature probe, a nitrogen feed and a gas outlet / gas outlet with a pressure relief valve. Subsequently, 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 in. Nitrogen was introduced at 10 L / h for 20 minutes, wherein the mixture was heated to 40° C. while stirring at 300 rpm. Subsequently, 0.001 g of neopentylamine was introduced and the solution was stirred at 180° C. for 15 hours (step (B)). A suspension was obtained.

[0186] With the help of D2SO4 1 H NMR determination of the molar mass M according to formula (II) n .

[0187] 1 g of the poly(o-aminobenzamide) suspension was dissolved in 1 ml of concentrated sulfuric acid. The precipitated solid (= diphenyl ether solvent) was removed by filtration (step (C)).

[0188] 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. at 0.05 bar for 24 hours.

[0189] Example 13: Using isatoic anhydride as a monomer and neopentylamine as an initiator in 1,3-dimethyl-2-imidazolidine Polymerization was prepared by ring-opening polymerization in a mixture of diethylmethylimidazolium ketone (DMI) and diethylmethylimidazolium phosphate (EMIM-DEP) as solvent. (o-aminobenzamide)

[0190] Isatoic anhydride, 1,3-dimethyl-2-imidazolidinone (DMI) and ethylmethylimidazolium diethylphosphate (EMIM-DEP) were from Sigma-Aldrich, and neopentylamine was from ABCR (step (A)).

[0191] A 100 ml four-necked flask was equipped with a distillation bridge, a precision glass stirrer, a temperature probe, a nitrogen feed and a gas outlet / gas outlet with a pressure relief valve. Subsequently, 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 in. Nitrogen was introduced at 10 L / h for 20 minutes, wherein the mixture was heated to 40° C. while stirring at 300 rpm. Subsequently, 0.001 g of neopentylamine was introduced and the solution was stirred at 180° C. for 15 hours (step (B)). A suspension was obtained.

[0192] With the help of D2SO4 1 H NMR determination of the molar mass M according to formula (II) n .

[0193] 1 g of the poly(o-aminobenzamide) suspension was dissolved in 1 ml of concentrated sulfuric acid. The precipitated solid (= diphenyl ether solvent) was removed by filtration (step (C)).

[0194] 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. at 0.05 bar for 24 hours.

[0195] The table below compares the analysis results.

[0196] Table 4: Properties of poly(o-aminobenzamide) prepared in Examples 9 and 10

[0197]

Claims

1. A method for preparing poly(o-aminobenzamide) comprising the steps of: (A) providing isatoic anhydride; (B) polymerizing isatoic anhydride onto an initiator at a reaction temperature of 110° C. to 300° C., The initiator comprises any one of the following initiators or a mixture of at least two of them: an aliphatic primary or secondary monoamine having 5 to 13 carbon atoms or an aliphatic primary or secondary diamine having 5 to 13 carbon atoms, which comprises at least one of the following compounds: neopentylamine, hexamethylenediamine, methylenedicyclohexyldiamine or pentamethylenediamine, Aroaliphatic monoamines or diamines having 7 to 15 carbon atoms, including xylylenediamine, An aromatic diamine having 6 to 13 carbon atoms, comprising at least one of the following compounds: methylenediphenylenediamine, naphthalenediamine or toluenediamine, or A carboxamide of the formula Ar-(C=O)NHR, wherein Ar is an amine NH or NH 2 A substituted aromatic group and R is an aromatic or aliphatic group, which includes N-neopentyl anthranilamide, To obtain poly(o-aminobenzamide) based on the initiator, The molar ratio of isatoic anhydride to the initiator selected in step (B) is in the range of 20 to 2500.

2. The process as claimed in claim 1, wherein the reaction temperature is in the range of 120°C to 300°C.

3. The process of claim 1 or 2, wherein the polymerization is carried out in the absence of a solvent, wherein after step (B): (C) (i) dissolving poly(o-aminobenzamide) in an inorganic acid to obtain an inorganic acid solution of poly(o-aminobenzamide); (D) (i) isolating the poly(o-aminobenzamide) dissolved in the mineral acid from the mineral acid solution, which comprises the step of precipitation in water.

4. The process according to claim 1 or 2, wherein the polymerization of isatoic anhydride is carried out in the presence of a solvent, wherein the solvent comprises an organic solvent which is in liquid form at the reaction temperature, or a mixture of such an organic solvent and an ionic liquid, and in step (B), the initiator-based poly(o-aminobenzamide) is obtained in a suspended state in the solvent, wherein after step (B): (C)(ii) dissolving the poly(othaminobenzamide) suspended in the solvent in an inorganic acid and separating the solvent to obtain an inorganic acid solution of the poly(othaminobenzamide); (D)(ii) isolating the poly(o-aminobenzamide) dissolved in the inorganic acid from the inorganic acid solution, which comprises the step of precipitation in water.

5. The method according to claim 1 or 2, wherein the polymerization of isatoic anhydride is carried out in the presence of a solvent, wherein the solvent comprises an ionic liquid, or a mixture of an ionic liquid and an organic solvent that is in liquid form at the reaction temperature, and in step (B), the initiator-based poly(o-aminobenzamide) is obtained in a manner dissolved in the solvent, wherein after step (B): (D)(iii) isolating the poly(o-aminobenzamide) dissolved in the solvent from the solution in the solvent, which comprises the step of precipitation in water.

6. The method of claim 4, wherein The organic solvent comprises any one of the following organic solvents or a mixture of at least two of them: diphenyl ether, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone or hexamethylphosphoric triamide, and / or where The ionic liquid comprises any one of the following ionic liquids or a mixture of at least two thereof: 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium butyrate, 1-butyl-3-methylimidazolium nitrate, 1-butyl-3-methylimidazolium methanesulfonate or dialkylimidazolium phosphate.

7. The method of claim 5, wherein The organic solvent comprises any one of the following organic solvents or a mixture of at least two of them: diphenyl ether, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone or hexamethylphosphoric triamide, and / or where The ionic liquid comprises any one of the following ionic liquids or a mixture of at least two thereof: 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium butyrate, 1-butyl-3-methylimidazolium nitrate, 1-butyl-3-methylimidazolium methanesulfonate or dialkylimidazolium phosphate.

8. The method of claim 1 or 2, wherein the molar ratio of isatoic anhydride to the initiator selected in step (B) is in the range of 40 to 2500.

9. The method of claim 1 or 2, wherein the providing of isatoic anhydride in step (A) comprises chemical conversion of anthranilic acid.

10. The method of claim 9, wherein the anthranilic acid is obtained by fermenting a raw material comprising a fermentable carbon-containing compound selected from the group consisting of starch hydrolysate, sugar cane juice, beet juice, hydrolysate of lignocellulose-containing raw materials or mixtures thereof, and A nitrogen-containing compound selected from ammonia gas, ammonia water, an ammonium salt, urea or a mixture thereof.

11. Poly(o-aminobenzamide) having the following structure {H-[HN-(ortho-C 6 H 4 )-(C=O)] m } x -A-[(O=C)(ortho-C 6 H 4 )-NH] n -H in m and n refer to the number of repeating units, x is 0 or 1, A consists of amines NH or NH 2 The initiator molecules of the radical are formed by 2 The initiator molecule is formed by removing a hydrogen atom from the group an aliphatic primary or secondary monoamine having 5 to 13 carbon atoms or an aliphatic primary or secondary diamine having 5 to 13 carbon atoms, selected from neopentylamine, hexamethylenediamine, methylenedicyclohexyldiamine or pentamethylenediamine, Aroaliphatic monoamines or diamines having 7 to 15 carbon atoms, selected from xylylenediamine, an aromatic diamine having 6 to 13 carbon atoms selected from methylenediphenylenediamine, naphthalenediamine or toluenediamine, or A carboxamide of the formula Ar-(C=O)NHR, wherein Ar is an amine NH or NH 2 A substituted aromatic group and R is an aromatic or aliphatic group selected from N-neopentyl anthranilamide, Wherein m+n is in the range of 20 to 2500.

12. The poly(o-aminobenzamide) of claim 11, wherein m+n is in the range of 50 to 2400.

13. Use of a poly(anthranilide) as claimed in claim 11 or 12 for producing fibers or composite materials from poly(anthranilide) and another material comprising a metal, a mineral material or a polymer different from poly(anthranilide).

14. Use as claimed in claim 13, wherein the fibers or composite materials are used for producing protective equipment against fire, fragmentation, fragment penetration, mechanical impact or cuts.

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