Method for producing poly(anthranilamide), poly(anthranilamide), and use thereof

Abstract

The present invention relates to a method for producing poly(anthranilamide), which comprises the steps of: (A) providing an anthranilate ester; and (B) reacting the anthranilate ester in the presence of a catalyst to give poly(anthranilamide) by polycondensation and cleavage of the alcohol on which the anthranilate ester is based, the poly(anthranilamide) thus obtained, and its use in the production of fibers or composite materials.

Description

[Technical Field]

[0001] The present invention relates to a method for producing poly(anthranilate), comprising the steps of (A) preparing an anthranilate ester and (B) converting the anthranilate ester to poly(anthranilate) by polycondensation while cleaving the parent alcohol of the anthranilate ester in the presence of a catalyst, the poly(anthranilate) obtained in this way, and its use in the production of fibers or composite materials. [Background technology]

[0002] Aromatic polyamides (also known as aramids), in which amide groups are bonded to aromatic groups, are known from the prior art and are sold under trade names such as Kevlar, Twaron (poly(p-phenylene terephthalamide)), or Nomex, Teijinconex (poly(m-phenylene isophthalamide)). These are used in a variety of fields. A typical example is the manufacture of fibers, especially woven fabrics. Aramid fibers are known for their extremely high strength, high impact resistance, high elongation at break, and good vibration damping. In addition, these fibers have very high heat and fire resistance. A disadvantage is that they are more expensive to manufacture than many other polymers. Aramids are usually derived from aromatic dicarbonyl halides ClCO-Ar 1 -COCl and aromatic diamine H2N-Ar 2 It is produced by polycondensation of -NH2, but this polycondensation inevitably results in a polymer structure having alternating units derived from dicarboxylic acid and units derived from diamine (-[-CO-Ar 1 -CO-NH-Ar 2 -NH]-; (leading to an AABB polymer structure)

[0003] AF Amin, BP Suthar, and SR Patel describe in Non-Patent Document 1 the production of poly(anthranilamide) having 3 to 10 repeating units. Given the relatively small number of repeating units, the resulting product should rather be called an oligomer.

[0004] The reaction of isatoic anhydrides with ammonia at various concentrations was described as early as 1947 by RP. Staiger and EC. Wagner (in Non-Patent Literature 2, published in 1948). At low ammonia concentrations, carbon dioxide was cleaved to obtain anthranilamide. At high ammonia concentrations, water was cleaved instead to obtain cyclic benzoylurea. Referring to even earlier studies, it has also been reported that "unusual" products are formed from ammonia and isatoic anhydrides, specifically when the isatoic anhydride is treated with exactly half an equivalent amount of ammonia. This results in amorphous products, which have been described as condensates. Non-Patent Literature 1, which has already been cited, also refers to "unusual products" in reference to early studies (unusual in the sense that these products are insoluble in ethanol and melt over a wide range of temperatures). However, according to Non-Patent Literature 1, these unusual products have never been systematically characterized, and according to this reference, numerous reports suggest that such "unusual" products are merely mixtures of "normal" products.

[0005] Patent Document 1 describes a polymer having a CC skeleton, to which up to 10 anthranilamide units are grafted via divalent crosslinks. The base polymer forming the CC skeleton includes, in particular, variously substituted poly(methacrylate) or vinyl aromatic hydrocarbon polymers.

[0006] These references to literature do not describe the formation of high molecular weight poly(anthraniamides) that achieve high molar mass via numerous repeating anthranilamide units rather than by grafting onto another polymer (i.e., the formation of "true" anthranilamide polymers in contrast to oligomers or copolymers with fewer repeating units). Furthermore, more commonly used aramids, such as the initially mentioned (poly(p-phenylene terephthalamide)) and (poly(m-phenylene isophthalamide)), can be produced in high molar mass (although under highly corrosive conditions due to the use of acid chlorides, which is costly and inconvenient in terms of equipment and method operation), and possess very good performance characteristics, but are also very expensive. Moreover, the methods commonly used to produce such aramids are based on polycondensation reactions that form AABB polymer structures, and these reactions require very precise adherence to reaction stoichiometry in order to form polymers with high molar mass.

[0007] In Non-Patent Document 3, A. Hoorfar, W. David Ollis, and J. Fraser Stoddart describe the formation of cyclic anthranilamides from (linear) anthranilamide oligomers having up to four anthranilamide units. These anthranilamide oligomers are obtained through complex multi-step synthesis.

[0008] Oligomers based on anthranilamide units are also described in Non-Patent Document 4 by Yoshimoto Hamuro, Steven J. Geib, and Andrew D. Hamilton. These products are obtained as a result of acylation, hydrogenation, and acetylation using 2-nitrobenzoyl chloride, methyl anthranilate, and acetyl chloride as reactants.

[0009] Therefore, further improvements are needed in the field of aramid chemical reactions. [Prior art documents] [Patent Documents]

[0010]

Patent Document 1

Non-Patent Document

[0011]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Non-Patent Document 4

Summary of the Invention

[0012] In view of this need, accordingly, the present invention provides a method for producing poly(anthranilamide), the method comprising: (A) preparing an anthranilic acid ester (RO(O=C)(o-C6H4)-NH2); (B) converting the anthranilic acid ester by (self)-polycondensing while cleaving off an alcohol (the so-called parent alcohol ROH of the anthranilic acid ester) in the presence of a catalyst to yield poly(anthranilamide); and including.

[0013] The present invention further provides a poly(anthranilamide) of the formula: RO-[(O=C)(o-C6H4)-NH] n -H (I) (wherein R is an aliphatic organic radical (derived from the parent alcohol ROH of the anthranilic acid ester) and n represents the number of repeating units).

[0014] Finally, the present invention provides the use of the poly(anthranilamide) of the present invention in the production of fibers or composite materials from (at least) one other material comprising a poly(anthranilamide) and a metal, inorganic material or polymer other than the poly(anthranilamide).

[0015] In the terms of the present invention, an organic solvent is construed to mean a non-ionic organic solvent, as opposed to an ionic liquid (= a salt with a low melting point (i.e., less than 100 °C)).

[0016] In the context of the present invention, the essential method for specifying the number n of repeating units is 1 H NMR spectroscopy. This method gives the average of the number of repeating units, from which the number-average molar mass of the poly(anthranilamide) can be calculated. Details are further described in the "Analysis" section below.

[0017] From here, a brief summary of what is possible in various embodiments of the present invention is described.

[0018] The first embodiment of the method of the present invention can be combined with all other embodiments, and in this embodiment, the catalyst used in step (B) is (1) an alkyl compound of a metal of Group 1, 4, 11, 12, 13 or 14 of the Periodic Table an alkyl halide compound, acetylacetonate, carboxylate, alkoxide, and / or chloride, or (2) a Bronsted acid, and comprises.

[0019] The second embodiment of the method of the present invention is a specific configuration of the first embodiment, and in this embodiment, the metals of Group 1, 4, 11, 12, 13 or 14 of the Periodic Table include Li, Ti, Cu, Zn, Al, Hf, Zr, and / or Sn.​

[0020] A third embodiment of the method of the present invention is a specific configuration of the first and second embodiments, in which the alkyl compound comprises diethylzinc and / or triethylaluminum.

[0021] A fourth embodiment of the method of the present invention is a specific configuration of the first to third embodiments, in which the alkyl halide compound comprises dichloro(ethyl)aluminum and / or chloro(diethyl)aluminum.

[0022] A fifth embodiment of the method of the present invention is a specific configuration of the first to fourth embodiments, in which the acetylacetonate comprises titanium (monoxide) acetylacetonate, zinc acetylacetonate, and / or aluminum acetylacetonate.

[0023] A sixth embodiment of the method of the present invention is a specific configuration of the first to fifth embodiments, in which the carboxylate comprises zinc(II) acetate.

[0024] A seventh embodiment of the method of the present invention is a specific configuration of the first to sixth embodiments, in which the alkoxide includes methoxide, ethoxide, isopropoxide, butoxide, isobutoxide, and / or phenoxide.

[0025] An eighth embodiment of the method of the present invention is a specific configuration of the first to seventh embodiments, in which the alkoxide includes aluminum triisopropoxide, titanium tetrabutoxide, titanium tetraisobutoxide, and / or lithium methoxide.

[0026] A ninth embodiment of the method of the present invention is a specific configuration of the first to eighth embodiments, in which the chloride comprises zinc dichloride and / or ferric trichloride.

[0027] The tenth embodiment of the method of the present invention is the specific configuration of the first to ninth embodiments. In this embodiment, the Bronsted acid includes a mineral acid selected from sulfuric acid, hydrochloric acid, nitric acid, and / or phosphoric acid.

[0028] The eleventh embodiment of the method of the present invention can be combined with all other embodiments. In this embodiment, the anthranilic acid ester includes methyl anthranilate, ethyl anthranilate, propyl anthranilate, isopropyl anthranilate, butyl anthranilate, and / or isobutyl anthranilate.

[0029] The twelfth embodiment of the method of the present invention can be combined with all other embodiments. In this embodiment, step (B) is carried out at a reaction temperature in the range of 120°C to 300°C, or in the range of 160°C to 280°C, or in the range of 170°C to 250°C.

[0030] The thirteenth embodiment of the method of the present invention can be combined with all other embodiments. In this embodiment, step (B) is carried out at a pressure in the range of 0.10 bar (abs.) ~1.0 bar (abs.) less than, or in the range of 1.0 bar (abs.) ~1.5 bar (abs.) to.

[0031] The fourteenth embodiment of the method of the present invention can be combined with all other embodiments as long as the use of a solvent in step (B) is not assumed. In this embodiment, step (B) is carried out in the absence of a solvent. Following step (B), (C)(i) Dissolving poly(anthranilamide) in a mineral acid to obtain a mineral acid solution of poly(anthranilamide), (D)(i) Isolating poly(anthranilamide) dissolved in a mineral acid from the mineral acid solution, including the step of precipitating in water, is carried out.

[0032] A fifteenth embodiment of the method of the present invention is a specific configuration of the fourteenth embodiment, in which the mineral acid includes sulfuric acid, hydrochloric acid, nitric acid, and / or phosphoric acid, and is particularly sulfuric acid.

[0033] A sixteenth embodiment of the method of the present invention can be combined with all other embodiments except those that exclude the use of a solvent in step (B) or assume pure solvent polymerization in this step, in which step (B) is carried out in the presence of a solvent, the solvent includes an organic solvent, an ionic liquid, or a mixture of the solvents that are liquid under the reaction conditions of step (B) (particularly at the reaction temperature), in which step (B) the poly(anthranilamide) is obtained so as to be suspended in the solvent, and following step (B), (C)(ii) Dissolve poly(anthranilamide) suspended in a solvent in mineral acid, and then separate the solvent to obtain a mineral acid solution of poly(anthranilamide). (D)(ii) Isolating poly(anthranilamide) dissolved in mineral acid from the mineral acid solution, including a step of precipitation in water. It will take place.

[0034] A 17th embodiment of the method of the present invention is a specific configuration of the 16th embodiment, in which the mineral acid includes sulfuric acid, hydrochloric acid, nitric acid, and / or phosphoric acid, and is particularly sulfuric acid.

[0035] An eighteenth embodiment of the method of the present invention is a specific configuration of the sixteenth and seventeenth embodiments, in which the solvent is removed in step (C)(i) by filtration, centrifugation, or phase separation.

[0036] A 19th embodiment of the method of the present invention can be combined with all other embodiments except those that exclude the use of a solvent in step (B) or that assume suspension polymerization in this step, in which step (B) 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 this reaction temperature, and in step (B), the poly(anthranilamide) is obtained so as to be dissolved in the solvent, and following step (B), (D)(iii) Isolating poly(anthranilamide) dissolved in a solvent from the solvent solution, including the step of precipitation in water. It will take place.

[0037] A 20th embodiment of the method of the present invention is a specific configuration of the 16th to 19th embodiments, in which the organic solvent comprises diphenyl ether, (in particular CaCl2-containing) N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone (DMI), and / or hexamethylphosphoramide.

[0038] A 21st embodiment of the method of the present invention is a specific configuration of the 16th to 20th embodiments, in which the ionic liquid includes 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 (for example, in particular butyl-3-methylimidazolium phosphate, dimethylimidazolium diethyl phosphate ("MMIM-DEP"), and ethylmethylimidazolium diethyl phosphate ("EMIM-DEP")).

[0039] A 22nd embodiment of the method of the present invention can be combined with all embodiments, and in this embodiment, the preparation of the anthranilate ester in step (A) proceeds from anthranilate.

[0040] A 23rd embodiment of the method of the present invention is a specific configuration of the 22nd embodiment, in which step (A) comprises converting anthranilic acid to anthraniloyl chloride, the anthraniloyl chloride reacting with an alcohol (mainly the parent alcohol of the anthranilic acid ester) to yield the anthranilic acid ester.

[0041] A 24th embodiment of the method of the present invention is a second specific configuration of the 22nd embodiment, in which step (A) comprises converting anthranilic acid to isatoic anhydride, the isatoic anhydride reacting with an alcohol (mainly the parent alcohol of anthranilic acid ester) to yield anthranilic acid ester.

[0042] A 25th embodiment of the method of the present invention is a third specific configuration of the 22nd embodiment, in which step (A) comprises the reaction of anthranilic acid with an alcohol (a so-called parent alcohol of anthranilic acid ester) to yield an anthranilic acid ester, the reaction being carried out in particular at 1 mbar (abs.) ~100mbar (abs.) The reaction is carried out at a pressure in the range of 50°C to 100°C (to minimize yield loss through the reaction of anthranilic acid to produce aniline).

[0043] A 26th embodiment of the method of the present invention is a specific configuration of the 24th and 25th embodiments, in which the reaction with the alcohol (isatoic anhydride or anthranilic acid) in step (A) is carried out in the presence of a catalyst.

[0044] A 27th embodiment of the method of the present invention is a specific configuration of the 26th embodiment, in which the catalyst used in step (A) is (1) Metals of Group 1, 4, 11, 12, 13, or 14 of the periodic table Alkyl compounds, Alkyl halogenated compounds, Acetylacetonate, Carboxylate, Alkoxides, and / or Chloride, or, (2) Brønsted acid, The catalyst has a preferred configuration, which is as specified above for the second to tenth embodiments.

[0045] A 28th embodiment of the method of the present invention is a specific configuration of the 26th and 27th embodiments, in which step (B) is carried out without prior removal of the solvent used in step (A), and no catalyst other than the catalyst used in step (A) is added (i.e., steps (A) and (B) are carried out with the same catalyst).

[0046] The 29th embodiment of the method of the present invention is a specific configuration of the 22nd to 28th embodiments, in which anthranilic acid is, Fermentable carbon compounds, Nitrogen compounds and, It is obtained by fermenting raw materials containing [the specified ingredient].

[0047] A 30th embodiment of the method of the present invention is a specific configuration of the 29th embodiment, in which the fermentable carbon-containing compound comprises starch hydrolysate, sugarcane juice, sugar beet juice, and / or hydrolysate of lignocellulose-containing raw materials, and the nitrogen-containing compound comprises ammonia gas, aqueous ammonia, ammonium salts, and / or urea.

[0048] A 31st embodiment of the method of the present invention can be combined with all the other embodiments, in which the progress of polycondensation is controlled by the removal of the alcohol cleaved in the reaction of step (B).

[0049] A 32nd embodiment of the method of the present invention can be combined with all other embodiments, in which the method of the present invention provides a poly(anthranilamide) of formula (I), where n is in the range of 20 to 2500, preferably 40 to 2500, more preferably 50 to 2400, even more preferably 70 to 2000, particularly preferably 70 to 200, and especially 70 to 100.

[0050] The first embodiment of the poly(anthranilamide) of the present invention can be combined with all other embodiments, in which R is methyl, ethyl, propyl, isopropyl, butyl, or isobutyl.

[0051] A second embodiment of the poly(anthranilamide) of the present invention can be combined with all the other embodiments, in which n is in the range of 20 to 2500, preferably 40 to 2500, more preferably 50 to 2400, even more preferably 70 to 2000, particularly preferably 70 to 200, and especially 70 to 100.

[0052] The first embodiment of the use of the present invention can be combined with all other embodiments, in which the fibers or composite materials are useful in the manufacture of protective devices (in particular clothing, e.g., protective suits and bulletproof vests) for protection against flames, splinter formation, impact of splinter, mechanical impact (including bullets), or cutting.

[0053] A second embodiment of the use of the present invention can be combined with all other embodiments, in which the fibers or composite materials are useful in the manufacture of sports equipment. [Modes for carrying out the invention]

[0054] The embodiments briefly outlined above, as well as further embodiments of the present invention, will be described in detail below in this specification. All embodiments can be combined with each other as desired, unless otherwise specified or unless it is uniquely apparent from the context.

[0055] In step (A) of the method of the present invention, anthranilate esters (including mixtures of different anthranilate esters) are prepared for subsequent polycondensation. Anthranilate esters can, in principle, be produced by any method known to those skilled in the art of the synthesis of such compounds. Typically, the synthesis proceeds from anthranilic acid (= o-aminobenzoic acid). Preferred anthranilate esters are methyl anthranilate, ethyl anthranilate, propyl anthranilate, isopropyl anthranilate, butyl anthranilate, and / or isobutyl anthranilate.

[0056] Anthranilic acid can be produced by known chemical methods. 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 method is known. Industrial methods are also described in the patent literature. See, for example, German Patent Application Publication No. 2902978 and European Patent Application Publication No. 0004635. In addition, a fermentation production route for anthranilic acid has recently been published, which proceeds from renewable raw materials and is therefore possible to conserve fossil raw materials and reduce the size of the CO2 footprint. See, for example, International Publication No. 2018 / 002088, pp. 13, line 26 to pp. 22, line 15, and the literature cited therein. This fermentation method can also be adopted in the method of the present invention. Therefore, in this embodiment, step (A) of the method of the present invention comprises the fermentation of raw materials, the raw materials are 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 ammonia gas, aqueous ammonia, ammonium salt, urea, or a mixture thereof, Includes.

[0057] Preferably, the fermentable carbon-containing compound includes starch hydrolysates, sugarcane juice, sugar beet juice, and / or hydrolysates of lignocellulose-containing raw materials, and the nitrogen-containing compound includes ammonia gas, aqueous ammonia, ammonium salts, and / or urea. Microorganisms particularly suitable for carrying out fermentation include Escherichia coli, Pseudomonas putida, Corynebacterium glutamicum, Ashbya gossypii, Pichia pastoris, Hansenula polymorpha, Yarrowia lipolytica, Zygosaccharomyces bailii, or Saccharomyces cerevisiae.

[0058] In one possible embodiment, anthranilic acid is first converted to anthraniloyl chloride, and the anthraniloyl chloride is reacted with an alcohol to yield the desired anthranilic acid ester. A suitable method for conversion to an acid chloride is a conventional method known to those skilled in the art, such as a reaction with thionyl chloride.

[0059] As an alternative to converting to an acid chloride, anthranilic acid can be converted to isatoic anhydride, which is then reacted with an alcohol to yield anthranilic acid esters. For this purpose, anthranilic acid can be reacted with phosgene, particularly in a hydrochloric acid medium. In addition to phosgene, diphosgene, triphosgene, or further phosgenation media known in the prior art, such as oxalyl chloride, 1,1-carbonyldiimidazole, and dimethyl carbonate, can also be used. Similarly, to obtain isatoic anhydride, anthranilic acid can be reacted with carbon monoxide in the presence of a catalyst, particularly a Pd or Pt catalyst.

[0060] It is also possible to directly react anthranilic acid with an alcohol to obtain the desired anthranilic acid ester. To avoid the yield reduction resulting from the reaction of anthranilic acid to produce aniline, this esterification is performed at low temperatures (50°C to 100°C) and low pressures (1 mbar). (abs.) ~100mbar (abs.) It is appropriate to do so in this manner.

[0061] In all cases, the reaction with alcohol can be accelerated by using a catalyst, especially in the reaction of isoanhydride with alcohol and in the direct esterification of anthranilic acid. Suitable catalysts include, in particular: (1) Metals of Group 1, 4, 11, 12, 13, or 14 of the periodic table Alkyl compounds, Alkyl halogenated compounds, Acetylacetonate, Carboxylate, Alkoxides, and / or Chloride, or, (2) Brønsted acid.

[0062] With regard to catalysts, the following priorities apply: Suitable metals from groups 1, 4, 11, 12, 13, or 14 of the periodic table are, in particular, Li, Ti, Cu, Zn, Al, Hf, Zr, and / or Sn. Suitable alkyl compounds include, in particular, diethylzinc and / or triethylaluminum. Useful alkyl halide compounds are preferably dichloro(ethyl)aluminum and / or chloro(diethyl)aluminum. Suitable examples of acetylacetonates include titanium (monoxide) acetylacetonate, zinc acetylacetonate, and / or aluminum acetylacetonate. A suitable carboxylate is, in particular, zinc(II) acetate. Useful alkoxides are preferably methoxides, ethoxides, isopropoxides, butoxides, isobutoxides, and / or phenoxides. More preferably, the alkoxides include aluminum triisopropoxide, titanium tetrabutoxide, titanium tetraisobutoxide, and / or lithium methoxide. Suitable chlorides include, in particular, zinc chloride and / or ferric trichloride. Finally, the Brønsted acid used is preferably a mineral acid selected from sulfuric acid, hydrochloric acid, nitric acid, and / or phosphoric acid.

[0063] In step (B) of the method of the present invention, the anthranilic acid ester prepared in step (A) is subjected to polycondensation. In this case, the anthranilic acid ester reacts "with itself," and this is also called "autopolycondensation." As a result, the parent alcohol of the anthranilic acid ester is cleaved (separated from the terminal group). nRO(O=C)(o-C6H4)NH2→RO-[(O=C)(o-C6H4)-NH] n -H+(n-1)ROH

[0064] The catalysts suitable for this purpose are the same as those described above for step (A). The suitable configurations for these catalysts are also the same as those described above for step (A). This expands the option of carrying out step (B) without removing the catalyst used in step (A) beforehand, in which case no catalyst other than the one used in step (A) is added; that is, steps (A) and (B) are carried out with the same catalyst. Then, polycondensation is started simply by appropriately adjusting the reaction conditions (see the following paragraph for details).

[0065] Polycondensation can, in principle, be carried out over a wide temperature range, and the maximum temperature is limited only by the decomposition temperature of the supplied raw materials. Step (B) is preferably carried out at a reaction temperature in the range of 120°C to 300°C, preferably 160°C to 280°C, and particularly in the range of 170°C to 250°C.

[0066] Similarly, there are no special requirements regarding pressure. For example, process (B) can be carried out at atmospheric pressure or a slightly elevated pressure, particularly 1.0 bar. (abs.) ~1.5 bar (abs.) It is possible to carry out the process within the range of [this]. However, process (B) can be carried out under reduced pressure (especially 0.10 bar). (abs.) ~1.0 bar (abs.) It is also possible to carry out the reaction in the range of less than 50. As a result, the separated alcohol can evaporate more easily, and thus the reaction can be carried out in the desired direction.

[0067] Polycondensation can be carried out (i) without a solvent ("neat," "bulk polymerization") or 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 in case (ii) are, in particular, diphenyl ether, N-methyl-2-pyrrolidone (preferably in combination with CaCl2 as a solubilizer), 1,3-dimethyl-2-imidazolidinone (DMI), and / or hexamethylphosphoramide. These are liquid at the appropriate reaction temperature (see above). In the case of (iii), the use of ionic liquids known to those skilled in the art is generally expected, particularly 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 (for example, particularly butyl-3-methylimidazolium phosphate, dimethylimidazolium diethyl phosphate ("MMIM-DEP"), and ethylmethylimidazolium diethyl phosphate ("EMIM-DEP")).

[0068] (i) When ROP is performed without a solvent, the anthranilic acid ester is converted in a molten state. When performed without a solvent, polycondensation begins in a homogeneous phase (molten). However, as polymerization proceeds, a suspension is obtained in which the polymer is suspended in unconverted monomers, resulting in a rapid precipitation of the formed polymer. Further polymerization generally leads to substantial solidification of the entire reaction mixture.

[0069] In this case, the post-processing is preferably as follows: (C)(i) A step of dissolving poly(anthranilamide) in mineral acid to obtain a mineral acid solution of poly(anthranilamide), (D)(i) A step of isolating poly(anthranilamide) dissolved in mineral acid from the mineral acid solution, including a step of precipitation in water, Includes.

[0070] Suitable mineral acids for carrying out step (C)(i) are, in particular, sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. Sulfuric acid is preferred, and sulfuric acid with a mass concentration in the range of 96% to 100%, preferably 96% to 98%, is particularly preferred. Dissolution is preferably achieved at a temperature in the range of 20°C to 100°C.

[0071] (ii) When an organic solvent is used, a suspension of poly(anthranilamide) is generally obtained (suspension polymerization). In this case, the post-treatment of the product of step (B) is preferably as follows: (C)(ii) A step of dissolving poly(anthranilamide) suspended in a solvent in mineral acid, separating the solvent, and obtaining a mineral acid solution of poly(anthranilamide), (D)(ii) A step of isolating poly(anthraniamide) dissolved in mineral acid from the mineral acid solution, including a step of precipitation in water, Includes.

[0072] The preferred conditions described above for the dissolution and isolation steps in case (i) also apply to case (ii). In this case, any further removal of organic solvents is preferably achieved by filtration, centrifugation, or phase separation. Removal is performed either before dissolving the poly(anthranilamide) in the mineral acid (in this case, the captured organic solvent is generally still present in the solid polyanthranilamide, which is filtered off and then dissolved in the mineral acid) or after dissolution (in this case, the organic solvent is precipitated, i.e., insoluble in the mineral acid, and is separated).

[0073] If the solvent used in step B is (iii) an ionic liquid, this step generally yields a solution of poly(anthranilamide) (solution polymerization). In this case, since the polymer product is already in solution, a dissolution step (step (C) in cases (i) and (ii)) is not required. Therefore, in this case, the post-treatment of the product of step (B) is preferably as follows: (D)(iii) A step of isolating poly(anthraniamide) dissolved in a solvent from the solvent solution, including a step of precipitation in water. Includes.

[0074] The preferred conditions described above for the isolation step in case (i) also apply to case (iii).

[0075] If a mixture of an organic solvent and an ionic liquid is used in step (B), whether the product is a solution or a suspension depends on the mixing ratio. Depending on what is present, further post-treatment is as described above for (iii) (solution) or (ii) (suspension).

[0076] In any case, the recovered solvent is preferably reused. For this purpose, purification may be necessary, which can be achieved by methods known to those skilled in the art. The reuse of ionic liquids is particularly important because of the high cost of such purification. For this purpose, the ionic liquid obtained in the isolation of poly(anthraniamide) in step (D)(iii) or step (D)(iv) is purified at high temperature and under reduced pressure, particularly at temperatures in the range of 50°C to 100°C and 1 mbar. (abs.) ~100mbar (abs.) It is dried under pressure within this range.

[0077] If the product of step (B) is in the form of a solution, it is conceivable that this solution may be further processed directly to yield the desired final product, in particular, that poly(anthranilamide) fibers may be spun directly from the solution.

[0078] The method of the present invention enables the formation of high molecular weight poly(anthranilates). The number of repeating units, and therefore the molar mass, can be controlled by the removal of alcohol cleaved in the reaction. By determining the amount of alcohol removed, it is possible to use a (known) amount of anthranilate ester used to determine the degree of polymerization (Carozas's relation). The reaction can be stopped as soon as the desired degree of polymerization is reached.

[0079] According to the method of the present invention, formula: RO-[(O=C)(o-C6H4)-NH] n -H (I) A poly(anthranilamide) of the formula (wherein R is an aliphatic organic radical and n indicates the number of repeating units) is obtained. Preferably, R represents methyl, ethyl, propyl, isopropyl, butyl, or isobutyl. The number of repeating units n is, for example, in the range of 20 to 2500, preferably 40 to 2500, more preferably 50 to 2400, even more preferably 70 to 2000, and especially preferably 70 to 200, particularly 70 to 100. The desired number of repeating units naturally depends on the desired end use of the poly(anthranilamide), and therefore, it is also possible to use a value different from the numbers given above at the discretion of the user.

[0080] The poly(anthranilamide) obtained according to the present invention is suitable for a variety of applications. Therefore, the present invention further provides the use of the poly(anthranilamide) in the production of fibers or composite materials from poly(anthranilamide) and (at least) one other material, the other material including metals, inorganic materials (e.g., concrete), or polymers other than poly(anthranilamide) (e.g., polyurethane). The fibers or composite materials are preferably useful in the manufacture of protective devices (particularly clothing, e.g., protective suits and bulletproof vests) for protection against flames, shrapnel formation, impact from shrapnel, mechanical impacts (including bullets), or cuts. The fibers or composite materials can also be used in the manufacture of sporting goods.

[0081] The present invention will be described in more detail with reference to the following examples provided herein. [Examples]

[0082] analysis The number-average molar mass (M) of the resulting poly(anthranilamide) n )of, 1 The samples were identified by 1H NMR spectroscopy (Bruker AV III HD 600, 600 MHz; pulse sequence zg30, delay time d1: 10 seconds, 64 scans). Each sample was dissolved in deuterated sulfuric acid. 1The relevant resonances in the 1H NMR spectrum (based on TMS=0ppm) are as follows:

[0083] The signal in the 8.5 ppm to 7.1 ppm range is used for the aromatic protons of the anthranilamide (equivalent to the integral of 4 protons). The resonance of the protons at the methyl ester terminal group has a shift of 3.56 ppm (methyl group, equivalent to the integral of 3 protons).

[0084] Molar mass M of polymer n This is calculated using the following formula (I), and the following abbreviations are used: Resonance area of ​​aromatic protons (4 protons) at F(A) = 8.5 ppm to 7.1 ppm F(M) = Resonance area of ​​the methyl group (3 protons) of methyl anthranilate at 3.56 ppm

[0085] The number of repeating units was calculated from the polymer oAB(n) using the following formula (I): n = F(A) / F(M) × 3 / 4 (I)

[0086] Using a number n, the molar mass M of the polymer can be calculated using the following equation (II): n Calculated: M n =150.16g / mol+n×120.14g / mol+1g / mol (II)

[0087] Example 1 (Inventive Example): Production of poly(anthraniamide) by polycondensation of methyl anthranilate in the presence of Ti(OiPr)4 as a catalyst A 500 mL four-necked flask was fitted with a distillation system, a precision glass stirrer, a temperature probe, a nitrogen supply line, and a gas inlet / outlet equipped with a pressure relief valve. Subsequently, 50 g of methyl anthranilate and 49.4 g of Ti(OiPr) were weighed in. Nitrogen was introduced at a rate of 10 L / hour for 20 minutes, during which time the solution was stirred at 300 rpm. After that, the solution was stirred at 180 °C for 9 hours.

[0088] Molar mass M in D2SO4 determined by NMR nThey identified it.

[0089] Example 2 (Inventive Example): Production of poly(anthraniamide) by polycondensation of methyl anthranilate in the presence of Ti(OiPr)4 as a catalyst and diphenyl ether as a solvent. The reaction was carried out in the same manner as in Example 1, except in the presence of 50 mL of diphenyl ether.

[0090] Example 3: Production of poly(anthraniamide) by polycondensation of methyl anthranilate under reduced pressure in the presence of Ti(OiPr)4 as a catalyst and diphenyl ether as a solvent. The same procedure as in Example 2, except at 0.80 bar. (abs.) The reaction was carried out under pressure.

[0091] Example 4 (Comparative Example): Production of poly(anthranilamide) by polycondensation of methyl anthranilate in the absence of Ti(OiPr)4 as a catalyst. The reaction was carried out in the same manner as in Example 1, except in the absence of a catalyst. In this case, the monomer was not converted to yield poly(anthranilamide).

[0092] The following table compares the results:

[0093] [Table 1]

Claims

1. (A) A step to prepare anthranilate ester, (B) A step of converting the anthranilic acid ester to obtain poly(anthraniamide) by cleaving the alcohol and polycondensing it in the presence of a catalyst, A method for producing poly(anthranilamide) containing [the specified ingredient].

2. Step (B) is carried out at a reaction temperature in the range of 120°C to 300°C, or in the range of 160°C to 280°C, or in the range of 170°C to 250°C. The method according to claim 1.

3. Process (B) is 0.10 bar （ａｂｓ．） ~1.0 bar （ａｂｓ．） A range of less than 1.0 bar （ａｂｓ．） ~1.5 bar （ａｂｓ．） It is performed at pressures within the range of, The method according to claim 1 or 2.

4. Step (B) is carried out in the absence of a solvent, and following step (B), (C) (i) Dissolve the poly(anthranilamide) in a mineral acid to obtain a mineral acid solution of the poly(anthranilamide), (D) (i) Isolating the poly(anthraniamide) dissolved in the mineral acid from the mineral acid solution, including the step of precipitating it in water. The method according to any one of claims 1 to 3, wherein the procedure is carried out.

5. Step (B) is carried out in the presence of a solvent, the solvent includes an organic solvent, an ionic liquid, or a mixture of the solvent that is liquid under the reaction conditions of step (B), and in step (B), the poly(anthranilamide) is obtained in such a state that it is suspended in the solvent, and following step (B), (C) (ii) Dissolve the poly(anthraniamide) suspended in the solvent in mineral acid, separate the solvent to obtain a mineral acid solution of the poly(anthraniamide), (D) (ii) Isolating the poly(anthraniamide) dissolved in the mineral acid from the mineral acid solution, including the step of precipitating it in water. The method according to any one of claims 1 to 4, wherein the procedure is carried out.

6. Step (B) 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 the reaction temperature of step (B), wherein in step (B), the poly(anthraniamide) is obtained such that it is dissolved in the solvent, and following step (B), (D) (iii) Isolating the poly(anthraniamide) dissolved in the solvent from the solvent solution, including the step of precipitating it in water. The method according to any one of claims 1 to 5, wherein the procedure is carried out.

7. formula: RO-[(O=C)(o-C ６ H ４ )-NH] ｎ -H Poly(anthranilamide) (wherein R is an aliphatic organic radical, n indicates the number of repeating units, and n is in the range of 20 to 2500, or 40 to 2500, or 50 to 2400, or 70 to 2000, or 70 to 200, or 70 to 100).

8. The poly(anthranilamide) according to claim 7, wherein R is methyl, ethyl, propyl, isopropyl, butyl, or isobutyl.

9. The use of poly(anthraniamide) according to claim 7 or 8 in manufacturing a fiber or composite material from poly(anthraniamide) and another material containing a metal, an inorganic material, or a polymer other than poly(anthraniamide).

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