Complex form of tetraacetylethylenediamine

Abstract

The present invention relates to complex forms of tetraacetylethylenediamine (TAED) and methods for their preparation. The complex forms may include novel crystalline forms. The invention also relates to the crystalline forms themselves. The invention also relates to compositions containing tetraacetylethylenediamine in these forms.

Description

[Technical Field]

[0001] This invention relates to complex forms of tetraacetylethylenediamine (TAED) and methods for preparing them. The complex forms may include novel crystalline forms. This invention also relates to the crystalline forms themselves. Furthermore, this invention relates to compositions containing tetraacetylethylenediamine in these forms. [Background technology]

[0002] Tetraacetylethylenediamine (TAED; IUPAC name: N,N'-ethylenebis(diacetamide); CAS registry number: 10543-57-4) is a well-known bleach activator primarily used in solid detergents or additives for laundry and dishwashing.

[0003] Two crystalline forms of TAED, form I and form II, are known. Form I has very low solubility (0.2 g / liter at 20°C) and a low dissolution rate in water.

[0004] A particular embodiment of the present invention aims to provide a stable form of TAED, such as a stable crystalline form. A particular embodiment of the present invention aims to provide a form of TAED that is more stable than other forms, such as a crystalline form.

[0005] An object of certain embodiments of the present invention is to provide other forms, such as a form of TAED with higher solubility than other crystalline forms, for example, a crystalline form.

[0006] Certain embodiments of the present invention satisfy some or all of the above objectives. [Overview of the project]

[0007] In a first aspect of the present invention, a complex form of tetraacetylethylenediamine (TAED) is provided, wherein the complex form comprises TAED and an ionic component, the ionic component being selected from a deep eutectic solvent (DES), an ionic liquid (IL), or a mixture thereof.

[0008] The TAED in the composite form of the present invention generally has a solubility of about 2 g / L or more at 20°C (calculated by the mass of TAED present in the composite). Commercially available TAED generally has a solubility of about 200 mg / L. Similarly, in the presence of a bleaching agent, such as sodium percarbonate, the solubility of TAED in the composite form of the present invention is generally considerably higher at 20°C than that of the commercially available form (about 4 g / L). Therefore, the composite form of the present invention can yield a high concentration of peracetic acid in water when in contact with a suitable bleaching agent.

[0009] The composite form may be a gel. In this embodiment, TAED is the solid component of the gel, and the ionic component is the liquid component of the gel. TAED may be dispersed in a liquid consisting of the ionic component.

[0010] The composite form may be solid. TAED may be encapsulated within a solid ionic component. TAED may be a mixture with an ionic component.

[0011] The complex may contain a surfactant. The surfactant may be a solid surfactant. Generally, the complex containing a solid surfactant is solid. The solid surfactant may be a mixture of TAED and an ionic component.

[0012] If surfactants are present, they may be present in amounts ranging from 10 w / w% to 80 w / w% of the total weight of the complex.

[0013] TAED in the complex may be in crystalline form III.

[0014] The aforementioned composite form is achieved in the following steps: (a) Heating the TAED with a deep eutectic solvent (DES) forming component, DES solvent (DES), ionic liquid (IL), or a mixture thereof to a temperature of 150°C or higher; (b) A step to allow the mixture to cool and form a complex. It may be characterized by being obtainable (for example, being acquired) by [a certain method].

[0015] The molar ratio of TAED to ionic components may be in the range of 3:1 to 1:3. The molar ratio of TAED to ionic components may be in the range of 2:1 to 1:2. The molar ratio of TAED to ionic components may be approximately 1:1.

[0016] TAED may be present in amounts exceeding 10% of the total weight of TAED and ionic components. TAED may be present in amounts exceeding 25% of the total weight of TAED and ionic components. TAED may be present in amounts exceeding 50% of the total weight of TAED and ionic components. TAED may be present in amounts less than 95% of the total weight of TAED and ionic components. TAED may be present in amounts less than 90% of the total weight of TAED and ionic components. TAED may be present in amounts less than 80% of the total weight of TAED and ionic components.

[0017] In a second aspect of the present invention, a crystal form of TAED, which is form III, is provided.

[0018] The TAED in the composite form of the first embodiment may be the crystalline form of the second embodiment.

[0019] Similar to the composite form of the first embodiment, TAED Foam III has considerably higher solubility and dissolution rate than commercially available TAED at 20°C. Therefore, TAED Foam III of the present invention can yield a high concentration of peracetic acid in water when in contact with a suitable bleaching agent.

[0020] Said crystalline form (i.e. Form III) may be characterized by having an XRPD pattern with only two peaks at 2θ of 9.1746±0.2 and 18.1788±0.2 when dispersed in a DES solvent (DES), an ionic liquid (IL), wherein said XRPD is performed using K α2 / K α1 ratio of 0.5 Cu radiation.

[0021] For the avoidance of doubt, the two peaks are the only peaks in the XRPD pattern.

[0022] Said crystalline form (i.e. Form III) may be characterized as obtainable (e.g. obtained) by the following steps: (c) heating TAED with a deep eutectic solvent (DES) forming component, a DES solvent (DES), an ionic liquid (IL) or a mixture thereof to a temperature of 150°C or higher; (d) cooling the mixture to form TAED Form III crystals dispersed in the DES or IL which may be characterized as obtainable (e.g. obtained) thereby.

[0023] The TAED crystalline Form III may be associated with a DES or IL. The TAED crystalline Form III may be dispersed in a liquid DES or IL. The TAED crystalline Form III may be enclosed in a solid DES or IL.

[0024] Said crystalline form may have an XRPD pattern substantially as shown in Figure 2.

[0025] In the third aspect of the present invention, the following steps: (a) heating TAED with a deep eutectic solvent (DES) forming component, a DES solvent (DES), an ionic liquid (IL) or a mixture thereof to a temperature of 150°C or higher; and (b) cooling the mixture to form a complex form A method is provided for forming a composite morphology of TAED, for example, a first embodiment, including the above.

[0026] A third aspect of the present invention involves the following steps: (c) Heating the TAED with a deep eutectic solvent (DES) forming component, DES solvent (DES), ionic liquid (IL), or a mixture thereof to a temperature of 150°C or higher; and (d) The mixture is cooled to form TAED form III crystals dispersed in DES or IL. This may be a method for forming a crystal form of a second aspect of the present invention (e.g., crystal form III), which includes the above.

[0027] When TAED is heated together with the DES-forming component, the product of step (b) is solid TAED dispersed in DES (e.g., TAED form III crystals).

[0028] The temperature at which the mixture is heated in step (a) may be 155°C or higher. The temperature at which the mixture is heated in step (a) may be 190°C or lower. The temperature at which the mixture is heated in step (a) may be 175°C or lower.

[0029] The product of step (b) has a gel-like consistency, which can be controlled by altering the identity of DES or IL or mixtures thereof. This gel-like substance may solidify and form TAED form III by adding additives such as surfactants, polymers and other detergent-based components. The viscosity of the product of step (b) can be very viscous, ranging from 1000 cP to 120000 cP.

[0030] TAED may be heated together with choline chloride and urea.

[0031] The molar ratio of choline chloride to urea can range from 1:1 to 4:1 (for example, about 2:1).

[0032] The molar ratio of TAED to DES (or DES-forming components) or IL may be in the range of 3:1 to 1:3. The molar ratio of TAED to DES or IL may be in the range of 2:1 to 1:2. The molar ratio of TAED to DES or IL may be approximately 1:1.

[0033] When DES contains choline chloride and urea, the molar ratio of TAED to choline chloride may be in the range of 2:1 to 1:2. The molar ratio of TAED to choline chloride may be approximately 1:1.

[0034] TAED may be present in amounts exceeding 10% of the total weight of TAED and ionic components. TAED may be present in amounts exceeding 25% of the total weight of TAED and ionic components. TAED may be present in amounts exceeding 50% of the total weight of TAED and ionic components. TAED may be present in amounts less than 95% of the total weight of TAED and ionic components. TAED may be present in amounts less than 90% of the total weight of TAED and ionic components. TAED may be present in amounts less than 80% of the total weight of TAED and ionic components.

[0035] When TAED is heated with an ionic liquid or DES solvent at 150°C or above, or 155°C or above, a clear liquid is obtained, and when this is cooled, TAED can be recrystallized into Form III.

[0036] The stability of Form III when dispersed in DES or IL is excellent. When the product of step (b) has a viscosity of 5000 cP or greater, the dispersion system has been shown to be physically and chemically stable for 6 months under stable conditions of 40°C and 75% RH.

[0037] Therefore, the eutectic solvent (DES) forming component, DES solvent (DES), or ionic liquid (IL) may be selected such that the liquid component of the product in step (b) has a viscosity in the range of 5,000 cP to 120,000 cP.

[0038] The dissolution rate of TAED in DES or IL systems can be further increased by the addition of liquid additives, such as propylene glycol (1,2-propylene glycol) or sodium tripolyphosphate, caustic soda, sulfonic acid, or mixtures thereof. Therefore, the heating step (a) may be carried out in the presence of propylene glycol (1,2-propylene glycol) or sodium tripolyphosphate, caustic soda, sulfonic acid, or mixtures thereof.

[0039] The method may further include step (c): adding a surfactant to the product of (b) to solidify DES or IL and encase the crystalline form III of TAED.

[0040] The aforementioned surfactant may be a solid surfactant.

[0041] Suitable solid surfactants include cresol acid, denatonium benzoate, potassium peroxomonosulfate (KMPS), glycolic acid, sodium peroxodisulfate (NPS), surface-modifying polymers, sodium sulfate, zinc ricinoleate, ethylene glycol distearate, alkyl polypentosides (APPs), alkyl polyglucosides (APGs), amine oxides, amfoacetates, cocamide DEA and MEA, cocoaminopropionate, cocoamphodipropionate, cocoiminodipropionate, and didecyldimethylammonium carbon Examples include salts / bicarbonates, dodecylbenzenesulfonic acid (DDBSA), MEA & TEA neutralized DDBSA, ethoxylated aliphatic amines, fluorinated surfactants, octyliminodipropionate, oxoalcohol ethoxylate, PEG-7 glyceryl cocoate, propoxylates / ethoxylates, silicone surfactants, sodium C14-16 olefin sulfonate (AOS), sodium C14-17 alkylsec-sulfonate (SAS), sodium laureth sulfate (SLES), sodium lauryl sulfate (SLS), and urea.

[0042] The method of the third embodiment may be a method for forming the composite form of the first embodiment. The method of the third embodiment may be a method for forming the crystalline form of the second embodiment.

[0043] The composite form of the first embodiment may be prepared according to the method of the third embodiment. The crystalline form of the first embodiment may be prepared according to the method of the third embodiment.

[0044] In a fourth aspect of the present invention, a composition is provided comprising either a composite form of TAED according to the first aspect or a crystalline form of TAED according to the second aspect.

[0045] The composition may be a solid composition, such as a powder composition. The composition may be a suspension or paste in which the TAED complex exists as a solid.

[0046] The composition may be a detergent composition. The composition may be a bleaching composition.

[0047] The composition may contain 0.1% to 20% by weight of the crystalline form of TAED in the first embodiment.

[0048] Generally, TAED Form III is encapsulated in a solid DES or an ionic liquid.

[0049] The composition generally includes solid surfactants such as cresol acid, denatonium benzoate, potassium peroxomonosulfate (KMPS), glycolic acid, sodium peroxodisulfate (NPS), surface-modifying polymers, sodium sulfate, zinc ricinoleate, ethylene glycol distearate, alkyl polypentosides (APPs), alkyl polyglucosides (APGs), amine oxides, amfoacetates, cocamide DEA and MEA, cocoaminopropionate, cocoamphodipropionate, cocoiminodipropionate, didecyldimethylammonium carbonate / weight Solid surfactants selected from carbonates, dodecylbenzenesulfonic acid (DDBSA), MEA & TEA neutralized DDBSA, ethoxylated aliphatic amines, fluorinated surfactants, octyliminodipropionate, oxoalcohol ethoxylate, PEG-7 glyceryl cocoate, propoxylate / ethoxylate, silicone surfactants, sodium C14-16 olefin sulfonate (AOS), sodium C14-17 alkylsec-sulfonate (SAS), sodium laureth sulfate (SLES), sodium lauryl sulfate (SLS), and urea are also included.

[0050] The composition may contain one or more additional bleach activators. The one or more additional bleach activators may be selected from the group including crystalline form I of TAED, crystalline form II of TAED, triacetylethylenediamine, nonanoyloxybenzenesulfonate (NOBS), and dodecanoyloxybenzenesulfonate (DOBS).

[0051] The composition may further contain a bleaching agent. The bleaching agent may be a metal percarbonate. The bleaching agent may be an alkali metal percarbonate, such as sodium percarbonate or potassium percarbonate. The bleaching agent may be sodium percarbonate.

[0052] The composition may further contain at least one of a surfactant or a wetting agent. The composition may further contain at least one of an additive selected from the group consisting of pH adjusters, chelating agents, stabilizers, diluents, flow enhancers, binders, foaming agents, disintegrants, and coating agents. [Brief explanation of the drawing]

[0053] Embodiments of the present invention are further described below with reference to the accompanying drawings. [Figure 1] Figure 1 shows the PXRD patterns of TAED forms I and II (quoted from WO2017068348A1). [Figure 2] Figure 2 shows the PXRD pattern of TAED Form III. [Figure 3] Figure 3 is a graph showing the dissolution rates of the TAED and TAED Foam I composites of the present invention in water. [Modes for carrying out the invention]

[0054] Detailed explanation It is known in the art that X-ray powder diffraction patterns may have one or more measurement errors depending on the measurement conditions (such as the equipment used, sample preparation, or machinery). In particular, it is generally known that the intensity in an X-ray powder diffraction pattern may vary depending on the measurement conditions and sample preparation. For example, those skilled in the art of X-ray powder diffraction will understand that the relative intensity of peaks may differ depending on the orientation of the specimen and the type and settings of the equipment used. Those skilled in the art will also understand that the position of reflections may be affected by the exact height at which the sample is placed on the diffractometer and the zero calibration of the diffractometer. The flatness of the sample surface may also have a small effect. Therefore, those skilled in the art will understand that the diffraction pattern data presented herein should not be interpreted as absolute, and that any crystal form that provides a powder (power) diffraction pattern substantially identical to that disclosed herein is within the scope of this disclosure (see Jenkins, R & Snyder, RL 'Introduction to X-Ray Powder Diffractometry' John Wiley & Sons, 1996 for further details).

[0055] deep eutectic solvent Deep eutectic solvents are systems formed from eutectic mixtures of Lewis or Brønsted acids and bases, which may contain various anionic and / or cationic species. They are classified as a type of ionic solvent with specific properties. They incorporate one or more compounds into a mixture form, resulting in a eutectic mixture with a melting point much lower than any one of its individual components. One of the most important deep eutectic phenomena was observed with a 1:2 molar mixture of choline chloride and urea. The resulting mixture has a melting point of 12°C (much lower than the melting point of choline chloride, 302°C, and urea, 133°C) and is liquid at room temperature.

[0056] First-generation eutectic solvents were based on a mixture of quaternary ammonium salts and hydrogen bond donors (such as amines and carboxylic acids). Four types of eutectic solvents exist. Type I Quaternary Ammonium Salts + Metal Chlorides Type II quaternary ammonium salt + metal chloride hydrate Type III quaternary ammonium salt + hydrogen bond donor Type IV metal chloride hydrate + hydrogen bond donor

[0057] The eutectic solvent further comprises reacting an ammonium compound with a second compound selected from the group consisting of amines, amides, carboxylic acids, alcohols, metal halides, and combinations thereof.

[0058] Deep eutectic solvents or solutions (DES) are formed by combining ammonium compounds, such as N-(2-hydroxyethyl)trimethylammonium chloride (choline chloride), with hydrogen bond donors (HBDs), such as carboxylic acids, amines, amides, and alcohols. These liquids have physical and solvent properties similar to ionic liquids formed from lone ions and can be easily produced by simply mixing common general-purpose chemical products (e.g., choline chloride with carboxylic acids or amides).

[0059] Other examples include choline chloride: DES lactate, proline: DES lactate, choline chloride: citrate, dimethylurea: citrate, and propylene glycol: DES citrate.

[0060] The ionic component may be a DES selected from choline chloride:lactic acid DES; proline:lactic acid DES; choline chloride:citrate DES; and propylene glycol:citrate DES. The ionic component may be propylene glycol:citrate DES.

[0061] Ionic liquid Examples of ionic liquids include those described in WO2006050307, ​​US20190085273, and WO2017156141.

[0062] Examples of ionic liquids include imidazolium salts, such as 1-butyl-3-methylimidazolium hexafluorophosphate (also known as [bmim]). Other well-known ionic liquids include 1-ethyl-3-methylimidazolium chloride, aluminum(III) chloride (commonly called [emim]Cl-AlCl3) and N-butylpyridinium chloride, aluminum(III) chloride (commonly called [Nbupy]Cl-AlCl3). Another example of an ionic liquid is diisopropanolamine (DIPA).

[0063] Some, but not limited, examples of anions and cations suitable for use in ionic liquids for the present invention are disclosed below.

[0064] Anion The following substances are examples of anions suitable for use in the ionic liquid of the present invention, but are not limited to these.

[0065] (1) Alkyl sulfates (AS), alkoxy sulfates and alkylalkoxy sulfates; examples of alkoxy sulfates that are not limited to these include sulfated derivatives of commercially available alkoxy copolymers (e.g., Pluronics® (from BASF)).

[0066] (2) Monoesters and diesters of sulfosuccinates: Examples include saturated and unsaturated C 12-18 Monoester sulfosuccinates (such as lauryl sulfosuccinate, available as Mackanate LO-100® (registered trademark) from The McLntyre Group); saturated and unsaturated C6-C 12Examples include diester sulfosuccinates (such as dioctyl ester sulfosuccinate, available as Aerosol OT® (registered trademark) from Cytec Industries, Inc.).

[0067] (3) Methyl ester sulfonate (MES)

[0068] (4) Alkylaryl sulfonates, including but not limited to tosylates, linear or branched, saturated or unsaturated C8-C 14 Alkylaryl sulfonates having alkyl groups; alkylbenzene sulfonates (LAS) (e.g., C 11 -C 12 Examples include alkylbenzene sulfonates.

[0069] (5) Alkylglycerol ethersulfonates having 8 to 22 carbon atoms in the alkyl portion

[0070] (6) Diphenyl ether (bis-phenyl) derivatives: Examples, not limited to, include triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether) and diclosan (4,4'-dichloro-2'-hydroxydiphenyl ether), both of which are available from Ciba Specialty Chemicals as Irgasan®.

[0071] (7) Linear or cyclic carboxylates: Examples, not limited to, include citrates, lactates, tartrates, succinates, alkylene succinates, maleates, glucons, formates, cinnamates, benzoates, acetates, salicylates, phthalates, aspartates, adipates, acetylsalicylates, methyl 3-salicylate, 4-hydroxyisophthalates, dihydroxyfumarates, 1,2,4-benzenetricarboxylates, pentanoates, and mixtures thereof.

[0072] (8) Medium-chain branched alkyl sulfates (HSAS), medium-chain branched alkylaryl sulfates (MLAS), and medium-chain branched alkyl polyoxyalkylene sulfates; examples of MLAS that are not limited to those disclosed in US6,596,680; US6,593,285; and US6,202,303.

[0073] (9) Sarcosinates; examples not limited to these include ammonium lauroyl sarcosinate (available from Dow Chemicals as Hamposyl AL-30®) and sodium oleoyl sarcosinate (available from Dow Chemicals as Hamposyl O®).

[0074] (10) Straight-chain or branched-chain sulfated and sulfonated oils and fatty acids (e.g., sulfates or sulfonates derived from potassium coconut oil soap available from Norman, Fox & Co. as Norfox 1101® and potassium oleate from Chemron Corp.)

[0075] (11) Fatty acid ester sulfonates

[0076] (12) Anions derived from sweeteners: saccharinates and acesulfamates; [ka] In the formula, M+ is a cation selected from the cations of the following ionic liquids.

[0077] (13) Ethoxylated amide sulfates; sodium tripolyphosphate (STPP); dihydrogen phosphate; fluoroalkyl sulfonates; bis-(alkylsulfonyl)amines; bis-(fluoroalkylsulfonyl)amides; (fluoroalkylsulfonyl)(fluoroarcyl(allcyl)carbonyl)amides; bis(arylsulfonyl)amides; carbonates; tetrafluoroborates (BF4) - ); Hexafluorophosphate (PF6- ):

[0078] (14) Anionic bleach activators, non-limiting examples include, [Formula] 4-nonanoyloxybenzenesulfonate [Formula] 4-dodecanoyloxybenzenesulfonate [Formula] 4-decanoyloxybenzoate and the like, which are disclosed in US5,891,838; US6,448,430; US5,891,838; US6,159,919; US6,448,430; US5,843,879; US6,548,467.

[0079] Cation Cations suitable for use in the ionic liquids of the present invention include, but are not limited to, the following substances.

[0080] (a) Cations of amine oxides, phosphine oxides, or sulfoxides (i.e., in protonated, positively charged form) (b) Betaines; non-limiting examples of betaines include dodecyldimethylbetaine, acetyldimethylbetaine, dodecamidopropyldimethylbetaine, tetradecyldimethylbetaine, tetradecamidopropyldimethylbetaine, dodecyldimethylammonium hexanoate; and amidoalkylbetaines, which are disclosed in U.S. Patent Nos. 3,950,417; 4,137,191; and 4,375,421; as well as British Patent No. GB2,103,236, and in another embodiment, the cation may be a sulfobetaine, which is disclosed in U.S. Patent No. 4,687,602. (c) Diester quaternary ammonium (DEQA) cation, for example, the DEQA cation described in U.S. Patent No. 6,004,922 (d) Alkylene quaternary ammonium cations, for example Dialkylenedimethylammonium cation (such as dioleyldimethylammonium, available from Witco Corporation under the trademark name Adogen® 472); or monoalkenyltrimethylammonium (such as monooleyltrimethylammonium, monocanolatrimethylammonium, and soyatrimethylammonium). (e) Di-fatty amido quaternary ammonium cations, such as difatty amido quat, are commercially available from Witco under the trademark name Varisoft®. (f)C 8-22 Quaternary surfactants (such as isostearylethylimonium, available from Scher Chemicals, Inc. as Schercoquat IIS® in the form of an ethosulfate salt; quaternium-52, available from Cognis Corporation as Dehyquart SP®; and dicocodimethylammonium, available from Akzo Nobel Surface Chemistry LLC as Arquad 2C-75® in the form of a chloride salt)

[0081] (g) Cationic esters (e.g., those described in U.S. Patent Nos. 4,228,042, 4,239,660, 4,260,529 and 6,022,844)

[0082] (h)4,5-Dichloro-2-n-octyl-3-isothiazolon (available from Rohm and Haas as Kathon®)

[0083] (i) Quaternary aminopolyoxyalkylene derivatives (choline and choline derivatives)

[0084] (j) Alkyloxyalkylene cation

[0085] (k) Alkoxylate quaternary ammonium (AQA) as described in U.S. Patent No. 6,136,769

[0086] (1) Substituted and unsubstituted pyrrolidinium, imidazolium, benzimidazolium, pyrazorium, benzpyrazolium, thiazolium, benzthiazolium, oxazolium, benzoxazolium, isoxazolium, isothiazorium, imidazolidenium, guanidium, indazolium, quinuclidinium, triazolium, isoquinuclidinium, piperidinium, morpholinium, pyridazinium, pyrazinium, triazinium, azepinium, diazepinium, pyridinium, piperidonium, pyrimidinium, thiophenium; phosphonium

[0087] (m) Cationic bleach activators having a quaternary ammonium moiety, but not limited to the following, for example [ka] N,N-dimethyl-2-[(phenoxycarbonyl)oxy]-N-[2-[(phenoxycarbonyl)oxy]ethyl]ethanaminonium [ka] 4-(cyanomethyl)-4-methylmorpholinium; 1-cyano-N,N,N-trimethylmethaneaminium [ka] l-methyl-3-(l-oxoheptyl)-lH-imidazolium These are examples, and other cationic bleach activators suitable for use herein as cations in ionic liquids are disclosed in US 5,599,781, US 5,686,015, US 5,686,015, WO 95 / 29160, US 5,599,781, US 5,534,179, EP 1 253 190 Al, US 6,183,665, US 5,106,528, US 5,281,361, and Bulletin de Ia Societe Chimique de France (1973), (3)(Pt.2), 1021-7.

[0088] (n) Cationic antimicrobial agents (e.g., cetylpyridinium, chlorohexidine, and domifene)

[0089] (o) Alkylated caffeine cation

[0090] The present invention may also be described in accordance with the following numbered sections.

[0091] 1. A crystalline form (Form III) of TAED, characterized in that when the crystalline form is dispersed in a DES solvent (DES) or an ionic liquid (IL), it has an XRPD pattern having only two peaks at 2θ of 9.1746±0.2 and 18.1788±0.2, wherein the XRPD is K α2 / K α1 The crystal form, measured using Cu radiation with a ratio of 0.5.

[0092] 2. The crystal form described in item 1, having substantially the XRPD pattern as shown in Figure 2.

[0093] 3. Follow these steps: (a) Heating the TAED with a deep eutectic solvent (DES) forming component, a DES solvent (DES), an ionic liquid (IL), or a mixture thereof to a temperature of 150°C or higher; and (b) The step of cooling the mixture to form TAED form III crystals dispersed in DES or IL. A method for forming the crystalline form (form III) of TAED, including [the specified element].

[0094] 4. The method according to claim 3, wherein the eutectic solvent (DES) forming component, DES solvent (DES), or ionic liquid (IL) is selected such that the product of step (b) has a viscosity in the range of 5,000 cP to 120,000 cP.

[0095] 5. The method according to item 3, wherein a TAED solubility (4 grams or more of TAED in 100 ml of water) in the presence of sodium percarbonate can be achieved as a result of producing a high concentration of peracetic acid system.

[0096] 6. The method according to item 3, wherein the eutectic solvent (DES) forming component, DES solvent (DES), or ionic liquid (IL) is used to heat, melt, and recrystallize the TAED, and when the TAED is converted from Form III to Form I, its dissolution rate in water remains unchanged for a certain period of time (its water solubility remains unchanged).

[0097] 7. The method according to item 3 or 4, wherein the heating step (a) may be carried out in the presence of propylene glycol (1,2-propylene glycol) or sodium tripolyphosphate, caustic soda, sulfonic acid or a mixture thereof.

[0098] 8. The method according to any one of claims 3 to 5, comprising step (c): adding a solid surfactant to the product of (b) to solidify the DES or IL to obtain a crystalline form III of TAED encapsulated in the DES or IL.

[0099] 9. The surfactants include cresol acid, denatonium benzoate, potassium peroxomonosulfate (KMPS), glycolic acid, sodium peroxodisulfate (NPS), surface-modifying polymers, sodium sulfate, zinc ricinoleate, ethylene glycol distearate, alkyl polypentosides (APPs), alkyl polyglucosides (APGs), amine oxides, amfoacetate, cocamide DEA and MEA, cocoaminopropionate, cocoamphodipropionate, cocoiminodipropionate, didecyldimethylammonium carbonate / bicarbonate, and dodecyl The method according to item 6, selected from benzenesulfonic acid (DDBSA), MEA & TEA neutralized DDBSA, ethoxylated aliphatic amines, fluorinated surfactants, octyliminodipropionate, oxoalcohol ethoxylate, PEG-7 glyceryl cocoate, propoxylate / ethoxylate, silicone surfactant, sodium C14-16 olefin sulfonate (AOS), sodium C14-17 alkylsec-sulfonate (SAS), sodium laureth sulfate (SLES), sodium lauryl sulfate (SLS), urea, and mixtures thereof.

[0100] 10. A crystalline form (form III) of TAED, characterized by being obtainable by the method described in any one of items 3 to 7.

[0101] 11. A composition comprising a crystalline form of TAED as described in any one of items 1, 2, and 8.

[0102] 12. The composition described in item 9, which is a solid composition.

[0103] 13. The composition according to item 9 or 10, wherein TAED form III is encapsulated in a solid DES or an ionic liquid.

[0104] 14.0.1% to 20% by weight or 0.1% to 50% by weight or 75% or more by weight of the crystalline form of TAED form I as described in any one of items 1, 2, and 8, according to any one of items 9 to 11.

[0105] 15. The composition according to any one of items 9 to 12, further comprising a solid surfactant.

[0106] 16. The surfactants include cresol acid, denatonium benzoate, potassium peroxomonosulfate (KMPS), glycolic acid, sodium peroxodisulfate (NPS), surface-modifying polymers, sodium sulfate, zinc ricinoleate, ethylene glycol distearate, alkyl polypentosides (APPs), alkyl polyglucosides (APGs), amine oxides, amfoacetate, cocamide DEA and MEA, cocoaminopropionate, cocoamphodipropionate, cocoiminodipropionate, didecyldimethylammonium carbonate / bicarbonate, and dodecyl The composition according to item 13, selected from benzenesulfonic acid (DDBSA), MEA & TEA neutralized DDBSA, ethoxylated aliphatic amines, fluorinated surfactants, octyliminodipropionate, oxoalcohol ethoxylate, PEG-7 glyceryl cocoate, propoxylate / ethoxylate, silicone surfactant, sodium C14-16 olefin sulfonate (AOS), sodium C14-17 alkylsec-sulfonate (SAS), sodium laureth sulfate (SLES), sodium lauryl sulfate (SLS), urea, and mixtures thereof.

[0107] 17. A composition according to any one of items 9 to 14, further comprising a bleaching agent.

[0108] 18. The composition according to any one of items 9 to 15, further comprising at least one surfactant or wetting agent.

[0109] 19. The composition according to any one of claims 9 to 16, further comprising at least one additive selected from the group consisting of pH adjusters, chelating agents, stabilizers, diluents, flow enhancers, binders, foaming agents, disintegrants, and coating agents.

[0110] Throughout this description and claims, the words “comprise” and “contain” and their variations mean “including but not limited to” and are not intended to exclude (and do not exclude) other parts, additives, components, integers, or steps. Throughout this description and claims, the singular form includes the plural form unless the context should indicate otherwise. In particular, where the indefinite article is used, this specification should be understood to be plural and singular unless the context should indicate otherwise.

[0111] It should be understood that any features, integers, properties, compounds, chemical parts, or chemical groups described in conjunction with specific aspects, embodiments, or examples of the present invention are applicable to any other aspects, embodiments, or examples described herein, provided they are not incompatible. All features disclosed herein (including any appended claims, abstracts, and drawings) and / or all steps of any methods or processes disclosed herein may be combined in any combination, except for any combination in which at least some of such features and / or steps are mutually exclusive. The present invention is not limited to the details of any embodiments described above. The present invention extends to any novel features or any novel combination of features disclosed herein (including any appended claims, abstracts, and drawings), or any novel methods or processes or any novel combination of methods or processes disclosed herein.

[0112] The reader's attention is directed to all documents filed concurrently with or prior to this specification in connection with this application and published together with this specification, the contents of all such documents being incorporated herein by reference. [Examples]

[0113] General procedure Step I: Accurately weigh the ionic liquid or DES-forming component (e.g., propylene glycol and citric acid in a molar ratio of 1:2 or 1:1) into a glass beaker. Heat the mixture to over 150°C until a clear liquid is obtained. Add TAED to this mixture and stir until a clear liquid is obtained. Stop heating once a clear liquid is obtained. • Allow the final mixture to cool. TAED generally recrystallizes into polymorphic form III. After the mixture had cooled completely, PXRD was performed on the mixture to confirm that the TAED structure was polymorphic form III.

[0114] Step II: Accurately weigh the ionic liquid or DES-forming component (e.g., propylene glycol:citric acid in 1:2 and 1:1 molar ratios) and add the exact required amount of TAED to it. Mix these ingredients thoroughly. Heat the mixture to over 150°C while stirring. • As soon as a clear liquid is obtained, stop heating and let the mixture cool. • Perform PXRD on the cooled mixture to confirm TAED polymorphic form III.

[0115] Example 1 - Method for isolating the (S)-epimer of Form III Following step II, take 1 gram of TAED and equimolar ratios of DES-forming components (for example, if the ratio is propylene glycol:citric acid 1:2, take 0.76 grams of propylene glycol and 3.84 grams of citric acid). Mix all the above ingredients in a beaker and heat to above 150°C (155°C or 160°C) until a homogeneous liquid final product is obtained. • The final product should be allowed to cool.

[0116] Example 2 - X-ray powder diffraction (XRPD) A viscous sample of crystalline form III of TAED suspended in DES (TAED was 20% of the total weight of the complex; DES was propylene glycol:citric acid in a 1:1 molar ratio) was spread on a sample holder. PXRD patterns were analyzed using an instrument with a 40KV Cu(Kα) source with an X-ray wavelength of 1.54 Å and a filament emission of 40 mA. All samples were scanned from 5 to 35° (2θ) with a step size of 0.01° and a counting time of 1 second. The scattering and receiving slits were 0.2° and 1°, respectively.

[0117] The obtained spectrum is shown in Figure 2. The observed peaks were as follows: [Table 1] 2Th. = °2θ Generally, an error of ±0.2°2θ exists within the XRPD peak position.

[0118] The inventors also demonstrate that repeating Example 1 using choline chloride: DES lactate; proline: DES lactate; and choline chloride: DES citrate yields crystalline form III of TAED. The inventors also demonstrate that repeating Example 1 using diisopropanolamine ionic liquid yields crystalline form III of TAED.

[0119] Example 3: Procedure for performance and water miscibility at 20°C Peracetic acid is obtained by adding TAED to water in the presence of sodium percarbonate. The rate of peracetic acid formation was compared using TAED Foam III in the DES complex of the present invention (TAED is 20% of the total weight of the complex; DES is propylene glycol:citric acid in a 1:1 molar ratio) and commercially available TAED Foam I.

[0120] Experiment details: Experiments were conducted to investigate the properties and water miscibility of TAED in the presence of sodium percarbonate. 1 gram of TAED was added to 1 liter of water along with 2.5 grams of sodium percarbonate, and the mixture was stirred at 500 rpm using an overhead stirrer. In the experimental setup, 1.1 liters of water were used for the experiment. The weight of the remaining substance was calculated after 5 minutes. The results indicate that DES-based Form III exhibits complete miscibility or a clear solution compared to commercially available TAED. The results are shown in the table below. [Table 2]

[0121] The results above show how quickly TAED Foam III in DES / ionic liquid dissolves in water in the presence of sodium percarbonate to form peracetic acid.

[0122] Similar experiments were conducted with smaller amounts of water (100 ml, 250 ml, and 500 ml), and the same results were obtained in all experiments. After 5 minutes, the amount remaining was less than 5-10 mg for the TAED DES system in the 100 ml experiment, while 800 mg remained for the commercially available TAED. In the 250 ml experiment, the TAED DES system solution was clear, and the same was true for the 500 ml experiment, but the amounts remaining for the commercially available TAED were 750 mg and 690 mg, respectively. The results of a similar experiment conducted with 5 grams of TAED and 1 liter of water are shown in the table below. [Table 3]

[0123] The experiment was conducted with the maximum amount of TAED DES system (where the amount of TAED was 4 grams) in a smaller amount of water, i.e., 100 ml. After stirring for 5 minutes, the solution began to become clear, and with continued stirring, almost all of the solution became clear (less than 100 mg of substance remained after filtering the final solution). This indicates that the efficiency of the TAED DES system in terms of solubility in water and the maximum amount of peracetic acid generated can be achieved using the TAED DES system with water at room temperature without heating.

[0124] The inventors also show that similar results can be obtained with complexes containing choline chloride: DES lactate; proline: DES lactate; and choline chloride: DES citrate; and diisopropanolamine ion liquid.

[0125] Example 4 Peracetic acid is obtained when TAED is added to water in the presence of sodium percarbonate. The rate of peracetic acid formation was compared using the TAED form III in the DES complex of the present invention (TAED was 20% of the total weight of the complex; DES is propylene glycol:citric acid in a 1:1 molar ratio) and commercially available TAED form I.

[0126] Experiment details: Part I: Experiments were conducted to investigate the properties and water miscibility of the composite TAED of the present invention in the presence of sodium percarbonate. The TAED:sodium percarbonate ratio used for the experiment was 1:2.5 w / w. Weighed amounts of TAED (1 g of commercially available sample and equimolar amounts of the composite TAED of the present invention, i.e., 5 g) were added to 100 ml of water along with sodium percarbonate and stirred at 500 rpm using an overhead stirrer. This 100 ml solution was used as is, or further diluted with 900 ml of water to make a 1 L sample. The weight of the remaining substance was calculated after 5 minutes. Samples were examined immediately after stopping stirring (T=0) and after 6 months (T=6 months: samples maintained at 40°C and 75% relative humidity). The results show that TAED Form III exhibits complete miscibility or a clear solution compared to commercially available TAED (see table below). [Table 4]

[0127] The above results demonstrate that the composite TAED of the present invention dissolves in water in the presence of sodium percarbonate to a significantly greater extent than commercially available TAED.

[0128] Part II: The same experiment was conducted by increasing the amount of TAED in 100 ml of water to 3 grams (3 g of a commercially available sample and an equimolar amount of the composite TAED of the present invention, i.e., 15 g). The results are shown in the table below. [Table 5]

[0129] The above results demonstrate that the composite TAED of the present invention dissolves in water in the presence of sodium percarbonate to a significantly greater extent than commercially available TAED.

[0130] Example 5 - Dissolution Rate Procedure The dissolution rate of the TAED Form III complex of the present invention in DES (TAED was 20% of the total weight of the complex; DES is propylene glycol:citric acid in a 1:1 molar ratio) in water (500 ml) was compared to the dissolution rate of commercially available tetraacetylethylenediamine (Form I) using a USP II elution apparatus at 20°C. 1 g of commercially available sample and an equimolar amount of the TAED complex of the present invention, i.e., 5 g, were used. The powders of Examples 1 and 2 were rotated from a disk at 50 rpm, and samples were taken at intervals of 5, 10, 15, 20, and 25 minutes. The amount of dissolved tetraacetylethylenediamine was monitored by high-performance liquid chromatography. The results are shown in Figure 3.

[0131] Figure 3 clearly shows that the dissolution rate of the composite TAED of the present invention is more than 30 times greater than that of commercially available TAED. This is then reflected in the peracetic acid formation rate. This clearly shows that the composite TAED of the present invention forms peracetic acid at a greater rate, and that higher concentration peracetic acid solutions can be prepared at 20°C.

[0132] Example 6 - PAA release Four different samples of TAED in citrate and propylene glycol (1:1 molar ratio) were prepared, and the effect of the TAED-to-DES ratio on the peracetic acid release rate at room temperature (@20°C) was evaluated. Sample 1 (Liquid) TAED concentration: 20-25 w / w% of the composite form Sample 2 (liquid) TAED concentration: 45-50 w / w% of the composite form Sample 3 (semi-solid) TAED concentration: 60-65 w / w% of the composite form Sample 4 (solid powder; also containing sodium lauryl sulfate-like surfactants) TAED concentration: 70-75 w / w% relative to DES. The TAED / DES combination to surfactant ratio ranged from 4:1 to 6:1.

[0133] analysis The sample was mixed with sodium percarbonate in water (1:1.25). The sample was analyzed by titration using 0.1 M potassium permanganate solution and 0.01 M sodium thiosulfate solution. The sample was dissolved in 0.5 M sulfuric acid. After dissolution, potassium permanganate was added until the color changed. During the addition, the pH and temperature of the sample were monitored to ensure that these parameters did not change during the titration. After the color changed, potassium iodide was added. The sample was further titrated with sodium thiosulfate using a starch indicator solution until the color changed. The pH and temperature of the sample were also monitored during the titration.

[0134] The amount of hydrogen peroxide in both samples was determined by titration with potassium permanganate. Sample 4 contained 203947 ppm of hydrogen peroxide, and Sample 3 contained 141209 ppm of hydrogen peroxide. Both samples were analyzed as duplicates. Sample 1 contained 9380 ppm of hydrogen peroxide. Sample 2010013597 contained 155462 ppm of hydrogen peroxide. Determination of peracetic acid: Titration with sodium thiosulfate. The amount of peracetic acid in the samples was determined as duplicates by titration with sodium thiosulfate. The results show that Sample 4 contains 7599 ppm of peracetic acid. Sample 3 contains 3178 ppm of peracetic acid. Sample 1 contains 1387 ppm of peracetic acid. Sample 2 contains 2452 ppm of peracetic acid.

[0135] This indicates that, at 20°C, the composite of the present invention yields very high concentrations of hydrogen peroxide and / or peracetic acid when exposed to percarbonates, even when the weight of TAED is very high relative to the amount of DES. Solubility remains high, even in solid sample 4.

Claims

1. A composition comprising tetraacetylethylenediamine (TAED) and an ionic component, The ionic component is selected from deep eutectic solvents (DES), ionic liquids (IL), or mixtures thereof. The TAED is in crystalline form, and the crystalline form is characterized by having an XRPD pattern with only two peaks at 2θ of 9.1746±0.2 and 18.1788±0.2, where the XRPD is K α２ / K α１ The measurement is performed using Cu radiation with a ratio of 0.

5. composition.

2. The composition according to claim 1, wherein the composition is a gel, the TAED is a solid component, and the ionic component is a liquid component.

3. The composition according to claim 1, wherein the composition is a solid composition comprising TAED in a mixture with an ionic component.

4. The composition according to claim 3, wherein the solid composition comprises a mixture of a solid surfactant, TAED, and an ionic component.

5. The solid surfactants include alkyl polypentosides (APPs), alkyl polyglucosides (APGs), amine oxides, amphoacetates, cocamide DEA and MEA, cocoaminopropionate, cocoamphodipropionate, cocoiminodipropionate, didecyldimethylammonium carbonate / bicarbonate, MEA & TEA neutralized dodecylbenzenesulfonic acid (DDBSA), ethoxylated aliphatic amines, fluorinated surfactants, octyliminodipropionate, oxoalcohol ethoxylate, PEG-7 glyceryl cocoate, propoxylate / ethoxylate, silicone surfactants, and C １４－１６ Sodium olefin sulfonate (AOS), C １４－１７ The composition according to claim 4, selected from alkylsec-sodium sulfonate (SAS), sodium laureth sulfate (SLES), sodium lauryl sulfate (SLS), and mixtures thereof.

6. The composition according to any one of claims 3 to 5, wherein the solid composition is in the form of a powder.

7. The composition according to any one of claims 1 to 6, wherein the molar ratio of TAED to the ionic component is in the range of 3:1 to 1:

3.

8. The composition according to any one of claims 1 to 7, wherein the ionic component is DES.

9. The composition according to claim 8, wherein the DES is selected from choline chloride: DES lactate; proline: DES lactate; choline chloride: DES citrate; and propylene glycol: DES citrate.

10. The composition according to claim 8, wherein the DES is propylene glycol:citric acid DES.

11. The composition according to any one of claims 1 to 7, wherein the ionic component is an ionic liquid.

12. The following steps: (a) Heating TAED together with a deep eutectic solvent (DES) forming component, DES solvent (DES), ionic liquid (IL), or a mixture thereof to a temperature of 150°C or higher; and (b) The step of cooling the mixture to form a composition comprising the TAED described in claim 1. A method for forming the composition according to claim 1, comprising the above.

13. The method according to claim 12, wherein the eutectic solvent (DES) forming component, DES solvent (DES), or ionic liquid (IL) is selected such that the product of step (b) has a viscosity of 5,000 cP to 120,000 cP.

14. The method according to claim 12 or 13, wherein the heating step (a) is carried out in the presence of 1,2-propylene glycol or sodium tripolyphosphate, caustic soda, sulfonic acid or a mixture thereof.

15. The method according to any one of claims 12 to 14, wherein the composition formed in step (b) is a gel, and the method comprises step (c): adding a solid surfactant to the product of (b) to obtain the solid composition according to claim 4.

16. The method according to claim 15, wherein the solid surfactant is selected from alkyl polypentosides (APPs), alkyl polyglucosides (APGs), amine oxides, amphoacetates, cocamide DEA and MEA, cocoaminopropionates, cocoamphodipropionates, cocoiminodipropionates, didecyldimethylammonium carbonate / bicarbonate, MEA & TEA neutralized dodecylbenzenesulfonic acid (DDBSA), ethoxylated aliphatic amines, fluorinated surfactants, octyliminodipropionates, oxoalcohol ethoxylates, PEG-7 glyceryl cocoate, propoxylates / ethoxylates, silicone surfactants, sodium C14-16 olefin sulfonate (AOS), sodium C14-17 alkylsec-sulfonate (SAS), sodium laureth sulfate (SLES), sodium lauryl sulfate (SLS), and mixtures thereof.

17. The composition according to any one of claims 1 to 11, further comprising a bleaching agent.

18. The composition according to any one of claims 1 to 11 or 17, further comprising a wetting agent.

19. The composition according to any one of claims 1 to 11, 17, or 18, further comprising at least one additive selected from the group consisting of pH adjusters, chelating agents, stabilizers, diluents, flow promoters, binders, foaming agents, disintegrants, and coating agents.

20. A TAED crystal characterized by having an XRPD pattern having only two peaks at 2θ of 9.1746±0.2 and 18.1788±0.2, wherein the XRPD is K α２ / K α１ A crystal measured using Cu radiation with a ratio of 0.5.

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