Complex forms of tetraacetylethylenediamine

Abstract

The present invention relates to complex forms of tetraacetylethylenediamine (TAED) and methods of making the same. The complex form may include a novel crystalline form. The invention also relates to the crystalline forms themselves. The invention also relates to compositions comprising tetraacetylethylenediamine in these forms.

Description

[0001] This application is a divisional application of the invention patent application with application number 202180061607.9, application date September 8, 2021, and invention title "Complex Forms of Tetraacetylethylenediamine". Technical Field

[0002] 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 comprising these forms of tetraacetylethylenediamine. Background Technology

[0003] Tetraacetylethylenediamine (TAED; IUPAC name: N,N′-ethylenebis(diacetamide)); CAS Registry No. 10543-57-4) is a known bleaching activator, primarily used in solid detergents or additives for laundry and dishwashing.

[0004] TAED is known to exist in two crystalline forms, form I and form II. Form I has very low solubility in water (0.2 g / L at 20°C) and a low dissolution rate.

[0005] The purpose of certain embodiments of the present invention is to provide a stable form of TAED, such as a stable crystalline form. The purpose of certain embodiments of the present invention is to provide a form of TAED that is more stable than other forms, such as a crystalline form.

[0006] The purpose of certain embodiments of the present invention is to provide a form of TAED (e.g., crystalline form) that is more soluble than other forms (e.g., other crystalline forms).

[0007] Some embodiments of the present invention satisfy some or all of the above objectives. Summary of the Invention

[0008] In a first aspect of the invention, a composite form of tetraacetylethylenediamine (TAED) is provided, the composite form comprising TAED and an ionic component, wherein the ionic component is selected from deep eutectic solvents (DES), ionic liquids (IL), or mixtures thereof.

[0009] The solubility of the composite form of TAED of this invention at 20°C is typically greater than or equal to about 2 g / L (based on the mass of TAED present in the composite). The solubility of commercially available TAED is typically about 200 mg / L. Similarly, in the presence of a bleaching agent such as sodium percarbonate, the solubility of the composite form of TAED of this invention at 20°C is typically much higher than that of the commercially available form (about 4 g / L). Therefore, when contacted with a suitable bleaching agent, the composite form of this invention can produce high concentrations of peracetic acid in water.

[0010] The composite form can be a gel. In this embodiment, TAED will be the solid component of the gel, and the ionic component will be the liquid component of the gel. TAED can be dispersed in a liquid composed of the ionic component.

[0011] The composite form can be a solid. TAED can be encapsulated within a solid ionic component. TAED can be mixed with the ionic component.

[0012] The composite form may include a surfactant. The surfactant may be a solid surfactant. Typically, the composite form containing a solid surfactant will be solid. The solid surfactant may be mixed with TAED and an ionic component.

[0013] When a surfactant is present, it can be present in an amount ranging from 10% w / w to 80% w / w of the total weight in a compound form.

[0014] The TAED in the complex can be in crystalline form III.

[0015] The characteristic of the composite form may be that the form can be obtained by the following (e.g., by the following):

[0016] TAED is formed by heating a component of a deep eutectic solvent (DES), a DES solvent (DES), an ionic liquid (IL), or a mixture thereof to a temperature of ≥150°C;

[0017] The mixture is cooled to form a composite form.

[0018] The molar ratio of TAED to the ionic component can be in the range of 3:1 to 1:3. The molar ratio of TAED to the ionic component can be in the range of 2:1 to 1:2. The molar ratio of TAED to the ionic component can be approximately 1:1.

[0019] TAED can exist in quantities greater than 10% of the total weight of TAED and ionic components. TAED can exist in quantities greater than 25% of the total weight of TAED and ionic components. TAED can exist in quantities greater than 50% of the total weight of TAED and ionic components. TAED can exist in quantities less than 95% of the total weight of TAED and ionic components. TAED can exist in quantities less than 90% of the total weight of TAED and ionic components. TAED can exist in quantities less than 80% of the total weight of TAED and ionic components.

[0020] In a second aspect of the invention, a crystalline form of TAED is provided, which is form III.

[0021] The composite form of TAED in the first aspect can be the crystalline form of the second aspect.

[0022] Like the composite form of the first aspect, TAED form III exhibits significantly higher solubility and dissolution rate at 20°C than commercially available TAED. Therefore, when contacted with a suitable bleaching agent, TAED form III of the present invention is capable of producing high concentrations of peracetic acid in water.

[0023] The crystalline form (i.e., form III) is characterized in that, when dispersed in a DES solvent (DES) or an ionic liquid (IL), it has an XRPD plot with only two peaks at 2θ 9.1746±0.2 and 18.1788±0.2, where K is used. α2 / K α1 Cu radiation measurement XRPD with a ratio of 0.5.

[0024] Without a doubt, these two peaks are the only peaks in the XRPD plot.

[0025] The characteristic of the crystalline form (i.e., form III) is that the form can be obtained by means of the following (e.g., by means of the following):

[0026] TAED is formed by heating a component of a deep eutectic solvent (DES), a DES solvent (DES), an ionic liquid (IL), or a mixture thereof to a temperature of ≥150°C;

[0027] The mixture is cooled to form TAED III crystals dispersed in DES or IL.

[0028] TAED crystalline form III may be associated with DES or IL. TAED crystalline form III can be dispersed in liquid DES or IL. TAED crystalline form III can be encapsulated in solid DES or IL.

[0029] The crystalline form can have essentially the following characteristics: Figure 2 The XRPD diagram shown.

[0030] In a third aspect of the invention, a method for forming a composite form of, for example, TAED of the first aspect is provided, the method comprising:

[0031] The TAED component is formed by reacting it with a deep eutectic solvent (DES), a DES solvent, an ionic liquid (IL), or a mixture thereof, and heated to a temperature ≥150°C; and

[0032] The mixture is cooled to form a composite form.

[0033] The method of the third aspect of the present invention may be a method for forming the crystalline form of the second aspect of the present invention (e.g., crystalline form III), the method comprising:

[0034] The TAED component is formed by reacting it with a deep eutectic solvent (DES), a DES solvent, an ionic liquid (IL), or a mixture thereof, and heated to a temperature ≥150°C; and

[0035] The mixture is cooled to form TAED III crystals dispersed in DES or IL.

[0036] When TAED is heated together with the DES forming components, the product of step b will be solid TAED dispersed in DES (e.g., TAED form III crystals).

[0037] The temperature to which the mixture is heated in step a) can be 155°C or higher. The temperature to which the mixture is heated in step a) can be 190°C or lower. The temperature to which the mixture is heated in step a) can be 175°C or lower.

[0038] The product of step b) has a gel-like consistency, the properties of which can be controlled by altering the characteristics of DES or IL or mixtures thereof. This gel-like substance can be solidified to 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 range from a high viscosity of 1000 cP to 120000 cP.

[0039] TAED can be heated together with choline chloride and urea.

[0040] The molar ratio of choline chloride to urea can be in the range of 1:1 to 4:1 (e.g., about 2:1).

[0041] The molar ratio of TAED to DES (or DES forming component) or IL can be in the range of 3:1 to 1:3. The molar ratio of TAED to DES or IL can be in the range of 2:1 to 1:2. The molar ratio of TAED to DES or IL can be approximately 1:1.

[0042] When DES contains choline chloride and urea, the molar ratio of TAED to choline chloride can be in the range of 2:1 to 1:2. The molar ratio of TAED to choline chloride can be approximately 1:1.

[0043] TAED can exist in quantities greater than 10% of the total weight of TAED and ionic components. TAED can exist in quantities greater than 25% of the total weight of TAED and ionic components. TAED can exist in quantities greater than 50% of the total weight of TAED and ionic components. TAED can exist in quantities less than 95% of the total weight of TAED and ionic components. TAED can exist in quantities less than 90% of the total weight of TAED and ionic components. TAED can exist in quantities less than 80% of the total weight of TAED and ionic components.

[0044] When TAED is heated with an ionic liquid or DES solvent at a temperature of ≥150°C or ≥155°C or above, it produces a clear liquid. Upon cooling, TAED is allowed to recrystallize into form III.

[0045] Form III exhibits good stability when dispersed in DES or IL. When the product viscosity of step b) is ≥5000 cP, the dispersion shows physical and chemical stability for up to 6 months under stable conditions at 40°C and 75% RH.

[0046] Therefore, a deep eutectic solvent (DES), a DES solvent (DES), or an ionic liquid (IL) can be selected to form the component, such that the viscosity of the liquid component of the product in step b) is in the range of 5000 cP to 120000 cP.

[0047] The dissolution rate of TAED in the DES or IL system can be further increased by adding liquid additives such as propylene glycol (1,2-propanediol) or sodium tripolyphosphate, caustic soda, sulfonic acid, etc., or mixtures thereof. Therefore, heating step a) can be carried out in the presence of propylene glycol (1,2-propanediol) or sodium tripolyphosphate, caustic soda, sulfonic acid, or mixtures thereof.

[0048] The method may also include step c): adding a surfactant to the product of b) to cure DES or IL and encapsulate the crystalline form III of TAED.

[0049] The surfactant may be a solid surfactant.

[0050] Suitable solid surfactants include: toluene, denatumene, potassium peroxymonosulfonate (KMPS), glycolic acid, sodium peroxydisulfate (NPS), surface-modified polymers, sodium sulfate, zinc ricinoleate, ethylene glycol distearate, alkyl polypentoside (APP), alkyl polyglucoside (APG), amine oxides, amphoacetates, cocamide DEA and MEA, cocoaminopropionate, cocoamphodipropionate, cocoiminodipropionate, and didecyl dimethyl... Ammonium bicarbonate, dodecylbenzene sulfonic acid (DDBSA), MEA&TEA neutralized DDBSA, ethoxylated fatty amines, fluorinated surfactants, octanoyl imino dipropionate, OXO alcohol polyoxyethylene ether, PEG-7 glyceryl cocoate, propoxylated / ethoxylated compounds, siloxane surfactants, sodium C14-16 olefin sulfonate (AOS), sodium C14-17 alkyl secondary sulfonate (SAS), sodium lauryl ether sulfate (SLES), sodium dodecyl sulfate (SLS), urea.

[0051] The third approach can be a method for forming a composite form of the first approach. The third approach can also be a method for forming a crystalline form of the second approach.

[0052] The composite form of the first aspect can be prepared according to the method of the third aspect. The crystalline form of the first aspect can be prepared according to the method of the third aspect.

[0053] In a fourth aspect of the invention, a composition is provided comprising either a composite form of TAED from the first aspect or a crystalline form of TAED from the second aspect.

[0054] The composition can be a solid composition, such as a powder composition. The composition can be a suspension or a paste, wherein the TAED composite form exists in a solid state.

[0055] The composition may be a detergent composition. The composition may be a bleaching composition.

[0056] The composition may contain 0.1% to 20% by weight of the crystalline form of TAED of the first aspect.

[0057] Typically, TAED form III will be encapsulated in solid DES or ionic liquid.

[0058] The composition typically also includes a solid surfactant, such as those selected from: toluene, benzyl denatonium, potassium peroxymonosulfonate (KMPS), glycolic acid, sodium peroxydisulfate (NPS), surface-modified polymers, sodium sulfate, zinc ricinoleate, ethylene glycol distearate, alkyl polypentoside (APP), alkyl polyglucoside (APG), amine oxides, amphoteric acetates, cocoamide DEA and MEA, cocoaminopropionate, cocoamphodipropionate, cocoiminodipropionate, and didecyl... Dimethyl carbonate / ammonium bicarbonate, dodecylbenzene sulfonic acid (DDBSA), MEA&TEA neutralized DDBSA, ethoxylated fatty amines, fluorinated surfactants, octanoyl imino dipropionate, OXO alcohol polyoxyethylene ether, PEG-7 glyceryl cocoate, propoxylated / ethoxylated compounds, siloxane surfactants, C14-16 olefin sulfonate sodium (AOS), C14-17 alkyl secondary sulfonate sodium (SAS), sodium lauryl ether sulfate (SLES), sodium dodecyl sulfate (SLS), urea.

[0059] The composition may contain one or more additional bleaching activators. One or more additional bleaching activators may be selected from the group consisting of: crystalline form I of TAED, crystalline form II of TAED, triacetylethyldiamine, nonanoic acid sulfonyl ester (NOBS), and dodecyloxybenzenesulfonic acid (DOBS).

[0060] The composition may further comprise 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.

[0061] The composition may further comprise at least one surfactant or wetting agent. The composition may further comprise at least one additive selected from the group consisting of: pH adjusters, chelating agents, stabilizers, diluents, flow aids, binders, effervescent agents, disintegrants, and coating agents. Attached Figure Description

[0062] The embodiments of the present invention are further described below with reference to the accompanying drawings, wherein:

[0063] Figure 1 PXRD plots of TAED forms I and II are shown (excerpted from WO2017068348A1).

[0064] Figure 2 The PXRD plot of TAED form III is shown.

[0065] Figure 3 The graph shows the dissolution rates of the composite TAED and TAED form I of the present invention in water. Detailed Implementation

[0066] It is known in the art that X-ray powder diffraction patterns can be obtained with one or more measurement errors depending on the measurement conditions (e.g., equipment, sample preparation, or machine used). In particular, it is known that the intensity in an X-ray powder diffraction pattern can fluctuate depending on the measurement conditions and sample preparation. For example, those skilled in the art of X-ray powder diffraction will recognize that the relative intensity of peaks can vary depending on the orientation of the sample being tested and the type and settings of the instrument used. Those skilled in the art will also recognize that the position of the reflections can be affected by the precise height of the sample in the diffractometer and the zero-point calibration of the diffractometer. The surface flatness of the sample may also have a minor effect. Therefore, those skilled in the art will understand that the diffraction pattern data given herein should not be interpreted as absolute, and any crystalline form providing substantially the same power diffraction patterns as those disclosed herein falls within the scope of this disclosure (further information can be found in Jenkins, R&Snyder, RL'Introduction to X-Ray Powder Diffractometry' John Wiley & Sons, 1996).

[0067] Deep eutectic solvent

[0068] Deep eutectic solvents are systems formed from eutectic mixtures of Lewis or Brønsted acids and bases (which can contain a variety of anionic and / or cationic species). They are classified as ionic solvents with special properties. They are added in the form of a mixture of one or more compounds, resulting in a eutectic with a melting point much lower than that of any single component. One of the most significant deep eutectic phenomena was observed with a mixture of choline chloride and urea in a molar ratio of 1:2. The resulting mixture has a melting point of 12 °C (far lower than the melting point of choline chloride (302 °C) and urea (133 °C), making it a liquid at room temperature.

[0069] First-generation eutectic solvents are based on mixtures of quaternary ammonium salts and hydrogen-bonding donors such as amines and carboxylic acids. There are four types of eutectic solvents:

[0070] Type I Quaternary ammonium salt + metal chloride

[0071] Type II Quaternary ammonium salt + metal chloride hydrate

[0072] Type III Quaternary Ammonium Salt + Hydrogen Bond Donor

[0073] Type IV metal chloride hydrates + hydrogen bond donors

[0074] The eutectic solvent also includes reacting an ammonium compound with a second compound selected from the group consisting of amines, amides, carboxylic acids, alcohols, metal halides, and combinations thereof.

[0075] Deep eutectic solvents or solutions (DES) are formed by complexing 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 discrete ions and are readily produced by simply mixing common everyday chemicals such as choline chloride with carboxylic acids or amides.

[0076] Other examples include: choline chloride: lactate DES, and proline: lactate DES, choline chloride: citric acid and dimethylurea: citric acid, and propylene glycol: citric acid DES.

[0077] The ionic component can be selected from the following DES: choline chloride: lactate DES; and proline: lactate DES; choline chloride: citrate DES and propylene glycol: citrate DES. The ionic component can also be propylene glycol: citrate DES.

[0078] Ionic liquids

[0079] Illustrative ionic liquids include those described in WO2006050307, ​​US20190085273, and WO2017156141.

[0080] Illustrative ionic liquids include:

[0081] Imidazolium salts, such as 1-butyl-3-methylimidazolium hexafluorophosphate, are also known as [bmim]. Other known ionic liquids include: 1-ethyl-3-methylimidazolium chloride-aluminum(III), commonly referred to as [emim]Cl-AlCl3; and n-butylpyridine aluminum(III) chloride, commonly referred to as [Nbupy]Cl-AlCl3.

[0082] Another illustrative ionic liquid is diisopropanolamine (DIPA).

[0083] The following are non-limiting examples of anions and cations applicable to the ionic liquids of the present invention.

[0084] anions

[0085] The anions suitable for the ionic liquids of this invention include, but are not limited to, the following substances:

[0086] (1) Alkyl sulfates (AS), alkoxy sulfates and alkylalkoxy sulfates; non-limiting examples of alkoxy sulfates include sulfated derivatives of commercially available alkoxy copolymers, such as Pluronics® (from BASF).

[0087] (2) Sulfosuccinic acid monoesters and diesters: Non-limiting examples include saturated and unsaturated C64-2 ... 12-18 Monoester sulfosuccinates, such as lauryl sulfosuccinate available as Mackanate LO-100® (from Mclintyre Group); saturated and unsaturated C6–C 12 Diester sulfosuccinate, such as dioctyl sulfosuccinate (from Cytec Industries), which is available as Aerosol OT®.

[0088] (3) Methyl ester sulfonate (MES);

[0089] (4) Alkyl aryl sulfonates, non-limiting examples including toluene sulfonates, having a straight or branched chain, saturated or unsaturated C8-C 14 Alkyl alkyl aryl sulfonates; alkylbenzene sulfonates (LAS), such as C 11 -C 12 Alkylbenzene sulfonates;

[0090] (5) Alkyl glycerol ether sulfonates having 8 to 22 carbon atoms in the alkyl moiety;

[0091] (6) Diphenyl ether (biphenyl) derivatives: Non-limiting examples include triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether) and diclosan (4,4'-dichloro-2-hydroxydiphenyl ether), both of which are available as Irgasan® from Ciba Specialty Chemicals;

[0092] (7) Linear or cyclic carboxylates: Non-limiting examples include citrate, lactate, tartrate, succinate, alkyl succinate, maleate, gluconate, formate, cinnamate, benzoate, acetate, salicylate, phthalate, aspartate, adipate, acetylsalicylate, 3-methylsalicylate, 4-hydroxyisophthalate, dihydroxyfumarate, 1,2,4-benzenetricarboxylate, valerate, and mixtures thereof;

[0093] (8) Medium-chain branched alkyl sulfates (HSAS), medium-chain branched alkyl aryl sulfonates (MLAS) and medium-chain branched alkyl polyoxyethylene sulfates; non-limiting examples of MLAS are disclosed in US 6,596,680, US 6,593,285 and US 6,202,303;

[0094] (9) Sarcosine salts; non-limiting examples include lauroyl sarcosine ammonium, available from Dow Chemicals as Hamposyl AL-30®, and sodium oleoyl sarcosine, available from Dow Chemicals as Hamposyl O®;

[0095] (10) Straight-chain or branched sulfated and sulfonated oils and fatty acids, such as those sulfates or sulfonates derived from potassium coconut oil soap available from Norman, Fox & Co. as Norfox 1101® and from potassium oleate available from Chemron Corp.

[0096] (11) Fatty acid ester sulfonates;

[0097] (12) Sweetener-derived anions: saccharin salts and acetaminophen;

[0098]

[0099] Saccharin acetaminosulfonate

[0100] Where M+ is a cation selected from the cations of the following ionic liquids;

[0101] (13) Ethoxylated amide sulfates; Sodium tripolyphosphate (STPP); Dihydrogen phosphates; Fluoroalkyl sulfonates; Bis(alkylsulfonyl)amines; Bis-(fluoroalkylsulfonyl)amides; (fluoroalkylsulfonyl)(fluoroacryloylcarbonyl)amides; Bis(arylsulfonyl)amides; Carbonates; Tetrafluoroborate (BF4) - ); hexafluorophosphate (PF6) - );

[0102] (14) Anionic bleaching activators, including, for example:

[0103]

[0104] 4-Nonanoyloxybenzenesulfonate

[0105]

[0106] 4-Dodecanoyloxybenzene sulfonate

[0107]

[0108] 4-decanoyloxybenzoate disclosed in US 5,891,838, US 6,448,430, US 5,891,838, US 6,159,91, US 6,448,430, US 5,843,879, and US 6,548,467.

[0109] cation

[0110] The anions used in the ionic liquids of this invention include, but are not limited to, the following substances:

[0111] (a) A cation of amine oxide, phosphine oxide, or sulfoxide (i.e., a protonated cation form);

[0112] (b) Betaine; non-limiting examples of betaine include dodecyl dimethyl betaine, acetyl dimethyl betaine, dodecylamidopropyl dimethyl betaine, tetradecyl dimethyl betaine, tetradecylamidopropyl dimethyl betaine, ammonium dodecyl dimethyl hexanoate; and amamide alkyl betaine (disclosed in U.S. Patent Nos. 3,950,417, 4,137,191, and 4,375,421; and British Patent No. GB ​​2,103,236); in another embodiment, the cation may be sulfobetaine, disclosed in U.S. Patent 4,687,602;

[0113] (c) Diester quaternary ammonium (DEQA) cation, such as the DEQA cation discussed in US 6,004,922; (d) Alkylene quaternary ammonium cation, such as diallyl dimethylammonium cation, such as dioleyl dimethylammonium available from Witco Corporation under the trade name Adogen® 472; or monoalkenyl trimethylammonium, such as monooleyl trimethylamine, monomustine trimethylammonium, and soybean oil-based trimethylammonium;

[0114] (e) Difatty amide quaternary ammonium cation, for example, difatty amide quaternary ammonium is available from Witco under the trade name Varisoft®;

[0115] (f)C 8-22 Quaternary ammonium surfactants, such as isostearyl ethyliminoonium, which is available from Scher Chemicals, Inc. as ethanol sulfate, Schercoquat IIS®, Quaternary ammonium salt-52, which is available from Cognis Corporation as Dehyquart SP®, and dicosyl dimethylammonium, which is available from Akzo Nobel Surface Chemistry LLC as chloride salt, Arquad 2C-75®;

[0116] (g) Cationic esters, as discussed in US 4,228,042, US 4,239,660, US 4,260,529 and US 6,022,844;

[0117] (h) 4,5-Dichloro-2-n-octyl-3-isothiazolinone, which is available as Kathon® from Rohm and Haas;

[0118] (i) Quaternary amino polyoxyethylene derivatives (choline and choline derivatives);

[0119] (j) Alkyl oxide cation;

[0120] (k) Alkoxylated quaternary ammonium (AQA) as discussed in US 6,136,769;

[0121] (1) Substituted and unsubstituted pyrrolizidine onions, imidazolium onions, benzimidazole onions, pyrazolium onions, benzopyrazolium onions, thiazolyl onions, benzothiazolyl onions, oxazolium onions, benzoxazolium onions, isoxazolium onions, isotazolium onions, imdazolidenium, guanidine onions, indazole onions, quinuclidinium, triazolium onions, isoquinine onions, piperidinium onions, morpholinium onions, pyrazine onions, triazine onions, azepinium, diazepine, pyridinium, piperidonium, pyrimidine onions, thiophene onions; phosphonium;

[0122] (m) Cationic bleaching activators having a quaternary ammonium moiety, including but not limited to

[0123]

[0124] N,N-dimethyl-2-[(phenoxycarbonyl)oxy]-N-[2-[(phenoxycarbonyl)oxy]ethyl]ethanaminium

[0125]

[0126] 4-(cyanomethyl)-4-methylmorpholinium; 1-cyano-N,N,N-trimethylmethanaminium

[0127]

[0128] methyl-3-(l-oxoheptyl)-1H-imidazolium

[0129] These and other cationic bleaching 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 A1, US 6,183,665, US 5,106,528, US 5,281,361 and Bulletin deIa Societe Chimique de France (1973), (3)(Pt.), 1021-7;

[0130] (n) Cationic antimicrobial agents, such as cetylpyridinium, chlorhexidine and domiphen.

[0131] (o) Alkylated caffeine cation.

[0132] The present invention can also be described according to the following numbered paragraphs:

[0133] 1. A crystalline form of TAED (Form III), characterized in that, when dispersed in a DES solvent (DES) or an ionic liquid (IL), the form has an XRPD plot with only two peaks at 2θ 9.1746±0.2 and 18.1788±0.2, wherein the XRPD uses K... α2 / K α1 Cu radiation measurement with a ratio of 0.5.

[0134] 2. The crystalline form according to paragraph 1, wherein the crystalline form has substantially the following characteristics: Figure 2 The XRPD diagram shown.

[0135] 3. A method for forming a crystalline form (form III) of TAED, the method comprising:

[0136] a) Heating TAED with a deep eutectic solvent (DES) to form a component, DES solvent (DES), an ionic liquid (IL), or a mixture thereof to a temperature ≥150°C; and

[0137] b) Cool the mixture to form TAED III crystals dispersed in DES or IL.

[0138] 4. The method according to paragraph 3, wherein the deep eutectic solvent (DES) forming component, DES solvent (DES) or ionic liquid (IL) is selected such that the viscosity of the product of step b) is in the range of 5000 cP to 120000 cP.

[0139] 5. The method described in paragraph 3, wherein the TAED solubility (more than 4 grams of TAED per 100 ml of water) of the high-concentration peracetic acid system obtained in the presence of sodium percarbonate can be achieved.

[0140] 6. The method according to paragraph 3, wherein a eutectic solvent (DES) is used to form the component, a DES solvent (DES) or an ionic liquid (IL) is used to heat, melt and recrystallize TAED, and if TAED is converted from form III to form I, its dissolution rate in water does not change over a period of time (water solubility does not change).

[0141] 7. The method according to paragraph 3 or paragraph 4, wherein the heating step a) may be carried out in the presence of propylene glycol (1,2-propanediol) or sodium tripolyphosphate, caustic soda, sulfonic acid or a mixture thereof.

[0142] 8. The method according to any one of paragraphs 3 to 5, wherein the method comprises step c): adding a solid surfactant to the product of b) to cure DES or IL to obtain crystalline form III of TAED encapsulated in DES or IL.

[0143] 9. The method according to paragraph 6, wherein the surfactant is selected from: toluene, denatonium benzoate, potassium peroxymonosulfonate (KMPS), glycolic acid, sodium peroxydisulfate (NPS), surface-modified polymers, sodium sulfate, zinc ricinoleate, ethylene glycol distearate, alkyl polypentoside (APP), alkyl polyglucoside (APG), amine oxide, amphoteric acetate, cocoamide DEA and MEA, cocoaminopropionate, cocoamphodipropionate, cocoiminodipropionate, and didecyl dimethyl ammonium carbonate / carbon. Ammonium bicarbonate, dodecylbenzene sulfonic acid (DDBSA), MEA&TEA-neutralized DDBSA, ethoxylated fatty amines, fluorinated surfactants, octanoyl imino dipropionate, OXO alcohol polyoxyethylene ether, PEG-7 glyceryl cocoate, propoxylated / ethoxylated compounds, siloxane surfactants, sodium C14-16 olefin sulfonate (AOS), sodium C14-17 alkyl secondary sulfonate (SAS), sodium lauryl ether sulfate (SLES), sodium dodecyl sulfate (SLS), urea, and mixtures thereof.

[0144] 10. A crystalline form of TAED (Form III), characterized in that it can be obtained by any one of paragraphs 3 to 7.

[0145] 11. A composition comprising the crystalline form of TAED as described in any one of paragraphs 1, 2 and 8.

[0146] 12. The composition according to paragraph 9, wherein the composition is a solid composition.

[0147] 13. The composition according to paragraph 9 or paragraph 10, wherein the TAED form III is encapsulated in a solid DES or ionic liquid.

[0148] 14. The composition according to any one of paragraphs 9 to 11, wherein the composition comprises 0.1% to 20% by weight, or 0.1% to 50% by weight, or more than 75% by weight of the crystalline form of TAED form I according to any one of paragraphs 1, 2 and 8.

[0149] 15. The composition according to any one of paragraphs 9 to 12, wherein the composition further comprises a solid surfactant.

[0150] 16. The composition according to paragraph 13, wherein the surfactant is selected from: toluene, benzyl denatonium, potassium peroxymonosulfonate (KMPS), glycolic acid, sodium peroxydisulfate (NPS), surface-modified polymers, sodium sulfate, zinc ricinoleate, ethylene glycol distearate, alkyl polypentoside (APP), alkyl glucoside (APG), amine oxide, amphoteric acetate, cocoamide DEA and MEA, cocoaminopropionate, cocoamphodipropionate, cocoiminodipropionate, didecyl dimethyl ammonium carbonate / Ammonium bicarbonate, dodecylbenzene sulfonic acid (DDBSA), MEA&TEA-neutralized DDBSA, ethoxylated fatty amines, fluorinated surfactants, octanoyl imino dipropionate, OXO alcohol polyoxyethylene ether, PEG-7 glyceryl cocoate, propoxylated / ethoxylated compounds, siloxane surfactants, sodium C14-16 olefin sulfonate (AOS), sodium C14-17 alkyl secondary sulfonate (SAS), sodium lauryl ether sulfate (SLES), sodium dodecyl sulfate (SLS), urea, and mixtures thereof.

[0151] 17. The composition according to any one of paragraphs 9 to 14, wherein the composition further comprises a bleaching agent.

[0152] 18. The composition according to any one of paragraphs 9 to 15, wherein the composition further comprises at least one surfactant or wetting agent.

[0153] 19. The composition according to any one of paragraphs 9 to 16, wherein the composition may further comprise at least one additive selected from the group consisting of: pH adjusters, chelating agents, stabilizers, diluents, flow aids, binders, effervescent agents, disintegrants, and coating agents.

[0154] Throughout the description and claims of this specification, the words “comprising” and “containing” and their variations mean “including but not limited to”, and they are not intended to (and do not) exclude other parts, additives, components, integers, or steps. Throughout the description and claims of this specification, the singular includes the plural unless the context requires otherwise. In particular, where the indefinite article is used, the specification should otherwise be understood to consider both the plural and the singular.

[0155] Features, integrals, properties, compounds, chemical parts, or groups described in connection with a particular aspect, embodiment, or example of the invention should be understood to be applicable to any other aspect, embodiment, or example described herein, unless incompatible therewith. All features disclosed in this specification (including any appended claims, abstract, and drawings), and / or all steps of any method or process so disclosed, may be combined in any combination, except for combinations in which at least some of such features and / or steps are mutually exclusive. The invention is not limited to the details of any of the foregoing embodiments. The invention (including any appended claims, abstract, and drawings) extends to any novel one or any novel combination of features disclosed in this specification, or to any novel one or any novel combination of steps of any method or method so disclosed.

[0156] Readers should note all papers and documents submitted concurrently with or prior to this specification that are related to this application and are publicly available together with this specification, and the contents of all such papers and documents are incorporated herein by reference.

[0157] Example

[0158] General Procedure

[0159] Program I:

[0160] Accurately weigh the ionic liquid or DES forming components (e.g., propylene glycol and citric acid in a 1:2 or 1:1 molar ratio) into a glass beaker.

[0161] Heat the mixture above 150°C until a clear liquid is obtained.

[0162] Add TAED and stir the mixture until a clear liquid is obtained.

[0163] Once a clear liquid is obtained, turn off the heating.

[0164] Allow the final mixture to cool. TAED typically recrystallizes into polymorphic form III.

[0165] PXRD was performed on the mixture after it had completely cooled to confirm the formation of TAED polymorph III.

[0166] Program II:

[0167] Accurately weigh the ionic liquid or DES forming component (e.g., propylene glycol:citric acid in a 1:2 or 1:1 molar ratio) and add the exact required amount of TAED.

[0168] Mix these components thoroughly

[0169] Heat the mixture at above 150°C with stirring.

[0170] Once a clear liquid is obtained, turn off the heat and allow the mixture to cool.

[0171] PXRD was performed on the cooled mixture to confirm the TAED polymorph III.

[0172] Example 1 - Method for separating (S)-epomers in form III

[0173] According to Procedure II, take 1 gram of TAED and an equimolar ratio of DES to form a component (e.g., propylene glycol:citric acid 1:2, take 0.76 grams of propylene glycol and 3.84 grams of citric acid).

[0174] Mix all the above ingredients and heat them in a beaker to above 150°C (155°C or 160°C) until a homogeneous final product is obtained.

[0175] The final product should be cooled.

[0176] Example 2 - X-ray Powder Diffraction (XRPD)

[0177] A viscous sample of TAED crystal form III (TAED comprising 20% ​​of the total weight of the composite, and DES being a 1:1 molar ratio of propylene glycol:citric acid) suspended in DES of Example 1 was spread on a sample holder. The PXRD pattern was analyzed using an X-ray instrument at 1.54 Å wavelength and a 40 kV Cu(Kα) source with 40 mA filament emission. All samples were scanned from 5 to 35° (2θ) using a 0.01° step and a 1-second time count. The scattering and receiving slits were 0.2° and 1°, respectively.

[0178] The obtained spectrum is as follows Figure 2 As shown. The observed peaks are as follows:

[0179]

[0180] 2Th. = °2θ. Typically, ±0.2 exists at the XRPD peak position. o The error is 2θ.

[0181] The inventors also demonstrate that when Example 1 was repeated using choline chloride: lactate DES; proline: lactate DES; and choline chloride: citrate DES, crystalline form III of TAED was produced. The inventors further demonstrate that when Example 1 was repeated using diisopropanolamine ionic liquid, crystalline form III of TAED was produced.

[0182] Example 3: Performance and water miscibility program at 20°C

[0183] When TAED is added to water in the presence of sodium percarbonate, peracetic acid is produced. The peracetic acid formation rate of TAED crystal form III (TAED accounts for 20% of the total weight of the complex, and DES is propylene glycol:citric acid in a molar ratio of 1:1) and commercially available TAED form I were compared.

[0184] Experimental details:

[0185] This experiment was conducted to examine the performance and water miscibility of TAED in the presence of sodium percarbonate. 1 g of TAED and 2.5 g of sodium percarbonate were added to 1 liter of water and stirred at 500 rpm using a top-mounted stirrer. The volume of water used in the experimental setup was 1 liter. The weight of the remaining substance after 5 minutes was calculated. The results showed that, compared to commercially available TAED, form III based on DES exhibited complete miscibility or a clear solution. The results are shown in the table below.

[0186] Table 2

[0187]

[0188] The above results demonstrate how rapidly TAED form III in DES / ionic liquids enters water to form peracetic acid in the presence of sodium percarbonate.

[0189] Similar studies were conducted using smaller amounts of water (100ml, 250ml, 500ml), and all studies yielded similar results to those described above. In the 100ml study, the residual amount after 5 minutes in the TAED DES system was less than 5-10mg, compared to 800mg for commercial TAED. For the 250ml study, the TAED DES solution was clear, and the results were similar in the 500ml experiment, while the residual amounts for commercial TAED were 750mg and 690mg, respectively.

[0190] A similar study was conducted, in which the amount of TAED was increased to 5 grams per liter of water, and the results are shown in the table below.

[0191] Table 3

[0192]

[0193] One study was conducted in a small volume (i.e., 100 ml) of water containing the largest amount of TAED DES system (4 g of TAED in the TAED DES system). After stirring for 5 minutes, the solution began to become clear, and after continued stirring, almost the entire solution became clear (the final solution contained less than 100 mg of substance after filtration). This demonstrates the efficiency of the TAED DES system's solubility in water and shows that the highest amount of peracetic acid can be generated using the TAED DES system in water at room temperature without heating.

[0194] The inventors also demonstrated that similar results were obtained using compositions comprising choline chloride: lactate DES; proline: lactate DES and choline chloride: citrate DES and diisopropanolamine ionic liquid.

[0195] Example 4

[0196] When TAED is added to water in the presence of sodium percarbonate, peracetic acid is produced. The peracetic acid formation rate of the composite TAED of the present invention (TAED form III) (TAED accounts for 20% of the total weight of the composite, and DES is propylene glycol:citric acid in a molar ratio of 1:1) and commercially available TAED were compared using the DES composite of the present invention.

[0197] Experimental details:

[0198] Part I:

[0199] Experiments were conducted to examine the performance and water miscibility of the composite TAED of the present invention in the presence of sodium percarbonate. The TAED:sodium percarbonate ratio used in the study was 1:2.5 w / w. Weighed TAED (1 g of commercial sample and an equimolar amount of the composite TAED of the present invention, i.e., 5 g) and sodium percarbonate were added to 100 mL of water and stirred at 500 rpm using a top-mounted stirrer. The 100 mL solution was used as is, or it was further diluted with 900 mL of water to prepare 1 L of sample. The weight of the remaining substance was calculated after 5 minutes. The sample was tested after stirring was stopped (T=0) and after 6 months (T=6 months, sample stored at 40°C and 75% relative humidity). The results showed that TAED form III exhibited complete miscibility or provided a clear solution compared to commercially available TAED (see table below).

[0200] Table 4

[0201]

[0202] The above results indicate that, in the presence of sodium percarbonate, the solubility of the composite TAED of the present invention in water is significantly higher than that of commercially available TAED.

[0203] Part II:

[0204] A similar study was conducted in which the amount of TAED was increased to 3 grams per 100 ml of water (3 grams of commercial sample and an equimolar amount of the composite TAED of the present invention, i.e., 15 grams). The results are shown in the table below.

[0205] Table 5

[0206]

[0207] The above results indicate that, in the presence of sodium percarbonate, the solubility of the composite TAED of the present invention in water is significantly higher than that of commercially available TAED.

[0208] Example 5 - Dissolution Process Rate

[0209] Using a USP II dissolution apparatus, the dissolution rate of the composite TAED form III (TAED being 20% ​​of the total weight of the composite, and DES being propylene glycol:citric acid in a 1:1 molar ratio) in water (500 ml) of the DES of the present invention was compared with the dissolution rate of commercially available tetraacetylethylenediamine (form I) at 20°C. 1 g of a commercially available sample and an equimolar amount of the composite TAED of the present invention, i.e., 5 g, were used. Powders from Examples 1 and 2 were rotated from a disc 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 as follows: Figure 3 As shown.

[0210] Figure 3 It is clearly shown that the dissolution rate of the composite TAED of the present invention is more than 30 times faster than that of commercially available TAED. This will then be reflected in the rate of peracetic acid formation. This clearly demonstrates that the composite TAED of the present invention will produce peracetic acid at a faster rate and can prepare a more concentrated peracetic acid solution at 20°C.

[0211] Example 6 - PAA Release

[0212] Four different TAED samples in citric acid and propylene glycol (molar ratio 1:1) were prepared to assess whether the TAED to DES ratio at room temperature (@20℃) had any effect on the release rate of peracetic acid.

[0213] Sample 1 (liquid) TAED concentration: 20-25% w / w composite form

[0214] Sample 2 (liquid) TAED concentration: 45-50% w / w composite form

[0215] Sample 3 (semi-solid) TAED concentration: 60-65% w / w composite form

[0216] Sample 4 (solid powder; also contains sodium dodecyl sulfate surfactants) TAED concentration: 70-75% w / w relative to DES. The ratio of TAED / DES to surfactant ranged from 4:1 to 6:1.

[0217] analyze

[0218] The sample was mixed with sodium percarbonate in water (1:1.25). The sample was titrated with 0.1M potassium permanganate solution and 0.01M sodium thiosulfate solution. The sample was dissolved in 0.5M sulfuric acid. After dissolution, potassium permanganate was added until a color change occurred. During the addition, the pH and temperature of the sample were monitored to see if these parameters changed during titration. After the color change, potassium iodide was added. The sample was further titrated with sodium thiosulfate using a starch indicator solution until a color change occurred. The pH and temperature of the sample were also monitored during titration.

[0219] The amount of hydrogen peroxide in the two samples was determined by potassium permanganate titration. Sample 4 contained 203,947 ppm of hydrogen peroxide, and Sample 3 contained 141,209 ppm of hydrogen peroxide. Repeat analyses were performed on both samples. Sample 1 contained 9,380 ppm of hydrogen peroxide. Sample 2 contained 155,462 ppm of hydrogen peroxide. Peracetic acid was determined by titration with sodium thiosulfate. The amount of peracetic acid in the samples was repeatedly determined by titration with sodium thiosulfate. The results showed that Sample 4 contained 7,599 ppm of peracetic acid. Sample 3 contained 3,178 ppm of peracetic acid. Sample 1 contained 1,387 ppm of peracetic acid. Sample 2 contained 2,452 ppm of peracetic acid.

[0220] This indicates that at 20°C, the complex of the present invention provides very high levels of hydrogen peroxide and / or peracetic acid when exposed to percarbonate, even with a very high loading of TAED relative to the amount of DES. Even in solid sample 4, the solubility remains high.

Claims

1. A crystalline form of TAED (Form III), characterized in that, when dispersed in a DES solvent (DES) or an ionic liquid (IL), the form has an XRPD plot with only two peaks at 2θ 9.1746 ± 0.2 and 18.1788 ± 0.2, and wherein the XRPD uses K... α2 / K α1 Cu radiation measurement with a ratio of 0.

5.

2. The crystalline form according to claim 1, wherein the crystalline form has an XRPD pattern substantially as shown in FIG2.

3. A composition comprising the crystalline form of TAED as described in claim 1 or claim 2.

4. The composition according to claim 3, wherein the composition further comprises a bleaching agent.

5. The composition according to claim 4, wherein the bleaching agent is a metal percarbonate.

6. The composition according to claim 5, wherein the bleaching agent is sodium percarbonate or potassium percarbonate.

7. The composition according to any one of claims 3 to 6, wherein the composition further comprises at least one surfactant or wetting agent.

8. The composition according to any one of claims 3 to 7, wherein the composition further comprises at least one additive selected from the group consisting of: pH adjusters, chelating agents, stabilizers, diluents, flow aids, binders, effervescent agents, disintegrants, and coating agents.

9. The composition according to any one of claims 3 to 8, wherein the composition further comprises an ionic component selected from DES and ionic liquids.

10. The composition according to any one of claims 3 to 9, wherein the composition is a solid composition.

11. The composition according to claim 10, wherein the composition is a powder composition.

12. The composition according to any one of claims 3 to 11, wherein the composition is a detergent composition.

13. The composition according to any one of claims 3 to 11, wherein the composition is a bleaching composition.

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