Process for producing thermoplastic polyoxazolidinones

Abstract

A method for producing thermoplastic polyoxazolidinone includes copolymerizing a diisocyanate compound (A) with a diepoxide compound (B) in a solvent (E) optionally in the presence of a specific quaternary ammonium, quaternary phosphorus, and / or quaternary antimony-based catalyst (C), compound (D), and compound (F), wherein compound (D) and compound (F) independently comprise at least one of a monofunctional isocyanate, a monofunctional epoxide, a cyclic carbonate, a monofunctional alcohol, and a monofunctional amine, and wherein the method is free of solvents (G) with a boiling point above 200°C (absolute) at 1 bar, preferably above 190°C, and more preferably above 180°C. The invention also relates to the resulting thermoplastic polyoxazolidinone.

Description

[0001] A method for producing thermoplastic polyoxazolidinone includes copolymerizing a diisocyanate compound (A) with a diepoxide compound (B) in a solvent (E) optionally in the presence of a specific quaternary ammonium, quaternary phosphorus, and / or quaternary antimony (STI)-based catalyst (C), compound (D), and compound (F), wherein compound (D) and compound (F) independently comprise at least one of a monofunctional isocyanate, a monofunctional epoxide, a cyclic carbonate, a monofunctional alcohol, and a monofunctional amine, and wherein the method is free of solvents (G) with a boiling point above 200°C (absolute) at 1 bar, preferably above 190°C, and more preferably above 180°C. The invention also relates to the resulting thermoplastic polyoxazolidinone.

[0002] Oxazolidinones are widely used structural motifs in pharmaceutical applications, and the cycloaddition of epoxides and isocyanates appears to be a convenient one-pot synthetic route. Expensive catalysts, reactive polar solvents, long reaction times, and low chemoselectivity were common in early reports on oxazolidinone synthesis (MEDyen and D. Swern, Chem. Rev., 67, 197, 1967). Due to these drawbacks, alternative methods for the production of oxazolidinones are needed, especially for their application as structural motifs in polymer applications.

[0003] Scientific publication J. Polym. Sci. 8 (1970) 2759-2773 discloses the preparation of polyoxazolidinones from various bicyclic oxides and various diisocyanates in the presence of an alkali metal halide catalyst. Equimolar amounts of solutions of bicyclic oxides and diisocyanates were added dropwise over 1 hour under reflux to a reactor containing a LiCl catalyst dissolved in DMF, followed by a post-reaction under reflux for 12 to 23 hours to complete the reaction. The addition of monofunctional chain-group regulators was not disclosed.

[0004] WO 2015 / 173110 A1 and WO 2016 / 128380 A1 disclose a method for producing polyoxazolidinone by reacting diisocyanate, diepoxide and monofunctional isocyanate in the presence of phosphonic catalyst and N-methylpyrrolidone as a high-boiling solvent.

[0005] WO 2019 / 052991 A1 and WO 2019 / 052994 A1 disclose methods for producing thermoplastic polyoxazolidinones, comprising copolymerizing diisocyanate compounds with diepoxides and monofunctional epoxides in N-methylpyrrolidone and sulfolane as high-boiling-point cosolvents in the presence of lithium chloride and lithium bromide as catalysts.

[0006] WO 2018 / 149844 A1 discloses a method for producing polyoxazolidinones by reacting a diisocyanate and a diepoxide with sulfolane as a high-boiling-point co-solvent and an ionic liquid as a catalyst. It does not disclose the use of monofunctional epoxides in addition to the diepoxide. The resulting oxazolidinone product contains a significant amount of isocyanurate, generated via the trimerization of the diisocyanate, as a second product, wherein the oxazolidinone / isocyanurate ratio, as determined by infrared spectroscopy, is between 0.62 and 0.71.

[0007] WO 2020 / 016276 A1 discloses a method for producing polyoxazolidinones by bulk polymerization of diisocyanates and diepoxides using an ionic liquid as a catalyst in the absence of a solvent, wherein the reaction temperature is increased during the addition of the diisocyanate. It does not disclose the use of monofunctional epoxides in addition to diepoxides.

[0008] The object of this invention is therefore to find an optimized and simple method for preparing thermoplastic polyoxazolidinones, which have improved or at least comparable thermal stability and lower or at least comparable polydispersity compared to known thermoplastic polyoxazolidinones prepared via addition polymerization routes. In particular, suitable process conditions should be developed, for example by introducing a suitable catalyst system, to obtain polyoxazolidinone products with high chemoselectivity and to reduce the amount of undesirable crosslinking of the reaction products and undesirable byproducts such as isocyanurates that adversely affect thermoplastic properties. Therefore, a high oxazolidinone / isocyanurate ratio is ideal for obtaining good thermoplastic properties for subsequent molding processes.

[0009] Furthermore, high-boiling-point solvents can adversely affect subsequent extrusion and injection molding processes of thermoplastic polyoxazolidinones (POPs), such as causing undesirable foaming, unsuitable viscosity, and explosive atmospheres. Therefore, solvents typically necessary for the synthesis of PPOs should be quantitatively removed, for example, by distillation at elevated temperatures and reduced pressures to below 1500 ppm, where thermal decomposition of PPOs leads to high polydispersity, and the undesirable coloring of desolvated PPOs should be minimized to obtain desolvated PPOs with good thermoplastic properties and improved thermal stability.

[0010] Surprisingly, it has been found that this problem can be solved by a method for producing thermoplastic polyoxazolidinone, which involves copolymerizing a diisocyanate compound (A) with a biepoxide compound (B) in a solvent (E) in the presence of a catalyst (C), compound (D), and compound (F).

[0011] The catalyst (C) is represented by formula (I).

[0012] [A] + n [Y]n- (I)

[0013] Where n is an integer with a value of 1, 2, or 3;

[0014] Among them, [A] + n It is quaternary ammonium, quaternary phosphorus, and / or quaternary antimony; phosphorus is preferred.

[0015] Among them, [Y] n- It is a monovalent, divalent, trivalent or tetravalent anion, preferably a monovalent anion;

[0016] The compound (D) comprises at least one of a monofunctional isocyanate, a monofunctional epoxide, a cyclic carbonate, a monofunctional alcohol, and a monofunctional amine, preferably a monofunctional epoxide;

[0017] The compound (F) comprises at least one of a monofunctional isocyanate, a monofunctional epoxide, a cyclic carbonate, a monofunctional alcohol, and a monofunctional amine, preferably a monofunctional epoxide. The method is carried out in the absence of a solvent (G) with a boiling point above 200°C, preferably above 190°C, and more preferably above 180°C at 1 bar (absolute). The method includes:

[0018] (α) A diisocyanate compound (A) reacts with a diepoxide compound (B) in a solvent (E) in the presence of a catalyst (C) and a compound (D) to form an intermediate compound; and

[0019] (β) Reacts compound (F) with the intermediate compound formed in step (α).

[0020] As used herein, the term "thermoplastic polyoxazolidinone" is intended to refer to compounds containing at least two oxazolidinone groups in their molecules. Thermoplastic polyoxazolidinones can be obtained by reacting diisocyanate compounds with diepoxide compounds.

[0021] In one embodiment of the present invention, method step (α) includes:

[0022] (α-1) A solvent (E) and a catalyst (C) are placed in a reactor to provide a mixture (α-1).

[0023] (α-2) Compound (A), biepoxide (B), and compound (D) are placed in a second container to provide mixture (α-2), and

[0024] (α-3) Add mixture (α-2) to mixture (α-1) to form a copolymerization product.

[0025] The copolymerization product is the reaction product of diisocyanate compound (A) with diepoxide compound (B) and compound (D).

[0026] In a preferred embodiment of the invention, mixture (α-2) is added to mixture (α-1) in a continuous manner in step (α-3). In an alternative embodiment of the invention, which is less preferred than a continuous addition step, mixture (α-2) is added to mixture (α-1) in a stepwise manner having two or more independent addition steps.

[0027] In a preferred embodiment of the present invention, step (α) further includes

[0028] (α-4) The second part (C-2) of the catalyst (C) is added to the copolymerization product formed in step (α-3).

[0029] In one embodiment of the method according to the invention, step (α) is carried out at a reaction temperature of ≥130°C to ≤280°C, preferably ≥140°C to ≤240°C, and more preferably ≥155°C to ≤210°C. If the temperature is set below 130°C, the reaction is generally very slow and byproducts such as isocyanurates are formed. At temperatures above 280°C, the amount of undesirable byproducts increases significantly.

[0030] In one embodiment of the method according to the invention, step (α) is carried out over a reaction time of 1 h to 20 h, preferably 1 h to 10 h, and more preferably 1 h to 6 h.

[0031] In one embodiment of the method according to the invention, step (α) is carried out at a reaction temperature of ≥130°C to ≤280°C and a reaction time of 1 h to 6 h.

[0032] In one embodiment of the method according to the invention, step (β) is carried out at a reaction temperature of ≥130°C to ≤280°C, preferably ≥140°C to ≤240°C, and more preferably ≥155°C to ≤210°C. If the temperature is set below 130°C, the reaction is typically very slow. At temperatures above 280°C, the amount of undesirable byproducts increases significantly.

[0033] In one embodiment of the method according to the invention, step (β) is carried out over a reaction time of 1 h to 20 h, preferably 1 h to 10 h, and more preferably 1 h to 6 h.

[0034] In one embodiment of the method according to the invention, step (β) is carried out at a reaction temperature of ≥130°C to ≤280°C and a reaction time of 1 h to 6 h.

[0035] As used herein, the term "diisocyanate compound (A)" is intended to refer to a diisocyanate compound having two isocyanate groups (I=2), isocyanate-terminated biuret, isocyanurate, diurea, urethane, and / or isocyanate-terminated prepolymer.

[0036] In one embodiment of the method according to the invention, the diisocyanate compound (A) is selected from at least one of the following compounds: tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methylpentamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate (THDI), dodecanemethylene diisocyanate, 1,4-diisocyanate cyclohexane, 3-isocyanate methyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) IPDI), diisocyanate dicyclohexylmethane (H12-MDI), diphenylmethane diisocyanate (MDI), 4,4′-diisocyanate-3,3′-dimethyldicyclohexylmethane, 4,4′-diisocyanate-2,2-dicyclohexylpropane, poly(hexamethylene diisocyanate), octamethylene diisocyanate, toluene-α,4-diisocyanate, poly(propylene glycol) toluene-2,4-diisocyanate-terminated, poly(ethylene adipate) toluene-2,4-diisocyanate-terminated, 2,4,6-trimethyl-1,3 1,4-phenylene diisocyanate, 4-chloro-6-methyl-1,3-phenylene diisocyanate, poly[1,4-phenylene diisocyanate-co-poly(1,4-butanediol)] diisocyanate, poly(tetrafluoroethylene oxide-co-difluoromethylene oxide) α,ω-diisocyanate, 1,4-diisocyanate oxybutane, 1,8-diisocyanate oxyoctane, 1,3-bis(1-isocyanate oxy-1-methylethyl)benzene, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, naphthalene-1,5-diisocyanate, 1,3-phenylene diisocyanate, 1,4-diphenylene diisocyanate, Isocyanate benzene, 2,4- or 2,5- and 2,6-diisocyanate toluene (TDI) or mixtures of these isomers, 4,4′-, 2,4′- or 2,2′-diisocyanate diphenylmethane or mixtures of these isomers, 4,4′-, 2,4′- or 2,2′-diisocyanate-2,2-diphenylpropane-p-xylene diisocyanate and α,α,α′,α′-tetramethyl-m- or-p-xylene diisocyanate (TMXDI) and biuret, isocyanurate, carbamate and diurea of ​​the above isocyanates.

[0037] The diisocyanate compound (A) is more preferably selected from toluene-α,4-diisocyanate, poly(propylene glycol) toluene-2,4-diisocyanate-terminated, 2,4,6-trimethyl-1,3-phenyl diisocyanate, 4-chloro-6-methyl-1,3-phenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-, 2,4'- or 2,2'-diisocyanate diphenylmethane or mixtures of these isomers, 4,4'-, 2... 4′- or 2,2′-diisocyanate-2,2-diphenylpropane-p-xylene diisocyanate and α,α,α′,α′-tetramethyl-m- or p-xylene diisocyanate (TMXDI), diphenylmethane diisocyanate (MDI), naphthalene-1,5-diisocyanate, 1,3-phenyl diisocyanate, 1,4-diisocyanate-phenylene, 2,4- or 2,5- and 2,6-diisocyanate-toluene (TDI) or mixtures of these isomers.

[0038] Furthermore, the diisocyanate compound (A) is most preferably selected from diphenylmethane diisocyanate (MDI), naphthalene-1,5-diisocyanate, 1,3-phenyl diisocyanate, 1,4-diisocyanate benzene, 2,4- or 2,5- and 2,6-diisocyanate toluene (TDI), or mixtures of these isomers.

[0039] In a further preferred embodiment of the invention, the diisocyanate compound (A) is added in at least two portions (A-1) and (A-2).

[0040] In a further preferred embodiment, a second portion (A-2) of the diisocyanate compound (A) and compound (D) are added to the solvent (E) in step (α-4). The presence of solvent (E) reduces the temperature rise by diluting the exothermic reaction that forms the thermoplastic polyoxazolidinone in the reactor. Furthermore, the presence of solvent (E) reduces the viscosity of the reaction system, thus eliminating the need for technically complex high-viscosity techniques.

[0041] A mixture of two or more of the diisocyanate compounds (A) mentioned above can also be used.

[0042] The term “biepoxide (B)” as used in this article is intended to refer to a diepoxide compound (F=2) having two epoxy groups.

[0043] In a preferred embodiment of the invention, the diepoxide compound (B) is selected from at least one of the following compounds: resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, hydrogenated bisphenol-A diglycidyl ether, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, bisphenol-S diglycidyl ether, 9,9-bis(4-epoxypropoxyphenyl)fluorene (9,9-bis(4-glycidyloxy) (phenyl)fluorine), tetrabromobisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, tetramethylbisphenol A diglycidyl ether, tetramethylbisphenol F diglycidyl ether, tetramethylbisphenol S diglycidyl ether, diglycidyl terephthalate, diglycidyl phthalate, 1,4-cyclohexanedicarboxylic acid diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether Polypropylene glycol diglycidyl ether, polybutadiene diglycidyl ether, butadiene diepoxide, vinylcyclohexene diepoxide, limonene diepoxide, diepoxide of C1-C18 alkyl esters of diunsaturated fatty acids, 2-dihydroxyphenyl diglycidyl ether, 1,4-dihydroxyphenyl diglycidyl ether, 4,4′-(3,3,5-trimethylcyclohexyliden)bisphenyl diglycidyl ether, and diglycidyl isophthalate.

[0044] The biepoxide compound (B) is more preferably selected from resorcinol diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol F diglycidyl ether.

[0045] The biepoxide compound (B) is most preferably selected from bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.

[0046] In a further preferred embodiment of the invention, the biepoxide compound (B) comprises an epoxide-terminated oxazolidinone prepolymer, wherein such epoxide-terminated oxazolidinone prepolymer yields a less colored thermoplastic polyoxazolidinone (lower Gardener color).

[0047] In a more preferred embodiment, the epoxide-terminated oxazolidinone prepolymer constitutes at least 90 mol%, preferably 95 mol%, and more preferably 98 mol% of the diepoxide compound (B).

[0048] In a preferred embodiment of the invention, the epoxide-terminated oxazolidinone prepolymer is formed in step (α-3).

[0049] In a preferred embodiment of the invention, the epoxide-terminated oxazolidinone prepolymer formed in step (α-3) is a copolymerization product of a first portion (A-1) of a diisocyanate compound (A) and a diepoxide compound (B) optionally in a solvent (E) in the presence of a first portion (C-1) of a catalyst (C), wherein the molar ratio of the epoxide groups of the polyepoxide compound (B) to the isocyanate groups of the first portion (A-1) of the polyisocyanate compound (A) is 1.1:1 to less than 25:1, preferably 1.4:1 to less than 5:1.

[0050] In a preferred embodiment of the invention, the epoxide-terminated oxazolidinone prepolymer is formed in the absence of solvent (E). Therefore, it is unnecessary to remove the solvent (E) through time- and energy-intensive separation processes, such as distillation. Furthermore, the total amount of solvent used in the production of the thermoplastic polyoxazolidinone can also be reduced.

[0051] In a preferred embodiment of the present invention, the method for preparing an epoxide-terminated oxazolidinone prepolymer includes the steps of:

[0052] i) The first portion (A-1) of the diisocyanate compound (A) is mixed with the first catalyst portion (C-1) of the diepoxide compound (B) and the catalyst (C) to form mixture (i);

[0053] ii) Copolymerize the mixture (i).

[0054] In an alternative preferred embodiment of the present invention, the method for preparing the epoxide-terminated oxazolidinone prepolymer includes the steps of:

[0055] a) Mix the polyepoxide compound (B) and the first catalyst portion (C-1) of the catalyst (C) to form mixture (a);

[0056] b) Under copolymerization conditions, the first portion (A-1) of the diisocyanate compound (A) is added to the mixture (a).

[0057] Alternatively, a mixture of two or more of the aforementioned biepoxide compounds (B) and two or more of the aforementioned epoxide-terminated oxazolidinone prepolymers may be used. A mixture of the aforementioned biepoxide compounds (B) and epoxide-terminated oxazolidinone prepolymers may also be used.

[0058] The molecular weight of the resulting thermoplastic polyoxazolidinone was determined by the molar ratio of the biepoxide compound (B) to the diisocyanate compound (A) and to the compound (D).

[0059] The molar ratio of the diepoxide compound (B) to the diisocyanate compound (A) is preferably in the range of 1:2 to 2:1, more preferably in the range of 45:55 to 2:1, and even more preferably in the range of 47.8:52.2 to 52.2:47.8.

[0060] When diisocyanate compound (A) is used in excess, a monoepoxide is preferably used as compound (D). When diepoxide compound (B) is used in excess, a monoisocyanate is preferably used as compound (D).

[0061] In one embodiment of the invention, the catalyst (C) comprises at least one of tetraalkylphosphonium halide, tetracycloalkylphosphonium halide, tetraarylphosphonium halide, tetraalkylammonium halide, tetracycloalkylammonium halide and / or tetraarylammonium halide, preferably tetraalkylphosphonium halide, tetracycloalkylphosphonium halide and tetraarylphosphonium halide.

[0062] In a preferred embodiment of the invention, the catalyst (C) is at least one compound selected from: tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, tetrahexylammonium bromide, tetraheptylammonium bromide, tetraoctylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrapentylammonium chloride, tetrahexylammonium chloride, tetraheptylammonium chloride, tetraoctylammonium chloride, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, bis(triphenylphosphine)chloroimine, tetraphenylphosphonium nitrate, tetraphenylphosphonium carbonate, and compounds represented by formula (I).

[0063] [A] n + [Y] n- (I)

[0064] Among them, [A] n + It is selected from at least one of the following compounds: p-phenol triphenyl-phosphonium; p-phenol triphenyl-ammonium; p-chlorophenyl triphenyl-phosphonium; ethyl-ammonium; methyl trioctyl-ammonium; choline cation; 1-allyl-3-methyl-imidazolium; 1-butyl-2,3-dimethyl-imidazolium; 1-butyl-3-methyl-imidazolium; 1,2-dimethyl-3-propyl-imidazolium; 1,3-dimethyl-imidazolium; 1-ethyl-3-methyl-imidazolium; 1- Hexadecyl-3-methyl-imidazolium; 1-hexyl-3-methyl-imidazolium; 1-methyl-3-octyl-imidazolium; 1-methyl-3-propyl-imidazolium; Trihexyltetradecyl-phosphonium; 1-methyl-1-propylpiperidinium; 1-butyl-pyridinium; 1-butyl-3-methyl-pyridinium; 1-butyl-4-methyl-pyridinium; 1-butyl-1-methyl-pyrrolidineonium; 1-methyl-1-propyl-pyrrolidineonium; Triethyl-sulfonium,

[0065] Among them, [Y] n- It is selected from at least one of the following compounds: bis(trifluoromethyl-sulfonyl)imide anion; iodide ion; bromide ion; chloride ion; dicyandiamide anion; diethyl phosphate; dihydrogen phosphate; dimethyl phosphate; ethyl sulfate; hexafluorophosphate; hydrogen sulfate; nitrate; tetrafluoroborate; thiocyanate; trifluoromethanesulfonate.

[0066] In a more preferred embodiment of the present invention, the catalyst (C) is selected from at least one of the following compounds: tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, tetrahexylammonium bromide, tetraheptylammonium bromide, tetraoctylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrapentylammonium chloride, tetrahexylammonium chloride, tetraheptylammonium chloride, tetraoctylammonium chloride, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, bis(triphenylphosphine)chlorinated imine, tetraphenylphosphonium nitrate, and tetraphenylphosphonium carbonate.

[0067] In one or even a more preferred embodiment of the invention, the catalyst (C) is at least one compound selected from the group consisting of tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, bis(triphenylphosphine)chlorinated imine, tetraphenylphosphonium nitrate, and tetraphenylphosphonium carbonate.

[0068] In a most preferred embodiment of the invention, the catalyst (C) is at least one compound selected from tetraphenylphosphonium chloride, tetraphenylphosphonium bromide and tetraphenylphosphonium iodide.

[0069] In a preferred embodiment of the invention, the catalyst (C) is added in at least two parts comprising a first part (C-1) and a second part (C-2), wherein such addition of the catalyst in at least two parts yields a thermoplastic polyoxazolidinone with lower polydispersity.

[0070] In a more preferred embodiment of the invention, the first part (C-1) of the catalyst (C) is added in step (α-1).

[0071] In a more preferred embodiment of the invention, step (α) further includes

[0072] (α-4) The second part (C-2) of the catalyst (C) is added to the copolymerization product formed in step (α-3).

[0073] In a more preferred embodiment of the invention, the molar ratio of the first part (C-1) of catalyst (C) to the second part (C-2) of catalyst (C) is 0.05:1 to 1:2, preferably 0.2:1 to 1:1.

[0074] In one embodiment of the method according to the invention, the catalyst (C) is present in an amount of ≥0.001 to ≤5.0% by weight based on the theoretical yield of thermoplastic polyoxazolidinone, preferably in an amount of ≥0.01 to ≤3.0% by weight, more preferably in an amount of ≥0.05 to ≤2.0% by weight.

[0075] According to the present invention, compound (D) is one or more compounds selected from monofunctional isocyanates, monofunctional epoxides, cyclic carbonates, monofunctional alcohols, and monofunctional amines, preferably monofunctional epoxides, wherein compound (D) acts as a chain regulator for thermoplastic polyoxazolidinone and further improves the thermal stability of thermoplastic polyoxazolidinone.

[0076] In one embodiment of the invention, compound (D) is a branched, unbranched aliphatic, alicyclic, and / or aromatic monofunctional alcohol.

[0077] Suitable monofunctional alcohols are, for example, straight-chain primary alcohols, such as methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, and n-eicosanool. Suitable branched monofunctional primary alcohols are, for example, isobutanol, isoamyl alcohol, isohexanol, isooctanol, isostearyl alcohol and isopalmitol, 2-ethylhexanol, 3-n-propylheptanol, 2-n-propylheptanol, and 3-isopropylheptanol. Suitable monofunctional secondary alcohols are, for example, isopropanol, sec-butanol, sec-pentanol (pentan-2-ol), pentan-3-ol, cyclopentanol, cyclohexanol, sec-hexanol (hexan-2-ol), hexan-3-ol, sec-heptanol (heptan-2-ol), heptan-3-ol, sec-decanol, and decan-3-ol. Examples of suitable monofunctional tertiary alcohols are tert-butanol and tert-pentanol.

[0078] Aromatic monofunctional alcohols, such as phenol, cresol, thymol, benzyl alcohol, and 2-phenylethanol, can also be used.

[0079] In a further embodiment of the invention, compound (D) is a branched, unbranched aliphatic, alicyclic, and / or aromatic monofunctional isocyanate.

[0080] Suitable monofunctional isocyanates include, for example, n-hexyl isocyanate, cyclohexyl isocyanate, ω-chlorohexamethylene isocyanate, 2-ethylhexyl isocyanate, n-octyl isocyanate, dodecyl isocyanate, stearyl isocyanate, methyl isocyanate, ethyl isocyanate, butyl isocyanate, isopropyl isocyanate, octadecyl isocyanate, 6-chloro-hexyl isocyanate, cyclohexyl isocyanate, 2,3,4-trimethylcyclohexyl isocyanate, 3,3,5-trimethylcyclohexyl isocyanate, 2-norbornylmethyl isocyanate, decyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, 3-butoxypropyl isocyanate, 3-(2-ethylhexoxy)-propyl isocyanate, and trimethylsilyl isocyanate. Esters, phenyl isocyanates, o-, m-, and p-toluene isocyanates, chlorophenyl isocyanate (2,3,4-isomers), dichlorophenyl isocyanate, 4-nitrophenyl isocyanate, 3-trifluoromethylphenyl isocyanate, benzyl isocyanate, dimethylphenyl isocyanate (technical mixtures and independent isomers), 4-dodecylphenyl isocyanate, 4-cyclohexylphenyl isocyanate, 4-pentylphenyl isocyanate, 4-tert-butylphenyl isocyanate, and 1-naphthyl isocyanate.

[0081] In one embodiment of the invention, compound (D) is a branched, unbranched aliphatic, alicyclic, and / or aromatic monofunctional amine. Specific examples of aliphatic monofunctional amines include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, and heptadecanylamine. Examples include amines, octadecylamine, nonadecanylamine, eicosylamine, henecosylamine, and dodecylamine. Specific examples of alicyclic monofunctional amines include cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2,3-dimethylcyclohexylamine, 2,4-dimethylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 3-n-propylcyclohexylamine, 4-n-propylcyclohexylamine, 2-isopropylcyclohexylamine, 3-isopropylcyclohexylamine, 4-isopropylcyclohexylamine, 2-n-butylcyclohexylamine, 3-n-butylcyclohexylamine, 4-n-butylcyclohexylsilamine, 2-isobutylcyclohexylamine, 3-isobutylcyclohexylamine, and 4-isobutylcyclohexylsilamine. Amines, 4-isobutylcyclohexylamine, 2-tert-butylcyclohexylamine, 3-tert-butylcyclohexylamine, 4-tert-butylcyclohexylamine, 2-n-octylcyclohexylamine, 3-n-octylcyclohexylamine, 4-n-octylcyclohexylamine, cyclohexylmethylamine, 2-methylcyclohexylmethylamine, 3-methylcyclohexylmethylamine, 4-methylcyclohexylmethylamine, dimethylcyclohexylmethylamine, trimethylcyclohexylmethylamine, methoxycyclohexylmethylamine, ethoxycyclohexylmethylamine, dimethylcarboxymethylcyclohexylmethylamine, methoxycyclohexylethylamine, dimethoxycyclohexylethylamine, methylcyclohexylaminepropylamine, dodecylaminecyclohexylamine.

[0082] Specific examples of aromatic monofunctional amines include aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, o-toluidine, p-toluidine, m-toluidine, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-propylaniline, 3-propylaniline, 4-propylaniline, cumylamine, 2-n-butylaniline, 3-n-butylaniline, 4-n-butylaniline, 2-isobutylaniline, 3-isobutylaniline, 4-isobutylaniline, 2-sec-butylaniline, and 3-sec-butylaniline. 4-sec-butylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 2-N-pentylaniline, 3-n-pentylaniline, 4-n-pentylaniline, 2-isopentylaniline, 3-isopentylaniline, 4-isopentylaniline, 2-sec-pentylaniline, 3-sec-pentylaniline, 4-sec-pentylaniline, 2-tert-pentylaniline, 3-tert-pentylaniline, 4-tert-pentylaniline, 2-hexylaniline, 3-hexylaniline, 4-hexylaniline, 2-heptyl Aniline, 3-heptylaniline, 4-heptylaniline, 2-octylaniline, 3-octylaniline, 4-octylaniline, 2-nonylaniline, 3-nonylaniline, 4-nonylaniline, 2-decylaniline, 3-decylaniline, 4-decylaniline, cyclohexylaniline, dianiline, dimethylaniline, diethylaniline, dipropylaniline, diisopropylaniline, di-n-butylaniline, di-sec-butylaniline, di-tert-butylaniline, trimethylaniline, triethylaniline, tripropylaniline Amines, tri-tert-butylaniline, anisidine, ethoxyaniline, dimethoxyaniline, diethoxyaniline, trimethoxyaniline, tri-n-butoxyaniline, benzylamine, methylbenzylamine, dimethylbenzylamine, trimethylbenzylamine, methoxybenzylamine, ethoxybenzylamine, dimethoxybenzylamine, α-phenylethylamine, β-phenylethylamine, methoxyphenylethylamine, dimethoxyphenylethylamine, α-phenylpropylamine, β-phenylpropylamine, γ-phenylpropylamine, methylphenylpropylamine.

[0083] In one embodiment of the present invention, compound (D) is at least one compound selected from 4-phenyl-1,3-dioxolane-2-one (styrene carbonate), 1,3-dioxolane-2-one (ethylene carbonate), and 4-methyl-1,3-dioxolane-2-one (propylene carbonate).

[0084] In a preferred embodiment of the invention, compound (D) is at least one compound selected from the following: phenyl glycidyl ether, o-cresol glycidyl ether, m-cresol glycidyl ether, p-cresol glycidyl ether, 1-naphthyl glycidyl ether, 2-naphthyl glycidyl ether, 4-chlorophenyl glycidyl ether, 2,4,6-trichlorophenyl glycidyl ether, 2,4,6-tribromophenyl glycidyl ether, pentafluorophenyl glycidyl ether, cyclohexyl glycidyl ether, Benzyl glycidyl ether, glycidyl benzoate, glycidyl acetate, glycidyl cyclohexylcarboxylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, octyl glycidyl ether, C10-C18 alkyl glycidyl ether, allyl glycidyl ether, ethylene oxide, propylene oxide, styrene oxide, 1,2-butene oxide, 2,3-butene oxide, 1,2-hexene oxide, oxides of C10-C18 α-olefins, cyclohexene oxide, vinylcyclohexene monooxide, limonene monooxide, butadiene monoepoxide, N-glycidyl phthalimide, and 4-tert-butylphenyl glycidyl ether.

[0085] In a preferred embodiment of the invention, compound (D) is 4-tert-butylphenyl glycidyl ether and / or phenyl glycidyl ether and / or o-cresol glycidyl ether and / or styrene oxide.

[0086] In one embodiment of the method according to the invention, compound (D) is present in an amount of ≥0.1 to ≤7.0% by weight based on the theoretical yield of thermoplastic polyoxazolidinone, preferably in an amount of ≥0.2 to ≤5.0% by weight, more preferably in an amount of ≥0.5 to ≤3.0% by weight.

[0087] In one embodiment of the invention, the method is carried out in an aprotic halogenated aromatic solvent, a high-boiling aprotic aliphatic heterocyclic solvent, a halogenated aromatic or aliphatic heterocyclic solvent with a boiling point of 1 bar (absolute) equal to or lower than 200°C, preferably equal to or lower than 190°C, and more preferably equal to or lower than 180°C.

[0088] In a preferred embodiment of the invention, the method is carried out in the presence of a solvent (E), wherein the solvent (E) is one or more compounds selected from chlorobenzene, different isomers of dichlorobenzene, dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1-methoxy-2-(2-methoxyethoxy)ethane, different isomers of dioxane, preferably chlorobenzene and o-dichlorobenzene.

[0089] According to the present invention, compound (F) is one or more compounds selected from monofunctional isocyanates, monofunctional epoxides, cyclic carbonates, monofunctional alcohols, and monofunctional amines, preferably monofunctional epoxides, wherein compound (F) acts as a chain regulator for thermoplastic polyoxazolidinone and further improves the thermal stability of thermoplastic polyoxazolidinone.

[0090] In one embodiment of the invention, compound (F) is a branched, unbranched aliphatic, alicyclic, and / or aromatic monofunctional alcohol.

[0091] Suitable monofunctional alcohols are, for example, straight-chain primary alcohols, such as methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, and n-eicosanool. Suitable branched monofunctional primary alcohols are, for example, isobutanol, isoamyl alcohol, isohexanol, isooctanol, isostearyl alcohol and isopalmitol, 2-ethylhexanol, 3-n-propylheptanol, 2-n-propylheptanol, and 3-isopropylheptanol. Suitable monofunctional secondary alcohols are, for example, isopropanol, sec-butanol, sec-pentanol (pentan-2-ol), pentan-3-ol, cyclopentanol, cyclohexanol, sec-hexanol (hexan-2-ol), hexan-3-ol, sec-heptanol (heptan-2-ol), heptan-3-ol, sec-decanol, and decan-3-ol. Examples of suitable monofunctional tertiary alcohols are tert-butanol and tert-pentanol.

[0092] Aromatic monofunctional alcohols, such as phenol, cresol, thymol, benzyl alcohol, and 2-phenylethanol, can also be used.

[0093] In a further embodiment of the invention, compound (F) is a branched, unbranched aliphatic, alicyclic, and / or aromatic monofunctional isocyanate.

[0094] Suitable monofunctional isocyanates include, for example, n-hexyl isocyanate, cyclohexyl isocyanate, ω-chlorohexamethylene isocyanate, 2-ethylhexyl isocyanate, n-octyl isocyanate, dodecyl isocyanate, stearyl isocyanate, methyl isocyanate, ethyl isocyanate, butyl isocyanate, isopropyl isocyanate, octadecyl isocyanate, 6-chloro-hexyl isocyanate, cyclohexyl isocyanate, 2,3,4-trimethylcyclohexyl isocyanate, 3,3,5-trimethylcyclohexyl isocyanate, 2-norbornylmethyl isocyanate, decyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, 3-butoxypropyl isocyanate, 3-(2-ethylhexoxy)-propyl isocyanate, and trimethylsilyl isocyanate. Esters, phenyl isocyanates, o-, m-, and p-toluene isocyanates, chlorophenyl isocyanate (2,3,4-isomers), dichlorophenyl isocyanate, 4-nitrophenyl isocyanate, 3-trifluoromethylphenyl isocyanate, benzyl isocyanate, dimethylphenyl isocyanate (technical mixtures and independent isomers), 4-dodecylphenyl isocyanate, 4-cyclohexylphenyl isocyanate, 4-pentylphenyl isocyanate, 4-tert-butylphenyl isocyanate, and 1-naphthyl isocyanate.

[0095] In one embodiment of the invention, compound (F) is a branched, unbranched aliphatic, alicyclic, and / or aromatic monofunctional amine. Specific examples of aliphatic monofunctional amines include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, and heptadecanylamine. Examples include amines, octadecylamine, nonadecanylamine, eicosylamine, henecosylamine, and dodecylamine. Specific examples of alicyclic monofunctional amines include cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2,3-dimethylcyclohexylamine, 2,4-dimethylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 3-n-propylcyclohexylamine, 4-n-propylcyclohexylamine, 2-isopropylcyclohexylamine, 3-isopropylcyclohexylamine, 4-isopropylcyclohexylamine, 2-n-butylcyclohexylamine, 3-n-butylcyclohexylamine, 4-n-butylcyclohexylsilylamine, 2-isobutylcyclohexylamine, 3-isobutylcyclohexylamine, 4-isobutylcyclohexylamine, etc. Butylcyclohexylamine, 2-tert-butylcyclohexylamine, 3-tert-butylcyclohexylamine, 4-tert-butylcyclohexylamine, 2-n-octylcyclohexylamine, 3-n-octylcyclohexylamine, 4-n-octylcyclohexylamine, cyclohexylmethylamine, 2-methylcyclohexylmethylamine, 3-methylcyclohexylmethylamine, 4-methylcyclohexylmethylamine, dimethylcyclohexylmethylamine, trimethylcyclohexylmethylamine, methoxycyclohexylmethylamine, ethoxycyclohexylmethylamine, dimethylcarboxymethylcyclohexylmethylamine, methoxycyclohexylethylamine, dimethoxycyclohexylethylamine, methylcyclohexylaminepropylamine, dodecylaminecyclohexylamine.

[0096] Specific examples of aromatic monofunctional amines include aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, o-toluidine, p-toluidine, m-toluidine, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-propylaniline, 3-propylaniline, 4-propylaniline, cumylamine, 2-n-butylaniline, 3-n-butylaniline, 4-n-butylaniline, 2-isobutylaniline, 3-isobutylaniline, 4-isobutylaniline, 2-sec-butylaniline, and 3-sec-butylaniline. 4-sec-butylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 2-N-pentylaniline, 3-n-pentylaniline, 4-n-pentylaniline, 2-isopentylaniline, 3-isopentylaniline, 4-isopentylaniline, 2-sec-pentylaniline, 3-sec-pentylaniline, 4-sec-pentylaniline, 2-tert-pentylaniline, 3-tert-pentylaniline, 4-tert-pentylaniline, 2-hexylaniline, 3-hexylaniline, 4-hexylaniline, 2-heptyl Aniline, 3-heptylaniline, 4-heptylaniline, 2-octylaniline, 3-octylaniline, 4-octylaniline, 2-nonylaniline, 3-nonylaniline, 4-nonylaniline, 2-decylaniline, 3-decylaniline, 4-decylaniline, cyclohexylaniline, dianiline, dimethylaniline, diethylaniline, dipropylaniline, diisopropylaniline, di-n-butylaniline, di-sec-butylaniline, di-tert-butylaniline, trimethylaniline, triethylaniline, tripropylaniline Amines, tri-tert-butylaniline, anisidine, ethoxyaniline, dimethoxyaniline, diethoxyaniline, trimethoxyaniline, tri-n-butoxyaniline, benzylamine, methylbenzylamine, dimethylbenzylamine, trimethylbenzylamine, methoxybenzylamine, ethoxybenzylamine, dimethoxybenzylamine, α-phenylethylamine, β-phenylethylamine, methoxyphenylethylamine, dimethoxyphenylethylamine, α-phenylpropylamine, β-phenylpropylamine, γ-phenylpropylamine, methylphenylpropylamine.

[0097] In one embodiment of the present invention, compound (F) is at least one compound selected from 4-phenyl-1,3-dioxolane-2-one (styrene carbonate), 1,3-dioxolane-2-one (ethylene carbonate), and 4-methyl-1,3-dioxolane-2-one (propylene carbonate).

[0098] In a preferred embodiment of the invention, compound (F) is at least one compound selected from the group consisting of: phenyl glycidyl ether, o-cresol glycidyl ether, m-cresol glycidyl ether, p-cresol glycidyl ether, 1-naphthyl glycidyl ether, 2-naphthyl glycidyl ether, 4-chlorophenyl glycidyl ether, 2,4,6-trichlorophenyl glycidyl ether, 2,4,6-tribromophenyl glycidyl ether, pentafluorophenyl glycidyl ether, cyclohexyl glycidyl ether, benzyl glycidyl ether, glycidyl benzoate, glycidyl acetate, cyclohexylformate, methyl Glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, octyl glycidyl ether, C10-C18 alkyl glycidyl ether, allyl glycidyl ether, ethylene oxide, propylene oxide, styrene oxide, 1,2-butene oxide, 2,3-butene oxide, 1,2-hexene oxide, oxides of C10-C18 α-olefins, cyclohexene oxide, vinylcyclohexene monooxide, limonene monooxide, butadiene monoepoxide, N-glycidyl phthalimide, and 4-tert-butylphenyl glycidyl ether.

[0099] In a preferred embodiment of the invention, compound (F) is 4-tert-butylphenyl glycidyl ether and / or phenyl glycidyl ether and / or o-cresol glycidyl ether and / or styrene oxide.

[0100] In a preferred embodiment of the invention, compounds (D) and (F) are monofunctional epoxides.

[0101] In a more preferred embodiment of the invention, compounds (D) and (F) are 4-tert-butylphenyl glycidyl ether and / or phenyl glycidyl ether and / or o-cresol glycidyl ether and / or styrene oxide.

[0102] In one embodiment of the method according to the invention, compound (F) is present in an amount of ≥0.1 to ≤10.0% by weight based on the theoretical yield of thermoplastic polyoxazolidinone, preferably in an amount of ≥0.2 to ≤8.0% by weight, more preferably in an amount of ≥0.5 to ≤7.0% by weight.

[0103] The reaction according to the invention is carried out in the absence of a solvent (G) with a boiling point above 200°C, preferably above 190°C, and more preferably above 180°C at 1 bar (absolute).

[0104] Such solvents (G) include, for example, cyclic carbonates such as ethylene carbonate or propylene carbonate, N-methylpyrrolidone (NMP), and sulfolane. The absence of this additional solvent (G) reduces the energy-intensive and time-consuming removal processes of such high-boiling solvents, such as distillation.

[0105] Another aspect of the invention is a thermoplastic polyoxazolidinone obtainable by the method according to the invention, wherein the number-average molecular weight Mn of the thermoplastic polyoxazolidinone, as determined by gel permeation chromatography (GPC), is preferably ≥500 to ≤500,000 g / mol, more preferably ≥1,000 to ≤50,000 g / mol, and even more preferably ≥5,000 to ≤250,000 g / mol. GPC was performed on an Agilent 1100 Series instrument with N,N-dimethylacetamide (DMAC) + LiBr (1.7 g·L⁻¹). -1 As the eluent, the PSS GRAM analytical column from PSS ( The column was equipped with a refractive index (RI) detector. The column flow rate was set to 1 mL·min⁻¹ for all measurements. For molecular weight determination, calibration was performed using a poly(styrene) standard (ReadyCal-Kit PS-Mp 370-2520000Da from PSS). Samples were analyzed using PSS WinGPC UniChromV 8.2 software.

[0106] Preferably, the molar amount of the monoepoxide and / or monoisocyanate compound added as compound (D) satisfies certain criteria relative to the molar amounts of the diepoxide compound (B) and the diisocyanate compound (A). The ratio r is defined as the molar amount (n) of compound (D) according to the following formula (II). D The molar amount (n) of the bicyclic oxide (B) 双环氧化物 The molar amounts (n) of the diisocyanate compound (A) and the diisocyanate compound (A) 二异氰酸酯 The absolute value of the difference between )

[0107] r = |n D / (n 双环氧化物 -n 二异氰酸酯 (II)

[0108] It is preferably in the range of ≥1.5 to ≤2.5, more preferably in the range of ≥1.9 to ≤2.1, and particularly preferably in the range of ≥1.95 to ≤2.05. While not bound by theory, when such a quantity of chain regulator is used, all epoxide groups and all isocyanate groups will react at the end of the reaction.

[0109] Alternatively, after the reaction between the diepoxide and the diisocyanate has been completed, an excess of a monofunctional isocyanate, monofunctional epoxide, cyclic carbonate, monofunctional alcohol, or monofunctional amine (preferably a monofunctional epoxide) as a chain regulator is added to the reaction mixture. Unrestricted by theory, the terminal epoxide or terminal isocyanate groups generated from the reaction of the diepoxide and diisocyanate will be converted into inert end groups by reacting with the regulator. The excess regulator is then removed from the product, for example, by extraction, precipitation, distillation, stripping, or thin-film evaporation.

[0110] The present invention further relates to spun fibers comprising the thermoplastic polyoxazolidinone according to the invention and textiles comprising such spun fibers.

[0111] The method according to the invention is applicable to the synthesis of oxazolidinones having useful properties for use as, for example, pharmaceuticals or antimicrobial agents.

[0112] Thermoplastic polyoxazolidinones obtained by the method according to the invention are particularly suitable as polymer building blocks in polyurethane chemistry. For example, epoxide-terminated oligooxazolidinones (oligoxazolidinones) can react with polyols or polyamines to form foams or thermosetting materials. Such epoxide-terminated oligooxazolidinones are also suitable for preparing composite materials. Epoxide-terminated oligooxazolidinones (oligoxazolidinones) can also react with their NCO-terminated counterparts to form high molecular weight thermoplastic polyoxazolidinones that can be used as transparent, high-temperature stable materials. The high molecular weight thermoplastic polyoxazolidinones obtained by the method according to the invention are particularly suitable as transparent, high-temperature stable thermoplastic materials.

[0113] Conventional additives for these thermoplastic materials, such as fillers, UV stabilizers, heat stabilizers, antistatic agents, and pigments, can also be added in conventional amounts to the thermoplastic polyoxazolidinone according to the invention; release properties, flow properties, and / or flame retardancy can also be optionally improved by adding external release agents, flow agents, and / or flame retardants (e.g., alkyl and aryl phosphites and phosphates, alkyl- and aryl phosphines and low molecular weight carboxylic acid alkyl and aryl esters, halogen compounds, salts, chalk, quartz powder, glass fibers and carbon fibers, pigments, and combinations thereof. Such compounds are described, for example, in the corresponding sections of WO 99 / 55772, pp. 15-25, and "Plastics Additives Handbook", edited by Hans Zweifel, 5th edition 2000, Hanser Publishers, Munich).

[0114] The thermoplastic polyoxazolidinone obtained according to the present invention has excellent properties in terms of stiffness, hardness and chemical resistance.

[0115] They can also be used in polymer blends with other polymers such as polystyrene, high-impact polystyrene (polystyrene modified with rubber for toughening, typically polybutadiene), styrene copolymers such as styrene-acrylonitrile copolymer (SAN), styrene, α-methylstyrene and acrylonitrile copolymers, styrene-methyl methacrylate copolymers, styrene-maleic anhydride copolymers, styrene-maleimide copolymers, styrene-acrylic acid copolymers, SAN (acrylonitrile-butadiene-styrene polymer) modified by grafting toughening rubber such as ABS, ASA (... Acrylonitrile-styrene-acrylate), AES (acrylonitrile-EPDM-styrene), ACS (acrylonitrile-chlorinated polyethylene-styrene) polymers, styrene modified with rubber such as polybutadiene or EPDM, copolymers of α-methylstyrene and acrylonitrile, MBS / MABS (methyl methacrylate-styrene modified with rubber such as polybutadiene or EPDM), aromatic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), aliphatic polyamides such as PA6, PA6,6, PA4,6, PA11 or PA to 12, polylactic acid, aromatic polycarbonates such as polycarbonate of bisphenol A, copolycarbonates such as copolycarbonate of bisphenol A and bisphenol TMC, polymethyl methacrylate (PMMA), polyvinyl chloride, polyoxymethylene (POM), polyphenylene ether, polyphenylene sulfide (PPS), polysulfone, polyetherimide (PEI), polyethylene, polypropylene.

[0116] They can also be combined with the above-mentioned polymers or other polymers for blends, such as blends of polycarbonate and ABS, blends of polycarbonate and PET, blends of polycarbonate and PBT, blends of polycarbonate and ABS and PBT, or blends of polycarbonate and ABS and PBT.

[0117] The properties of the thermoplastic polyoxazolidinone or blends thereof with the above-mentioned polymers or other polymers according to the present invention can also be modified by fillers such as glass fibers, hollow or solid glass spheres, silica (e.g., fumed silica or precipitated silica), talc, calcium carbonate, titanium dioxide, carbon fibers, carbon black, natural fibers such as straw, flax, cotton or wood fibers.

[0118] Thermoplastic polyoxazolidinone can be mixed with any common plastic additives, such as antioxidants, light stabilizers, impact modifiers, acid removers, lubricants, processing aids, anti-blocking additives, slip additives, anti-fogging additives, antistatic additives, antimicrobial agents, chemical foaming agents, colorants, brighteners, fillers and reinforcing materials, as well as flame retardant additives.

[0119] Suitable impact modifiers are typically high molecular weight elastomers derived from olefins, monovinyl aromatic monomers, acrylic acid and methacrylic acid and their ester derivatives, as well as conjugated dienes. Polymers formed from conjugated dienes can be fully or partially hydrogenated. The elastomer material can be in the form of homopolymers or copolymers, including random, block, radial block, graft, and core-shell copolymers. Combinations of impact modifiers can be used.

[0120] One particular type of impact modifier is an elastomeric graft copolymer comprising (i) an elastomeric (i.e., rubbery) polymer substrate having a Tg of less than 10°C, more particularly less than -10°C or more particularly -40°C to -80°C, and (ii) a rigid polymer shell grafted onto the elastomeric polymer substrate. Materials suitable as the elastomeric phase include, for example, conjugated diene rubbers, such as polybutadiene and polyisoprene; copolymers of conjugated dienes with less than 50% by weight of copolymerizable monomers, such as monovinyl compounds, such as styrene, acrylonitrile, n-butyl acrylate, or ethyl acrylate; olefin rubbers, such as ethylene-propylene copolymer (EPR) or ethylene-propylene-diene monomer rubber (EPDM); ethylene-vinyl acetate rubber; silicone rubber; elastomeric (meth)acrylate C1-8 alkyl esters; elastomeric copolymers of (meth)acrylate C1-8 alkyl esters with butadiene and / or styrene; or combinations comprising at least one of the above elastomeric phases. Materials suitable for use as rigid phases include, for example, monovinyl aromatic monomers such as styrene and α-methylstyrene, and monovinyl monomers such as acrylonitrile, acrylic acid, methacrylic acid, and C1-C6 esters of acrylic acid and C1-C6 esters of methacrylic acid, especially methyl methacrylate.

[0121] Specific exemplary elastomer-modified graft copolymers include those formed from styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS (acrylonitrile-butadiene-styrene), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), and styrene-acrylonitrile (SAN).

[0122] Impact modifiers are typically present in an amount of 1 to 30% by weight, particularly 3 to 20% by weight, based on the total weight of the polymer in the flame retardant composition. An exemplary impact modifier comprises an amount of 2 to 15% by weight, particularly 3 to 12% by weight, based on the total weight of the flame retardant composition, of an acrylic polymer.

[0123] The composition may also contain mineral fillers. In one embodiment, the mineral filler acts as a synergist. Compared to a comparative thermoplastic polyoxazolidinone composition containing the same amount of all the same components except for the synergist, the synergist promotes improved flame-retardant properties when added to the flame-retardant composition. Examples of mineral fillers are mica, talc, calcium carbonate, dolomite, wollastonite, barium sulfate, silica, kaolin, feldspar, barite, etc., or combinations containing at least one of the above-mentioned mineral fillers. The mineral filler may have an average particle size of 0.1 to 20 micrometers, particularly 0.5 to 10 micrometers, and more particularly 1 to 3 micrometers. An exemplary mineral filler is talc having an average particle size of 1 to 3 micrometers.

[0124] The mineral filler is present in an amount of 0.1 to 20% by weight, particularly 0.5 to 15% by weight, and even more particularly 1 to 5% by weight, based on the total weight of the flame retardant composition.

[0125] Thermoplastic polyoxazolidinone can also be colored with various soluble organic dyes and pigments that can be organic or inorganic.

[0126] Further feasible uses of the thermoplastic polyoxazolidinone according to the present invention are:

[0127] 01. The casing of electrical appliances (such as household appliances, computers, mobile phones, displays, televisions, etc.), including transparent or translucent casing components, such as lampshades.

[0128] 02. Light guide plate and BLU

[0129] 03. Optical data storage (CD, DVD, Blu-ray disc)

[0130] 04. Electrically insulating materials for electrical conductors, plug housings and plug connectors; carrier materials for organic optoelectronic conductors; chip boxes and chip supports; fuse packaging.

[0131] 05. Static dissipation / conductive agents for explosion-proof applications and other applications with their own specific requirements.

[0132] 06. Optical components, diffusers, reflectors, light guides, and housings for LED and conventional lighting, such as streetlights, industrial lights, searchlights, traffic lights, etc.

[0133] 07. Thermal management agents, such as those used in radiators.

[0134] 08. Applications in automobiles and other transport vehicles (cars, buses, trucks, trains, airplanes, ships) as mounting glass, as well as safety glass, lighting (e.g., headlight lenses, taillights, turn signals, reversing lights, fog lights; condensers and reflectors), sunroofs and panoramic sunroofs, canopies, cladding of railway carriages or other compartments, windshields, and interior and exterior components (e.g., instrument covers, consoles, dashboards, mirror housings, radiator grilles, bumpers, spoilers).

[0135] 09. EVSE and Battery

[0136] 10. Metal substitutes in gears, seals, and support rings

[0137] 11. Roofing structures (e.g., for stadiums, stations, conservatories, greenhouses)

[0138] 12. Windows (including burglar bars and bulletproof windows, teller windows, and barriers inside the bank)

[0139] 13. Partition wall

[0140] 14. Solar panels

[0141] 15. Medical devices (components of blood pumps, auto-injectors and portable medical infusion pumps, intravenous infusion devices, kidney treatment and inhalation devices (such as nebulizers, inhalers), sterilizable surgical instruments, medical implants, oxygenators, dialyzers, ...)

[0142] 16. Food contact applications (kitchenware, tableware, glassware, tumblers, food containers, institutional food trays, water bottles, water filtration systems)

[0143] 17. Sports equipment, such as ski poles or ski boot buckles.

[0144] 18. Household items, such as kitchen sinks and mailbox shells.

[0145] 19. Safety Applications (eyeglasses, goggles or corrective lenses, helmets, riot gear (helmets and shields), safety panes)

[0146] 20. Sunglasses, swimming goggles, diving masks

[0147] 21. Protection of signage, displays, and posters

[0148] 22. Lightweight suitcase

[0149] 23. Water fittings, pump impellers, fine hollow fibers for water treatment

[0150] 24. Industrial pumps, valves and seals, connectors

[0151] 25. Membrane

[0152] 26. Gas separation

[0153] 27. Coating applications (e.g., anti-corrosion paints, powder coatings)

[0154] This application also provides molded articles, molded articles, and extrusions made from polymers according to the invention. Example

[0155] The invention will be further described with reference to the following embodiments, but it is not intended to be limited thereto.

[0156] Diisocyanate compound (A)

[0157] MDI-14,4′-Diphenylmethane diisocyanate, 98%, Covestro AG, Germany

[0158] 98% mixture of MDI-24,4′-diphenylmethane diisocyanate and 4,2′-diphenylmethane diisocyanate, Covestro AG, Germvny, used without further purification.

[0159] Epoxy compounds (B)

[0160] BADGE 2-[[4-[2-[4-(ethylene oxide-2-ylmethoxy)phenyl]prop-2-yl]phenoxy]methyl]ethylene oxide (bisphenol A-diglycidyl ether), a bifunctional epoxide, DER332 (Dow), used without any further purification (EEW: 171-175 g / eq.).

[0161] Catalyst (C)

[0162] TPPCl tetraphenylphosphonium chloride (Sigma-Aldrich, 98%)

[0163] TPPBr (Tetraphenylphosphonium bromide, Sigma-Aldrich, 97%)

[0164] Lithium chloride (LiCl, Sigma-Aldrich, >99.9%)

[0165] Compounds (D) and (F)

[0166] BPGE p-tert-butylphenyl glycidyl ether (ABCR to Dr. Braunagel GmbH+Co.KG)

[0167] Solvent (E)

[0168] o-DCB (o-dichlorobenzene), 99% pure, anhydrous, obtained from Sigma-Aldrich, Germany

[0169] TCB 1,2,4-Trichlorobenzene (TCB), 99% pure, anhydrous, obtained from Sigma-Aldrich, Germany

[0170] Solvent (G)

[0171] Acros Organic, 99% sulfolane

[0172] o-DCB, TCB, sulfolane, MDI-1, MDI-2, NMP, TPPC1, TPPBr, LiCl, BADGE, and BPGE were used as per samples without further purification. BADGE and sulfolane were used after melting at 50°C, while BPGE was stored at 7°C.

[0173] Characterization of thermoplastic polyoxazolidinone

[0174] The average chain length of thermoplastic polyoxazolidinone is controlled by the molar ratio of diepoxide, diisocyanate and / or compound (D).

[0175] The following formula gives the general mathematical formula for calculating the average chain length n in the polymer products obtained from diisocyanate (A) and biepoxide (B):

[0176] n=(1+q) / (1+q-2pq)(III)

[0177] Where q = n x / n y ≤1 and x, y = biepoxide (B) or diisocyanate (A)

[0178] and conversion rate p

[0179] Therefore n x and n y These are the molar amounts of either diepoxide or diisocyanate.

[0180] The average molecular weight M of thermoplastic polyoxazolidinone can be calculated using the formula given below.

[0181] M = n * (M A +M B ) / 2)+(2*M D (IV)

[0182] Where M A MB and M D These are the molar masses of compounds (A), (B), and (D).

[0183] Solid-state IR analysis was performed on a Bruker ALPHA-P IR spectrometer equipped with a diamond probe. OPUS 6.5 software was used for data processing. Background spectra were recorded against ambient air. Subsequently, a small sample (2 mg) of thermoplastic polyoxazolidinone was applied to the diamond probe, and infrared spectra were recorded from 4000 to 400 cm⁻¹. -1 Within a range of 4cm -1 The average was obtained from 24 spectra at a resolution of [resolution value missing].

[0184] OXA: PIR ratio is calculated using the signal height in infrared spectroscopy. Therefore, the oxazolidinone group is used at 1750 cm⁻¹. -1 The characteristic carbonyl band at 1715 cm⁻¹, and at 1715 cm⁻¹ -1 The signal at the point is used to determine the amount of isocyanurate. The OXA:PIR ratio is calculated based on the following formula:

[0185]

[0186] Number-average molecular weight, weight-average molecular weight, and polydispersity index were determined by gel permeation chromatography (GPC). GPC was performed on an Agilent 1100 Series instrument with N,N-dimethylacetamide (DMAC) + LiBr (1.7 g·L⁻¹). -1 As the eluent, the PSS GRAM analytical column from PSS ( It is equipped with a refractive index (RI) detector. The column flow rate was set to 1 mL / min in all measurements. -1 To determine the molecular weight, calibration was performed using a poly(styrene) standard (ReadyCal-Kit PS-Mp 370-2520000Da from PSS). Samples were analyzed using PSS WinGPC UniChrom V 8.2 software.

[0187] The determination of residual solvent in heat-treated polymer samples was performed by GC analysis. Therefore, 20–30 mg of polymer sample was weighed into a GC vial, and 20–30 mg of a stock solution of 1.125 wt% tetradecane in DMAC was added. 1 mL of pure DMAc was added, and the sample was vortexed to homogenize it. Measurements were performed using an Agilent Technologies 7890AGC System equipped with an Agilent 19091Z-115HP-1 methylsiloxane column (48 m x 320 μm x 0.52 μm). The inlet was heated to 200 °C, while the oven temperature was 100 °C. Helium was used as the carrier gas, and 1 μL of sample was injected at a 1:10 split ratio. An FID detector was used for analysis. Solvent retention times were as follows: 1.56 min (ethanol), 3.804 min (NMP), 3.992 min (o-DCB), 4.900 min (sulfolane), and 6.450 min (tetradecane (standard)).

[0188] The Gardner color index was determined using a Lico 620 from Hach. Therefore, samples of the product mixture were filled into cuvettes and subsequently analyzed according to DIN EN ISO 1557.

[0189] Example 1 (Comparative): The reaction of diphenylmethane diisocyanate (MDI-1) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) uses LiCl as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) added in step (α) and compound (F) added in step (β), and o-DCB as solvent (E) and sulfolane as solvent (G).

[0190] Under a continuous nitrogen stream, LiCl (0.0999 g) and sulfolane (28 mL) were loaded into a 500 mL glass flask and stirred at 175 °C for 15 min. Then, o-dichlorobenzene (95 mL) was added. Diphenylmethane diisocyanate (M-1) (29.4931 g), bisphenol A diglycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g), and o-dichlorobenzene (85 mL) were loaded into a 250 mL glass flask. The monomer solution was slowly added to the catalyst solution over 90 min. After the addition was complete, the reaction was stirred at 175 °C for an additional 30 min. After a total reaction time of 120 min, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in o-dichlorobenzene (10 mL) was added to the reaction solution. After the addition, the reaction was stirred at 175 °C for an additional 180 min. The absence of an isocyanate band (2260 eM) in the infrared spectrum of the reaction mixture was observed.-1 The reaction was confirmed to be complete. The mixture was then allowed to cool to ambient temperature. Precipitation of the polymer was carried out in ethanol at ambient temperature: therefore, the product mixture (approximately 50 mL) was slowly added to 200 mL of ethanol and milled using an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered, and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160 °C for 6 hours.

[0191] For pure heat post-treatment, the crude reaction mixture was dried under vacuum (50 mbar) at 200°C for 16 hours or at 290°C for 3 hours.

[0192] Example 2: The reaction of diphenylmethane diisocyanate (MDI-1) as diisocyanate (A) and bisphenol A diglycidyl ether (BADGE) as diepoxide (E) uses tetraphenylphosphonium chloride (TPPCl) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound added in step (α) (D) and compound added in step (β) (F), and o-DCB as solvent (E) and no solvent (G).

[0193] Tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and o-dichlorobenzene (92 mL) were loaded into a glass flask (500 mL) under a continuous nitrogen stream. The mixture was then heated to 175 °C and stirred for 15 minutes. Diphenylmethane diisocyanate (MDI-1) (29.4931 g), bisphenol A glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g), and o-dichlorobenzene (77 mL) were loaded into a glass vial (250 mL). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 °C for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in o-dichlorobenzene (10 mL) was added to the reaction solution. After the addition, the reaction was stirred at 175 °C for an additional 180 minutes. The absence of an isocyanate band (2260 eM) in the infrared spectrum of the reaction mixture was observed. -1 The reaction was confirmed to be complete. The mixture was then allowed to cool to ambient temperature. Precipitation of the polymer was carried out in ethanol at ambient temperature: therefore, the product mixture (approximately 50 mL) was slowly added to 200 mL of ethanol and milled using an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered, and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160 °C for 6 hours.

[0194] For pure heat post-treatment, the crude reaction mixture was dried at 200°C for 16 hours under vacuum (50 mbar).

[0195] Example 3: The reaction of diphenylmethane diisocyanate (MDI-1) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) uses tetraphenylphosphonium bromide (TPPBr) as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound added in step (α) (D) and compound added in step (β) (F), and o-DCB as solvent (E) and no solvent (G).

[0196] Tetraphenylphosphonium bromide (TPPBr, 0.9882 g) and o-dichlorobenzene (92 mL) were loaded into a 500 mL glass flask under a continuous nitrogen stream. The mixture was then heated to 175 °C and stirred for 15 minutes. Diphenylmethane diisocyanate (MDI-1) (29.4931 g), bisphenol A glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g), and o-dichlorobenzene (77 mL) were loaded into a 250 mL glass vial. The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 175 °C for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in o-dichlorobenzene (10 mL) was added to the reaction solution. After the addition, the reaction was stirred at 175 °C for an additional 180 minutes. The absence of an isocyanate band (2260 eM) in the infrared spectrum of the reaction mixture was observed. -1 The reaction was confirmed to be complete. The mixture was then allowed to cool to ambient temperature. Precipitation of the polymer was carried out in ethanol at ambient temperature: therefore, the product mixture (approximately 50 mL) was slowly added to 200 mL of ethanol and milled using an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered, and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160 °C for 6 hours.

[0197] For pure heat post-treatment, the crude reaction mixture was dried at 200°C for 16 hours under vacuum (50 mbar).

[0198] Example 4 (Comparative): The reaction of diphenylmethane diisocyanate (MDI-1) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) was carried out using tetraphenylphosphonium chloride (TPPCl) as catalyst (C), and o-DCB as solvent (E) and no solvent (G).

[0199] Tetraphenylphosphonium chloride (TPPCl, 0.8834 g) and o-dichlorobenzene (92 mL) were loaded into a glass flask (500 mL) under a continuous nitrogen flow. The mixture was then heated to 175 °C and stirred for 15 min. Diphenylmethane diisocyanate (MDI-1) (29.4931 g), bisphenol A glycidyl ether (38.5141 g), and o-dichlorobenzene (77 mL) were loaded into a glass vial (250 mL). The monomer solution was slowly added to the catalyst solution over 90 min. After the addition was complete, the reaction was stirred at 175 °C for an additional 210 min. The reaction mixture was analyzed by the absence of an isocyanate band (2260 cm⁻¹) in its infrared spectrum. -1 The reaction was confirmed to be complete. The mixture was then allowed to cool to ambient temperature. Precipitation of the polymer was carried out in ethanol at ambient temperature: therefore, the product mixture (approximately 50 mL) was slowly added to 200 mL of ethanol and milled using an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered, and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160 °C for 6 hours.

[0200] Example 5: The reaction of diphenylmethane diisocyanate (MDI-1) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (E) uses tetraphenylphosphonium bromide (TPPBr) as catalyst (C-1) and catalyst (C-2), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) added in step (α) and compound (F) added in step (β), and o-DCB as solvent (E), and no solvent (G).

[0201] Tetraphenylphosphonium bromide (TPPBr, 0.4941 g) and o-dichlorobenzene (92 mL) were loaded into a glass flask (500 mL) under a continuous nitrogen stream. The mixture was then heated to 175 °C and stirred for 15 minutes. Diphenylmethane diisocyanate (MDI-1) (29.4931 g), bisphenol A glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g), and o-dichlorobenzene (77 mL) were loaded into a glass vial (250 mL). The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, a second dose of TPPBr (0.4941 g) was added, and the reaction mixture was stirred at 175 °C for another 30 minutes. After a total reaction time of 120 minutes, 4.8637 g of p-tert-butylphenyl glycidyl ether dissolved in 10 mL of o-dichlorobenzene was added to the reaction solution, and the reaction was then stirred at 175 °C for an additional 180 minutes. The presence of an isocyanate band (2260 cm⁻¹) in the infrared spectrum of the reaction mixture was observed. -1The reaction was confirmed to be complete. The mixture was then allowed to cool to ambient temperature. Precipitation of the polymer was carried out in ethanol at ambient temperature: therefore, the product mixture (approximately 50 mL) was slowly added to 200 mL of ethanol and milled using an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered, and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160 °C for 6 hours.

[0202] For pure heat post-treatment, the crude reaction mixture was dried at 200°C for 16 hours under vacuum (50 mbar).

[0203] Example 6: Step-by-step reaction: The first reaction of diphenylmethane diisocyanate (MDI-2) as diisocyanate (A) and bisphenol A diglycidyl ether (BADGE) as diepoxide (B) is carried out using tetraphenylphosphonium chloride (TPPCl) as catalyst (C-1) to obtain the prepolymer. Second step: chain growth, which uses diphenylmethane diisocyanate (MDI-1) as diisocyanate (A), tetraphenylphosphonium chloride (TPPCl) catalyst (C-2), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) added in step (α) and compound (F) added in step (β), and o-DCB as solvent (E) and no solvent (G).

[0204] Under a continuous nitrogen stream, tetraphenylphosphonium chloride (0.9718 g) and bisphenol A diglycidyl ether (220.6453 g) were loaded into a 500 mL glass flask. The mixture was then stirred and heated to 160 °C. Diphenylmethane diisocyanate (MDI-2) (71.3734 g) was loaded into a 250 mL glass vial. The diphenylmethane diisocyanate was slowly added to the catalyst solution over 30 minutes. The reaction was stirred at 160 °C for another 30 minutes, then transferred to an alumina tray and allowed to cool to ambient temperature.

[0205] Under a continuous nitrogen stream, 50 g of the synthesized prepolymer, o-dichlorobenzene (138 mL), and tetraphenylphosphonium chloride (0.442 g) were loaded into a fresh glass flask (500 mL). The solution was stirred and heated to 175 °C, and then a mixture of diphenylmethane diisocyanate (MDI-1) (16.655 g), p-tert-butylphenyl glycidyl ether (1.9014 g), and o-dichlorobenzene (46 mL) was metered into the preheated solution over 60 minutes. After the addition was complete, the reaction mixture was stirred at 175 °C for another 30 minutes. After a total reaction time of 90 minutes, p-tert-butylphenyl glycidyl ether (4.7536 g) dissolved in o-dichlorobenzene (11 mL) was added to the reaction solution, and the reaction was stirred at 175 °C for another 180 minutes. The reaction mixture was analyzed by the absence of an isocyanate band (2260 cm⁻¹) in the infrared spectrum of the reaction mixture. -1 The reaction was confirmed to be complete. The mixture was then allowed to cool to ambient temperature. Precipitation of the polymer was carried out in ethanol at ambient temperature. Therefore, the product mixture (approximately 50 mL) was slowly added to 200 mL of ethanol and milled using an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered, and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160 °C for 6 hours.

[0206] For pure heat post-treatment, the crude reaction mixture was dried at 200°C for 16 hours under vacuum (50 mbar).

[0207] Example 7: Step-by-step reaction: The first reaction of diphenylmethane diisocyanate (MDI-2) as diisocyanate (A) and bisphenol A diglycidyl ether (BADGE) as diepoxide (B) is carried out using tetraphenylphosphonium bromide (TPPBr) as catalyst (C-1) to obtain the prepolymer. Second step: chain growth, which uses diphenylmethane diisocyanate (MDI-1) as diisocyanate (A), tetraphenylphosphonium bromide (TPPBr) catalyst (C-2), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) added in step (α) and compound (F) added in step (β), and o-DCB as solvent (E) and no solvent (G).

[0208] Tetraphenylphosphonium bromide (1.087 g) and bisphenol A diglycidyl ether (220.6453 g) were loaded into a 500 mL glass flask under a continuous nitrogen flow. The mixture was then stirred and heated to 160 °C. Diphenylmethane diisocyanate (MDI-2) (79.3218 g) was loaded into a 250 mL glass vial. The diphenylmethane diisocyanate was slowly added to the catalyst solution over 30 minutes. The reaction was stirred at 160 °C for another 30 minutes, then transferred to an alumina tray and allowed to cool to ambient temperature.

[0209] Under a continuous nitrogen stream, 50 g of the synthesized prepolymer, o-dichlorobenzene (138 mL), and tetraphenylphosphonium bromide (0.494 g) were loaded into a fresh glass flask (500 mL). The solution was stirred and heated to 175 °C, and then a mixture of diphenylmethane diisocyanate (MDI-1) (14.889 g), p-tert-butylphenyl glycidyl ether (1.8505 g), and o-dichlorobenzene (46 mL) was metered into the preheated solution over 60 minutes. After the addition was complete, the reaction mixture was stirred at 175 °C for another 30 minutes. After a total reaction time of 90 minutes, p-tert-butylphenyl glycidyl ether (4.6263 g) dissolved in o-dichlorobenzene (11 mL) was added to the reaction solution, and the reaction was stirred at 175 °C for another 180 minutes. The reaction mixture was analyzed by the absence of an isocyanate band (2260 cm⁻¹) in the infrared spectrum of the reaction mixture. -1 The reaction was confirmed to be complete. The mixture was then allowed to cool to ambient temperature. Precipitation of the polymer was carried out in ethanol at ambient temperature. Therefore, the product mixture (approximately 50 mL) was slowly added to 200 mL of ethanol and milled using an IKA Ultra-Turrax dispersing instrument. The product was washed with ethanol, filtered, and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160 °C for 6 hours.

[0210] For pure heat post-treatment, the crude reaction mixture was dried at 200°C for 16 hours under vacuum (50 mbar).

[0211] Example 8 (Comparative): Step-by-step reaction: The first reaction of diphenylmethane diisocyanate (MDI-2) as diisocyanate (A) and bisphenol A diglycidyl ether (BADGE) as diepoxide (B) is carried out using tetraphenylphosphonium chloride (TPPCl) as catalyst (C-1) to obtain the prepolymer. Second step: chain growth, which uses diphenylmethane diisocyanate (MDI-1) as diisocyanate (A), p-tert-butylphenyl glycidyl ether (BPGE) as compound (D) added in step (α) and compound (F) added in step (β), and o-DCB as solvent (E) and no solvent (G).

[0212] Under a continuous nitrogen stream, tetraphenylphosphonium chloride (0.9718 g) and bisphenol A diglycidyl ether (220.6453 g) were loaded into a 500 mL glass flask. The mixture was then stirred and heated to 160 °C. Diphenylmethane diisocyanate (MDI-2) (71.3734 g) was loaded into a 250 mL glass vial. The diphenylmethane diisocyanate was slowly added to the catalyst solution over 30 minutes. The reaction was stirred at 160 °C for another 30 minutes, then transferred to an alumina tray and allowed to cool to ambient temperature.

[0213] Under a continuous nitrogen stream, 50 g of the synthesized prepolymer and 138 mL of o-dichlorobenzene were loaded into a fresh glass flask (500 mL). The solution was stirred and heated to 175 °C, and then a mixture of diphenylmethane diisocyanate (MDI-1) (16.655 g), p-tert-butylphenyl glycidyl ether (1.9014 g), and o-dichlorobenzene (46 mL) was metered into the preheated solution over 60 minutes. After the addition was complete, the reaction mixture was stirred at 175 °C for another 30 minutes. After a total reaction time of 90 minutes, p-tert-butylphenyl glycidyl ether (4.7536 g) dissolved in 11 mL of o-dichlorobenzene was added to the reaction solution, and the reaction was stirred at 175 °C for another 180 minutes. The reaction still showed a strong isocyanate band (2260 cm⁻¹) in the infrared spectrum. -1 This indicates that only a small amount of the added diphenylmethane diisocyanate was converted. The mixture was allowed to cool to ambient temperature. Precipitation of the polymer was carried out in ethanol at ambient temperature. Therefore, the product mixture (approximately 50 mL) was slowly added to 200 mL of ethanol and milled using an Ultra-Turrax dispersing instrument from IKA. The product was washed with ethanol, filtered, and dried overnight at ambient temperature. Subsequently, the product was dried under vacuum (50 mbar) at 160 °C for 6 hours.

[0214] Example 9 (Comparative): The reaction of diphenylmethane diisocyanate (MDI-1) as diisocyanate (A) with bisphenol A diglycidyl ether (BADGE) as diepoxide (B) uses LiCl as catalyst (C), p-tert-butylphenyl glycidyl ether (BPGE) as compound added in step (α) (D) and compound added in step (β) (F), and TCB as solvent (E) and no solvent (G).

[0215] Under a continuous nitrogen stream, tetraphenylphosphonium chloride (LiCl, 0.0999 g) and 1,2,4-trichlorobenzene (82 mL) were loaded into a 500 mL glass flask. The mixture was then heated to 185 °C and stirred for 15 minutes. Diphenylmethane diisocyanate (MDI-1) (29.4931 g), bisphenol A glycidyl ether (38.5141 g), p-tert-butylphenyl glycidyl ether (1.9449 g), and 1,2,4-trichlorobenzene (68 mL) were loaded into a 250 mL glass bottle. The monomer solution was slowly added to the catalyst solution over 90 minutes. After the addition was complete, the reaction was stirred at 185 °C for an additional 30 minutes. After a total reaction time of 120 minutes, p-tert-butylphenyl glycidyl ether (4.8637 g) dissolved in 1,2,4-trichlorobenzene (10 mL) was added to the reaction solution. After the addition, the reaction was stirred at 185°C for another 180 minutes. The reaction still showed a strong isocyanate band (2260 cm⁻¹) in the infrared spectrum. -1 This indicates that diphenylmethane diisocyanate was not converted, or only minimally converted. The mixture was then allowed to cool to ambient temperature. Since no product was produced (at 1750 cm⁻¹), -1 The oxazolidinone band was observed, but no further post-processing was performed.

[0216]

Claims

1. A method for producing thermoplastic polyoxazolidinone, comprising copolymerizing a diisocyanate compound (A) with a diepoxide compound (B) optionally in a solvent (E) in the presence of a catalyst (C), a compound (D) and a compound (F); The catalyst (C) is represented by formula (I). [TO] + n [AND] n- (YO) Where n is an integer with a value of 1, 2, or 3; Among them, [A] + n It is quaternary ammonium, quaternary phosphorus, and / or quaternary antimony; wherein [Y] n- is a monovalent, divalent, trivalent, or tetravalent anion; Compound (D) includes at least one of monofunctional isocyanates, monofunctional epoxides, cyclic carbonates, monofunctional alcohols, and monofunctional amines. Compound (F) includes at least one of monofunctional isocyanates, monofunctional epoxides, cyclic carbonates, monofunctional alcohols, and monofunctional amines. The method described herein is carried out in the absence of a solvent (G) with a boiling point above 200°C at 1 bar absolute pressure. The biepoxide compound (B) comprises at least 90 mol% of an epoxide-terminated oxazolidinone prepolymer, wherein the method for preparing the epoxide-terminated oxazolidinone prepolymer includes the steps of: a) Mix the polyepoxide compound and the first catalyst portion (C-1) of the catalyst (C) to form mixture (a); b) Under copolymerization conditions, the first portion (A-1) of diisocyanate compound (A) is added to mixture (a). And the method described therein includes: (α) The second part (A-2) of the diisocyanate compound (A) reacts with the biepoxide compound (B) in a solvent (E) in the presence of the second catalytic part (C-2) of the catalyst (C) and the compound (D) to form an intermediate compound; and (β) Reacts compound (F) with the intermediate compound formed in step (α).

2. The method of claim 1, wherein [A] + n is a quaternary phosphonium.

3. The method of claim 1, wherein [Y] n- is a monovalent anion.

4. The method according to claim 1, wherein compound (D) comprises a monofunctional epoxide.

5. The method according to claim 1, wherein the compound (F) comprises a monofunctional epoxide.

6. The method according to claim 1, wherein the method is carried out in the absence of a solvent (G) with a boiling point above 190°C at 1 bar absolute pressure.

7. The method according to claim 1, wherein the method is carried out in the absence of a solvent (G) with a boiling point above 180°C at 1 bar absolute pressure.

8. The method according to claim 1, wherein the catalyst (C) comprises at least one selected from tetraalkylphosphonium halide, tetracycloalkylphosphonium halide, tetraarylphosphonium halide, tetraalkylammonium halide, tetracycloalkylammonium halide and / or tetraarylammonium halide.

9. The method according to claim 1, wherein the catalyst (C) comprises at least one of tetraalkylphosphonium halide, tetracycloalkylphosphonium halide, and tetraarylphosphonium halide.

10. The method according to claim 1, wherein the catalyst (C) is at least one compound selected from tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, bis(triphenylphosphine)chlorinated imine, tetraphenylphosphonium nitrate, and tetraphenylphosphonium carbonate.

11. The method according to claim 1, wherein the catalyst (C) is at least one compound selected from tetraphenylphosphonium chloride, tetraphenylphosphonium bromide and tetraphenylphosphonium iodide.

12. The method according to claim 1, wherein the molar ratio of the epoxide group of the polyepoxide compound to the isocyanate group of the first portion (A-1) of the polyisocyanate compound (A) is from 1.1:1 to less than 25:

1.

13. The method according to claim 12, wherein the molar ratio of the epoxide group of the polyepoxide compound to the isocyanate group of the first portion (A-1) of the polyisocyanate compound (A) is 1.4:1 to less than 5:

1.

14. The method according to claim 1, wherein the method is carried out in the presence of a solvent (E), wherein the solvent (E) is one or more compounds selected from chlorobenzene, isomers of dichlorobenzene, dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1-methoxy-2-(2-methoxyethoxy)ethane, and isomers of dioxane.

15. The method of claim 14, wherein the solvent (E) is one or more compounds selected from chlorobenzene and o-dichlorobenzene.

16. The method according to claim 1, wherein compounds (D) and (F) are monofunctional epoxides.

17. A thermoplastic polyoxazolidinone obtainable by the method of claim 1, wherein the thermoplastic polyoxazolidinone has a number-average molecular weight M of ≥ 500 to ≤ 500,000 g / mol as determined by gel permeation chromatography (GPC). n The instrument used was an Agilent 1100 Series, which has N,N-dimethylacetamide (DMAC) + 1.7 g·L⁻¹. -1 LiBr was used as the eluent in a PSS GRAM analytical column from PSS, equipped with a refractive index RI detector, wherein the column flow rate was set to 1 mL·min in all measurements. -1 The samples were calibrated using polystyrene standards, and the PSS WinGPC UniChrom V8.2 software was used to analyze the samples.

18. The thermoplastic polyoxazolidinone of claim 17, wherein the thermoplastic polyoxazolidinone has a number-average molecular weight M of ≥ 1,000 to ≤ 50,000 g / mol as determined by gel permeation chromatography (GPC). n .

19. The thermoplastic polyoxazolidinone of claim 17, wherein the thermoplastic polyoxazolidinone has a number-average molecular weight M of ≥ 5,000 to ≤ 25,0000 g / mol as determined by gel permeation chromatography (GPC). n .

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